WO2005090065A1

WO2005090065A1 - Layered tube

Info

Publication number: WO2005090065A1
Application number: PCT/JP2005/005625
Authority: WO
Inventors: Hideki Fujimura; Koji Nakamura; Tsuyoshi Iwasa; Atsushi Funaki; Eiichi Nishi
Original assignee: Ube Industries, Ltd.; Asahi Glass Company, Limited
Priority date: 2004-03-18
Filing date: 2005-03-18
Publication date: 2005-09-29
Also published as: JP2007216387A

Abstract

A layered tube composed of at least two layers comprising a layer (a) formed from a polyamide elastomer (A) having a terminal amino concentration of 20 μeq/g or higher and a layer (b) formed from a fluoropolymer (B) having, introduced into the molecular chain, a functional group reactive with the polyamide resin. The layered tube is excellent in interlaminar adhesion, impermeability to liquid chemicals, flexibility, low-temperature impact resistance, and chemical resistance.

Description

Laminated tube

Technical field

The present invention provides a layer comprising a polyamide elastomer having a specific terminal amino group concentration and a functional group having a reactivity with the polyamide.

Layered tube containing at least a layer made of a fluorine-containing polymer into which is introduced, especially a chemical liquid permeation prevention property, interlayer adhesion, flexibility, and low-temperature impact resistance

The present invention relates to a laminated tube having excellent chemical resistance.

Background art

Fluorocarbon resins are used in a wide range of fields because of their excellent heat resistance, chemical resistance, weather resistance, non-adhesion, low friction and low dielectric properties, and are particularly excellent in chemical resistance. Therefore, the tube for transporting chemicals is an important application.

However, fluororesins are not always satisfactory in terms of adhesiveness, paintability, printability, dyeability, flexibility and the like. For this reason, molded products in which a fluororesin is combined with another thermoplastic resin, that is, the defects of the fluororesin are compensated for by the other thermoplastic resin, and the excellent properties of the fluororesin are maintained as they are Thus, molded articles that effectively express the advantages of both resins are expected. For example, in a tube for transporting chemicals, it is necessary to use a resin that is highly resistant to corrosive solvents such as ethanol and methanol, and other chemicals, and has excellent resistance to chemicals permeation, for the inner layer directly in contact with the chemical. As the inner layer material, fluorocarbon resin is considered as one of the most preferable material candidates. However, fluororesin has very low adhesiveness to other materials, and has problems such as peeling off when bonded to other thermoplastic resins. Strong interlayer adhesion is required to prevent delamination. As a means for increasing the interlayer adhesion strength, a method of forming a fluororesin tube in advance, performing surface treatment such as corona discharge treatment or sodium etching treatment, and then coating another thermoplastic resin, A method of forming a resin-based resin tube, applying an adhesive to the outer surface of the tube, coating other thermoplastic resins and bonding them together, melt-extruding, and simultaneously laminating inside or outside the die Co-extrusion molding method. The necessity of a surface treatment step and an adhesive application step complicates the production work, and also requires equipment to increase the production cost.The co-extrusion molding method requires these processing steps. Since this method is not necessary, it can be said to be a low cost method.

The laminated tube may be a rigid tube, but it can be transported in the form of a spiral or bend as desired, which is convenient for piping work. There is a need to provide flexible laminated tubes.

In particular, in an image forming apparatus such as an ink jet recording apparatus, an ink supply tube connected to supply ink from a stored container (ink tank) to a discharge sheep such as a recording head is fixedly installed. Since the container is linked with a printing head that moves repeatedly, the container has high durability against repeated bending, that is, has excellent flexibility. Required. In particular, it is required that the material does not become rigid even at low temperatures such as in winter and can maintain excellent flexibility.

Polyamide-based resin, saturated polyester-based resin, polyolefin-based resin, thermoplastic polyurethane-based A tube has been proposed in which a resin or its elastomer is laminated with a fluororesin.

A laminated tube manufactured by a co-extrusion method using polyvinylidene fluoride for the inner layer and a polyurethane resin or a polyurethane-based elastomer for the outer layer has been described (JP-A-Hei. 8 — 1 4 2 1 5 1). In this two-layer tube, the polyvinylidene fluoride layer has a high hardness and turns white when bent. In particular, it has the disadvantage of becoming brittle in the low-temperature region.

A laminated tube using a vinylidene fluoride hexafluoropropylene copolymer for the inner layer and a urethane-based elastomer for the outer layer is described (Japanese Patent Application Laid-Open No. H10-286687). ). However, even with these laminated tubes, the interlayer adhesion strength is low and it is not worthy of actual use, or even if the initial interlayer adhesion strength is sufficient, it will be In some cases, the durability of the adhesive strength (hereinafter referred to as chemical resistance) is insufficient, or delamination may occur due to insufficient interlayer adhesive strength during bending. Therefore, it is desired to develop a laminated tube that is excellent in interlayer adhesiveness and chemical solution durability of interlayer adhesive strength, has flexibility, and can be manufactured stably at low cost by co-extrusion molding.

An object of the present invention is to solve the above-mentioned problems. In a laminated tube composed of a layer made of a polyamide elastomer and a layer made of a fluorine-containing polymer, interlayer adhesion and prevention of chemical liquid permeation are achieved. An object of the present invention is to provide a laminated tube having excellent properties, flexibility, low-temperature impact resistance, and chemical resistance. Disclosure of the invention

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, By laminating a polyamide elastomer that satisfies a certain terminal amino group concentration and a fluorine-containing polymer in which a functional group reactive with the polyamide resin is introduced into the molecular chain, The present inventors have found that a laminated tube having both layers strongly adhered, having extremely excellent interlayer adhesive strength, and also having flexibility can be obtained. Is below.

[1] (A) Layer (a) composed of a polyamide elastomer having a terminal amino group concentration of 20 μeq / g or more, and (B) a functional group reactive with the polyamide resin Having a (b) layer made of a fluorinated polymer introduced into a molecular chain, and comprising at least two layers.

[2] Polyamide elastomer having the terminal amino group concentration (A) of not less than 20 eqZg is represented by the following formula (1):

(1)

(However, χ and ζ are 1 to 20 and y is 4 to 50.) A triblock polyetherdiamine compound (A 1) represented by the following formula: a 2), and dicarboxylic acid compounds (a 3) is a polymer obtained by polymerizing a poly amino Tsuchie one Teruerasu Tomah one (X) 5 0 weight ⁰ /. The laminated tube according to the above [1], which is a polyamide elastomer having the above. .

[3] The dicarboxylic acid compound (A 3) in the polyamide ester (E) is represented by the following formula (2):

(However, R ¹ represents a linking group containing a hydrocarbon chain, and m represents 0 or 1.)

The laminated tube according to the above [2], which is represented by the following formula:

[4] The polyamide-forming monomer (A 2) in the polyamide ether elastomer (X) is represented by the following formula (3) and Z or the following formula (4):

H ₂ N—— R ² —— COOH (3)

(However, R ² represents a linking group containing a hydrocarbon chain.)

(However, R ³ represents a linking group containing a hydrocarbon chain.)

The laminated tube according to any one of the above [2] or [3], which is represented by:

[5] The laminate according to any one of the above [2] to [4], wherein the dicarboxylic acid compound (A 3) is an aliphatic dicarboxylic acid compound and a Z or alicyclic dicarboxylic acid compound. tube.

[6] The (B) fluorinated polymer having a functional group reactive with the polyamide resin introduced into the molecular chain is an ethylenenote trafluoroethylene copolymer, polyvinylidene fluoride, The laminated tube according to the above [1], which is at least one member selected from the group consisting of ethylene / hexafluoropropylene / vinylidene fluoride copolymer.

[7] The layer (b) made of a fluorinated polymer having a functional group reactive with the polyamide resin introduced into the molecular chain,

(A) any one of the above (1) to (6), wherein the terminal amino group concentration is 20 eqZg or more, and the polymer is disposed on the inner side with respect to the (a) layer composed of a polyamide elastomer. A laminated tube according to any of the above items. [8] (A) the terminal amino group concentration of from polyamylene Doerasu Tomah one is SO ^ eq Z g or more _(a) layer, the (1), characterized in that disposed in the outermost layer - The laminated tube according to any one of [7].

[9] The laminated tube according to any one of [1] to [7], further comprising at least three layers having a (c) layer made of polyurethane (C).

[10] The (A) layer comprising (A) a polyamide elastomer having a terminal amino group concentration of 2 or more is composed of (B) a functional group reactive with a polyamide resin. The above-mentioned [9], which is disposed between the (b) layer composed of a fluorine-containing polymer introduced into the chain and the (c) layer composed of (C) polyurethane. Laminated tubes.

[11] The laminated tube according to any one of [1] to [10], wherein each of the layers is manufactured by co-extrusion molding. '

[12] The laminated tube according to any one of the above [1] to [11], which is used as a tube for transporting a drug solution.

The laminated tube of the present invention has both interlayer adhesion, chemical liquid permeation prevention properties, and flexibility. By using a fluorine-based polymer as the inner layer material in the laminated tube, it is possible to suppress the penetration of the chemical solution from the tube partition. Further, by laminating a polyamide elastomer having a specific terminal group concentration and a fluorinated polymer reactive with the material, not only in the initial stage but also after immersion in fuel In addition, there are no drawbacks such as a decrease in interlaminar bond strength, and the interlaminar bond strength is excellent in chemical resistance, and the flexibility and bending resistance are also excellent. Brief Description of Drawings

FIG. 1 is a cross section showing a laminated tube according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a laminated tube according to another embodiment of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

As the polyamide elastomer (A) used in the present invention, known polyamide elastomers can be used as long as the terminal amino group concentration satisfies 20 μeqZg or more.

The (A) terminal amide group concentration of the polyamide elastomer used in the present invention is at least SO / zeq Z polymer lg, preferably 25 eq Z polymer 1 g or more, and 30 μeq More preferably, it is 1 g or more per polymer. If the terminal amino group concentration is less than 20 μeq / polymer 1 g, it is not preferable because the interlayer adhesion with a mating material to be laminated is poor. Further, it is preferable that the terminal amino group concentration is not more than 80 μeq nopolymer 1 g from the viewpoint of polymerization and productivity.

The terminal amino group concentration (eq / polymer lg) of the polyamide elastomer is measured by dissolving the polyamide elastomer in a phenol / methanol mixture solution and titrating with 0.05 N hydrochloric acid. be able to.

Polyamide elastomers include polyamide blocks consisting of at least one aliphatic nylon selected from Nylon 6, Nylon 66, Nylon 11 and Nylon 12. An elastomer composed of at least one kind of polyether block selected from polyoxyethylene, polyoxypropylene, and polyoxybutylene can be used. The polyamide elastomer is preferably a thermoplastic elastomer composed of a polyamide block and a polyether block. The hardness (Shore D) measured according to ASTM D-224 is 15 to 50%. It is preferably in the range of 70, more preferably in the range of 18 to 70, still more preferably in the range of 20 to 70, and more preferably in the range of 25 to 70. Is particularly preferred. Further, the flexural modulus measured according to ASTM D-790 is preferably from 20 to 450 MPa, more preferably from 20 to 400 MPa, and more preferably from 20 to 400 MPa. More preferably, it is 3350 MPa, particularly preferably 20-300 MPa.

The polyamide elastomer used in the present invention preferably contains the polyamide ether elastomer (X) shown below, and the polyamide ether elastomer (X) in the polyamide elastomer is preferably used. ) Is preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight, and at least 80% by weight. Is particularly preferred, and most preferably 90% by weight or more.

The polyamide ether elastomer (X) may be a polyamide thermoplastic elastomer in which the polyamide block and the polyether block are preferably bonded by an amide bond, and may be formed separately. Polyamide blocks and polyether blocks having a reactive group at the terminal can also be obtained by bonding them to each other with a reactive group at the terminal, but the triblock polyether represented by the formula (1) can be obtained. It is preferably a polymer obtained by polymerizing an ether diamine compound (A 1), a polyamide-forming monomer (A 2), and a dicarboxylic acid compound (A 3).

In the present invention, the polyamide ether elastomer (X) is a triblock polyether diamine compound (A1) represented by the formula (1). ), A polyamide-forming monomer (A 2), and a dicarboxylic acid compound (A 3).

(1)

(However, x and z are from 1 to 20 and y is from 4 to 50.) Polyamide ether elastomer (X) is melt-moldable, moldable, tough, and flex-resistant. Used as a constituent material of the laminated tube of the present invention because of its excellent fatigue resistance, rebound resilience, low specific gravity, low-temperature flexibility, low-temperature impact resistance, elongation recovery, sound-absorbing properties, rubber-like properties, and transparency be able to.

In the polyamide ether elastomer (X), a triblock polyether diamine compound (A1) represented by the formula (1), a polyamide-forming monomer (A2), and The ratio is preferably such that the terminal carboxylic acid and Z or carboxyl group contained in the dicarboxylic acid compound (A 3) and the terminal amino group are almost equimolar.

In particular, in the case of the polyamide ester monomer (X), when one end of the polyamide-forming monomer (A 2) is an amino group and the other end is a carboxylic acid and / or carboxylic acid group, a triblock is formed. The ratio is preferably such that the amino group of the polyetherdiamine compound (A1) and the carboxylic acid and Z or carboxyl group of the dicarboxylic oxide compound (A3) are substantially equimolar.

AB Type A triblock polyetherdiamin compound (A1) was converted to polypropylene glycol by adding propylene oxide to both ends of poly (oxytetramethylene) dalicol and the like. Then, a polyether diamine or the like produced by reacting ammonia or the like with the end of the polypropylene glycol is used. Can do.

A B In the triblock polyether diamine compound (A 1), X and z in the formula (1) are: ~ 20 and :! And preferably 18 to 18, more preferably 1 to 16, still more preferably 1 to 14, particularly preferably 1 to 12, and y is preferably 4 To 50, preferably 5 to 45, more preferably 6 to 40, still more preferably 7 to 35, and particularly preferably 8 to 30. .

Examples of the polyamide-forming monomer (A 2) include at least one kind of aliphatic or fatty acid selected from aminocarboxylic acid compounds, lactam compounds, compounds synthesized from diamine and dicarboxylic acid, and salts thereof. Those containing a cyclic and / or aromatic compound can be used.

In particular, the polyamide-forming monomer (A 2) includes at least one kind selected from an aminocarbonic acid compound, a lactam compound, a compound synthesized from diamine and dicarboxylic acid, and a salt thereof. Those composed of an aliphatic or alicyclic group are preferred.

In the polyamide-forming monomer (A 2), as the aminocarboxylic acid compound, a compound having an amino group and a carboxylic acid or a carboxyl group can be used. As the aminocarboxylic acid compound, an ω_aminocarboxylic acid compound is preferable, and a compound represented by the following formula (3) is more preferable.

H ₂ N—— R ² —— COOH (3)

(However, R ² represents a linking group containing a hydrocarbon chain.)

In the compound represented by the formula (3), R ² is preferably a hydrocarbon molecular chain having 2 to 20 carbon atoms or an alkylene group having 2 to 20 carbon atoms, and 3 carbon atoms. It is more preferable that the alkylene group has a molecular chain of 1 to 18 hydrocarbons or an alkylene group having 3 to 18 carbon atoms. More preferably, it is a hydrocarbon molecular chain having 4 to 15 carbon atoms or an alkylene group having 4 to 15 carbon atoms, more preferably a hydrocarbon molecular chain having 5 to 11 carbon atoms or Particularly preferred is an alkylene group having 5 to 11 carbon atoms.

In the polyamide-forming monomer (A 2), the aminocarboxylic acid compound is an aliphatic ω-aminocarboxylic acid having 5 to 20 carbon atoms, and specifically, 6-aminocaproic acid , 7-aminoheptanoic acid, 8-amino octanoic acid, 10-amino chloropuric acid, 11-amino undecanoic acid, and 12-amino dodecanoic acid. One or more of these can be used.

As the lactam compound, a compound represented by the following formula (4) can be used.

(However, R ³ represents a linking group containing a hydrocarbon chain.)

In the compound represented by the formula (4), R ³ is preferably a hydrocarbon chain having 3 to 20 carbon atoms or an alkylene group having 3 to 20 carbon atoms. More preferably, it is a hydrocarbon molecular chain having 4 to 18 carbon atoms or an alkylene group having 3 to 18 carbon atoms, and a hydrocarbon molecular chain having 4 to 15 carbon atoms or 4 to 5 carbon atoms. An alkylene group having 15 carbon atoms is more preferable, and an alkylene group having 5 to 11 carbon atoms of a hydrocarbon molecular chain or 5 to 11 carbon atoms is particularly preferable.

In the polyamide-forming monomer (A 2), the lactam compound is an aliphatic ratatam compound having 3 to 20 carbon atoms, and specifically, 2-pyrrolidone, ε-force. Proratatum, one-enantholactam, ω-ndecalactam, ω-dodecalactam, etc. The One or more of these can be used.

In those synthesized from diamine and dicarbonic acid in the polyamide-forming monomer (A 2) and salts thereof, the diamine may be aliphatic diamine, alicyclic diamine, aromatic diamine, or aromatic diamine. At least one kind of diamine compound selected from these derivatives is exemplified.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and at least one dicarboxylic acid selected from derivatives thereof.

Particularly, in the case of a compound synthesized from diamine and dicarboxylic acid and a salt thereof, a combination of an aliphatic diamine compound and an aliphatic carboxylic acid compound is preferable.o

The molar ratio of diamine and dicarboxylic acid (diamin / dicarboxylic acid)

) Is preferably in the range of 0.9 to 1.1, and 0.93 to 1.1.

The range H is more preferably in the range of 0.7, more preferably in the range of 0 • 95 to 1.05, particularly preferably in the range of 0.97 to 1.03. . Out of this range if there if force ^s molecular weight and difficulty Kunar.

The diamine is a diamine compound such as an aliphatic diamine having 2 to 20 carbon atoms, and specifically, ethylene diamine, 1, 3

—Propylene diamine, 1,4-butane diamine, 1,5-pentanediamine, 1, 6 —Hexane diamine, 1,7 heptane diamine, 1,8 —Otata diamine, 1,9-nonane diamine, 1 , 1

0—decandiamin, 1,1 1 1-pentanediamine, 1,12-dodecandiamine, 2 Z 3 —methyl-1,5-pentanediamine,

2-Methyl-1,8-octanediamine, 2,2,4 / 2,4,4-trimethyl-1,6,1-hexanediamine ミ 5—Methyl-1,9- Nonanediamine and the like. One or more of these can be used.

The dicarboxylic acid is a dicarboxylic acid compound (A 3) such as an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, and specifically, oxalic acid, kojic acid, dartalic acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like. One or more of these can be used.

Examples of the dicarboxylic acid compound (A 3) include at least one dicarboxylic acid selected from aliphatic dicarboxylic acids, alicyclic dicarboxylic acids / reponic acids, and aromatic dicarboxylic acids, and derivatives thereof.

As the dicarboxylic acid compound (A 3), a dicarboxylic acid conjugate represented by the formula (2) can be used. The dicarboxylic acid compound (A 3) is preferably an aliphatic or alicyclic dicarboxylic acid compound.

HOOC— (-R ^1- ) ^-COOH (2)

(However,: ¹ represents a linking group containing a hydrocarbon chain, and m represents 0 or 1.)

Examples of the dicarboxylic acid compound (A3) include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. 25 Dimerized aliphatic dicarboxylic acid having 2 to 500 carbon atoms obtained by dimerizing unsaturated fatty acid obtained by fractionation of linear aliphatic dicarboxylic acid and triglyceride of 5 (dimer monoacid) And aromatic dicarboxylic acids such as hydrogenated products thereof (hydrogenated dimer acid), alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic compounds such as terephthalic acid, isophthalic acid and phthalic acid. Group dicarboxylic acids. One or more of these can be used. Examples of the dimer acid and hydrogenated dimer acid include the trade names “Puripol 1004”, “Pripol 1006”, “Pripol 1009”, “Pripol 101”, etc. Can be used.

In the compound represented by the formula (2), m represents 0 or 1, and when m is 1, R ¹ represents a hydrocarbon chain having 1 to 12 carbon atoms or a carbon chain having 1 to 12 carbon atoms. And more preferably an alkylene group having 2 to 12 carbon atoms or an alkylene group having 2 to 12 carbon atoms, and more preferably an alkylene group having 2 to 12 carbon atoms. More preferably, it is a hydrocarbon chain having 2 to 4 carbon atoms or an alkylene group having 4 to 12 carbon atoms, and a hydrocarbon chain having 4 to 10 carbon atoms or a carbon chain having 4 to 10 carbon atoms is more preferable. It is particularly preferred that the compound has an alkylene group.

In the polyamide ester elastomer (X), the content of the unit derived from the formula (1) is preferably 15 to 80% by weight, and preferably 15 to 75% by weight, based on all the polymerized units. %, More preferably 18 to 70% by weight, and particularly preferably 20 to 60% by weight.

As an example of a method for producing a polyamide ester (X), a polyamide-forming monomer (A2), an ABA-type triblock polyether diamine (A1), and a dicarboxylic acid It is possible to use a method comprising a step of melt-polymerizing the three components of the acid compound (A 3) at the same time under pressure and under Z or normal pressure, or, if necessary, under a reduced pressure. In the production, there are no particular restrictions on the method and order of charging the raw materials, but the charging ratio of the polyamide-forming monomer (A2) is determined by the ABA-type triblock polyether diamine (A1), It is preferably from 10 to 95% by weight, and more preferably from 15 to 9% by weight, based on the total amount of the monomer of the polyamide-forming monomer (A 2) and the dicarboxylic acid compound (A 3). More preferably, it is 0% by weight. Among the raw materials, AB A-type triblock polyether diamine (A 1) and dicarboxylic acid compound (A 3) are obtained from AB A-type triblock polyether diamine (A 1). It is preferable to charge the amide group and the carboxyl group of the dicarboxylic acid conjugate (A3) so that they are almost equimolar.

In the production of the polyamide ether elastomer (X), polymerization is carried out at a temperature of preferably 150 to 300 ° C, more preferably 160 to 280 ° C, More preferably, the temperature is 180 to 250 ° C.

Polyamide ester elastomer (X) is prepared by using normal pressure melt polymerization or normal pressure melt polymerization followed by vacuum melt polymerization when ω-aminocarboxylic acid is used as the polyamide-forming monomer (A 2). It can be manufactured by a method consisting of the steps described above.

On the other hand, when a lactam, or a compound synthesized from diamine and dicarboxylic acid and Z or ^ are used as the polyamide-forming monomer (A 2), an appropriate amount of water is allowed to coexist. It can be produced by a method comprising melt polymerization under pressure of a, followed by normal pressure melt polymerization and Z or reduced pressure melt polymerization.

Polyamide elastomer (X) can be manufactured either batchwise or continuously. Batch reactors, single-tank or multi-tank continuous reactors, tubular continuous reactors, etc. can be used alone. Alternatively, they can be manufactured in combination.

Polyamide elastomers and polyamide elastomers (

X) is preferably a relative viscosity (r) force of 1.2 to 3.5 (0.5 wt.% By volume, methacrylate solution, 25 ° C), and a value of 1.4 to 3.0. Is more preferred.

The polyamide elastomer used in the present invention is a specific powder. Satisfies the terminal amino group concentration. At the time of the production, the polyamide raw material is produced by polymerizing or copolymerizing in the presence of an amine by a known method such as melt polymerization, solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of an amine after polymerization. As described above, the amines can be basically added at any stage during the polymerization or at any stage during the melt-kneading after the polymerization. In consideration of the resistance, it is preferable to add at the stage of polymerization. The polyamide elastomer used in the present invention preferably has 50% by weight or more of polyamide ether elastomer (X), more preferably 70% by weight or more, and more preferably 70% by weight or more. Since the tomer (X) contains a unit derived from the ABA-type triblock polyetherdiamine compound (A1), it is possible to satisfy the terminal amino group concentration defined in the present invention. .

Further, the polyamide elastomer can contain other polyamide-based resins or other thermoplastic resins as long as the properties are not impaired and the terminal amino group concentration specified in the invention is satisfied.

Other polyamide resins include polyamide proamide (polyamide 6), polyundecane amide (polyamide 11), polydodecane amide (polyamide 12), and polyethylene adipamide. (Polyamide 26), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azeramide (polyamide 69), polyhexamide Xamethylene Sepacamide (Polyamide 610), Polyhexamethylene Pendecamide (Polyamide 611), Polyhexamethylene Dodecamide (Polyamide 612), Polyhexamethylene Terephthalamide (polyamide 6T), polyhexamethyleneisophthalamide (polyamide 61), polynoname Tylene adipamide (polyamide 966), polynonamethylene azeramide (polyamide 990), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide) 912), polymethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene terephthalamide (polyamide 9T), polynonamethylenehexahydroterephthalamide (polyamide 9HT) Polyamide 9T (H)), Polynonamethylene naphthalamide (Polyamide 9N), Polydecamethylene Adipamide (Polyamide 106), Polydecamethyleneazeramide (Polyamide 109) ), Polydecamethylene sepakamide (polyamide 101), polydecamethylene dodecamide (polyamide 101), polydecamethylene terephthalamide (polyamide) Amide 10 T), Polydecamethylenehexahydroterephthalamide (Polyamide 1 OT (H)), Polydecamethylenenaphthalamide (Polyamide 1 ON), Polyundecamethyleneterephthalamide (Polyamide) Amide 11T), polyundecamethylenehexahydroterephthalamide (polyamide 11T (H)), polydecamethylene naphthalamide (polyamide 11N), polydodecamethylene adipami (Polyamide 126), polydodecamethyleneazeramide (polyamide 129), polydodecamethylene sepakamide (polyamide 122), polydodecamethylene dodecamide (polyamide) 1212), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylenehexahydrodoterephthalamide (polyamide 12T (H)), Lidodecamethylene naphthalamide (polyamide 12N), polyamide xylene diphenylamide (polyamide MX D6), polyamide xylylene velamide (polyamide MX D8), polymer Taxylenazeramide (Polyamide MXD 9), Polymexylylene Sepakamide (Polyamide MXD10), Polymexylylendecamide (Polyamide MXD12), Polymetaxi Rylene terephthalamide (polyamide MXD T), polymethyxylene resophthalamide (polyamide MX DI), polymethyacryl-silylene phthalamide (polyamide MXDN), polybis (4-aminocyclo) Hexyl) methanedodecamide (polyamide PACM12), polyvis (3-methylaminocyclohexyl) methanedodecamide (polyamide dimethyl PACM12), polybis (4 —Aminocyclohexyl) methane terephthalamide (Polyamide PA CMT), Polybis (4-aminohexyl hexyl) Methanisophthalamide (Polyamide PACM I), Polybis (3 —Methyl-4—aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polysophorone adipamide (polyamide IPD 6), polyiso B down Terefutarami de (polyamylene de IPDT) and a copolymer using several kinds of these polyamylene de raw mode Nomar the like. One or more of these can be used.

Other thermoplastic resins include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-high-density polyethylene. Molecular weight Polyethylene (UHMWP E), Polypropylene (PP), Ethylene Z propylene copolymer (EPR), Ethylene / butene copolymer (EBR), Ethylene vinyl acetate copolymer (EVA) , Ethylene / vinyl acetate copolymer copolymer (EVOH), ethylenenoacrylic acid copolymer (EAA), ethylene methacrylic acid copolymer (EMA A), ethylene / methyl acrylate / Polyolefin-based resins such as styrene copolymer (EMA), ethylene Z methyl methacrylate copolymer (EMMA), ethylene Z methyl acrylate copolymer (EEA), and carboxyl groups and salts thereof. Functional groups such as acid anhydride groups and epoxy groups Yes it has been the poly Orefui down resin, poly Buchirente Refuta rate ( PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polyethylene naphthalate (PEN), polybutylene naphthalate (PBT) PBN), polyester resins such as liquid crystal polyester, polyether resins such as polyacetal (POM), polyphenylene oxide (PPO), polysulfone (PSF), polyester ether sulfone (PES), etc. Polysulfone resin, polyphenylene sulfide (PPS), polythioether sulfone (PTES), etc., polythioether resins, polyether ether ketone (PEEK), polyallyl ether ketone (PAEK), etc. Polyketone resin, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile Z Copolymer (AS), methacrylonitrile / trinostyrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS ), Etc., polymethacrylate resins such as polymethacryl ^ methyl (PMMA) and polyethyl methacrylate (P EMA), and polyvinyl alcohol (PVA) Polyvinyl resin such as polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose acetate, butyric acid cell mouth Cellulose resins such as polyethylene, polyvinylidene fluoride (PVDF), polyvinylidene fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), and polychloroethylene Trifluoroethylene (PCTFE), Ethylene / Cro mouth Trifluoroethylene copolymer (ECTFE), Tetrafluoroethylenehexafluoropropylene copolymer (FEP), Tetrafluoroethylene / Hexafluoropro Pyrene / vinylidene fluoride copolymer (THV), tetra Fluororesins such as fluoroethylene / perfluoro (anolequinolebininoleate) copolymers (PFA), polycarbonate resins such as polycarbonate (PC), thermoplastic polyimides (PI), polyamide imides (PAI), polyimide resins such as polyetherimide, and thermoplastic polyurethane resins. One or more of these can be used.

The resin composition of the present invention may be a heat-resistant agent, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a lubricant, a slip agent, a crystal nucleating agent, a tackifier, as long as its properties are not impaired. , A sealability improver, an antifogging agent, a release agent, a plasticizer, a pigment, a dye, a fragrance, a flame retardant, a reinforcing material, a conductive filler, and the like.

The (B) fluorine-containing polymer having a functional group reactive with the polyamide resin introduced into the molecular chain used in the present invention has a reactive functional group having a molecular structure. (Hereinafter, may be referred to as "(B) fluorinated polymer".)

(B) The fluorinated polymer is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one kind of fluorinated monomer. There is no particular limitation as long as it is a fluorinated polymer that can be melted by heat. For example, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polycloth trifluoroethylene (PCTFE), tetrafluoro / leo ethylene / perfluoro (alkyl) Ether) copolymer

(PFA), tetrafluoroethylene / hexafenoleopene propylene copolymer (FEP), ethylene tetrafluoroethylene copolymer

(ETFE), ethylene / tetrafluoroethylene / hexafenole propylene copolymer, vinylidene fluoride / tetrafluoroethylene Copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / pentafluoropropylene copolymer, tetrafluoroethylene zhexafluoropropylene zvinylidene fluoride copolymer (THV), vinylidene fluoride / pentafluoropropylene / tetrafluoroethylene copolymer, vinylidene fluoride Z-perfluoroalkylbutyl ether / tetrafluoroethylene copolymer, ethylene // Oral trifluoroethylene copolymer (ECTFE), and vinylidene fluoride / cyclo-oral trifluoroethylene copolymer. It can use one or more of them.

Among the (B) fluorinated polymers exemplified above, among the fluorinated polymers having a tetrafluoroethylene unit as an essential component in terms of heat resistance and chemical resistance, and in terms of molding, vinylidene fluoride is preferred. A fluorine-containing polymer having a unit as an essential component is preferable. Ethylene Z tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene / hexafuno Preferable is propylene copolymer Z-futsudani vinylidene copolymer (THV).

Ethylene-note-trafluoroethylene copolymer (hereinafter sometimes referred to as ETFE) is composed of a polymerized unit based on ethylene (hereinafter sometimes referred to as E) and tetrafluoroethylene (hereinafter referred to as TFE). The polymerization ratio (mol ratio) is preferably from 80/20 to 20/80, and preferably from 70/30 to 30/70. Is more preferable, and more preferably 60 Z 40 to 40/60.

If the molar ratio of (polymerized unit based on E) / (polymerized unit based on TFE) is extremely large, the heat resistance, weather resistance, chemical resistance, chemical liquid permeation resistance, etc. of the ETFE may be reduced, On the other hand, if the molar ratio is extremely small, the mechanical strength, melt moldability, etc. may decrease. This range In this case, the ETFE is excellent in heat resistance, weather resistance, chemical resistance, prevention of chemical permeation, mechanical strength, melt moldability, and the like.

(B) The fluorine-containing polymer may contain, in addition to the above-mentioned polymerized units based on E and TFE, one or more other monomers as long as the essential characteristics are not impaired.

Other monomers include α-olefins such as propylene and butene, CΗ ₂ = CX (CF ₂ ) _η Υ (where X and Υ are independently a hydrogen or fluorine atom, and η is 2 to A hydrogen atom to an unsaturated group such as vinylidene fluoride (VDF), butyl fluoride (VF), trifluroylethylene, hexafluoroysobutylene (HFIB), etc. Hexafluoropropylene

(HFP), black mouth trifluorethylene (CTFE), perfluoro (methinolebininolete) ((Μ V Ε), perfluoro (ethyl vinyl ether) (Ρ Ε V Ε), perfluoro ( Propirviel ether) (Ρ Ρ V Ε), perphnoreo mouth (butyl vinyl ether)

(Ρ Β V Ε) and other fluorophores having no hydrogen atom in unsaturated groups such as perfluoro (alkyl butyl ether) (PAVE)

(However, excluding TFE.), Methyl vinyl ether (MV E), ethyl vinyl ether (EVE), butyl vinyl ether (BVE), isobutyl vinylinoleate (IBVE), cyclohexynolevinyl ether (CHVE) Vinyl ether, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl piperate, vinyl benzoate, vinyl benzoate vinyl ester, Alkyl (meth) acrylate, (fluoroanolequinole) acrylate, (fluoroalkyl) methacrylate, and the like are listed. One or more of these can be used.

(B) In the fluorine-containing polymer, the above-mentioned general formula CH. = C 5C (C It is preferable to use a compound represented by F ₂ ) _n Y (hereinafter, referred to as “F AE”). The content of polymerized units based on FAE, in total polymer units of in, 0.1 is preferably 0 1 2 0 mole ^_0/0, 0. 1 more preferably 1 to 5 mol ^_0/0 , more preferably 1 to Ru 1 0 mole ^_0/0 der. If the content of F AE is less than the above value, crack resistance may decrease, a rupture phenomenon such as cracking under stress may occur, and if it exceeds the above value, mechanical strength May decrease.

F AE is, as described above, a general formula CH ₂ = CX (CF ₂ ) _n Y (where X and Υ are each independently a hydrogen atom or a fluorine atom, and η is an integer of 2 to 8. ). If the η force is less than 2 in the formula, the modification of the fluorine-containing polymer (for example, the suppression of cracking of the molded product or the molded product) may be insufficient. If η exceeds 8, it may be disadvantageous in terms of polymerization reactivity

For F AE, 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 ) ₈ 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 = CF (CF ₂ ) ₈ H, CH ₂ = CH (CF ₂ ) ₂ F , CH ₂ = CH (CF ₂ ) 3 F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ = CH (CF ₂ ) ₅ F, CH ₂ = CH (CF ₂ ) ₈ F, CH ₂ = CH ( CF ₂ ) ₂ H, CH ₂ = CH (CF ₂ ) ₃ H, CH ₂ = CH (CF ₂ ) ₄ H, CH ₂ = CH (CF ₂ ) ₅ H, CH ₂ = CH (CF ₂ ) ₈ H, etc. Is mentioned. One or more of these can be used.

Among them, the conjugate represented by CH ₂ = CH (CF ₂ ) _n Y is more preferable. In this case, η in the formula is η = 2 to 4. Is more preferable because (B) the chemical solution permeation prevention property and the crack resistance of the fluorinated polymer are established.

The vinylidene fluoride copolymer is a copolymer comprising a polymerization unit based on vinylidene fluoride and at least one kind of fluorine-containing monomer copolymerizable therewith. Here, other monomers copolymerizable with the polymerized unit based on vinylidene fluoride include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and black trifluorene. (CTFE), hexafenoleoloiesobutylene, hexafenoleoloacetone, pentaphneolopropylene, trifonoleoloethylene, bulfluoride, fluoro (alkyl butyl ether), and clomouth trifluorethylene. One or more of these can be used. In the vinylidene fluoride copolymer, the amount of the polymerized units based on vinylidene fluoride is preferably at least 30 mol% or more in all the polymerized units. As the vinylidene fluoride copolymer, a tetrafluoroethylene / hexafluoropropyl P-pyrene Z vinylidene fluoride copolymer (THV) is preferable. The (B) fluorine-containing polymer used in the present invention can be obtained by (co) polymerizing monomers constituting the polymer by a conventional polymerization method. Among them, a method based on radical polymerization is mainly used. In other words, the means for initiating polymerization is not particularly limited as long as it proceeds radically, but is initiated by, for example, an organic or inorganic radical polymerization initiator, heat, light, or ionizing radiation.

(B) The method for producing the fluoropolymer is not particularly limited, and a polymerization method using a generally used radical polymerization initiator is used. Polymerization methods include bulk polymerization, fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, and solutions using organic solvents such as alcohols and hydrocarbons. Known methods such as liquid polymerization, suspension polymerization using an aqueous medium and, if necessary, an appropriate organic solvent, and emulsion polymerization using an aqueous medium and an emulsifier can be employed.

The polymerization can be performed in a batch or continuous operation using a single- or multi-tank type stirred polymerization apparatus or a tubular polymerization apparatus.

As the radical polymerization initiator, the decomposition temperature at which the half life is 10 hours is preferably from 0 ° C to 100 ° C, and more preferably from 20 ° C to 90 ° C. Specific examples include 2,2'-bazobisisobutyritol and 2,2'-azobis (2,4-dimethylnoreronitrile.

), 2,2, -azobis (2-methylpareronitrile), 2,2,

—Azobis (2-cyclopropylpropionitol), 2,2,2-dimethyl azobisisobutyrate, 2,2,1-azobis [2- (hydroxymethyl) propionitol), 4,4, azobis Azo compounds such as (4-cyanopentenoic acid), hydrogen peroxide, tertiary butylhydroxide, cumidehydropoperoxide, etc., and other metal oxides, di-tert-butyl peroxide, dicumyl peroxide, etc. Non-fluorinated diasil peroxides such as dianolepoxide, acetyl peroxide, isobutyrinoyl peroxide, octanoinoleperoxide, benzoinoleperoxide, lauroyl peroxide, etc. Ketone peroxides such as oxides, methinoleethyl ketone peroxide, Peroxydicarbonate such as diisopropyl bromide, peroxy dicarbonate, etc., peroxyester such as tert-butyl peroxyxipate, tert-butyl peroxyisoptilate, tert-butyl peroxyacetate, etc. Doropa one Okishi de like arsenide de "Paokishi de _{_{of, (Z (CF 2) p}} COO) 2 ( wherein, Z is hydrogen atoms, a fluorine atom or a chlorine atom, p is an integer of 1 to 1 0. :) Compound represented by And inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate. These may be used alone or in combination of two or more.

In the production of the fluorine-containing polymer (B), it is also preferable to use a usual chain transfer agent for adjusting the molecular weight. The chain transfer agent, methanol, alcohol such as ethanol, 1, 3 first axis B B one 1, 1, 2, 2, 3 - penta Full O Ropuro Nono ⁰ emissions, 1, 2 - di-click B port one 1, 1,2,2—Tetrafnoroletan, 1,1-dichloro mouth 1-Fnoroleotane, 1,1,2—Tricyclo mouth 1,2,2-Trifluoronoreloethane, etc. Hydrocarbons such as chlorofluorophenol, pentane, hexane and cyclohexene, and carbon hydrochloride such as carbon tetrachloride, chlorophonolem, methylene chloride, and methylene chloride, etc. Is mentioned. These can be used alone or in combination of two or more.

The polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 ° C. to 100 ° C., more preferably 20 ° C. to 90 ° C. In order to avoid a decrease in heat resistance due to ethylene-ethylene chain formation in the polymer, a low temperature is generally preferred. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent to be used, polymerization temperature, etc., and is preferably 0.1 to: OMPa, and is preferably 0.5 to 3 MPa. a is more preferable. The polymerization time is preferably from 1 to 30 hours.

The molecular weight of (B) the fluorinated polymer is not particularly limited, but is preferably a polymer which is a solid at room temperature and can be used as a thermoplastic resin, an elastomer or the like. The molecular weight is controlled by the concentration of the monomer used for the polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, and the temperature. (B) When co-extruding the fluorine-containing polymer with the polyamide resin (A) or the like, a sufficient melt flow can be obtained within a kneading temperature and a molding temperature range that does not cause significant deterioration of the polyamide resin. In order to ensure the properties, (B) the melt flow rate according to ASTM D 1238 at a temperature 50 ° C higher than the melting point of the fluoropolymer and at a load of 5 kg should be 0 Preferably between 5 and 200 g / l 0 min. More preferably, it is in the range of ~ 1OOgZlOmin.

In addition, the melting point and glass transition point of the (B) fluorine-containing polymer can be adjusted by selecting the type and composition ratio of the fluorine-containing monomer and other monomers.

(B) The melting point of the fluorinated polymer is appropriately selected depending on the purpose, application, and method of use. However, when co-extrusion with the polyamide resin (A) or the like, the molding of the polyamide resin is performed. Preferably it is close to the temperature. For this reason, it is preferable to appropriately adjust the proportions of the fluorine-containing monomer and other monomers and the functional group-containing monomer described below to optimize (B) the melting point of the fluorine-containing polymer.

The (B) fluorinated polymer of the present invention has a functional group having reactivity with the polyamide resin in the molecular structure, and the functional group is (B) the fluorinated polymer. It may be contained in any of the molecular terminal, the side chain or the main chain. Further, the functional group may be used alone or in combination of two or more kinds in the fluorine-containing polymer (B). The type and content of the functional group depend on (B) the type, shape, application, required interlayer adhesion, bonding method, functional group introduction method, etc. of the mating material to be laminated on the fluoropolymer. It is determined as appropriate.

Functional groups reactive with the polyamide resin include a carboxyl group, an acid anhydride group or a carboxylate, a hydroxyl group, a sulfo group or a sulfonate, an epoxy group, a cyano group, Carbonet And at least one selected from the group consisting of a carboxyl group, a carboxylic acid halide group, and a carboxyl group, an acid anhydride group or a carbonate, a hydroxyl group, an epoxy group, a carbonate group, and a carbonate group. It is preferable that at least one member selected from the group consisting of acid halide groups is used, and at least one member selected from the group consisting of carboxyl groups, acid anhydride groups, carbonate groups and carboxylic acid halide groups be used. Is more preferred.

(B) The method of introducing a reactive functional group into the fluorinated polymer is as follows: (i) When the (B) fluorinated polymer is polymerized, a copolymer having a functional group can be used. (Ii) a method of introducing a functional group into the molecular terminal of the fluorine-containing polymer at the time of polymerization with a polymerization initiator, a chain transfer agent, etc., (iii) reactivity. And a method of grafting a compound having a functional group having a functional group capable of being converted into a derivative (graft compound) to a fluorine-containing polymer. These introduction methods can be used alone or in an appropriate combination. In consideration of the durability of the interlaminar adhesive strength of the stack tube when immersed in fuel, the (B) fluorinated polymer produced from the above (i) and (ii) is preferable. Regarding (iii), JP-A-7-180035, JP-A-7-259952, JP-A-7-259954, JP-A-7-1732 Japanese Patent Publication No. 30, Japanese Patent Application Laid-Open No. 7-174334, Japanese Patent Application Laid-Open No. 7-173434, Japanese Patent Publication No. Please refer to. Hereinafter, (i) a method of copolymerizing a copolymerizable monomer having a functional group at the time of polymerization of the fluorinated polymer, and (ii) a method of terminating the fluorinated polymer with a polymerization initiator, etc. A method for introducing a functional group will be described.

(i) (B) When producing a fluorinated polymer, a copolymerizable monomer having a functional group (hereinafter sometimes abbreviated as a functional group-containing monomer) A method of copolymerizing at least one functional group selected from a carboxyl group, an acid anhydride group or a carboxylate, a hydroxyl group, a sulfo group or a sulfonate, an epoxy group, and a cyano group. The containing monomer is used as a polymerized monomer. Examples of the functional group-containing monomer include a functional group-containing non-fluorine monomer and a functional group-containing fluorine-containing monomer.

Acrylic acid, halogenated acrylic acid (excluding fluorine), methacrylic acid, halogenated methacrylic acid (excluding fluorine) as the functional group-containing non-fluorinated monomer , Maleic acid, halogenated maleic acid (however, excluding fluorine), fumaric acid, halogenated fumaric acid (however, excluding fluorine), itaconic acid, citraconic acid, crotonic acid, and endobicycloー [2.2.1] — Unsaturated carboxylic acids such as 5-heptene-1,2,3-dicanoleconic acid and its esters, maleic anhydride, itaconic anhydride, succinic anhydride, Traconic acid, Endobicyclo [2.2.1] — 5-Heptene-1,2,3-dicarboxylic acid # ί Carboxyl group-containing monomers such as hydrates and derivatives thereof, glycidyl acrylate, Guri Shizinoreme Takuri Epoxy group-containing monomers such as glycidinoleate ether, hydroxyshethyl acrylate, hydroxyshethyl methacrylate, hydroxypropynole atalinoleate, hydroxypropyl methacrylate, hydroxypropyl methacrylate Hydroxyl group-containing monomers such as Ninore et al. One or more of these can be used.

Specific examples of the functional group-containing fluorine-containing monomer.

CF ₂ = CFOCF ₂ CF ₂ CO OH

CF 2 = CFO (CF ₂ ) 3 COOH

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CO OH

CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ C O / S0SAV S90060 / D / idTId sssoosoo

N〇〇 Qfe "

.

) (3 Z fe〇〇 υofcooUOfco¾ uH-- χε

^U ZO〇 0 ^S H ( ^z d D) H 0 = ^Ζ Η 0 ¾ NOO 0 ² H 0 ^s H 0 '( ^z Λ 0) H 0-: ² Η 0' HN OO 0 ² H 3 ^ ( ^z d D) H 0 = ^Ζ Η 0 HOO 0 ² H 0 d O) H 0 = ^Ζ Η 0 HOOD ^Z HD ^Z HD ( ^z d 0) H 0 ^S H 0 HOO 0 ^ε Η 0 ^S HO ² ( ^z Λ Ό) H 0 'Η 0 Η Ο Ο Ο ζ Η 0 2 ^ Ο ε ^ Ο H 0 = Z UD Η Ο ε Η (ε d O) d DO z d O (d O) d DO z Λ Ο Λ 0 = Z HD

^{^{^{HO s H (ε dd DO z}}} d O Λ 0 Z HDHO Z H 0 2 H 0 8 (3 d 0) d 0 - Ζ Η 0 HO 'HO' d O 'd O ή 0 Z UDHO z HD z UD z Λ Ο ^ζ ά θ 0 = ^Z H 0

XI

ZOO ( ^z . Ο) d DO ^z d DOO Λ 0-- ^Z H 0

H

MOOD ( ^£ ή θ) ή θ Ο ^ζ Λ Ο ( ^ε d O) Λ DO ^z d D Λ 0 ^Z UD fH NOO 0 ( ^z ά θ) d OO ^z d D ή 0 = ^S H 0

UZOO ^S H Ξ. 0 ^S H 0 ^ NOO 0 ² «i O 'd O Λ 0 ² H 0 ^ ΗΝ Ο Ο Ο ^ θ', ί Ο Ο d D = ^S H 0 HOO 0 Λ Ο) d OO ^z d O ( ^E d O) d DO ^z d D d 0 = ^S H〇

^{HOOD (e d D) d OO} z d O d 0 2 H 0 HOO 0 Ή 0 '(z Λ Ο) d 0 S H 0 HOOD 8 (z Λ Ο) d 0 = Z H 0 UOOD z Λ Ο ζ d D Λ 0 ^Z H 0 UOOD ^Z KO ^Z d D ^z d O d 0 = ^S H 0 NO 'd O' d O ^ OO ^ d O ά 0 = ^g d 0

Sr9S00 / S00ZdT / X3d S90060 / S00Z OAV CH ₂ = CH CF ₂ CF ₂ CH ₂ CH ₂ OH

CH ₂ = CH (CF ₂ ) ₄ CH ₂ CH ₂ CH ₂ OH

CH ₂ = CH (CF ₂ ) ₆ CH ₂ CH ₂ OH

And the like. One or more of these can be used

(B) the content of the fluorine-containing polymer in the functional group-containing monomer is preferably all in Polymerization unit 0. 0 5-2 0 mole ^_0/0, 0. 0 5 to 1 is Ri preferably good that 0 mole ^_0/0, further preferably 0.1 to 5 mol%. When the content of the functional group-containing monomer is less than 0.05 mol%, it is difficult to obtain sufficient interlayer adhesiveness, and the interlayer adhesiveness is reduced depending on the use environment conditions. May be inferior in chemical resistance. On the other hand, if the content exceeds 20 mol%, the heat resistance is reduced, and when processing at high temperatures, poor adhesion, coloring or foaming, or when used at high temperatures, peeling due to decomposition, coloring, foaming, or elution may occur. is there. Further, as long as the above content is satisfied, a mixture of a fluorinated polymer into which a functional group is introduced and a fluorinated polymer into which a non-functional group is not introduced may be used.

(ii) In the method of introducing a functional group into the molecular terminal of a fluorinated polymer by using a polymerization initiator or the like, (B) the functional group is present at the molecular terminal of the fluorinated polymer, It is a polymer having a functional group at one end or both ends, and as the functional group introduced to the end, a carbonate group or a carboxylic acid halide group is preferable.

(B) The carbonate group introduced as a terminal group of the fluorinated polymer is generally a group having a _ OC (= O) o— bond, and specifically, — OC (= O) O — R group [R is a hydrogen atom, an organic group (for example, a C 1 -C 20 alkyl group, a C 2 -C 20 alkyl group having an ether bond, etc.) or a group I, II, or VII element . ] is there. Carbonate groups include one OC (= O) O CH ₃ , one OC (= O) OC ₃ H — OC (= O) OC ₈ H ₁₇ , one OC (-O) OCH ₂ CH ₂ OCH ₂ CH _{3 and the} like. The carboxylic acid halide group specifically has a structure of one C OY [Y is a halogen element], and includes —COF, one COC 1 and the like. One or more of these can be used.

Various methods using a polymerization initiator or a chain transfer agent can be employed to introduce a carbonate group into the molecular terminal of the polymer.However, peroxyside, particularly peroxycarbonate, is used as a polymerization initiator. The method used can be preferably used in terms of quality such as economy, heat resistance, and chemical resistance. The use of peroxycarbonate is preferable because the polymerization temperature can be lowered and the initiation reaction does not involve a side reaction.

Various methods can be used to introduce a carboxylic acid halide group into the molecular end of the polymer.For example, for example, the above-mentioned carbonate group of a fluorinated polymer having a carbonate group at the end is heated and heated. It can be obtained by decomposition (decarboxylation).

Examples of peroxycarbonates include diisopropylpropyl peroxy carbonate, di-n-isopropynolepine carbonate, t-butyl peroxy-sopropyl carbonate, and t-butyl peroxymethacrylic acid. Carbonate, bis (4-t-butylcyclohexynole), polycarbonate, G2-ethynolehexyl carbonate, and the like. One or more of these can be used.

The amount of peroxycarbonate used depends on the type (composition, etc.) of the target polymer, the molecular weight, the polymerization conditions, and the type of the initiator used, but is based on 100 parts by weight of the total polymer obtained by polymerization. For 0.0 It is preferably from 5 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight. The content of the carbonate group at the molecular terminal of the polymer can be controlled by adjusting the polymerization conditions. If the amount of the polymerization initiator used exceeds the above-mentioned value, it may be difficult to control the polymerization rate, and if the amount used is less than the above-mentioned value, the polymerization rate may be reduced. The method of adding the polymerization initiator is not particularly limited, and may be added all at once at the start of the polymerization, or may be added continuously during the polymerization. The addition method is appropriately selected depending on the decomposition reactivity of the polymerization initiator and the polymerization temperature.

(B) terminal officer ability radix to the main chain having 1 0 ⁶ carbon atoms, fluorine-containing polymer is preferably 1 5 0-3 0 0 0, 2 0 0-2 0 0 0 In More preferably, the number is more preferably from 300 to 100,000. When the number of functional groups is less than 150, it is difficult to obtain sufficient interlayer adhesiveness, and depending on the use environment conditions, interlayer adhesiveness may be reduced, and in particular, the interlayer adhesive strength may be poor in chemical resistance. In addition, when the number exceeds 300, heat resistance is reduced, and when processing at high temperatures, poor adhesion, coloring or foaming, or when used at high temperatures, peeling due to decomposition, coloring, foaming, or elution may occur. is there. Further, as long as the number of functional groups is satisfied, a mixture of a fluorinated polymer into which a functional group is introduced and a fluorinated polymer into which a functional group is not introduced may be used.

As described above, the (B) fluorine-containing polymer used in the present invention is a fluorine-containing polymer into which a functional group reactive with a polyamide resin has been introduced. As described above, the functional group was introduced (B

) Fluoropolymers themselves maintain excellent properties such as heat resistance, water resistance, low friction properties, chemical resistance, weather resistance, antifouling properties, and chemical liquid permeation properties inherent to fluorinated polymers. This is advantageous in terms of productivity and cost.

In addition, since the functional group is contained in the molecular chain, the laminated tube For various materials that have insufficient or impossible interlayer adhesion, no special treatment such as surface treatment or coating with an adhesive resin is performed, and the interlayer with other substrates that are excellent in direct contact Adhesiveness can be imparted.

The (B) fluorine-containing polymer used in the present invention may be any of various powders such as inorganic powders, glass fibers, carbon fibers, metal oxides, and carbon within a range that does not impair the performance according to the purpose or application. Fillers can be mixed. In addition to the filler, a pigment, an ultraviolet absorber, and other optional additives can be mixed. In addition to additives, other resins such as fluorocarbon resins and thermoplastic resins, synthetic rubbers, etc. can also be compounded to improve mechanical properties, weather resistance, impart design, prevent static electricity, and formability. Improvements can be made.

The laminated tube according to the present invention reacts with (A) a layer composed of a polyamide elastomer having a terminal amino group concentration of 20 ^ eq Zg or more, and (B) a polyamide resin. It has a (b) layer made of a fluorinated polymer ((B) a fluorinated polymer) in which a functional group having a property is introduced into the molecular chain, and is composed of at least two or more layers. In the laminated tube of the present invention, in a preferred embodiment, (A) the layer composed of a polyamide elastomer having a terminal amino group concentration of ZO ^ ueq Zg or more, (a) the layer is the outermost layer of the laminated tube Placed in. (A) A laminated tube having excellent flexibility and vibration resistance can be obtained by disposing a layer made of polyamide elastomer having a terminal amino group concentration of 20 / xeq / g or more as the outermost layer. Can be

In the laminated tube of the present invention, it is essential to include (B) a layer (b) made of a fluoropolymer, and the laminated tube has (A) a terminal amino group concentration of 20 μeq Zg or more. It is preferred to be disposed inside the (a) layer made of a polyamide elastomer. (B) If the layer (b) composed of the fluorine-containing polymer is not included, Decreases chemical permeation prevention and chemical resistance. Furthermore, (A) a layer composed of a polyamide elastomer having a terminal amino group concentration of 20 ^ eq / g or more, and (B) a layer composed of a fluoropolymer (b) "A direct J-bonded arrangement is more preferable because of its excellent interlayer adhesiveness, especially excellent chemical resistance of interlayer adhesive strength over a long period of time.

The outer diameter of the laminated tube is thick enough not to increase the permeability of the chemical solution, taking into account the flow rate of chemicals, etc. The thickness is designed so that the vibration resistance during use can maintain a good degree of flexibility, but is not limited thereto. It is preferable that the outer diameter be 1.5 to 150 mm, the inner diameter be 1 to 10 O mm, and the wall thickness be 0.25 to 25 mm. In the laminated tube of the present invention, the thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminated tube, the application, and the like. It is determined in consideration of the properties of the laminated tube such as chemical permeation prevention, low temperature impact resistance and flexibility. Generally, the thickness of the (a) layer and the (b) layer is preferably 3 to 90% of the thickness of the entire laminated tube. In consideration of the chemical liquid permeation prevention property, flexibility, cost, etc., the thickness of the layer (b) is preferably 1 to 50%, and more preferably 5 to 30%, based on the total thickness of the laminated tube. It is even more preferred.

Further, the total number of layers in the laminated tube of the present invention is as follows: (A) a layer composed of a polyamide elastomer having a terminal amino group concentration of 20 μeq / g or more; (B) a fluorine-containing system. The layer is not particularly limited as long as it has at least two layers, including a layer (b) composed of a polymer. Further, the laminated tube of the present invention may further comprise, in addition to the two layers (a) and (b) layers, a layer made of another thermoplastic resin in order to impart further functions or obtain an economically advantageous laminated tube. May have one or more layers. For example, (A) the layer (a) composed of a polyamide elastomer having a terminal amino group concentration of 20 eq / g or more, and (B) the functional group reactive with the polyamide resin are molecules. A laminated tube composed of at least three layers, having a (b) layer made of a fluorine-containing polymer introduced into the chain, and a (c) layer made of (C) polyurethane, may be mentioned.

In the laminated tube, (A) the layer (a) made of a polyamide elastomer having a terminal amino group concentration of 2 O ^ eq / g or more has reactivity with (B) a polyamide resin. It is preferable that the functional group is disposed between the (b) layer made of the fluorinated polymer introduced into the molecular chain and the (c) layer made of (C) polyurethane. Polyurethane (C) used in the present invention may be a polyurethane obtained by reacting a polyol and a polyisocyanate, a polyol obtained by reacting a polyol, a polyisocyanate, and a chain obtained by reacting a chain extender. Urethane or the like can be used. In particular, it is preferable to use a thermoplastic polyurethane.

Examples of the polyol include a condensed polyester polyol, a lactone-based polyester polyol, a polycarbonate polyol, and a polyester polyol.

Examples of the condensed polyester polyol include a polyester diol obtained by using one or more of a dicarboxylic acid and a diol.

Examples of the dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. 1,3 / 1,4-cyclohexanedicanolevonic acid, dicyclohexanemethane 1,4,4, dicarboxylic acid, norbornanedicarboxylic acid, etc. Carboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, 1,4Z1,5 / 2,6 / 2,7-naphthalenedicarboxylic acid, diphenylmethane 4,4, dicarboxylic acid, diphenylethane-1,4,4,1- Examples thereof include aromatic dicarboxylic acids such as dicarboxylic acid and diphenylpropane-1,4,4-dicarboxylic acid, and lower alkyl esters thereof, and one or more of these can be used. Among these, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid, and lower alkyl esters thereof are preferable.

Ethylene glycol, ゝ,

, Ethylene glycol, triethylene glycol, propylene glycol V, dipropylene glycol, 1,4-butanediol, 1? 5—Pentangi

1,6 1-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecaneol, 2 1-methyl-1,3-propanediol, 2,2-dimethyl-1,1,3-propanediol, 3

—Methyl-1,5-pentanediol, 2-Echinole — 1,3-Hexaneglycol, 2,5-dimethyl—2? 5 — hexanediol,

2,2,4 Trimethyl — 1,3 —Pentanediol, 2-methyl

— 1, 8 — octanediol, 2, 2, 4-trimethyl — 1, 6— Aliphatic diols such as hexanediol, 12/1, 3/1, 4-one-cycle pentadiol, 1 1,3 / 1,4-cyclohexanediol, 1,3 / 1,4-cyclohexanedimethanol, 1,1-bis

(4—Hydroxysik hexinole) methane, 4,4, dihydroxysik mouth hexylethane, 2,2-bis (4

Mouth hexyl) alicyclic diols such as propane, 1

Droxybenzene, p m—xylylene dioxo

/ 2, 6/2, 7-dihydroxynaphthalene, Aromatic diols such as xydiphenyl, 1,1-bis (4-hydroxyphenyl) methane, 4,4, dihydroxydiphenylethane, and 2,2-bis (4-hydroxyphenyl) propane. However, one or more of these can be used. Among them, 1,3-propanediole, 1,4-butanediole, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediole, 2 Aliphatic diols such as 1,8-octanediol and 1,9-nonanediol are preferred.

Examples of ratatone-based polyester polyols include j3_propiolactone, pivalolactone,] 3—petit mouth rattan, δ—palette mouth rattan, γ—methyl_δ—palet mouth rata Lactone compounds such as tontone, ε-one-prolacton, and methinolate — ε—force-pro-lactone, dimethyl-one-ε—force-prolactone, trimethyl-one- _ε —force-prolacton Examples thereof include a polyesterdiol obtained by reacting with a hydroxy compound such as a diol. '' Polycarbonate polyols include, for example, polycarbonate diols obtained by reacting a low molecular weight diol with a carbonate compound such as dialkynole carbonate, alkylene carbonate, diaryl carbonate and the like. Can be Examples of the low-molecular diol that is a raw material for producing a polycarbonate diol include the low-molecular diol exemplified above as a raw material for producing a polyester diol. The dialkyl carbonates include dimethyl carbonate, getinole carbonate, di-η-propyl carbonate, diisopropyl carbonate, g-η-butyrene carbonate, di-soptinole carbonate, di-1 t — Petinolecarbonate, di-n-aminolecarbonate, diisoamylcarbonate, etc., alkylene power is ethylene carbonate, propylene carbonate, and butylene power. Carbonate, hexamethylene carbonate, (3-methyl-1,5-pentylene) carbonate, etc., and diaryl carbonate, diphenyl carbonate, fenylone naphthinocarbonate, dinaphthorn Norecarbonate, 4-methinoresilifenolenocarbonate, 4_ ethinoresilifenorenocarbonate, 41-propinoresifeninolecarbonate, 4,4, dimethinolesifenefinolecarbonate, 4,4,1 And 4,4,1-dipropinoyl phenyl carbonate. One or more of these can be used.

Polyether polyols include, for example, polyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypentamethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. Polyether diols such as polyether diol and polyoxypropylene triol are exemplified. One or more of these can be used. In addition to the above, various known polyols for polyurethane can also be used.

As the (C) polyurethane, a thermoplastic polyurethane containing a polyester diol and Z or a polyether diol as a soft segment is preferable.

(C) The type of the polyisocyanate used for the polyurethane is not particularly limited, but is preferably a diisocyanate, and is preferably a diisocyanate conventionally used for the production of a polyurethane, preferably a thermoplastic polyurethane. Any of the associations can be used.

The diisocyanates include 1,3—propanedithiocyanate, 1,4—butanedithiocyanate, 1,5—pentanedithiocyanate, 1,6—hexanedithiocyanate, 1,8—octanediene Aliphatic such as isocyanate, 1,9-nonansigenic, 2,2,4 / 2,4,4—trimethyl-1,6—hexanediisocyanate, lizinzyi, dimer acid, etc. 1,3-Zl, 4-cyclohexanediocyanate, methinoresic hexone hexocyanate, 1,1-bis (4-bisocyanate hexyl) methane, 4,4, jii Sociane — Tosiccyclohexylethane, 2, 2 —Bis (4—Issocyanate) Mouthhexyl. 1,2-bis (3-methyl-4-isocyanocyclohexyl) methane, 2,2-bis (3-methyl-4-isocyanocyclohexyl) propane, lysine Alicyclic diisocyanates, such as isoisopropylidenecyclohexyl-1,4,4, diisocynate, isophoronediisonate, norbornenediisocitane, tricyclodecanediisocynate, 2,4 / 2, 6 — Tolylene diisocyanate, p / m — Xylylene diisocyanate, Tetramethyl xylylene diisocyanate, 4, 4 '— Diphenyl methane diisocyanate, 3 — Methyl diphenyl methane 1, 4, 4, 1 Sociate, 3,3, one dimethyl-1,4, —diphenylmethandiyl succinate, 3,3, 1,4,4,6,6-, 2-bis (4,4-isocyanate), propane, m / p-,-, 6,4- 2,4—diisocyanates, 1,4 Z 1,5 / 2,6 / 2,7—Aromatic diisocyanates such as naphtha-diene thiocyanates, trizindi thiocyanates, etc. One or more species can be used. Of these, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, and 4,4,1-diphenyl methane diisocyanate are preferred. The type of chain extender used in the production of polyurethane is not particularly limited, and any of the chain extenders conventionally used in the production of ordinary polyurethane can be used, but the activity capable of reacting with the isocyanate group can be used. It is preferable to use a low molecular compound having a molecular weight of 300 or less and having two or more hydrogen atoms in the molecule.

As chain extenders, ethylene glycol, diethylene glycol

, H Diethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol,

1,4-butanediole, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl 1,1,3-propanediol, 3-methyl_1,5, pentanedyl, 2,2, -jetinole, 1,3-propanediol, 2-ethyl, 1,3-hexanediol, 2,2, 4—Trimethyl-1,3_pentylenediol, 2-methyl-1-, 8-octanediol, 2-butynole-2-, ethyl-1,3-propanediol, 1,3 / 1, cyclohexanedioxane, p Z m-xylylene diphenol, 1, / 1,4-bis (2-hydroxyethoxy) benzene, 1,4 /, 52,6 / 2,7_bis (hydroxymethyl) naphthalene, sue (2- Diols such as terephthalate, drazine, ethylenediamine, 1,3-propylene diamine, 1,

4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine1,10—decanediamine

1,1,2-dodecanediamine, 2,2-dimethyl-1,3_propanediamine, 2Z3-methyl-1,5-pentanediamine, 2-methinole-1,8-octanedia,

2,2,4 / 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nona N-diamine, 2-butyl-2-ethyl_1,5-pentanediamine, p / m-xylylenediamine, isophoronediamine, 1,31,4-six mouth hexanediamine, 1,3 / 1,4-six Lohexane dimethylamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminohexyl) prono II. 4,4'-diamin, nonoleponolenenediamine, tricyclodecanediamine, piperazine and its derivatives, fuyulediamine, tridiamine , Xylene diamine, 4,4'-diamines such as diphenylmethanediamine, adipic acid dihydrazide, isophthalic acid dihydrazide, aminoamino alcohols, and amino alcohols such as aminoalkanols These may be used alone or in combination of two or more. Among them, aliphatic diols having 2 to 10 carbon atoms are preferable, and 1,4-butanediol is more preferable.

(C) Polyurethane is a thermoplastic polymer other than polyurethane, flexible thermoplastic polymer, elastomer, rubber, heat-resistant agent, UV absorber, light stabilizer, and oxidizing agent, as long as the properties are not impaired. Inhibitors, antistatic agents, lubricants, slip agents, crystal nucleating agents, tackifiers, sealant improvers, antifogging agents, release agents, plasticizers, pigments, dyes, fragrances, difficulties Fuel, reinforcing materials, conductive fillers, etc. can be added.

Examples of the thermoplastic resin constituting other layers in the laminated tube of the present invention include polyproamide (polyamide 6), polyvinyl decane amide (polyamide 11), and poly dodecane Mid (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene azinomid (polyamide 46), polyhexamethylene dipamide (polyamide 66), Polyhexamethylene azeramide (polyamide 69), polyhexamethylene sepakamide (polyamide 61) 0), polyhexamethylene pentade (polyamide, 61 1), polyhexamethylene amide (polyamide, 61 2), polyhexamethylene terephthalanoreamide K (Polyamide, 6T), polyhexamethylene disophtalamide (polyamide, 6I), polynonamethylene adipamide (poly SK966), polynonamethylene azela K (polyamide) Do

9 9), polynonamethylene cenoamide, (polyamide, 910), polynonamethylene dodecadide (polyamide 912), po]) h dimethylamine terephthalamide (polyamide) TMH T), polynonamethylene terephthalamide, (polyamide 9T), polynonamethylenehexahydrodoterephthala, pad (polyamide, 9T (H)), polynonamethylene terenaphthalamide (polyamide 9) N), polydecamethylene adipamide (polyamide 106), polydecamethyleneazeramide (polyamide 109), polydecamethylenesepacamide (polyamide 11010), polydeca Methylene dodecamide (polyamide 101), polydecane methylene terephthalate (polyamide 10T), polydecamethylene hexahydroterephthalate, (poly K10T (H) ), Polydecamethylene naphthalad, (Polyamide K10N), Polyundecamethylene terephthalamide K (Polyamide, 11T), Polydecamethylenehexahydroterephthalad, (Polyamide, 11) T (H)), polydecanemethylene naphthalamide (polyamide S, 11N), polymethylene diazide amide (polyamide K1226), polydedecamethylene naphthalamide (polyamide) Polyamide, 12 9), Poly K decamethylene cenoamide, (Polyamide 1210), Polyamide, Decamethylene dodecamide (Poly S

1 2 1), polide, tetramethylene terephthalamide (polyamide, 1 2

T), polydodecamethylene hexahide, oral terephthalamide (Posamide, 12T (H)), pododecamethylene naphthalamide (PolySd,

1 2 N), poly (mexylylene adipamide), (polyamid KMX D 6) , Polymexylylene Veramide (Polyamide MXD 8), Polymethyxylene Renazeramide (Polyamide MXD 9), Polymethaxylylene Sepacamide (Polyamide MXD10), Polymethyxylene Render Decamide (Polyamide MX D12), Polymethyxylene terephthalamide (Polyamide MX DT), Polymethyxylene lenisophthalamide (Polyamide MXD I), Polymethyxylene rennaphthalamide (Polyamide) MXDN), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (3-methyl141-aminocyclohexyl) methane dodecamine (Polyamide dodecyl PACM12), polybis (4-aminohexyl hexyl) methane terephthalamide (polyamide PA CMT), polybis (4-aminocyclohexyl) methanisophthalamide (polyamide PACM I), polyisophorone adipamide (polyamide IPD6), polyisophorone terephthalamide (polyamide IPDT) and these polyamides Copolymers using several kinds of raw material monomers are exemplified. Further, examples of the fluorine-containing polymer other than those defined in the present invention (herein, other than those defined in the present invention refer to a fluorine-containing polymer having no functional group.) Polyvinylidene fluoride (PVDF), Polyvinylene fluoride (PVF), Ethylene / tetrafluoroethylene copolymer (ETFE), Polyethylene trifluoroethylene (PCTFE), Ethylene Z Polymer (ECTFE), Tetrafluoroethylene Z hexafnoreoethylene propylene copolymer (FEP), Tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), Tetrafluoro Ethylene / fluoro (alkyl biel ether) copolymer (PFA) and the like.

In addition, high density polyethylene (HD PE), medium density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWP E), polypropylene (PP), ethylene Z propylene copolymer (EPR) ), Ethylene Z-butene copolymer (EBR), Ethylene / vinyl acetate copolymer (E VA), Utilene Z-vinyl acetate copolymer

(E VOH), Ethylene / acrylic acid copolymer (EAA), Ethylene Z methacrylic acid copolymer (EMAA), Ethylene / methyl acrylate copolymer (EMA), Ethylene nomethacrylic acid Methyl copolymer

(EMMA), polyolefin resins such as ethylene / ethyl acrylate copolymer (EEA), and acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and mesacon. Acids, citraconic acid, gnoreconic acid, cis-1-cyclohexene-1,2-dicarboxylic acid, endobicyclo [2.2.1] — 5-heptene-1,2,3-dicarboxylic acid Carboxyl group and its metal salts (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo [2. 2.1] — 5_Heptene-1,2,3—Anhydride groups such as dicarboxylic anhydrides, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and itaco Functional groups such as epoxy groups such as glycidyl phosphate and glycidyl citrate Polyolefin resin, polybutylene terephthalate contained

(PBT), Polyethylene Terephthalate (PET), Polyethylene Isophthalate (PEI), PET / PEI Copolymer, Polyarylate (PAR), Polybutylene Naphthalate (PBN), Poly Polyester resins such as ethylene naphthalate (PEN) and liquid crystal polyester (LCP); polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO); polysulfone (PSF); Polysulfone resin such as polyether sulfone (PES), Polyethylene ether resins such as polyphenylene sulfide (PPS) and polyetherethersulfone (PTES), and polyketones such as polyetheretherketone (PEEK) and polyalicyclic etherketone (PAEK) Tone-based resin, polyacrylonitrile (PAN), polymethacrylonitrile, atalononitrile / renostyrene copolymer (AS), copolymer of methacrylonitrile / styrene Polymers, such as polyacrylonitrile / butadiene / styrene copolymer (ABS), and metatrilonitrile / styrene / butadiene copolymer (MBS), etc. Resins, polymethyl acrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), and polyvinyl ester resins such as polyacetate butyl (PVAc). Polyvinylidene chloride (PVDC), Polyvinyl chloride (PVC), vinyl chloride Z polyvinylidene chloride copolymer, polyvinylidene chloride / methyl acrylate copolymer and other polyvinyl chloride resins, cellulose acetate and cellulose butyrate, and other cellulose resins, and polycarbonate ( Polycarbonate resins such as PC), thermoplastic polyimides (PI), polyamide imides (PAI), and polyimide resins such as polyetherimide.

It is also possible to laminate any substrate other than thermoplastic resin, for example, paper, metal-based material, unstretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, nonwoven fabric, metal cotton, wood, etc. It is. Metallic materials include metals and metal compounds such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, and cobalt. And alloy steels such as stainless steels composed of two or more of these, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.

Although the number of layers of the laminated tube of the present invention is two or more, it is preferably eight or less, as judged from the mechanism of the chemical transport tube manufacturing apparatus. , More preferably 2 to 7 layers, and even more preferably 2 to 5 layers.

As a method of manufacturing a laminated tube, a method of melt extrusion using an extruder corresponding to the number of layers or the number of materials, a method of simultaneously laminating inside or outside a die (co-extrusion method), or a method of once forming a single tube A method in which a laminated tube or a laminated tube manufactured by the above method is manufactured in advance, and the resin is integrated into the outside using an adhesive layer, if necessary, to integrate the resin. (Coating method).

The method for forming the laminated tube of the present invention is preferably co-extrusion.

In addition, when the obtained laminated tube has a complicated shape, or when subjected to heat bending after forming to form a molded product, the above laminated tube is formed in order to remove residual distortion of the molded product. Thereafter, it is also possible to obtain a target molded product by heat-treating at a temperature lower than the lowest melting point of the resin constituting the tube for 0.01 to 10 hours.

The laminated tube may have a corrugated region. The waveform region is a region formed in a waveform shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The corrugated region may not only be provided over the entire length of the laminated tube, but may be provided partially in an appropriate region in the middle. The corrugated region can be easily formed by first molding a straight tubular tube and then molding it into a predetermined corrugated shape. By having such a corrugated area, it has a shock absorbing property, and the mounting property becomes easy. Further, for example, it is possible to add necessary parts such as a connector, or to form an L-shape or U-shape by bending.

The whole or a part of the outer circumference of the laminated tube formed in this way should be made of Epiclorh Dragon in consideration of stone splash, abrasion with other parts and flame resistance. (ECO), acrylonitrile / butadiene rubber (NBR), a mixture of NBR and polychlorinated rubber, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, acrylyl rubber (ACM), chloroprene rubber (CR), ethylene propylene rubber (EPR), ethylene / propylene / gen rubber (EPDM), mixed rubber of NBR and EPDM, vinyl chloride-based, olefin-based, ester-based, amide-based, etc. A solid or sponge-like protection member (protector) made of a thermoplastic elastomer or the like can be provided. The protective member may be a sponge-like porous body by a known method. By using a porous body, a protective portion that is lightweight and has excellent heat insulating properties can be formed. Also, material costs can be reduced. Alternatively, the strength may be improved by adding glass fibers or the like. Although the shape of the protective member is not particularly limited, it is usually a tubular member or a block-shaped member having a concave portion for receiving the laminated tube. In the case of a tubular member, the laminated tube can be inserted later into a tubular member that has been prepared in advance, or the tubular member can be covered and extruded onto the laminated tube so that the two members come into close contact with each other. In order to adhere the two, an adhesive is applied to the inner surface of the protective member or the concave surface as needed, and a laminated tube is inserted or fitted into the inner surface and the two members are brought into close contact with each other. To form a structured structure. It is also possible to reinforce with metal or the like.

The laminated tube of the present invention is characterized in that the fluorine-containing polymer used as the inner layer material has heat resistance, chemical resistance, weather resistance, non-adhesion, low friction and low dielectric properties, and a polyamide elastomer used as the outer layer. It has various properties such as toughness, water resistance, aging resistance, flexibility, bending fatigue resistance, low-temperature impact resistance, etc.In addition, both materials have excellent interlayer adhesion, chemical resistance of interlayer adhesion strength At the same time, it is easy and inexpensive to manufacture. Also, by selecting the material to be used, the visibility of the transported chemical solution is improved. It is also possible to use a small tube.

Example

Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The analysis and measurement of physical properties in Examples and Comparative Examples were performed as follows.

The properties of the polyamide elastomer were measured by the following methods.

[Relative viscosity]

Using m-cresol, a special grade reagent, as a solvent, the concentration was measured at 25 ° C using a Ostold viscometer with a polymer concentration of 0.5%.

[Terminal amino group concentration]

A predetermined amount of the polyamide sample is placed in an Erlenmeyer flask with a stopcock, and 40 mL of a previously prepared solvent phenol / methanol (volume ratio: 9 to 1) is added, followed by stirring and dissolving with a magnetic stirrer. Using thymol blue as an indicator, titration was performed with NZ 20 hydrochloric acid to determine the terminal amino group concentration.

The characteristics of the fluorinated polymer were measured by the following methods.

[Composition of fluorinated polymer]

It was measured by melt NMR analysis and fluorine content analysis.

[Carboxyl group content in fluorinated polymer]

The content of the polymerization unit based on itaconic anhydride (IAN) in the fluorinated polymer was determined by infrared absorption spectroscopy analysis. The absorption peak of C = O stretching vibration in the polymerization unit was obtained. All appear at 1870 cm- ¹ , the absorbance of the absorption peak is measured, and the content of polymerized units based on IAN, M (mol%), is determined using the relational expression of M = aL. did. Where L is the absorbance at 1870 cm- ¹ and a is a coefficient. As a, a = 0.87 determined using IAN as a model compound was used.

[Number of terminal carbonate groups in fluorinated polymer]

The number of terminal carbonate groups in the fluorinated polymer was determined by infrared absorption spectrum analysis to indicate that the peak attributable to the carbonate group of the carbonate group (one OC (= 0) O—) was 180 c It appears to the absorption wavelength of Paiganma ^1, by measuring the absorbance of the absorption peak was calculated and the number of main chain carbonate groups to the number 1 0 ⁶ carbons in the fluorine-containing polymer by the following equation.

[The number of main chain Kabone preparative groups to the number 1 0 ⁶ carbon atoms, fluorine-containing _{polymer] = 5 0 0 AW / £} df

A: Absorbance of the peak of the carbonate group (one OC (= O) O-). Ε: Molar absorbance coefficient of the carbonate group (one OC (= Ο) Ο-) [c π ¹ · m 01 — ¹ ]. Ε = 170 from the model compound.

W: Composition average molecular weight calculated from monomer composition

d: density of the film [g / cm ^3]

f: Film thickness [mm]

Each physical property of the tube was measured by the following method.

[Bending stiffness]

The evaluation was carried out according to the method described in SAEJ 8449.8. When the bending stiffness was 7 N or less in the manufactured tube dimensions, it was determined that the flexibility was excellent.

[Interlayer adhesion]

The test piece was cut by cutting the tube cut to 20 O mm in half in the vertical direction. A 180 ° peel test was performed using a Tensilon universal testing machine at a tensile speed of 50 mmZ. The peel strength was read from the maximum point of the S-S curve, and the interlayer adhesion was evaluated.

[Drug resistance of interlayer adhesion strength] Close one end of the tube cut to 200 mm, and put glycerin / urea diethylene dalicol Z pure water used as a solvent for aqueous dye ink inside the tube = 20/15/15/50 The drug solution mixed in a volume ratio was sealed and both ends were sealed. This was set in an oven at 600 ° C. and kept for 1000 hours. Thereafter, after completely removing the inclusions, the tube was dried, and the adhesive strength was measured by the above method, and the chemical resistance of the interlayer adhesive strength was evaluated.

[Chemical solution penetration prevention]

One end of the tube cut to 200 mm was sealed, the above mixed drug solution was put inside, and the other end was also sealed. Thereafter, the entire weight was measured, and then the test tube was placed in an oven at 60 ° C, and the weight change was measured every day. The change in weight per day was divided by the surface area per lm of the tube to calculate the fuel permeation coefficient (g / m ² -day).

[Materials used in Examples and Comparative Examples]

(A) Manufacture of polyamide polyamide

(A- 1) Production of polyamide ether elastomer (X)

12-Amino dodecanoic acid (Ube Industries, Ltd.) in a 70-liter pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator, and polymer outlet 7000 kg, ABA type A triplic polyether diamin (HUNT MAN, XTJ-542) 1 1.380 kg and adipic acid 1. 62 kg and were charged. After the inside of the vessel was sufficiently purged with nitrogen, heating was gradually performed while supplying nitrogen gas at a flow rate of 300 liter / min. The temperature was raised from room temperature to 230 ° C over 3 hours, and polymerization was performed at 230 ° C for 6 hours. After the heating was started, the pressure in the vessel was adjusted to 0.05 MPa. Next, the stirring was stopped, and a colorless and transparent polymer in a molten state was drawn out from the polymer outlet in a string form, cooled with water, and then pelletized. About 13 kg of pellets were obtained.

The obtained pellet was a flexible polyamide ether elastomer having a white vitreous mass and rich in rubber elasticity, with a relative viscosity of 1.95 and a terminal amino group concentration of 27 / eq / g (hereinafter, referred to as The polyamide elastomer is referred to as (A-1).

(A-2) Manufacture of polyamide resin (X)

(A- 1) Polyamide ester Terelastomer (X) was manufactured by using 12-aminododecanoic acid (manufactured by Ube Industries, Ltd.) 11.00 kg, AB A type triblock polymer Ether diamine (HUNT MAN, XT J — 55 9) White tough and rubber elastic in the same way, except that 7.87 kg and adipic acid 1.122 kg A flexible, rich polyamide-elastomer was obtained. The relative viscosity was 2.04, and the terminal amino group concentration was 45 / xeqZg (hereinafter, this polyamide elastomer is referred to as (A-2)).

(A-3) Production of polyamide ether ester elastomer 70 liter equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure regulator, and polymer removal fcfcl outlet 9. 800 kg of 12-aminododecanoic acid (manufactured by Ube Industries, Ltd.) and 0.766 kg of adipic acid were charged into a pressure vessel. After the vessel was sufficiently purged with nitrogen, the vessel was gradually heated while supplying nitrogen gas at a flow rate of 300 liter Z. Stirring was performed at a speed of 20 rpm. The temperature was raised from room temperature to 240 ° C. over 3 hours, and polymerization was carried out at 230 ° C. for 4 hours to synthesize a nylon 12 oligomer.

To this oligomer, polytetramethylene glycol (BASF, made by h, PolyTHF 1800) 9.434 kg, tetrabutyl dinoreconate 0.020 kg, and an antioxidant (Tominox 917 manufactured by Yoshitomi Pharmaceutical Co., Ltd.) 0.050 kg was charged. Nitrogen is sufficiently exchanged in the container. Then, heating was gradually performed while supplying nitrogen gas at a flow rate of 300 liter / hour. Stirring was performed at a speed of 20 rpm. Raise the temperature from room temperature to 210 ° C over 3 hours, heat at 210 ° C for 3 hours, then gradually reduce the pressure to 50 Pa over 1 hour, and polymerize for 2 hours. After the reaction, the temperature was raised and the pressure was reduced over 30 minutes, and the polymerization was completed at 230 ° C. and about 30 Pa for 3 hours to complete the polymerization. Next, stirring was stopped, and nitrogen gas was supplied into the polymerization layer to return the pressure to normal pressure. Next, a colorless and transparent polymer in a molten state was drawn out from the polymer outlet in a string form, cooled with water, and pelletized to obtain a pellet of about 13 kg.

The pellet obtained was a flexible white polyamide ether ester elastomer with high toughness and high rubber elasticity, a relative viscosity of 1.89, and a terminal amino group concentration of 0 μeqg, which could not be measured. (Hereinafter, this polyamide elastomer is referred to as (A-3)).

(B) Fluorine-containing polymer

(B-1) Manufacture of fluorinated polymer '' Deaeration of a polymerization tank with a stirring blade with an internal volume of 94 L, 1-hydrotridecafuro hexane 71.3 Kg, chain transfer agent in a 1, 3-Axis b b - 1, 1, 2, 2, 3-penta full O b propane (manufactured by Asahi Glass Co., AK 2 2 5 cb) 2 0. 4 K g, CH 2 = CH ( CF ₂ ) ₂ F 5 62 g and itaconic anhydride (IAN) 4.45 g were charged, and the temperature in the polymerization vessel was raised to 66 ° C, and TFEZE (molar ratio: 89/11) The pressure was increased to 1.5 MPa a ZG with the gas in (). As a polymerization initiator, 1 L of a 0.7% solution of tert-butyl peroxypivalate in hydrotridecafluorohexane was charged to initiate polymerization.

A monomer mixed gas of TF EZE (molar ratio: 59, 5 / 40.5) was continuously charged so that the pressure was kept constant during the polymerization. Further, corresponding to 3.3 mole ^_0/0 of the total moles of TFE and E to be charged during the polymerization The amount of CH ₂ = CH (CF ₂ ) ₂ F and ^0.8 mol ⁰ /. The amount of IAN corresponding to 4.45 was continuously charged with a 1% solution of AK225 cb. 9.9 hours after the start of the polymerization, when 7.28 Kg of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to room temperature, and purged to normal pressure.

The obtained slurry-like fluorine-containing polymer was charged with 77 kg of water.

The mixture was put into a 200 L granulation tank, and the temperature was raised to 105 ° C. with stirring, and the mixture was granulated while distilling and removing the solvent. The obtained granulated product was dried at 150 ° C. for 15 hours to obtain 6.9 kg of a fluorinated polymer granulated product.

The composition of those fluorinated polymers, polymerized units based on polymerized units / I AN based on polymerized units ZE based on TFE Roh _{_{CH 2 = CH (CF 2)}} 5 7. 2 at a molar ratio of polymerized units based on ₂ F /38.5/0.4.8/

It was 3.5. The melting point was 230 ° C.

The granulated product was melted at 280 ° C. and a residence time of 2 minutes using an extruder to obtain a pellet of a fluorinated polymer (hereinafter referred to as (B-1) ).

(B-2) Production of fluorinated polymer

A polymerization tank with a stirring blade having an internal volume of 94 L was degassed, and 19.7 Kg of ion-exchanged water, 77.1 Kg of perfluoropentyl difluoromethane, CH ₂ = CH (CF ₂ ) F 427 g, tetrafluoroethylene (TFE) 3.36 Kg, and ethylene (E) 127 g were injected, and the inside of the polymerization tank was heated to 66 ° C. The pressure at this time was 0.65 MPa. Diisopropyl propyl peroxycarbonate as polymerization initiator

72 g was charged to initiate polymerization.

A monomer mixed gas of TF EZE (molar ratio: 60/40) was continuously charged so as to keep the pressure constant during the polymerization. Also charge during polymerization CH ₂ = CH (CF ₂ ) ₂ F in an amount corresponding to 6.0 mol% with respect to the total number of moles of TFE and E was continuously tfc incorporated. 5.6 hours after the start of the polymerization, when 11.5 kg of the monomer-mixed gas was charged, the internal temperature of the polymerization tank was lowered to room temperature and purged to normal pressure.

The obtained fluorinated polymer is charged into a 300 L granulation tank charged with 10 OK g of water, and the temperature is raised to 105 ° C with stirring, and the solvent is distilled off and removed. Granulated. The obtained granulated product was dried at 135 ° C. for 3 hours to obtain 12.1 Kg of a fluoropolymer-based granulated product. the composition of was 5 7.2 / 3 7.0 / 6.0 polymerized units / CH ₂ = CH-based polymer units ZE based on TFE (CF ₂₎ molar ratio of polymerized units based on ₂ F . The melting point was 204 ° C. Carbonate terminal groups you from the polymerization initiator were mainly chain Number 1 0 6 Z 2 to ⁶ per carbon in the polymer.

The granulated product was melted at 260 ° C. and a residence time of 2 minutes using an extruder to obtain a pellet of a fluorinated polymer (hereinafter referred to as (B-2) ).

(B-3) Production of fluorinated polymer

A polymerization tank with a stirring volume of 94 L was degassed, and 20 Kg of ion-exchanged water, 16 Kg of perphnolerocyclobutane, 4 Kg of hexafluoropropylene (HFP), and Tetraf-Nororoethylene ( (TFE) 0.95 kg and vinylidene fluoride (VDF) 0.3 kg were injected, and the inside of the polymerization tank was heated to 35 ° C. 250 g of diisopropyl peroxycarbonate was charged as a polymerization initiator to initiate polymerization.

During the polymerization, a monomer mixed gas of TFE VD FZHFP (molar ratio: 50/40 × 10) was continuously supplied so as to keep the pressure constant, and the pressure in the system was kept constant. 30 hours after the start of the polymerization, the temperature inside the polymerization tank was raised to room temperature Then, the temperature was lowered to a normal pressure.

The obtained fluorinated polymer is charged into a 300 L granulation tank charged with 10 OK g of water, and the temperature is raised to 105 ° C with stirring, and the solvent is distilled off and removed. Granulated. The obtained granulated product was dried at 135 ° C. for 3 hours to obtain 10.0 kg of a fluorinated polymer granule.The composition of the fluorinated polymer was as follows: The molar ratio of the polymerized unit based on the polymerized unit ZHPF based on the polymerized unit ZVDF was 51.3 / 38.9 / 9.8. The melting point was 170 ° C. Carbonate terminal groups derived from the heavy initiator was 3 1 1 main chain having 1 0 ⁶ per carbon in the polymer.

The granulated product was melted using an extruder at 250 ° C. and a residence time of 2 minutes to obtain a pellet of a fluorinated polymer (hereinafter referred to as (B-3) ).

(B-4) Production of fluorinated polymer

(B-1) In the production of the fluorinated polymer, except that itaconic anhydride (IAN) was not charged, the same method was used to obtain 7. OK g of the fluorinated polymer granules. Was.

The composition of those fluorinated polymers, polymerized units / CH based on polymerized units / E based on _{_{TFE 2 = CH (CF 2)}} 5 in molar ratio of polymerized units based on ₂ F 7. 6/3 8. 7 / 3.7. Further, the melting point was 2332.degree.

The granulated product was melted using an extruder at 280 ° C. and a residence time of 2 minutes to obtain a pellet of a fluorinated polymer (hereinafter referred to as (B-4) ).

(C) Polyurethane Elastomer

(C-1) Polyurethane Elastomer (ether) BASF '' Elastolan manufactured by Japan Co., Ltd.

(C-12) Polyurethane Elastomer (ester type) BAS F. Japan Co., Ltd. Elastran 690 A15

Example 1

Using the (A) polyamide elastomer (A-1) and (B) the fluoropolymer (B-1) shown above, P labor (Plastic Engineering Laboratory Co., Ltd.) In a two-layer tube molding machine, (A) is melted separately at an extrusion temperature of 220 ° C, and (B) is melted separately at an extrusion temperature of 270 ° C. It was formed into a laminated tubular body. Subsequently, it is cooled by a sizing die for controlling the size and taken off, and (A) a layer (outer layer) composed of polyamide elastomer (A-1), and (B) a fluoropolymer ( When the (b) layer (inner layer) is composed of B-1), the layer configuration is (a) / (b) = 0.80 / 0.20111111, with an inner diameter of 6111111 and an outer diameter of 8 mm. A tube was obtained. Figure 1 shows the cross section of this laminated tube. In FIG. 1, 1 is an outer (a) layer, and 3 is an inner (b) layer. Table 1 shows the measurement results of the physical properties of the laminated tube.

Example 2

In Example 1, (B) the fluorinated polymer (B-1) was replaced with (B—

A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner as in Example 1, except that (B) was melted at an extrusion temperature of 240 ° C. instead of 2). Table 1 shows the measurement results of the physical properties of the laminated tube.

Example 3

In Example 1, (B) the fluorine-containing polymer (B-1) was replaced with (B--

A laminated tube having a layer configuration shown in Table 1 was obtained in the same manner as in Example 1 except that (B) was melted at an extrusion temperature of 220 ° C. instead of 3). Table 1 shows the measurement results of the physical properties of the laminated tube. Example 4

Example 1 was repeated except that (A) the polyamide elastomer (A-1) was changed to (A-2), and a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. Table 1 shows the measurement results of the physical properties of the laminated tube.

Example 5

Using the (A) polyamide elastomer (A-1), (B) fluorinated polymer (B-1), and (B-4) shown above, PI ab 0r (Plastic engineering research) Tosho Co., Ltd.)

(A) was melted at an extrusion temperature of 220 ° C., and (B) was melted at an extrusion temperature of 280 ° C., and the discharged molten resins were combined by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for controlling dimensions and taken off, and (A) a layer (outer layer) composed of polyamide elastomer (A-1), and (B) a fluorine-containing polymer ( When the (b) layer (intermediate layer) composed of B-1) and the (b ') layer (inner layer) composed of (B) a fluorinated polymer (B-4), the layer composition is (a) / (b) /

(b,) = 0.80 / 0.05 / 0.15mm, a laminated tube with an inner diameter of 6mm and an outer diameter of 8mm was obtained. Figure 2 shows the cross section of this laminated tube. In FIG. 2, 1 is an outer (a) layer, 2 is an intermediate (b) layer, and 3 is an inner (b ′) layer. Table 1 shows the measurement results of the physical properties of the laminated tube.

Example 6

In Example 5, (B) the fluorine-containing polymer (B-4) was changed to (C) a polyurethane elastomer (C-11), and (C) was melted at an extrusion temperature of 200 ° C. Except for this, in the same manner as in Example 5, (C) layer (outer layer) composed of (C) polyurethane elastomer (C-11), (A) polyamide elastomer (A-1) (A) layer consisting of (medium (C) / (a) / (b) = 0.4 when the (b) layer (inner layer) composed of the fluorine-containing polymer (B-1) and the (B) fluorine-containing polymer (B-1) is used. A laminated tube having a diameter of 5 / 0.35 / 0.20 mm and an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. Table 1 shows the measurement results of the physical properties of the laminated tube. In this case, 1 is an outer layer (a), 2 is an intermediate layer (c), and 3 is an inner layer (b) on the new horizontal surface of the laminated tube of FIG.

Example 7

In Example 6, a laminated tube having the layer configuration shown in Table 1 was obtained in the same manner as in Example 6, except that (C) the polyurethane elastomer (C-1) was changed to (C-2). Was. Table 1 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 1

A tube having a layer constitution shown in Table 1 was obtained in the same manner as in Example 1 except that (B) the fluorinated polymer (B-1) was not used. Table 1 shows the measurement results of the physical properties of the tube.

Comparative Example 2

A tube having a layer configuration shown in Table 1 was obtained in the same manner as in Example 1 except that (A) the polyamide elastomer (A-1) was not used. Table 1 shows the measurement results of the physical properties of the tube. Comparative Example 3

A laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1 except that (B) the fluoropolymer (B-1) was changed to (B-4). Got. Physical properties of the laminated tube. The measurement results are shown in Table 1.

Comparative Example 4

Table 1 is shown in the same manner as in Example 1 except that (A) polyamide elastomer (A-1) was changed to (A-3). A laminated tube having a three-layer structure was obtained. Table 1 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 5

A laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 6, except that (A) the polymer elastomer (A-1) was changed to (A-3). I got Table 1 shows the measurement results of the physical properties of the laminated tube.

Table 1 Outer layer Middle layer Inner layer Interlayer adhesion [N / cm] Chemical liquid permeability coefficient Flexural stiffness [N]

Thickness Thickness Thickness

Type After chemical treatment [g / m ² -day]

[mm] Type [mm] Type [mm] Initial Example 1 A-1 0.80--B-1 0.20 4.0 42 32 2.7 Example 2 A-1 0.80--B-2 0.20 3.8 40 29 2.8 Example 3 A -1 0.80--B-3 0.20 3.5 39 31 3.4 Example 4 A-2 0.80 1-B-1 0.20 6.8 45 34 2.3 Example 5 A-1 0.80 B-1 0.05 B-4 0.15 4.0 41 32 2.4 Example Example 6 C-1 0.45 A-10-35 B-1 0.20 3.5 23 18 3.0 Example 7 C-2 0.45 A-1 0-35 B-1 0.20 3.7 19 15 3.1 Comparative example 1 A-1 1.00-- --3.0--11.5 Comparative Example 2--One-B-1 1.00 23--0.7 Comparative Example 3 A-1 0.80 One-B-4 0.20 4.1 3 0 2.3 Comparative Example 4 A-3 0.80--B-1 0.20 4.2 14 5 2.9 Comparative Example 5 C-1 0.45 A-3 0.35 B-1 0.20 4.2 11 4 2.9

Industrial applicability

The laminated tube of the present invention can be used for automobile parts, internal combustion engine applications, power tool housings and other mechanical parts, industrial materials, industrial materials, electric and electronic parts, medical care, food, home and office supplies, building materials, Various applications such as furniture parts.

Further, the laminated tube of the present invention is excellent in chemical solution permeation prevention, and is therefore suitable for a chemical solution conveying pipe. Chemicals include, for example, Τ, benzene, toluene, xylene, and other aromatic hydrocarbon solvents, methanol, ethanol, propanol, butanol, pentanole, ethylene glycol, propylene glycol, and diethyl alcohol. Alcohol, phenolic, phenolic, polyethylene glycol, polypropylene glycol and other alcohols, phenolic solvents, dimethyl ether, dimethyl ether, dimethyl ether, methyl alcohol, t-butyl alcohol, dioxane , Ether solvents such as tetrahydrofuran and the like, black form, methylene chloride, trichloroethylene, ethylene dichloride, perchloronoleethylene, monochloronoletan, dichloronoletan, tetrachloronene, phenol Mouth Noletan, K Mouth Noleven Halogen solvents such as ketones, ketone solvents such as atton, methylethylketone, getylketone, and acetophenone, gasoline, kerosene, diesel gasoline, oxygenated gasoline, and amide gasoline. , Sour gasoline, castor oil-based brake fluid, glycol ether-based brake fluid, borate ester-based brake fluid, brake fluid for extreme cold regions, silicone oil-based brake fluid, mineral oil-based brake fluid, pastry oil, sulfur-containing Hydrogen oil, wind washer fluid

, Engine coolant, urea solution, glycerin solution, pharmaceutical agent, ink, paint, beverage, and the like. The laminated tube of the present invention is suitable as a tube for transporting the above-mentioned chemical solution, specifically, a cooler tube for cooling water, a refrigerant and the like, a tube for an air conditioner refrigerant, a tube for a tube, Fuel tubes such as fire extinguishers and fire extinguisher tubes, medical cooling equipment tubes, ink, paint tubes, feed tubes, return tubes, evaporative tubes, fuel tubes, ORVR tubes, reserve tubes, vent tubes, etc. , Oil tubes, brake tubes, wind washer fluid tubes, radiator tubes, oil drilling tubes, and other chemical solution tubes.

In addition, Front 1 1 1, Front 1 1 2, Front 1 2 1, Front 2

2, Fluorine 1 1 3, Fluorine 1 1 4, Fluorine 1 1 5, Fluorine 1

1 3 4 A, Fluorine 1 32, Fluorine 1 2 3, Fluorine 1 2 4, Fluorine 1 2 5, Fluorine 1 4 3 Α, Fluorine 1 4 1 b, front-1 4

2 b, Fluorine 1 225, Fluorine 1 C 3 18, Fluorine 1 502, Methyl chloride, Ethyl chloride, Air, Hydrogen, Nitrogen, Oxygen, Carbon dioxide, Methan, Propane, Isobutane, η-butane, argon, helium, xenon, etc. can be used as tubes for transporting various gases o

Claims

Range of request

1. (A) Layer (a) made of a polyamide elastomer having a terminal amino group concentration of 20 / ieq / g or more, and (B) a functional group reactive with the polyamide resin Having a (b) layer made of a fluorine-containing polymer introduced into a molecular chain, and comprising at least two layers.

2. The (A) polyamide elastomer having a terminal amino group concentration of 20 μeq / g or more is represented by the following formula (1):

(Where x and z are from 1 to 20 and y is from 4 to 50), a polyblock diether compound (A 1) represented by the formula: monomer (a 2), and characterized in that it is a polyamide Doerasu Tomah having dicarboxylic acid compound (a 3) is a polymer obtained by polymerizing a polyamide Tsuchie one Teruerasu Tomah one (X) 5 0 wt ^_0/0 or more 2. The laminated tube according to claim 1, wherein:

3. The dicarboxylic acid compound (A 3) force in the polyamide ester (X) is represented by the following formula (2):

HOOCH "R

(Where, R ¹ represents a linking group containing a hydrocarbon chain, and m represents 0 or 1.)

3. The laminated tube according to claim 2, wherein:

4. The polyamide-forming monomer (A 2) in the polyamide ester (X) is represented by the following formula (3) and / or the following formula (4): H ₂ N—— R ² —— COOH (3)

(However, R ² represents a linking group containing a hydrocarbon chain.) R ³ —— CONH ”( ⁴ )

(However, R ³ represents a linking group containing a hydrocarbon chain.)

3. The laminated tube according to claim 2, wherein:

5. The laminated tube according to claim 2, wherein the dicarboxylic acid compound (A3) is an aliphatic dicarboxylic acid compound and a di- or alicyclic dicarboxylic acid compound.

6. The (B) fluorine-containing polymer having a functional group reactive with the polyamide resin introduced into the molecular chain is an ethylene / tetrafluoroethylene copolymer, polyvinylidene fluoride, 3. The laminated tube according to claim 1, wherein the laminated tube is at least one member selected from the group consisting of tetrafluoroethylene / hexafenoleopropylene propylene and vinylidene fluoride copolymer.

7. The layer (b) composed of the fluorine-containing polymer (B) having a functional group reactive with the polyamide resin introduced into the molecular chain, the (B) layer having (A) a terminal amino group concentration of 2 2. The laminated tube according to claim 1, wherein the laminated tube is arranged inside the (a) layer made of a polyamide elastomer having 0 μeq, g or more. 3.

8. The method according to claim 1, wherein the (A) layer composed of _a polyamide elastomer having a terminal amino group concentration of 20 ii eq / g or more is disposed as an outermost layer. Laminated tube.

9. The laminated tube according to claim 1, further comprising at least three layers having (C) a layer made of polyurethane (C).

10. The (A) layer comprising a polyamide elastomer having a terminal amino group concentration of 20 eq / g or more (A), and (B) a functional group having reactivity with a polyamide resin. 10. The lamination according to claim 9, wherein the layer is disposed between the (b) layer made of a fluorine-containing polymer introduced into the molecular chain and the (c) layer made of (C) polyurethane. Tube. .

1 1. The laminated tube according to claim 1, wherein each of the layers is manufactured by co-extrusion molding.

1 2. The laminated tube according to claim 1, which is used as a tube for transporting a chemical solution.