JP4897193B2 - Laminated hose comprising a conductive fluorine-containing copolymer composition - Google Patents

Description

  The present invention relates to a conductive fluorine-containing copolymer composition excellent in conductivity, chemical resistance and fuel barrier properties and excellent in adhesion to a polyamide resin, and a laminated hose comprising a polyamide resin.

  Fluorine-containing copolymers such as polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers, and ethylene / tetrafluoroethylene copolymers have chemical resistance, heat resistance, weather resistance, gas barrier properties, etc. It has excellent characteristics and is used in various fields such as the semiconductor industry and the automobile industry.

  For example, the application of fluorine-containing polymers to components such as tanks, hoses and tubes, particularly to fuel hoses used in automobile engine rooms exposed to harsh conditions such as high-temperature environments has been studied. The fuel hose is a piping hose for transferring a gasoline-based fuel containing an alcohol or an aromatic compound such as methanol or ethanol.

  In particular, a fuel hose composed of a multilayer laminated hose containing a fluorine-containing copolymer (hereinafter simply referred to as “laminated hose”) has been studied as satisfying various required characteristics. In the laminated hose, the inner layer material that comes in direct contact with the fuel must use a resin that has a fuel barrier property that does not easily permeate the fuel and a chemical resistance to erosive liquids such as ethanol and methanol contained in the fuel. It is. In this respect, the fluorine-containing copolymer is suitable as an inner layer material because it is excellent in chemical resistance, heat resistance and fuel barrier properties. In addition, the inner layer material must also have anti-static properties so that static electricity generated when the fuel passes does not accumulate.

  On the other hand, as a material for the outer layer of the fuel hose, polyamide resins such as polyamide 6, polyamide 11 and polyamide 12 having excellent mechanical properties and durability have excellent properties, so that a laminated hose is laminated with a fluorine-containing copolymer. Preferred to form.

  In recent years, in order to prevent air pollution due to fuel emissions from automobiles, strict laws and regulations restricting the amount of gasoline permeated from the fuel hose have been enacted. It has been requested. As a constituent material of the fuel hose, an ethylene-tetrafluoroethylene copolymer having excellent fuel barrier properties and mechanical properties is used among the fluorine-based polymers. As laws and regulations become more stringent in the future, development of fluoropolymers with further improved fuel barrier properties is strongly demanded.

  Conventionally, when trying to manufacture a laminated hose including a laminated structure of an inner layer made of a fluorine-containing copolymer and an outer layer made of a polyamide resin, there has been the following problem. That is, the fluorine-containing copolymer inherently has poor adhesiveness, and even when the hose or the like of the fluorine-containing copolymer is directly covered with a base material made of a polyamide resin as an outer layer, sufficient adhesive strength cannot be obtained. If the adhesive force is insufficient, the layers are peeled off during use, which may cause major problems such as hose blockage and increased fuel permeation.

  Thus, a technique for improving the adhesion between layers in a laminated hose has been studied. For example, after the fluorocopolymer is first formed into a tube by extrusion, the outer surface of the fluorocopolymer tube is treated by various methods such as chemical treatment, corona discharge treatment, plasma discharge treatment, etc. Are introduced into the surface and chemically activated. Next, after applying an adhesive as required, a polyamide resin is extruded and laminated on the outside of the tube of the fluorine-containing copolymer (see, for example, Patent Document 1).

  According to such a method, a fuel hose excellent in adhesion between layers is manufactured. However, in this method, first, a three-step process of forming a hose of a fluorine-containing copolymer, activating this surface, and melt-extruding a polyamide tube on its outer surface must be carried out. However, there is a problem that the process is complicated and the productivity of the laminated hose is low.

  Therefore, it has excellent fuel permeability and crack resistance, does not require surface treatment such as corona discharge treatment of the fluorinated copolymer, and coextrusion molding a laminated hose of the fluorinated polymer and polyamide resin Thus, there is a demand for a method that can be molded in a single step by a simple method such as, for example, obtaining a fluorine-containing copolymer having such properties.

US Pat. No. 5,554,425 (claims 1-9)

  The present invention is strongly required to be realized on the basis of the background as described above, and has excellent fuel barrier properties, chemical resistance, excellent conductivity, and excellent adhesion to a polyamide resin. It is a basic problem to provide a fluorine-containing copolymer excellent in coextrudability with a resin.

  As a result of intensive investigations from such a viewpoint, the inventors of the present invention are composed of a fluorine-containing copolymer having a specific composition containing a polymer unit based on a polycarboxylic acid anhydride having a polymerizable unsaturated bond such as itaconic anhydride and a conductive filler. According to the composition, it has been found that such a problem can be achieved, and thus a laminated hose of the fluorine-containing copolymer composition and the polyamide resin can be created, and the present invention has been completed.

According to the present invention, the following laminated hose is provided.
[1]
In a laminated hose including a laminate in which a layer of a conductive fluorine-containing copolymer composition (AB) and a polyamide resin (PA) layer are directly laminated, the conductive fluorine-containing copolymer composition (AB) Contains a polymerized unit (a) based on tetrafluoroethylene, a polymerized unit (b) based on ethylene and a polymerized unit (c) based on a polycarboxylic acid anhydride having a polymerizable unsaturated bond, and (a) / ( The fluorine-containing copolymer (A) having a molar ratio of b) of 20/80 to 80/20 and a molar ratio of (c) / ((a) + (b)) of 1/1000 to 5/100 And a conductive filler (B), wherein (A) / (B) is a conductive fluorine-containing copolymer composition (AB) having a mass ratio of 70/30 to 99/1. Laminated hose.

[2]
The conductive filler (B) is a carbon-based conductive filler having a BET specific surface area of 50 to 1000 m ² / g and a DBP oil absorption of 100 ml / 100 g to 1000 ml / 100 g. Laminated hose.

[3]
In addition to the polymerized unit (a), polymerized unit (b) and polymerized unit (c), the fluorine-containing copolymer (A) further contains CH ₂ ═CX (CF ₂ ) _n Y (where X, Y is independently a hydrogen atom or a fluorine atom, and n is an integer of 2 to 5.) and contains a polymerized unit (d) based on the monomer represented by (d) / ((a) + ( The laminated hose according to item [1] or [2], wherein b)) is 1/1000 to 15/100 in molar ratio.

[4]
The laminated hose according to any one of items [1] to [3], wherein the conductive fluorine-containing copolymer composition (AB) further contains a polyphenylene sulfide resin (C) or a polybutylene aromatic polyester (D).

[5]
A laminated hose having a layer of the conductive fluorine-containing copolymer composition (AB) according to any one of items [1] to [4] as an innermost layer.

[6]
The laminated hose according to any one of items [1] to [5], wherein the laminate is obtained by coextrusion molding.

Hereinafter, preferred embodiments of the present invention will be described in detail.
(Fluorine-containing copolymer)
The laminated hose of the present invention (in the present invention, hose, tube and pipe are basically used as terms having the same meaning), a layer of a conductive fluorine-containing copolymer composition (AB), a polyamide resin ( A laminated hose including a laminate in which a layer of (PA) is directly laminated,

The conductive fluorine-containing copolymer composition (AB) is polymerized based on a polycarboxylic acid anhydride having a polymerized unit (a) based on tetrafluoroethylene, a polymerized unit (b) based on ethylene, and a polymerizable unsaturated bond. It is a conductive fluorine-containing copolymer composition (AB) containing a fluorine-containing copolymer (A) containing a unit (c) and a conductive filler (B).

  Here, the fluorine-containing copolymer (A) in the present invention includes a polymer unit (a) based on tetrafluoroethylene (hereinafter referred to as “TFE”) and a polymer unit (b) based on ethylene (hereinafter referred to as “E”). ) And a polymerized unit (c) based on a polycarboxylic anhydride (hereinafter referred to as “CM”) having a polymerizable unsaturated bond.

  The molar ratio of the polymerized unit (a) based on TFE and the polymerized unit (b) based on E is 20/80 to 80/20, preferably 50/50 to 70/30. If (a) / (b) is too small, the chemical resistance, heat resistance, weather resistance, fuel barrier property, gas barrier property, etc. of the fluorinated copolymer (A) will be reduced, while it will be too large. When too large, mechanical strength, melt moldability, etc. will fall. That is, when the molar ratio is in the range specified above, the fluorinated copolymer (A) has chemical resistance, heat resistance, weather resistance, fuel barrier properties, gas barrier properties, mechanical strength, melt moldability, etc. It will be remarkably superior.

  The content of the polymerized units (c) based on the polycarboxylic acid anhydride CM is such that the molar ratio of (c) / ((a) + (b)) is 1/1000 to 5/100, preferably 3 / 1000 to 3/100. When (c) / ((a) + (b)) is too small, the fluorine-containing copolymer (A) has low adhesion to the polyamide resin. Decreases. Therefore, when the molar ratio is within this range, the fluorinated copolymer (A) has excellent adhesion and fuel barrier properties.

  The CM is not particularly limited as long as it is a polycarboxylic acid anhydride having a polymerizable unsaturated bond, that is, an anhydride of a polyfunctional carboxylic acid.

  Specific examples of CM include maleic anhydride (hereinafter referred to as “MAn”), itaconic anhydride (hereinafter referred to as “IAH”), citraconic anhydride (hereinafter referred to as “CAH”), butenyl succinic anhydride, and the like. Among these, at least one selected from the group consisting of MAn, IAH and CAH is preferable, and IAH or CAH is more preferable.

  The polycarboxylic acid anhydrides may be used alone or as a mixture. The above molar ratio represents the total amount of these when used as a mixture.

  In the above, a part of the polycarboxylic acid anhydride may be hydrolyzed before polymerization. For example, IAH may be a mixture of IAH and itaconic acid in which a part of IAH is hydrolyzed, and CAH is a mixture of CAH and citraconic acid in which a part of CAH is hydrolyzed. Also good. Furthermore, some of the polymer units based on CM in the fluorinated copolymer (A) may be hydrolyzed after polymerization. These polymerized units generated by hydrolysis before or after polymerization are regarded as a part of the polymerized unit (c) in the present invention. For example, the amount of polymerized units (c) represents the total amount of polymerized units based on CM and polymerized units based on polycarboxylic acid having a polymerizable unsaturated bond in which a part of CM is hydrolyzed.

  In the fluorinated copolymer (A), ((a) + (b) + (c)) is preferably 65 mol% or more, more preferably 70 mol% or more, and most preferably 75 mol% or more with respect to all the polymerized units. preferable. In addition, ((a) + (b) + (c)) represents the total of the polymerization unit (a), the polymerization unit (b), and the polymerization unit (c).

In addition to the above (a), (b) and (c), the fluorine-containing copolymer (A) in the present invention is further CH ₂ ═CX (CF ₂ ) _n Y (where X and Y are independent of each other). It is also preferable to contain a polymer unit (d) based on a monomer (hereinafter referred to as “FAE”) represented by a hydrogen atom or a fluorine atom, and n is an integer of 2 to 5.

  As for the content of the polymerized unit (d) based on the monomer FAE, (d) / ((a) + (b)) is in a molar ratio of 1/1000 to 15/100, more preferably 1/200 to 7/100. And most preferably 1/100 to 5/100. When the molar ratio is within this range, the fluorine-containing copolymer (A) is excellent in strength, fuel barrier properties, and crack resistance, and cracks hardly occur even under stress.

Examples of the monomer FAE include CH ₂ ═CH (CF ₂ ) ₂ F, CH ₂ ═CH (CF ₂ ) ₃ F, CH ₂ ═CH (CF ₂ ) ₄ F, and CH ₂ ═CH (CF ₂ ) ₅ F. CH ₂ = CF (CF ₂ ) ₂ F, CH ₂ = CF (CF ₂ ) ₃ F, CH ₂ = CF (CF ₂ ) ₄ F, CH ₂ = CF (CF ₂ ) ₅ F, CH ₂ = CF ( _{CF 2) 2 H, CH 2} = CF (CF 2) 3 H, CH 2 = CF (CF 2) 4 H, CH 2 = CF (CF 2) 5 H, CH 2 = CH (CF 2) 2 H, _{CH 2 = CH (CF 2)} 4 H , and the like.

As the monomer FAE, more preferably, n is 2 to 4, X is a hydrogen atom, and Y is a fluorine atom. For example, CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F or CH ₂ ═CH (CF ₂ ) ₄ F may be mentioned, and most preferably, n is 2, X is a hydrogen atom, Y is a fluorine atom, and CH ₂ = CH (CF ₂ ) ₂ F is exemplified.

  The fluorine-containing copolymer (A) in the present invention is polymerized based on the above-mentioned polymerized units (a), polymerized units (b), polymerized units (c) and polymerized units (d), and other monomers. Unit (e) may be included.

  Examples of such other monomers include hydrocarbon olefins such as propylene and butene; fluoroolefins having a hydrogen atom at an unsaturated bond such as vinyl fluoride and vinylidene fluoride (excluding FAE); hexafluoropropylene , Fluoroolefins having no hydrogen atom in the unsaturated bond such as chlorotrifluoroethylene and perfluoro (alkyl vinyl ether) (excluding TFE); alkyl vinyl ether, (fluoroalkyl) vinyl ether, glycidyl vinyl ether, hydroxybutyl vinyl ether, methyl Vinyl ethers such as vinyloxybutyl carbonate; vinyl esters such as vinyl acetate and vinyl butyrate; (meth) acrylates such as (polyfluoroalkyl) acrylate and (polyfluoroalkyl) methacrylate Le ester; undecylenic acid, acrylic acid, and unsaturated carboxylic acids such as methacrylic acid. These other monomers may be used alone or in combination of two or more.

  When the polymerized unit (e) based on another monomer is contained, the content is preferably (e) / ((a) + (b)) in a molar ratio of 1/10000 to 15/100. More preferably, the ratio is 1/1000 to 10/100.

  The conductive fluorine-containing copolymer composition (AB) used in the present invention is formed from the polyamide resin so that the laminate can be formed by co-extrusion with the polyamide resin to form the outer layer. It is preferable to have a molding temperature close to the temperature. Therefore, the content ratio of the polymerization unit (a), the polymerization unit (b), the polymerization unit (c), the polymerization unit (d) and the polymerization unit (e) contained as necessary is appropriately adjusted within the above range. The melting point of the fluorinated copolymer is preferably optimized in relation to the molding temperature of the polyamide resin.

  Moreover, it is preferable that the fluorine-containing copolymer (A) contains a polymer unit (e) because coextrusion moldability with the polyamide resin and adhesion with other layers in the laminate can be improved. In order to improve adhesiveness, the polymerized unit (e) preferably has a functional group such as an ester group, a carbonate group, a hydroxyl group, and an epoxy group.

  In the present invention, the end group of the fluorine-containing copolymer has a functional group having reactivity with the polyamide resin, such as an ester group, a carbonate group, a hydroxyl group, a carboxyl group, a carbonyl fluoride group, and an acid anhydride. Is preferable because adhesion to the polyamide layer is improved. The terminal group is desirably introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent, and the like used in the production of the fluorine-containing copolymer.

  There is no restriction | limiting in particular about the manufacturing method of the fluorine-containing copolymer used in this invention, The polymerization method using the radical polymerization initiator generally used is employ | adopted. Examples of polymerization methods include bulk polymerization known per se; solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons; aqueous media and, if necessary, Suspension polymerization using an appropriate organic solvent; emulsion polymerization using an aqueous medium and an emulsifier may be mentioned, and solution polymerization is most preferable. The polymerization can be carried out as a batch operation or a continuous operation using a one-tank or multi-tank stirring polymerization apparatus, a tube polymerization apparatus, or the like.

  Here, the radical polymerization initiator preferably has a decomposition temperature of 0 to 100 ° C. for obtaining a half-life of 10 hours, more preferably 20 to 90 ° C.

  Specific examples of preferable radical polymerization initiators include azo compounds such as azobisisobutyronitrile; non-fluorinated diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide; diisopropyl peroxydicarbonate, etc. Peroxydicarbonates; peroxyesters such as tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate;

Fluorine-containing diacyl peroxide such as a compound represented by the formula (1);
(Z (CF ₂ ) _p COO) ₂ (1)
(Here, Z is a hydrogen atom, a fluorine atom or a chlorine atom, and p is an integer of 1 to 10.)
Examples include inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate.

  In this invention, as the usage-amount of a radical polymerization initiator, 0.001-10 mass parts is preferable with respect to 100 mass parts of the prepared monomer, and 0.01-1 mass part is more preferable.

  In the present invention, a chain transfer agent is preferably used in order to control the molecular weight of the fluorinated copolymer (A). Examples of the chain transfer agent include alcohols such as methanol and ethanol; 1,3-dichloro-1,1,2,2,3-pentafluoropropane (manufactured by Asahi Glass Co., Ltd., trade name, hereinafter referred to as “AK225cb”). ), Chlorofluorohydrocarbons such as 1,1-dichloro-1-fluoroethane; and hydrocarbons such as pentane, hexane and cyclohexane.

  In this case, when a chain transfer agent having a functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxyl group, or a carbonyl fluoride group is used, as described above, the terminal group having reactivity with the polyamide resin is formed. Since it is introduced, it is preferable. Examples of such chain transfer agents include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

  The polymerization conditions of the fluorine-containing copolymer used in the present invention are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. Furthermore, the polymerization time is preferably 1 to 30 hours.

  If the concentration of polycarboxylic acid anhydride CM such as IAH or CAH in the reaction system during polymerization is too high, the polymerization rate tends to decrease. Therefore, the concentration of CM (the total concentration of these when mixed) is preferably 0.001 to 5%, more preferably 0.01 to 3% of the total molar ratio of TFE and E, 0.01 -1% is most preferred. When the concentration of CM is within this range, the polymerization rate during production does not substantially decrease, and the adhesiveness of the fluorinated copolymer becomes good. In order to maintain the concentration within this range during the polymerization, it is desirable to supply the consumed amount into the polymerization tank continuously or intermittently as the CM is consumed in the polymerization.

  The fluorine-containing copolymer (A) in the present invention is characterized by excellent fuel barrier properties. As a measure for evaluating the fuel barrier property, it is desirable to use a fuel permeation coefficient measured in accordance with the cup method defined in JIS Z0208, as shown in Examples below. A lower fuel permeability coefficient indicates better fuel barrier properties.

Fluorocopolymer (A) in the present invention is characterized in that the fuel permeability coefficient is low. As the numerical value, preferably less ^{3.5gmm / m 2 / 24h, 3.0gmm} / m 2 / 24h or less still more preferably, less and most preferably 2.7gmm / m ² / 24h.

  The conductive fluorine-containing copolymer composition (AB) of the present invention comprises the above-mentioned fluorine-containing copolymer (A) and a conductive filler (B), and (A) / (B) is a mass. The ratio is 70/30 to 99/1, more preferably 85/15 to 99/1. When the mass ratio of the copolymer composition is within this range, the composition has sufficient conductivity, and a molded product such as a hose from the composition is excellent in tensile elongation and impact resistance. Therefore, it is preferable.

(Conductive filler)
As the conductive filler (B) in the present invention, a carbon-based conductive filler is preferable.
As the conductive filler (B), those usually used can be basically used. Particularly preferably, the BET specific surface area is 50 to 1000 m ² / g and the DBP oil absorption is 100 ml. It is a carbon-type conductive filler which is / 100g-1000ml / 100g. More preferably, the carbon-based conductive filler has a BET specific surface area of 60 to 600 m ² / g and a DBP oil absorption of 150 to 1000 ml / 100 g.

When the BET specific surface area is less than 50 m ² / g, the conductivity of the composition is low. On the other hand, when the BET specific surface area is greater than 1000 m ² / g, the conductive filler aggregates to form a molded article such as a hose formed from the composition. The surface smoothness tends to be lost, which is not preferable.

  Further, when the DBP oil absorption is less than 100 ml / 100 g, the conductivity is low, and when it is larger than 1000 ml / 100 g, the surface smoothness of a molded product such as a hose is lost. Therefore, by setting the values of the BET specific surface area and the DBP oil absorption in this range, the composition has high conductivity, and a molded product such as a hose is preferable because of excellent surface smoothness.

  Specific examples of carbon-based conductive fillers that can be used include carbon nanotubes, carbon nanohorns, carbon blacks such as acetylene black and ketjen black, and the like. Carbon nanotubes are also called hollow carbon microfibers.

  The carbon nanotubes and carbon nanohorns have a diameter of 3.5 to 70 nm and an aspect ratio of preferably 5 to 200, a diameter of 5 to 60 nm, and an aspect ratio of 5 to 200. It is more preferable that the diameter is 10 to 55 nm and the aspect ratio is 10 to 100. When the numerical value is within this range, a molded article such as a hose made of a composition containing this is preferable because of excellent surface smoothness.

  The carbon black preferably has an average particle size of 3.5 to 70 nm, more preferably 5 to 50 nm, and most preferably 10 to 40 nm. When the average particle diameter is in this range, the molded product is excellent in surface smoothness, which is preferable.

The volume resistivity of these carbon-based conductive filler is preferably ^{1 × 10 -4 ~1 × 10 2} Ω / cm, more preferably ^{1 × 10 -4 ~10Ω / cm,} 1 × 10 -4 ~1Ω / cm Is most preferred.

(Polyphenylene sulfide resin, polybutylene aromatic polyester)
The conductive filler (B) such as a carbon-based conductive filler may be directly blended and mixed with the fluorine-containing copolymer (A) as a simple substance, but a small amount of the fluorine-containing copolymer (A) or further necessary in advance. Depending on the above, it may be blended as a master batch dispersed in the polyphenylene sulfide resin (C) or polybutylene aromatic polyester (D) described below.

  The conductive fluorine-containing copolymer composition (AB) of the present invention is basically composed of the above-mentioned fluorine-containing copolymer (A) and a conductive filler (B). Accordingly, it is also preferable to contain a polyphenylene sulfide resin (hereinafter referred to as “PPS”) (C) and / or a polybutylene aromatic polyester (hereinafter referred to as “PBPE”) (D). By containing these PPS (C) and / or PBPE (D) components, the fuel barrier property can be further improved.

  As PPS (C), the melt viscosity of PPS (C) measured by the method described later is preferably 100 to 5000 Pa · s, more preferably 200 to 3000 Pa · s, and more preferably 300 to 2000 Pa · s. Is most preferred. When the melt viscosity is within this range, a molded product such as a hose of a composition containing the melt viscosity is preferable because it has excellent surface smoothness and fuel barrier properties. As PPS, deionized PPS is preferable, and PPS crosslinked or polymerized by heating or the like is also preferable.

  On the other hand, examples of PBPE (D) include aromatic polyesters having a butylene chain such as polybutylene naphthalate (hereinafter referred to as “PBN”) and polybutylene terephthalate, and are particularly excellent in flexibility and fuel barrier properties. PBN is preferred.

  PBN may contain an ether segment or an ester segment in the molecule, and may contain additives such as a plasticizer. The inclusion of a plasticizer is preferable because the melting point decreases. Examples of the plasticizer to be added include phthalic acid esters such as dimethyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; phosphoric acid esters such as tricresyl phosphate and cresyl diphenyl phosphate; and sulfonamides such as toluenesulfonamide.

  The melt viscosity of PBPE (D) is preferably 100 to 5000 Pa · s, more preferably 200 to 3000 Pa · s, and most preferably 300 to 2000 Pa · s. When the melt viscosity is within this range, a molded product such as a hose of a composition containing the melt viscosity is preferable because it is excellent in surface smoothness and fuel barrier properties.

  When blended into the conductive fluorine-containing copolymer composition (AB), the content of PPS (C) and / or PBPE (D) is the mass ratio of (A) / (C) and / or (D). It is preferably 50/50 to 99/1, more preferably 70/30 to 99/1, and most preferably 80/20 to 99/1. When the ratio of PPS (C) and / or PBPE (D) is within this range, a molded product from the composition is preferable because it is excellent in flexibility and fuel barrier properties.

(Preparation of conductive fluorine-containing copolymer composition)
In the present invention, a method of adjusting the conductive fluorine-containing copolymer composition by mixing the fluorine-containing copolymer (A) and the conductive filler (B), and, if necessary, further PPS (C) and / or As a method for preparing a composition in which PBPE (D) is further mixed, melt kneading is preferable.

  Examples of the melt kneading apparatus include a twin screw extruder, a single screw extruder, a pressure kneader, a kneader, and a Brabender, and are not particularly limited. The speed, residence time and temperature can be easily controlled, which is preferable.

The melt kneading conditions include a shear rate of 100 to 1500 sec ⁻¹ , a residence time of 30 seconds to 10 minutes, and a temperature of 200 to 350 ° C., more preferably a shear rate of 300 to 1000 sec ⁻¹ and a residence time. Is 1 to 5 minutes, and the temperature is 220 to 310 ° C.

If the shear rate is less than 100 sec ⁻¹ , the surface smoothness of the molded product such as a hose obtained is not sufficient, and if it is greater than 1500 sec ⁻¹ , the melt viscosity of the conductive fluorine-containing copolymer composition becomes too large. The tensile elongation and stress crack resistance of the molded product are not sufficient.

  If the residence time is less than 30 seconds, the surface smoothness of a molded product such as a hose is not sufficient, and if it is longer than 10 minutes, the tensile elongation and stress crack resistance of the molded product are not sufficient.

  Further, if the temperature is less than 200 ° C., the surface smoothness of the molded product is not sufficient, and if it is higher than 350 ° C., the tensile elongation and stress crack resistance of the molded product are not sufficient.

  As described above, if kneading conditions such as shear rate, residence time, temperature, etc. are within this range, the resulting molded article such as a hose is excellent in surface smoothness, tensile elongation and stress crack resistance. ,desirable.

The surface resistance value of the electroconductive fluorocopolymer composition of the present invention (AB) ^{is, 1 × 10 0 ~1 × 10} 9 Ω / □ is preferably prepared by as described above, 1 × 10 ⁰ ~1 × 10 ⁷ Ω / □ is more preferable, and 1 × 10 ⁰ to 1 × 10 ⁶ Ω / □ is most preferable.

(Polyamide resin)
In the present invention, as the polyamide resin (PA) used for forming the laminated hose by being laminated with the conductive fluorine-containing copolymer composition (AB), a known one can be suitably used. That is, since the conductive fluorine-containing copolymer composition in the present invention itself has high adhesiveness to the polyamide resin, the polyamide resin is not particularly limited. Examples thereof include polyamides such as polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, and polyamide MXD6 (semi-aromatic polyamide).

  Other known polyamide resins that can be used include polyamide 26, polyamide 69, polyamide 610, polyamide 611, polyamide 612, polyamide 6T, polyamide 6I, polyamide 912, polyamide 1012, polyamide 1212, polyamide PACM12, and the like. The above polyamide resins may be used alone or in a blend. Moreover, it can also be set as the copolymerization polyamide resin using the raw material monomer which forms these.

(Layer structure of laminated hose)
The laminated hose of the present invention has a laminated structure in which the inner layer (I) made of the conductive fluorine-containing copolymer composition (AB) and the outer layer (II) made of a polyamide resin are laminated, that is, [(II) / ( I)]. And since the laminated hose of the present invention comprises the conductive fluorine-containing copolymer composition (AB) as the inner layer (usually the innermost layer) in contact with the fuel, when used for transporting liquid fuel, Static electricity generated during fuel transportation can be removed.

  As long as the laminated hose of the present invention includes the above basic laminated structure, that is, the inner layer (I) made of a conductive fluorine-containing copolymer composition and the outer layer (II) made of a polyamide resin are laminated in direct contact. As long as the structure is included, it may be a multi-layer hose including other fluororesin or polyamide resin. The total number of layers in the case of a multi-layer hose is not particularly limited and can be at least 2 layers, but is usually 2 to 6 layers, more preferably 2 to 5 layers.

  In the laminated hose of the present invention, the adhesive strength between the layer (I) made of the conductive fluorine-containing copolymer composition and the polyamide resin layer (II) is preferably 30 N / cm or more as the peel strength between the two layers, 40 N / Cm or more is more preferable.

  The outer diameter of the laminated hose of the present invention is appropriately designed in consideration of the flow rate of the fuel to be handled, and the thickness thereof is a thickness that allows the fuel to be sufficiently permeable and can maintain the normal hose breaking pressure. In addition, the thickness is designed so as to maintain flexibility with a satisfactory degree of ease of assembling the hose and vibration resistance during use. Although these are not specifically limited, Usually, the outer diameter is preferably 4 to 30 mm, the inner diameter is 3 to 25 mm, and the wall thickness is preferably about 0.05 to 5 mm.

  Further, in the laminated hose of the present invention, the thickness of each layer is not particularly limited, and can be changed as needed depending on the physical properties of the resin, the total number of layers, usage, etc. The thickness of the layer is determined in consideration of characteristics such as fuel barrier properties, low temperature impact resistance, and flexibility of the laminated hose.

Specifically, the thickness of the inner layer (I) and the outer layer (II) is preferably 3 to 90%, respectively, with respect to the thickness of the entire laminated hose, and the thickness of the inner layer (I) is In consideration of the fuel barrier property, it is more preferably 5 to 80%, and further preferably 10 to 50% with respect to the thickness of the entire laminated hose.
As an example, a laminated hose having an outer diameter of 8 mm, an inner diameter of 6 mm, and a thickness of 1 mm (an inner layer of 0.25 mm and an outer layer of 0.75 mm) can be mentioned.

(Co-extrusion molding)
As a method of forming the laminated hose of the present invention, the polyamide resin forming the outer layer and the conductive fluorine-containing copolymer composition of the inner layer are co-extruded in a molten state, and both are heat-sealed (melt-bonded) to form a single step. And most preferably by coextrusion forming a two-layer hose. Further, when it includes a laminated structure of three or more layers, it can be co-extruded according to this.

  Usually, the coextrusion molding method is a method of obtaining a laminate of two or more layers in the shape of a film, a tube or the like. That is, the melt of the resin that is to be kneaded and melted in two or more extruders equipped with screws to form the respective layers coming out from the discharge port is placed in a die placed at the tip of the extruder while in contact in the molten state. It is extruded and formed into a laminate.

  Regarding the extrusion temperature, the screw temperature is preferably 100 to 350 ° C, and the die temperature is preferably 200 to 350 ° C. The screw rotation speed is not particularly limited, but is preferably 10 to 200 rpm, and the residence time of the melt in the extruder is preferably 1 to 20 minutes.

  In general, it is preferable to pelletize each resin of the outer layer and the inner layer in advance, as shown in Examples below. That is, a predetermined amount of various additives such as a resin and a plasticizer to be mixed with the conductive fluorine-containing copolymer composition or polyamide resin is mixed with a low-speed rotary mixer such as a V-type blender or tumbler or a high-speed rotation such as a Henschel mixer. After mixing using a mixer, the mixture is melt-kneaded with a single-screw extruder, twin-screw extruder, twin-screw kneader, etc., and pelletized. A plasticizer or the like that is liquid at room temperature can be poured from the middle of a cylinder of a melt kneader to be melt kneaded.

  Pelletization is preferably performed by mechanically kneading and pelletizing at a temperature at which all resin components melt. In particular, in order to perform uniform mixing, it is preferable to use the same direction twin screw extruder.

  In addition, when performing coextrusion molding, by supplying all the components that form the composition of each layer to the hopper of the extruder, compounding each layer in the extruder, and subsequently performing coextrusion molding, Compounding and coextrusion can be performed almost simultaneously.

(Example)
Hereinafter, the present invention will be specifically described with reference to examples, but the technical scope of the present invention is not limited thereto.

  The conductivity, fuel permeability coefficient, IAH or CAH content, melt viscosity and delamination strength were measured by the following methods.

〔Conductivity〕
The conductivity of the inner surface of the multilayer hose was measured according to the conductivity test of SAE J2260. Copper pins were inserted at both ends of the hose in a room at a temperature of 25 ° C. and a humidity of 50%, and after measuring the resistance value with an ohmmeter, the surface resistance value was obtained by the following calculation formula, and used as a measure of conductivity. It shows that the said multilayer hose is excellent in electroconductivity, so that this surface resistance value is low.
Surface resistance value = Rπd / (L-2a)
(In the formula, R represents a resistance value, d represents a hose inner diameter, L represents a hose length, and a represents a copper pin insertion depth.)

[Fuel permeability coefficient]
The fuel permeation coefficient of the conductive fluorine-containing copolymer composition (AB) was measured in accordance with the cup method defined in JIS Z0208. That is, 9.5 to 10 g of fuel (E10) (isooctane / toluene / ethanol = 50/50/10 volume ratio) was put into a cup having a permeation area of 28.26 cm ² , and a 100 μm thick fluorine-containing product obtained by press formation. The upper part of the cup was covered with a film of a copolymer composition (AB), the amount of mass decrease after storage in a thermostatic bath at 60 ° C. for 10 days was measured, and the fuel permeability coefficient was calculated. The film of the said fluorine-containing copolymer composition shows that it is excellent in fuel barrier property, so that the fuel permeability coefficient is low.

[Content of IAH or CAH]
The fluorine-containing copolymer (A) was press-molded to obtain a 200 μm film. In the infrared absorption spectrum, the absorption peak of C═O stretching vibration in the polymer unit based on IAH or CAH in the fluorine-containing copolymer (A) appears at 1870 cm ⁻¹ . The absorbance of the absorption peak was measured, and the content M (mol%) of the polymerized units based on IAH or CAH was determined using the relational expression of M = aL. Here, L is the absorbance at 1870 cm ⁻¹ , and a is a coefficient. As a, a = 0.87 determined using IAH as a model compound was used.

[Melt viscosity]
Using a capillary rheometer (barrel inner diameter 9.55 mmφ, orifice hole diameter 1.00 mmφ, orifice length 10.00 mm) manufactured by Toyo Seiki Co., Ltd., 35 g of a fluorine-containing copolymer sample was put into a barrel heated to 310 ± 1 ° C. After holding for a minute, the melt viscosity at a shear rate of 608 sec ⁻¹ was measured.

[Delamination strength]
A laminated hose is cut to a length of 20 cm, and further cut vertically to make a test piece. The outer layer and the inner layer were forcibly peeled 1 cm from the end, and the outer layer and the inner layer were sandwiched by using a Tensilon universal testing machine as a device to be used, and a 180 ° adhesion test was performed at a pulling speed of 50 mm / min. The maximum strength was read from the maximum point of the SS curve and taken as the delamination strength (N / cm).

[Synthesis Example 1]
(Preparation of fluorine-containing copolymer)
(1) A polymerization tank equipped with a stirrer having an internal volume of 94 liters was degassed, and 67.2 kg of 1-hydrotridecafluorohexane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (Asahi Glass Co., Ltd., AK225c) 4.5 kg, IAH 33.3 g, CH ₂ ═CH (CF ₂ ) ₄ F 527.3 g, and TFE 9.4 kg, E 0.6 kg were injected. .

(2) The temperature in the polymerization tank was raised to 66 ° C., and 433 mL of a 1% AK225cb solution of tert-butylperoxypivalate was charged as a polymerization initiator to initiate polymerization. A monomer mixed gas of 51/49 molar ratio of TFE / E was continuously charged so that the pressure was constant during the polymerization. Further, IAH in an amount corresponding to 0.3 mol% with respect to the total number of moles of TFE and E charged during the polymerization was continuously charged. 5.5 hours after the start of polymerization, when 8.0 kg of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

(3) The obtained slurry-like fluorine-containing copolymer 1 is put into a 200 L granulation tank charged with 75 kg of water, and then heated to 105 ° C. while stirring to produce a solvent while distilling off. Grained. The obtained granulated product was dried at 150 ° C. for 5 hours to obtain 8.3 kg of the granulated product 1 of the fluorinated copolymer 1.

(4) From the results of melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis, the composition of the fluorinated copolymer 1 is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on IAH / CH ₂ = Molar ratio of polymerized units based on CH (CF ₂ ) ₄ F was 57.98 / 38.65 / 0.17 / 3.19. The melting point was 221 ° C. and the melt viscosity was 638 Pa · s.

(Preparation of two-layer laminated hose)
The granulated product 1 and carbon nanotubes (hereinafter referred to as CNT) having a diameter of 10 nm, a DBP oil absorption of 450 ml / 100 g, and a BET specific surface area of 250 m ² / g are mixed at a mass ratio of 95/5 and rotated in the same direction. Using a mold twin screw extruder, melt kneading at a shear rate of 500 sec ⁻¹ , a cylinder temperature of the kneading part of 300 ° C. and a residence time of 5 minutes, and extruding to produce pellets 1 of the conductive fluorine-containing copolymer composition 1 did. The conductive fluorine-containing copolymer composition 1 had a fuel permeability coefficient of 3.1 gmm / m ² / 24h.

  Using a two-layer coextrusion tube molding machine, polyamide 12 (Ube Industries, 3030JLX2) is supplied to the cylinder forming the outer layer, and the conductive fluorine-containing copolymer composition pellets 1 are supplied to the cylinder forming the inner layer. Were transferred to the transport zone of each cylinder. The heating temperatures in the transport zone of polyamide 12 and conductive fluorine-containing copolymer composition 1 were 240 ° C. and 260 ° C., respectively. Two-layer multilayer extrusion was carried out at a multilayer extrusion die temperature of 260 ° C. to obtain a two-layer laminated hose.

  The outer diameter of the laminated hose was 8 mm, the inner diameter was 6 mm, and the thickness was 1 mm. The thickness of the outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 1 were 0.85 mm and 0.15 mm, respectively. .

The surface resistance value of the obtained hose was 4 × 10 ⁵ Ω / □. Although an attempt was made to measure the peel strength of this laminated hose, the outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 1 were firmly bonded and could not be peeled off. Broke.

[Synthesis Example 2]
(Preparation of fluorine-containing copolymer)
The polymerization tank of Synthesis Example 1 was degassed, and before the polymerization, 79.9 kg of 1-hydrotridecafluorohexane, 11.2 kg of AK225cb, CH ₂ = CH (CF ₂ ) ₄ F was replaced with CH ₂ = CHCF ₂ 8.2 kg of granulated product 2 of fluorinated copolymer 2 was obtained in the same manner as in Synthesis Example 1, except that 562 g of CF ₃ and 97.0 g of CAH were charged instead of IAH. The polymerization time was 7.4 hours.

From the results of melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis, the composition of the fluorine-containing copolymer 2 is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on CAH / CH ₂ = The molar ratio of polymerized units based on CHCF ₂ CF ₃ was 57.91 / 38.61 / 0.29 / 3.19. The melting point was 230 ° C. and the melt viscosity was 590 Pa · s.

(Preparation of two-layer laminated hose)
Using the granulated product 2, a pellet 2 of the conductive fluorine-containing copolymer composition 2 was obtained in the same manner as in Example 1. Fuel permeability coefficient of electroconductive fluorocopolymer composition 2 was 3.2gmm / m ² / 24h.

  A two-layer laminated hose was obtained in the same manner as in Example 1 except that pellet 2 was used instead of pellet 1. The outer diameter of the laminated hose was 8 mm, the inner diameter was 6 mm, and the thickness was 1 mm. The outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 2 were 0.85 mm and 0.15 mm, respectively.

The surface resistance value of the laminated hose was 4 × 10 ⁶ Ω / □. In addition, an attempt was made to measure the peel strength of the laminated hose, but the outer layer of the polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 2 were firmly bonded and could not be peeled. The inner layer broke.

(Preparation of two-layer laminated hose)
The granulated product 1 of the fluorinated copolymer 1 of Example 1, CNT and PPS (manufactured by Dainippon Ink Co., Ltd., LC-6, melt viscosity 400 Pa · s) were mixed at a mass ratio of 90/5/5. Then, using a co-rotating twin screw extruder, the mixture was melt-kneaded at 300 ° C. and a residence time of 5 minutes, and extruded to produce pellets 3 of the conductive fluorine-containing copolymer composition 3. This conductive fluorine-containing copolymer composition 3 had a fuel permeability coefficient of 2.6 gmm / m ² / 24h.

  The polyamide 12 of Example 1 was supplied to the cylinder forming the outer layer, the pellet 3 was supplied to the cylinder forming the inner layer, and each was transferred to the transport zone of the cylinder. The heating temperatures in the transport zone for polyamide 12 and pellet 3 were 240 ° C. and 300 ° C., respectively. Two-layer multilayer extrusion was performed at a temperature of the common die of 260 ° C. to obtain a two-layer laminated hose.

  The outer diameter of the laminated hose was 8 mm, the inner diameter was 6 mm, and the thickness was 1 mm. The outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 3 were 0.85 mm and 0.15 mm, respectively.

The surface resistance value of the laminated hose was 1 × 10 ⁶ Ω / □. Although an attempt was made to measure the peel strength, the outer layer of the polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 3 were firmly bonded and could not be peeled off.

(Preparation of two-layer laminated hose)
The granulated product 1 of the fluorinated copolymer 1 of Example 1, CNT and PBN (Duranex 500FP manufactured by Polyplastics Co., Ltd.) were mixed at a mass ratio of 90/5/5, and the same direction rotating biaxial Using an extruder, the mixture was melt-kneaded at a shear rate of 500 sec ⁻¹ , a cylinder temperature of the kneading part of 300 ° C. and a residence time of 5 minutes, and extruded to produce pellets 4 of the conductive fluorine-containing copolymer composition 4. Fuel permeability coefficient of the electroconductive fluorocopolymer composition 4 was 2.5gmm / m ² / 24h.

  A two-layer laminated hose was obtained in the same manner as in Example 3 except that the pellet 4 was used instead of the pellet 3. The outer diameter of the laminated hose was 8 mm, the inner diameter was 6 mm, and the thickness was 1 mm. The outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 4 were 0.85 mm and 0.15 mm, respectively. .

The surface resistance value of the laminated hose was 1 × 10 ⁶ Ω / □. Although an attempt was made to measure the peel strength, the outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 4 were firmly bonded and could not be peeled off. .

(Preparation of two-layer laminated hose)
The granulated product 1 of the fluorinated copolymer 1 of Example 1, carbon black (Denka Black, manufactured by Denki Kagaku) and PBN having an average particle size of 35 nm, a DBP oil absorption of 160 ml / 100 g, and a BET specific surface area of 69 m ² / g. (Juranex 500FP manufactured by Polyplastics Co., Ltd.) at a mass ratio of 74/13/13, using a co-rotating twin screw extruder, a shear rate of 500 sec ⁻¹ , a cylinder temperature of the kneading part of 300 ° C., The mixture was melt-kneaded with a residence time of 5 minutes and extruded to produce pellets 5 of the conductive fluorine-containing copolymer composition 5. Fuel permeability coefficient of electroconductive fluorocopolymer composition 5 was 2.0gmm / m ² / 24h.

  A two-layer laminated hose was obtained in the same manner as in Example 1 except that the pellet 5 was used in place of the pellet 1. The outer diameter of the laminated hose was 8 mm, the inner diameter was 6 mm, and the thickness was 1 mm. The outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 5 were 0.85 mm and 0.15 mm, respectively.

The surface resistance value of the laminated hose was 1 × 10 ⁶ Ω / □. As a result of measuring the peel strength, the peel strength between the inner layer and the outer layer was 45.0 N / cm.

[Comparative Example 1]
(Preparation of two-layer laminated hose)
8.0 kg of fluorinated copolymer 3 and granulated product 3 were obtained in the same manner as in Synthesis Example 1 and Example 1 except that IAH was not charged before and during the polymerization. The polymerization time was 1.8 hours.

From the results of the melt NMR analysis and the fluorine content analysis, the composition of the fluorinated copolymer 3 is as follows: polymerized units based on TFE / polymerized units based on E / CH ₂ ═CH (CF ₂ ) ₄ F moles of polymerized units based on F The ratio was 58.1 / 38.7 / 3.19. The melting point was 219 ° C.

A pellet 6 of the conductive fluorine-containing copolymer composition 6 was obtained in the same manner as in Example 1 except that the granulated product 3 was used in place of the granulated product 1. Fuel permeability coefficient of electroconductive fluorocopolymer composition 6 was 5.1gmm / m ² / 24h.

A two-layer laminated hose was obtained in the same manner as in Example 3 except that pellet 6 was used instead of pellet 3. The outer diameter of the laminated hose is 8 mm, the inner diameter is 6 mm, and the thickness is 1 mm. The outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 6 are 0.85 mm and 0.15 mm, respectively. The value was 1 × 10 ¹² Ω / □. However, the inner layer and the outer layer did not adhere.

[Comparative Example 2]
(Preparation of two-layer laminated hose)
Granulated product 3 of Comparative Example 1, average particle size 85 nm, DBP oil absorption 62 ml / 100 g, BET specific surface area 28 m ² / g carbon black (manufactured by Mitsubishi Chemical, Diablack R) and PPS (manufactured by Kureha Chemical Co., MZ200) ) At a mass ratio of 70/17/13, and melt-kneaded using a co-rotating twin screw extruder at a shear rate of 500 sec ⁻¹ , a cylinder temperature of the kneading part of 300 ° C. and a residence time of 5 minutes, The pellet 7 of the electroconductive fluorine-containing copolymer composition 7 was produced by extrusion. The fuel permeation coefficient of the conductive fluorine-containing copolymer composition 7 was 4.5 gmm / m ² / 24h.

A two-layer laminated hose was obtained in the same manner as in Example 3 except that pellet 7 was used instead of pellet 3. The outer diameter of the laminated hose is 8 mm, the inner diameter is 6 mm, and the thickness is 1 mm. The outer layer of polyamide 12 and the inner layer of the conductive fluorine-containing copolymer composition 7 are 0.85 mm and 0.15 mm, respectively. The value was 1 × 10 ¹² Ω / □. However, the inner layer and the outer layer did not adhere.

  The laminated hose of the present invention comprising the conductive fluorine-containing copolymer composition and the polyamide resin is derived from the fluorine-containing copolymer composition, has low fuel barrier properties, excellent conductivity, and crack resistance. As well as excellent chemical resistance, heat resistance, corrosion resistance, oil resistance, weather resistance, etc., fuel tube or hose for automobile, fuel filler neck, coolant hose, brake hose, air conditioner hose, fuel transfer tube Or it can use suitably as tubes, hoses, such as a hose, an oil drilling pipe, a paint spray tube, an industrial hose, and a food hose.

  The laminated hose of the present invention can be formed by coextrusion molding, and is a laminated hose having high peel strength between the fluorine-containing copolymer composition layer and the polyamide resin layer.

Claims (6)

In a laminated hose including a laminate in which a layer of a conductive fluorine-containing copolymer composition (AB) and a polyamide resin (PA) layer are directly laminated, the conductive fluorine-containing copolymer composition (AB) Contains a fluorine-containing copolymer (A) and a conductive filler (B), and the fluorine-containing copolymer (A) comprises a polymer unit (a) based on tetrafluoroethylene, a polymer unit (b) based on ethylene (b) And a copolymer (A) containing polymer units (c) based on itaconic anhydride or citraconic anhydride, wherein the molar ratio of (a) / (b) is 20/80 to 80/20 Yes, the molar ratio of (c) / ((a) + (b)) is 1/1000 to 5/100, and the fluorine-containing copolymer (A) is tetrafluoroethylene, ethylene in a polymerization tank. , And itaconic anhydride or citraconic anhydride Were charged, the radical copolymerization and then start were charged a radical polymerization initiator, so as to hold the vessel inside pressure at a constant, continuous charging a mixed gas of tetrafluoroethylene and ethylene, and tetrafluoroethylene Excellent adhesion to polyamide resin (PA) obtained by radical copolymerization while continuously supplying itaconic anhydride or citraconic anhydride corresponding to 0.01-1% of the total molar amount of ethylene and ethylene A laminated hose characterized by being a conductive fluorine-containing copolymer composition (AB) having a mass ratio of (A) / (B) of 70/30 to 99/1. The laminate according to claim 1, wherein the conductive filler (B) is a carbon-based conductive filler having a BET specific surface area of 50 to 1000 m ² / g and a DBP oil absorption of 100 ml / 100 g to 1000 ml / 100 g. hose. In addition to the polymer unit (a), the polymer unit (b) and the polymer unit (c), the fluorine-containing copolymer (A) further contains CH ₂ ═CX (CF ₂ ) nY (where X, Y Each independently represents a hydrogen atom or a fluorine atom, and n is an integer of 2 to 5.) and contains a polymerized unit (d) based on a monomer represented by (d) / ((a) + (b The laminated hose according to claim 1 or 2, wherein the molar ratio is 1/1000 to 15/100.   The laminated hose according to any one of claims 1 to 3, wherein the conductive fluorine-containing copolymer composition (AB) further contains a polyphenylene sulfide resin (C) or a polybutylene aromatic polyester (D).   The laminated hose which has the layer of the electroconductive fluorine-containing copolymer composition (AB) in any one of Claims 1-4 in an innermost layer.   The laminated hose according to any one of claims 1 to 5, wherein the laminated body is obtained by coextrusion molding.