JPH11156970A - Multi-layer hollow molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-layer hollow molding made of thermoplastic resin which shows outstanding heat resistance, hot water resistance, chemical resistance, antigas hole permeability, tenacity, interlayer adhesive properties or the like, all of these being well-balanced, and further, conductivity. SOLUTION: This multilayer hollow molding is made up of at least, two or more thermoplastic resin layers and at least, one or more adhesive layer, and at least, one layer among the other thermoplastic resin layers is formed of a composition which is composed mainly of a polyphenylene sulfide resin, and at least, one layer of the thermoplastic resin layers is formed of a thermoplastic resin composition which is composed mainly of a thermoplastic resin other than the polyphenylene sulfide resin. In addition, between (A) layer and (B) layer, an adhesive layer which has adhesive properties with the (A) layer and the (B) layer (provided, however, that the main constituent components of the adhesive layer are different from those of the (A) layer and the (B) layer), is present.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention is excellent in heat resistance, hot water resistance, chemical resistance, alcohol gasoline permeability, adhesion between layers, low-temperature toughness, surface smoothness, etc., and has excellent conductivity. The present invention relates to a multilayer hollow molded article.

[0002]

2. Description of the Related Art A hollow molded article of a thermoplastic resin is manufactured by, for example, a blow molding method using a polyamide resin, mainly for ducts in an engine room of an automobile, or a saturated polyester resin or polyamide for a tube. 2. Description of the Related Art A technique of manufacturing by extrusion using a resin, a polyolefin resin, or a thermoplastic polyurethane has been widely used.

However, conventional single-layer hollow molded articles made of thermoplastic resins such as polyamide resins, saturated polyester resins, polyolefin resins and thermoplastic polyurethane resins have insufficient heat resistance, hot water resistance and chemical resistance. Therefore, the range of application is limited, and products with further improved heat resistance, hot water resistance, chemical resistance, and the like are required.

[0004] In particular, polyamide resins, especially flexible polyamide resins such as polyamide 11 and polyamide 12, are widely used for automobile fuel tubes. However, if the polyamide resin is used alone, it is required to reduce environmental pollution and improve fuel efficiency. It has been pointed out that it is not sufficient for the permeation prevention property of alcohol gasoline, and improvement thereof is desired.

[0005] In applications where a non-conductive liquid such as fuel flows through a blown hollow molded article or a tube molded article, the molded article may be charged, and it is also required to suppress this.

[0006] On the other hand, polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) is an engineering plastic excellent in heat resistance, hot water resistance, chemical resistance, flame retardancy, electric properties, and the like. Demand is increasing for applications such as parts. Recently, a tubular molded product utilizing the features of the PPS resin is disclosed in Japanese Patent Publication No. 2-200415.

The use of such a PPS resin hollow molded article is thought to solve the above-mentioned concerns about heat resistance, hot water resistance, chemical resistance, and permeability, but it is often required in toughness, especially in automotive applications. In some cases, the toughness at low temperatures is insufficient, and the applicability is limited in some applications.

[0008] Therefore, we laminated the PPS resin layer excellent in heat resistance, hot water resistance, chemical resistance and alcohol gasoline permeability and the layer composed of another thermoplastic resin and conductive resin composition excellent in toughness. Considering that all the problems could be solved, we started studying.

A laminate structure of a PPS resin and another thermoplastic resin has been studied so far.
No. 145131 discloses a method of coating the surface of a PPS tubular body with another thermoplastic resin. However, JP-A-59-145131 describes that simply by laminating other resins on the surface of a tubular body made of a PPS resin, a tubular body can be obtained that utilizes the properties of PPS and is excellent in strength and cost. However, no consideration is given to interlayer adhesion, low-temperature toughness, and conductivity.

Japanese Patent Application Laid-Open No. 7-299855 describes P
A multilayer tube including a PS layer is disclosed, and a method for activating the PPS layer surface by corona treatment to improve interlayer adhesion is disclosed. However, secondary processing such as corona treatment is disadvantageous in terms of cost and is not a preferable method. No consideration is given to the toughness.

[0011]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of a study aimed at improving the problems in the above-mentioned conventional multilayer hollow molded article. That is, the present invention relates to a multilayer hollow molded article excellent in heat resistance, hot water resistance, chemical resistance, alcohol gasoline permeability, toughness, surface smoothness, adhesion between layers, and the like. The present invention relates to a multilayer hollow molded article having:

[0012]

That is, the present invention comprises the following.

1. A multilayer hollow molded article comprising at least two or more thermoplastic resin layers and at least one or more adhesive layers, wherein at least one of the thermoplastic resin layers comprises (a) a polyphenylene sulfide resin as a main component. And at least one of the thermoplastic resin layers is a layer composed of a thermoplastic resin composition containing a thermoplastic resin other than (ii) a polyphenylene sulfide resin as a main component, and (C) an adhesive layer having an adhesive property with both layers between the (a) layer and the (b) layer (provided that (c)
A multi-layer hollow molded article characterized in that the main constituent components of the adhesive layer are different from those of the above-mentioned (a) layer and (b) layer.

2. (B) The thermoplastic resin other than the polyphenylene sulfide resin constituting the layer is a polyamide resin,
2. The multilayer hollow molded article according to 1 above, wherein the multilayer hollow molded article is at least one selected from a thermoplastic polyester resin, a thermoplastic polyurethane resin, and a polyolefin resin.

3. (2) The multilayer hollow molded article according to the above (2), wherein the thermoplastic resin other than the polyphenylene sulfide resin constituting the layer is a polyamide resin.

4. (A) The polyphenylene sulfide resin composition constituting the layer is selected from (B) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester based on 100 parts by weight of the polyphenylene sulfide resin (A). The multilayer hollow molded article according to any one of the above 1 to 3, which is a polyphenylene sulfide resin composition containing 1 to 200 parts by weight of at least one kind of a copolymer containing at least one functional group.

5. (A) The functional group-containing copolymer (B) in the polyphenylene sulfide resin composition constituting the layer,
5. The multilayer hollow molded article according to the above item 4, which is an epoxy group-containing olefin-based copolymer (B) containing a glycidyl ester of an α-olefin and an α, β-unsaturated acid as main components.

6. (A) The functional group-containing copolymer (B) in the polyphenylene sulfide resin composition constituting the layer,
4. The olefin copolymer according to the above item 4, which is an olefin copolymer containing an α-olefin (1), a glycidyl ester of an α, β-unsaturated acid (2) and a monomer (3) represented by the following general formula. Multi-layer hollow molded body.

[0019]

Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Is -COOR ² group, groups selected from -CN group or an aromatic group, also R ² represents an alkyl group having 1 to 10 carbon atoms)

[7] FIG. (A) The polyphenylene sulfide resin composition constituting the layer comprises (B) an olefin copolymer containing an epoxy group as a functional group-containing copolymer and (B2) an olefin copolymer containing an acid anhydride group. A polyphenylene sulfide resin composition containing, as an essential component, at least two kinds of functional group-containing olefin copolymers with a copolymer, wherein the weight% of (B1) and (B2) is (B1)
1): The multilayer hollow molded article according to any one of the above 4 to 6, wherein (B2) = 1 to 99:99 to 1 (total 100% by weight).

8. (A) The polyphenylene sulfide resin composition constituting the layer is (C) a polyphenylene sulfide resin composition further containing an elastomer containing no epoxy group, acid anhydride group, carboxyl group and salts thereof, and carboxylic acid ester group. (A) 100 parts by weight of polyphenylene sulfide resin, (C) epoxy group,
A copolymer containing (B) a functional group and (C) an epoxy group, containing 1 to 200 parts by weight of at least one kind of an elastomer not containing an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group; (4) the total of (A) 100 parts by weight of the polyphenylene sulfide resin is 200 parts by weight or less based on 100 parts by weight of the elastomer containing no acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester group.
8. The multilayer hollow molded article according to any one of claims 7 to 7.

9. (A) The polyphenylene sulfide resin composition constituting the layer further comprises (D) an alkoxysilane having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group. At least one kind of the compound is used, based on 100 parts by weight of the polyphenylene sulfide resin (A).
The above 5 which is obtained by adding 0.05 to 5 parts by weight.
9. The multilayer hollow molded article according to any one of items 8 to 8.

10. (A) The multilayer hollow molded article according to any one of (1) to (9) above, wherein (A) the polyphenylene sulfide resin used in the polyphenylene sulfide resin composition constituting the layer is a deionized one.

11. (C) The adhesive layer contains at least one compound having at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group, an isocyanate group, an amino group, and a hydroxyl group. 11. The multilayer hollow molded article according to any one of 1 to 10 above.

12. (C) the adhesive layer, wherein the adhesive layer is an olefin copolymer having at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group, an isocyanate group, an amino group, and a hydroxyl group.
2. The multilayer hollow molded article according to 1.

13. 13. The conductive multilayer hollow molded article according to any one of the above items 1 to 12, wherein at least one of the layers constituting the multilayer hollow molded article is made of a conductive thermoplastic resin composition.

14. 14. The conductive multilayer hollow molded article according to the above 13, wherein the conductive layer is made of a conductive thermoplastic resin composition containing (E) a conductive filler or a conductive polymer.

15. (E) The conductive multilayer as described in (14) above, wherein the conductive filler or the conductive polymer is a non-fibrous or a fibrous conductive filler having a length / diameter ratio of 200 or less. Hollow molded body.

16. (E) The conductive multilayer hollow molded article according to the above (14) to (15), wherein the conductive filler is carbon black.

17. (A) The conductive multilayer hollow molded article according to any one of the above (13) to (16), wherein the layer comprising the composition containing a polyphenylene sulfide resin as a main component is a conductive layer.

18. 18. The conductive multilayer hollow molded article according to any one of the above items 13 to 17, wherein the resistance of the conductive layer is 10 ⁷ Ω / m or less.

19. 19. The conductive multilayer hollow molded article according to any one of the above 1 to 18, wherein the multilayer hollow molded article is a multilayer tubular molded article produced by a coextrusion molding method.

20. The multilayer hollow molding according to any one of the above 13 to 19, wherein the conductive multilayer hollow molded article has a total thickness of 0.2 mm or more and 3 mm or less, and a conductive layer has a thickness of 1% or more and 50% or less of the total thickness. body.

21. 21. The multilayer hollow molded article according to any one of the above 1 to 20, which is used as an automobile fuel tube.

22. 22. The multilayer hollow molded article according to any one of the above items 1 to 21, which is used as an automobile engine coolant tube or pipe.

[0036]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The basic structure of the present invention is a multilayer hollow molded article composed of at least two or more thermoplastic resin layers and at least one or more adhesive layers. At least one layer is a layer composed of a composition containing (a) a polyphenylene sulfide resin as a main component, and at least one layer of the thermoplastic resin layer is composed of a thermoplastic resin other than the (b) polyphenylene sulfide resin as a main component. A multilayer hollow molded article characterized in that it comprises a layer made of a thermoplastic resin composition as described above, and further comprising, between the layer (a) and the layer (b), an adhesive layer (c) having adhesiveness to both layers. It is.

First, a thermoplastic resin composition containing a thermoplastic resin other than the polyphenylene sulfide resin constituting the layer (b) as a main component will be described.

(B) The thermoplastic resin other than the polyphenylene sulfide resin constituting the layer is not particularly limited. Specific examples thereof include a saturated polyester resin, a polysulfone resin, a polytetrafluoroethylene resin, a polyetherimide resin, Polyamide imide resin, polyamide resin, polyimide resin, polycarbonate resin, polyether sulfone resin, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, thermoplastic polyurethane resin, polyolefin resin,
ABS resin, polyamide elastomer, polyester elastomer, and the like may be mentioned, and these may be used as a mixture of two or more kinds. Among them, polyamide resins, thermoplastic polyester resins, thermoplastic polyurethane resins, and polyolefin resins are more preferably used.

Here, the polyamide resin is an amino acid,
It is a polyamide containing lactam or diamine and dicarboxylic acid as main components. Representative examples of the main components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid, ε-aminocaprolactam,
lactams such as ω-laurolactam, tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5- Methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane,
1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4- Aliphatic, alicyclic and aromatic diamines such as aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine and 2-methylpentamethylenediamine, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecane Aliphatic or alicyclic such as diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Tribe, aromatic It includes dicarboxylic acids, in the present invention, it is possible to use a polyamide homopolymer or copolymer derived from these raw materials each alone or in the form of mixtures.

In the present invention, useful polyamide resins include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), and polyhexamethylene sebacamide. (Nylon 610), polyhexamethylene dodecamide (nylon 612), polydodecaneamide (nylon 12), polyundecaneamide (nylon 1
1), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD6)
And mixtures or copolymers thereof.

In particular, the number of carbon atoms per amide group is 8 to
A polyamide resin having a structural unit in the range of 15 is preferable, and a polyamide resin containing an aminocarboxylic acid or a derivative thereof as a monomer is particularly preferable in terms of obtaining better low-temperature toughness. Examples of such polyamides include polydodecaneamide (nylon 12) and polyundecaneamide (nylon 11). Alternatively, the relative viscosity measured at 25 ° C. in metacresol (polymer concentration 0.5% by weight) is 1.0 to 1.0. 7.0, especially 1.5 to
A polyamide resin having a range of 5.0 can be exemplified.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution (1 g of polymer, 100 ml of concentrated sulfuric acid) is 1.5 to 1.5%.
7.0, especially 2.0-6.5, and more preferably 2.5-
Those having a range of 5.5 are preferred.

The thermoplastic polyester resin used herein refers to a polyester obtained from a dicarboxylic acid such as terephthalic acid and an aliphatic diol. Examples of dicarboxylic acids other than terephthalic acid include azelaic acid, sebacic acid, adipic acid, dodecanedicarboxylic acid, isophthalic acid, and other aliphatic dicarboxylic acids having 2 to 20 carbon atoms, isophthalic acid, and aromatic dicarboxylic acids such as naphthalenedicarboxylic acid. Or an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, which may be used alone or in a mixture. As the aliphatic diol,
Examples include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, 1,4-cyclohexanedimethanol, and hexamethylene glycol.

Preferred examples of the thermoplastic polyester used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and polyethylene naphthalate. Polyester comprising polybutylene terephthalate or terephthalic acid having a high mechanical strength of at least 60 mol%, preferably at least 70 mol%, a dicarboxylic acid component containing dodecanedicarboxylic acid and / or isophthalic acid and a 1,4-butanediol component Is particularly preferably used.

The degree of polymerization of these thermoplastic polyester resins is not particularly limited. For example, in the case of polybutylene terephthalate (hereinafter abbreviated as PBT resin) and copolyester, which are preferably used, the degree of polymerization is
The relative viscosity of a 0.5% orthochlorophenol solution measured at 25 ° C. is in the range of 0.5 to 2.5, especially 0.8 to 2.
Those in the range of 0 are preferred. In the case of polyethylene terephthalate, the intrinsic viscosity of a 0.5% orthochlorophenol solution measured at 25 ° C. is preferably in the range of 0.54 to 1.5, particularly preferably 0.6 to 1.2.

The thermoplastic polyurethane resin used here is a chain polymer composed of a polyisocyanate and a diol. Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate, hexamethylene diisocyanate and meta-isocyanate. Xylene diisocyanate,
And 4,4'-diphenylmethane diisocyanate. Diols include polyester type and polyether type.Specific examples of the former include organic acids such as phthalic acid, adipic acid, dimerized linoleic acid, and maleic acid, and glycols such as ethylene, propylene, butylene, and diethylene. The specific examples of the latter include polyoxypropylene glycol, poly (oxypropylene) poly (oxymethylene) glycol, poly (oxybutylene) glycol, poly (oxytetramethylene) glycol, and the like, respectively. Used for

The degree of polymerization of these polythermoplastic polyurethanes is not particularly limited.
A melt viscosity of 1000 to 100,000 poise / sec is used.

The polyolefin resin used here includes polyethylene, polypropylene, chlorinated polyethylene, chlorinated polypropylene and polymethylpentene.

The thermoplastic resin composition other than the polyphenylene sulfide resin constituting the layer (b) may contain additives such as a plasticizer, an antioxidant, a nucleating agent, and a coloring agent suitable for each resin. .

The thermoplastic resin composition comprising a thermoplastic resin other than the polyphenylene sulfide resin or a thermoplastic resin other than the polyphenylene sulfide resin constituting the layer (b) as a main component has a Young's modulus of 18,000 kg / c.
A thermoplastic resin or a thermoplastic resin composition having a m ² or less, more preferably 15,000 kg / cm ² or less is preferable in view of the kink resistance of the tube molded body.

The thermoplastic resin composition having a thermoplastic resin other than the polyphenylene sulfide resin in the layer (b) as a main component is defined as the resin component in the thermoplastic resin composition constituting the layer (b). Shown is a thermoplastic resin composition in which any of the thermoplastic resins other than the polyphenylene sulfide resin occupies the largest weight ratio. When the thermoplastic resin other than the polyphenylene sulfide resin and the polyphenylene sulfide resin are in the same amount, the polyphenylene sulfide resin is considered to occupy the maximum weight ratio. If the chemical structures are the same, the components are considered to be the same even if they have different molecular weights. For example, olefin-based copolymers having different chemical structures are considered to be different components.

Next, the polyphenylene sulfide resin composition constituting the layer (a) will be described.

The (A) PPS resin constituting (A) is:
A repeating unit represented by the following structural formula

Embedded image It is a polymer containing 70 mol% or more, more preferably 90 mol% or more. When the repeating unit is less than 70 mol%, heat resistance is unfavorably deteriorated. Also PPS
Less than 30 mol% of the repeating unit of the resin can be composed of a repeating unit having the following structural formula.

[0054]

Embedded image

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
0 to 20,000 poise (320 ° C., shear rate of 1,000
0 sec ^-1 ) is used, and the range of 100 to 5000 poise is more preferable.

Such a PPS resin can be prepared by a known method, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or a method disclosed in JP-B-52-12240 or JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the gazette. In the present invention, the PPS resin obtained as described above is crosslinked / high molecular weight by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with an organic solvent, hot water, an acid aqueous solution or the like, Of course, it is also possible to use after performing various treatments such as activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, and a functional group-containing disulfide compound.

As a specific method for crosslinking / high molecular weight of the PPS resin by heating, the method is as follows: in an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method in which heating is performed in a heating vessel at a predetermined temperature under an atmosphere until a desired melt viscosity is obtained. The heat treatment temperature is usually
170-280 ° C is selected, preferably 200-27 ° C.
The temperature is 0 ° C., and the time is generally selected from 0.5 to 100 hours, preferably from 2 to 50 hours. By controlling both of them, a target viscosity level can be obtained. The heating device may be an ordinary hot air dryer or a heating device with a rotary or stirring blade, but for efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. Is more preferred.

When the PPS resin is heat-treated in an inert gas atmosphere such as nitrogen or under reduced pressure, a specific method is as follows.
Heat treatment temperature 150 to 280 ° C, preferably 200 to 2
70 ° C., heating time is 0.5 to 100 hours, preferably 2 hours
A method of performing heat treatment for up to 50 hours can be exemplified. The heating device may be an ordinary hot-air dryer or a rotary or heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary or stirring blade is required. More preferably, it is used.

The PPS resin used in the present invention is preferably a deionized PPS resin. Specific examples of such a deionization treatment include an acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment, and these treatments may be used in combination of two or more kinds of methods.

The following method can be exemplified as a specific method for washing the PPS resin with an organic solvent. That is,
The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethylsulfoxide, dimethyl Sulfoxide and sulfone solvents such as sulfone, acetone, methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, ether solvents such as tetrahydrofuran, chloroform, methylene chloride,
Halogen solvents such as trichloroethylene, dichlorinated ethylene, dichloroethane, tetrachloroethane, and chlorobenzene; alcohol and phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol And aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferred. These organic solvents are used alone or in combination of two or more.
As a method of washing with an organic solvent, PP in an organic solvent is used.
There are methods such as immersing the S resin, and if necessary, stirring or heating can be performed. P in organic solvent
There is no particular limitation on the washing temperature for washing the PS resin, and any temperature from room temperature to about 300 ° C. can be selected.
Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect can usually be obtained at a cleaning temperature of normal temperature to 150 ° C. Further, the PPS resin subjected to the organic solvent washing is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

The following method can be exemplified as a specific method for treating the PPS resin with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a favorable effect of chemical modification of the PPS resin by washing with hot water. The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin into a predetermined amount of water, and heating and stirring the mixture at normal pressure or in a pressure vessel. The proportion of PPS resin to water is preferably as high as possible, but a bath ratio of 200 g or less of PPS resin to 1 liter of water is usually selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid. That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of an acid, or the like, and if necessary, stirring or heating can be performed. The acid to be used is not particularly limited as long as it does not have an action of decomposing PPS, and is a saturated aliphatic monocarboxylic acid such as formic acid, acetic acid, propionic acid, and butyric acid; Carboxylic acids, acrylic acid, aliphatic unsaturated monocarboxylic acids such as crotonic acid, benzoic acid, aromatic carboxylic acids such as salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, dicarboxylic acids such as fumaric acid, sulfuric acid, Examples include inorganic acidic compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Among them, acetic acid and hydrochloric acid are more preferably used. The PPS resin subjected to the acid treatment is preferably washed several times with water or hot water in order to remove the remaining acid or salt. Further, the water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

In the thermoplastic resin composition of the present invention containing the polyphenylene sulfide resin constituting the layer (a) as a main component, (B) an epoxy group, an acid anhydride group,
Incorporation of a copolymer containing at least one functional group selected from a carboxyl group and a salt thereof, and a carboxylic acid ester is effective in obtaining excellent interlayer adhesion, toughness, flexibility as a tube, and the like. desirable.

Preferred examples of the functional group-containing copolymer include an olefin polymer containing at least one selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. it can.

Examples of the epoxy group-containing polyolefin polymer include an olefin copolymer having a glycidyl ester, glycidyl ether, glycidyl diamine or the like in a side chain or a double bond portion of an olefin copolymer having a double bond. Olefin-based copolymers obtained by copolymerizing a monomer having an epoxy group are preferred. Particularly, glycidyl esters of α-olefins and α, β-unsaturated acids are main components. Is preferably used.

Specific examples of such α-olefin include:
Examples thereof include ethylene, propylene, butene-1, 4-methylpentene-1, hexene 1, decene-1, and octene-1, and among them, ethylene is preferably used. Also, two or more of these can be used simultaneously.

On the other hand, glycidyl esters of α, β-unsaturated acids are represented by the general formula

Embedded image (Where R represents a hydrogen atom or a lower alkyl group), specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, among which glycidyl methacrylate is preferably used. .

The olefin-based copolymer containing the α-olefin and the glycidyl ester of an α, β-unsaturated acid as main constituents can be obtained by randomizing the α-olefin and the glycidyl ester of an α, β-unsaturated acid. Any of alternating, block and graft copolymers may be used.

The copolymerization amount of the glycidyl ester of an α, β-unsaturated acid in an olefin-based copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated acid as the main constituents may have a desired effect. From the viewpoints of the influence on the polymer, gelation, heat resistance, fluidity, and strength.
5 to 40% by weight, especially 3 to 30% by weight is preferred.

In the present invention, in addition to the α-olefin (1) and the glycidyl ester of an α, β-unsaturated acid (2), the epoxy group-containing olefin copolymer further comprises a monomer represented by the following general formula: Epoxy group-containing olefin copolymers containing 3) as an essential component are also suitably used.

[0071]

Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Represents a group selected from a —COOR ² group, a —CN group or an aromatic group, and R ² represents an alkyl group having 1 to 10 carbon atoms. )

The details of the α-olefin (1) and the glycidyl ester of an α, β-unsaturated acid (2) used in the olefin copolymer are the same as (B) the olefin copolymer.

On the other hand, specific examples of the monomer (3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, Α, β-unsaturated carboxylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate, acrylonitrile, styrene, Examples thereof include α-methylstyrene, styrene in which an aromatic ring is substituted with an alkyl group, and acrylonitrile-styrene copolymer, and two or more of these can be used simultaneously.

Such an olefin-based copolymer is obtained by randomly or / and / or alternately / and / or block // of the α-olefin (1), the glycidyl ester of an α, β-unsaturated acid (2) and the monomer (3). And graft copolymers may be used. For example, a random copolymer of α-olefin (1) and glycidyl ester of α, β-unsaturated acid (2) may be added to monomer (3). ) May be a copolymer in which two or more copolymerization modes are combined, such as a copolymer obtained by graft copolymerization.

The copolymerization ratio of the olefin-based copolymer depends on the α-olefin (1) / α-olefin (1) / Glycidyl esters of α, β-unsaturated acids (2)
= 60-99% by weight / 40-1% by weight is preferably selected. The copolymerization ratio of the monomer (3) is based on the total amount of the α-olefin (1) and the glycidyl ester of the α, β-unsaturated acid (2) being 95 to 40% by weight, and A range of 5 to 60% by weight is preferably selected.

Examples of the polyolefin polymer preferably containing a carboxyl group and a salt thereof, a carboxylic acid ester group, and an acid anhydride group used in the present invention include polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, and ethylene. -Butene copolymer, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), Polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-ethylene / butylene-styrene block copolymer (SEB
S), polyolefin resins such as styrene-ethylene-propylene-styrene block copolymer (SEPS), and maleic anhydride, succinic anhydride, fumaric anhydride,
Acrylic acid, methacrylic acid, vinyl acetate and its Na,
Olefin type copolymerized with salts of Zn, K, Ca, Mg, etc., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, etc. Copolymers and the like, more specifically, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-isopropyl acrylate copolymer , Ethylene-n-butyl acrylate copolymer, ethylene-t-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, Ethylene-n-propyl methacrylate copolymer, ethylene-methacrylic Olefin- (meth) acrylate copolymers such as isopropyl acrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, Methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, methacrylic acid (Meth) acrylic acid ester-acrylonitrile copolymer such as butyl-acrylonitrile copolymer, ethylene- (meth) acrylic acid copolymer and its metal salt such as Na, Zn, K, Ca, Mg, ethylene-malein Acid anhydride copolymer, Tylene-butene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer or maleic anhydride-modified SBS, SIS, SEBS, SE
PS, ethylene-ethyl acrylate copolymer and the like can be exemplified.

There is no particular limitation on the copolymerization mode of the olefin copolymer, and any copolymer mode such as a random copolymer, a graft copolymer, and a block copolymer may be used.

The blending amount of the (B) olefin copolymer containing at least one functional group selected from the group consisting of an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is selected from the group consisting of permeability, From the viewpoints of flexibility, impact resistance, tube moldability, and the like, the range of 1 to 200 parts by weight, preferably 1 to 100 parts by weight, and more preferably 3 to 100 parts by weight per 100 parts by weight of the (A) PPS resin is selected. A range of 50 parts by weight is selected.

The above (B) epoxy group, acid anhydride group,
Two or more olefin copolymers containing at least one functional group selected from a carboxyl group, a salt thereof, and a carboxylic acid ester group may be used in combination. Especially,
It is preferable to use (B1) an olefin-based copolymer containing an epoxy group and (B2) an olefin-based copolymer containing an acid anhydride group in view of obtaining particularly excellent toughness and interlayer adhesion. Specific examples of (B1) an olefin copolymer containing an epoxy group and (B2) an olefin copolymer containing an acid anhydride group are as described above.

When the olefin-based copolymer containing two kinds of functional groups is used in combination, the weight% of (B1) and (B2) is (B1) :( B2) = 1-99: 99-1 ( (Total 100% by weight), especially (B1) :( B
2) = 5-50: More preferably in the range of 95-50 (100% by weight in total).

Further, (C) an elastomer containing no epoxy group, acid anhydride group, carboxyl group and its salt, and carboxylate group is used. In particular, (B) the epoxy group, acid anhydride group, carboxyl group and its When used in combination with an olefin-based copolymer containing at least one functional group selected from a salt and a carboxylic acid ester group, in order to obtain more excellent inner surface smoothness, more excellent toughness, It is effective in obtaining moldability of a hollow molded article.

The (C) epoxy group, acid anhydride group,
Examples of the elastomer not containing a carboxyl group and a salt thereof, and a carboxylic acid ester group include, for example, polyolefin-based elastomer, diene-based elastomer, silicone rubber,
Fluorine rubber, urethane rubber, various thermoplastic elastomers and the like are included. Specific examples of the polyolefin-based elastomer include an ethylene-propylene copolymer, an ethylene-butene copolymer, a polybutene, and an ethylene-propylene-diene copolymer. Specific examples of the diene-based elastomer include a styrene-butadiene copolymer,
Polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, S
BS, SIS, SEBS, SEPS and the like.

Among them, ethylene-propylene copolymer, ethylene-butene copolymer and ethylene-propylene-diene copolymer are particularly preferred.

The elastomer (C) containing no epoxy group, acid anhydride group or carboxyl group may be used in combination of two or more.

(C) When an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is used, the preferable compounding amount is alcohol gasoline permeability, flexibility and impact resistance. From the viewpoint of tube moldability, (A) 100 parts by weight of PPS resin
A range of 5 to 200 parts by weight is selected, 5 to 100 parts by weight is more preferred, and 10 to 80 parts by weight is even more preferred.

When used in combination with the olefin copolymer containing a functional group (B), the olefin copolymer containing a functional group (B) and the olefin copolymer containing a functional group (B) are particularly preferred from the viewpoint of alcohol gasoline permeability. C) The total amount of the elastomer containing no epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester group is preferably not more than 200 parts by weight, more preferably not more than 100 parts by weight, based on 100 parts by weight of the (A) PPS resin. Further, the amount is more preferably 70 parts by weight or less.

The addition of (D) an alkoxysilane having at least one functional group selected from the group consisting of an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group can provide mechanical strength, toughness, It is effective for improving the adhesiveness and the moldability of the hollow body. Specific examples of such compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
epoxy group-containing alkoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
-Mercapto group-containing alkoxysilane compounds such as mercaptopropyltriethoxysilane; ureide group-containing such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane Alkoxysilane compound, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane;
Amino-containing alkoxysilane compounds such as -aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ- Hydroxy group-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane, and the like. Among them, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxy group-containing alkoxysilane compounds such as ethyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane Any ureido group-containing alkoxysilane compound, amino group-containing alkoxysilane such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane Compound, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ- Isocyanato group-containing alkoxysilane compounds such as isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane are particularly preferred.

The addition amount of the (D) alkoxysilane compound is 0.0 to 100 parts by weight of the (A) PPS resin.
A range of 5 to 5 parts by weight is selected, and a range of 0.1 to 3 parts by weight is more preferably selected.

Further, (a) the thermoplastic resin composition containing the PPS resin constituting the layer as a main component can be a saturated polyester resin, a polysulfone resin, a polyethylene tetrafluoride resin, or the like, as long as the object of the present invention is not impaired. Polyetherimide resin, polyamideimide resin, polyamide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, thermoplastic polyurethane resin, polyolefin resin, ABS resin, polyamide elastomer, Other resins such as polyester elastomers may be contained.

The thermoplastic resin composition containing a polyphenylene sulfide resin as a main component in the layer (a) is defined as the polyphenylene sulfide resin in the thermoplastic resin composition constituting the layer (a). 1 shows a thermoplastic resin composition occupying the largest proportion by weight. In addition,
When the same amount of thermoplastic resin other than polyphenylene sulfide resin and polyphenylene sulfide resin are used, it is considered that polyphenylene sulfide resin occupies the maximum weight ratio. If the chemical structures are the same, the components are considered to be the same even if they have different molecular weights. For example, olefin-based copolymers having different chemical structures are considered to be different components.

Next, (c) the adhesive layer will be described. The adhesive layer in the present invention includes (a) a layer made of a composition containing a polyphenylene sulfide resin as a main component, and (b)
This is a layer that is disposed between layers made of a thermoplastic resin composition containing a thermoplastic resin other than polyphenylene sulfide resin as a main component and has adhesiveness to both layers. However, here, (c) the main constituent components of the adhesive layer are different from the main constituent components of the (a) layer and (b) layer. When the layer (c) is a thermoplastic resin composition, the main component of the layer (c) is the thermoplastic resin composition constituting the layer (c), which accounts for the largest proportion by weight of the thermoplastic resin composition. Shows the resin component. If the chemical structures are the same, the components are considered to be the same even if they have different molecular weights. For example, olefin-based copolymers having different chemical structures are considered to be different components.

The adhesive layer (c) contains a compound containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group or a salt thereof, an isocyanate group and an amino group. Preferred for developing adhesion to the layer, especially epoxy groups, acid anhydride groups,
An olefin copolymer having at least one functional group selected from a carboxyl group or a salt thereof, an isocyanate group, an amino group, and a hydroxyl group, or a thermoplastic resin composition containing 50% by volume or more of such an olefin copolymer. Is preferred. Among them, an olefin copolymer containing an epoxy group or a thermoplastic resin composition containing 50% by volume or more of such an olefin copolymer is preferable.

(C) The epoxy group-containing olefin copolymer used as the adhesive layer includes an olefin copolymer having glycidyl ester, glycidyl ether, glycidylamine or the like in the side chain, or an olefin copolymer having a double bond. Epoxy-oxidized double bond moieties of the copolymer may be mentioned. Among them, olefin copolymers obtained by copolymerizing a monomer having an epoxy group are preferable, and α-olefins and α, β-non-olefins are particularly preferable. An olefin copolymer containing a glycidyl ester of a saturated acid as a main component is preferably used.

Specific examples of such α-olefin include:
Examples thereof include ethylene, propylene, butene-1, 4-methylpentene-1, hexene 1, decene-1, and octene-1, and among them, ethylene is preferably used. Also, two or more of these can be used simultaneously.

On the other hand, the glycidyl ester of an α, β-unsaturated acid is represented by the following general formula:

Embedded image (Where R represents a hydrogen atom or a lower alkyl group), specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, among which glycidyl methacrylate is preferably used. .

The olefin-based copolymer containing the α-olefin and the glycidyl ester of an α, β-unsaturated acid as main constituents can be obtained by randomizing the α-olefin and the glycidyl ester of an α, β-unsaturated acid. Any of alternating, block and graft copolymers may be used.

The amount of the glycidyl ester of the α, β-unsaturated acid in the olefin-based copolymer containing the glycidyl ester of the α-olefin and the glycidyl ester of the α, β-unsaturated acid as a main component may have the desired effect. From the viewpoints of the influence on the polymer, gelation, heat resistance, fluidity, and strength.
5 to 40% by weight, especially 3 to 30% by weight is preferred.

Further, other epoxy group-containing olefin copolymers include, in addition to α-olefin (1) and glycidyl ester of α, β-unsaturated acid (2), a monomer represented by the following general formula (1): Epoxy group-containing olefin copolymers having 3) as an essential component can also be exemplified.

[0099]

Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Is a group selected from a —COOR ² group, a —CN group and an aromatic group. R ² represents an alkyl group having 1 to 10 carbon atoms)

The details of the α-olefin (1) and the glycidyl ester of an α, β-unsaturated acid (2) used in the olefin copolymer are the same as (B) the olefin copolymer.

On the other hand, specific examples of the monomer (3) include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, Α, β-unsaturated carboxylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate, acrylonitrile, styrene, Examples thereof include α-methylstyrene, styrene in which an aromatic ring is substituted with an alkyl group, and acrylonitrile-styrene copolymer, and two or more of these can be used simultaneously.

Such an olefin-based copolymer comprises a random or / and / or alternating or / and / or a block // of an α-olefin (1), a glycidyl ester of an α, β-unsaturated acid (2) and a monomer (3). And graft copolymers may be used. For example, a random copolymer of α-olefin (1) and glycidyl ester of α, β-unsaturated acid (2) may be added to monomer (3). ) May be a copolymer in which two or more copolymerization modes are combined, such as a copolymer obtained by graft copolymerization.

The copolymerization ratio of the olefin-based copolymer is determined from the viewpoint of the effect on the intended effect, the polymerizability, gelation, heat resistance, fluidity, strength, etc. Glycidyl esters of α, β-unsaturated acids (2)
= 60-99% by weight / 40-1% by weight is preferably selected. The copolymerization ratio of the monomer (3) is based on the total amount of the α-olefin (1) and the glycidyl ester of the α, β-unsaturated acid (2) being 95 to 40% by weight, and A range of 5 to 60% by weight is preferably selected.

(C) The olefin copolymer containing a carboxyl group and its salt, an acid anhydride group, an amino group and an isocyanate group used as an adhesive layer includes polyethylene, polypropylene, polystyrene and ethylene-propylene copolymer. Copolymer, ethylene-butene copolymer, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, styrene-butadiene-
Styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, styrene-ethylene / butylene-styrene block copolymer Polymer (S
EBS), polystyrene resins such as styrene-ethylene-propylene-styrene block copolymer (SEPS), and maleic anhydride, succinic anhydride, fumaric anhydride, acrylic acid, methacrylic acid, vinyl acetate and its N
a, salts of Zn, K, Ca, Mg, etc., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, etc. were copolymerized. Olefin-based copolymers and the like, more specifically, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-n-propyl acrylate copolymer, ethylene-isopropyl acrylate copolymer Polymer, ethylene-n-butyl acrylate copolymer, ethylene-t-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer Coalescence, ethylene-n-propyl methacrylate copolymer, ethylene-meth Isopropyl copolymer acrylic acid, ethylene - methacrylic acid n- butyl copolymer, ethylene -
Olefin- (meth) acrylate copolymers such as t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer, methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, (Meth) acrylate-acrylonitrile copolymers such as propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer, butyl acrylate-acrylonitrile copolymer, butyl methacrylate-acrylonitrile copolymer Copolymer, ethylene- (meth) acrylic acid copolymer and its metal salt such as Na, Zn, K, Ca, Mg, ethylene-maleic anhydride copolymer, ethylene-
Butene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer or maleic anhydride-modified SBS, SIS, SEB
S, SEPS, ethylene-ethyl acrylate copolymer,
An olefin copolymer obtained by copolymerizing an amino group-containing vinyl monomer, an isocyanate group-containing vinyl monomer, and the like can be exemplified.

The copolymerization mode of the olefin copolymer is not particularly limited, and any copolymer mode such as a random copolymer, a graft copolymer, an alternating copolymer, and a block copolymer may be used. good.

One of the preferred embodiments of the present invention is a multilayer hollow molded article composed of at least two or more thermoplastic resin layers and at least one or more adhesive layers. One layer is a layer composed of a composition containing (a) polyphenylene sulfide resin as a main component, and at least one layer of the thermoplastic resin layer is (b)
A layer made of a thermoplastic resin composition containing a thermoplastic resin other than the polyphenylene sulfide resin as a main component,
And a multilayer hollow molded article having an adhesive layer (c) having an adhesive property with both layers between the layers (a) and (b), wherein each layer constituting the multilayer hollow molded article is provided. Wherein at least one of the layers is made of a conductive thermoplastic resin composition.

In the present invention, the layer composed of the composition containing (a) polyphenylene sulfide resin as a main component may be a conductive layer, and (b) a thermoplastic resin other than polyphenylene sulfide resin as a main component. The layer made of the thermoplastic resin composition may be a conductive layer, or both may be conductive layers. Further, it is a multilayer hollow molded article including two or more layers of (a) a layer composed of a composition containing a polyphenylene sulfide resin as a main component, and one or more of the layers may be a conductive layer. . Further, it is a multilayer hollow molded article including two or more layers of a thermoplastic resin composition containing a thermoplastic resin other than the polyphenylene sulfide resin as a main component, and one or more layers among them. May be a conductive layer.

The conductive thermoplastic resin composition constituting the conductive layer is preferably a conductive thermoplastic resin composition containing (E) a conductive filler or a conductive polymer.

The thermoplastic resin used in the conductive thermoplastic resin composition includes PPS resin, saturated polyester resin, polysulfone resin, polyethylene tetrafluoride resin, polyetherimide resin, polyamideimide resin, polyamide resin, polyimide resin. Resins, polycarbonate resins, polyethersulfone resins, polyetherketone resins, polythioetherketone resins, polyetheretherketone resins, thermoplastic polyurethane resins, polyolefin resins, ABS resins, polyamide elastomers, polyester elastomers, and the like. It may be used as a mixture of more than one species. Among them, a PPS resin, a polyamide resin, a thermoplastic polyester resin, a thermoplastic polyurethane resin, and a polyolefin resin are more preferably used, and details of such a thermoplastic resin are the same as those of the layer (a) and the layer (b). Omitted.

Next, (E) a conductive filler or a conductive polymer suitably used for the conductive thermoplastic resin composition constituting the conductive layer will be described.

[0111] The conductive filler is not particularly limited as long as it is a conductive filler that is usually used for making a resin conductive. Specific examples thereof include metal powder, metal flake, metal ribbon, and the like.
Examples include metal fibers, metal oxides, inorganic fillers coated with a conductive substance, carbon powder, graphite, carbon fibers, carbon flakes, and flaky carbon.

Specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal species of the metal fiber include iron,
Examples thereof include copper, stainless steel, aluminum, and brass.

The metal powder, metal flake, metal ribbon, and metal fiber may be subjected to a surface treatment with a titanate-based, aluminum-based, or silane-based surface treatment agent.

As a specific example of the metal oxide, SnO
₂ (antimony doping), In ₂ O ₃ (antimony doping), ZnO (aluminum doping) and the like.
These may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped),
In ₂ O ₃ (antimony doping) can be exemplified. As the inorganic filler to be coated, mica, glass beads, glass fiber, carbon fiber, potassium whisker,
Examples include barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide whiskers, titanic acid whiskers, and silicon carbide whiskers. Examples of the coating method include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. These may be subjected to a surface treatment with a surface treating agent such as titanate, aluminum, or silane.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black and the like according to the raw material and the production method. The raw material and the production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used. Various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in these properties, but from the viewpoint of strength and electrical conductivity, the average particle size is 500 nm or less, particularly 5 to 100 nm,
Further, the thickness is preferably 10 to 70 nm. The surface area (BET
Law) is 10 m ² / g or more, more preferably at least 30 m ² / g is, 500 meters ² / g or more, further more preferably at least 800 m ² / g. The DBP lubrication amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. The ash content is preferably 0.5% or less, particularly preferably 0.3% or less.

The carbon powder may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum or silane. It is also possible to use those granulated for improving the workability of the melt-kneading.

The innermost layer or the outermost layer of the hollow body often requires a smooth surface. From such a viewpoint, the conductive filler used in the present invention is more powdery, granular, plate-like, scale-like than the fibrous filler having a high aspect ratio,
Alternatively, the resin composition is preferably in a fibrous form having a length / diameter ratio of 200 or less.

Specific examples of the conductive polymer used in the present invention include polyaniline, polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, and polyphenylenevinylene.

The conductive filler and / or the conductive polymer may be used in combination of two or more. Among such conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and cost.

The conductive filler used in the present invention and / or
Alternatively, the content of the conductive polymer varies depending on the type of the conductive filler and / or the conductive polymer to be used, and therefore cannot be unconditionally specified. The conductive filler and / or the conductive polymer are used in an amount of 1 to 1 part by weight based on 100 parts by weight of the main thermoplastic resin composition constituting the conductive thermoplastic resin composition.
It is preferable that the compounding amount is 00 parts by weight, more preferably 1 to 50 parts by weight.

The conductive resin composition preferably has a resistance value of 10 ⁷ Ω / m or less, and more preferably 10 ⁶ Ω / m, for the conductive layer in the multilayer hollow molded article in order to obtain sufficient antistatic performance.
/ M or less.

Further, a fibrous and / or non-fibrous filler may be added to the thermoplastic resin composition for forming each layer used in the present invention depending on the purpose and application within a range not to impair the scope of the present invention. Is also good. Specific examples of such a fibrous and / or non-fibrous filler include glass fiber, glass milled fiber, carbon fiber, potassium whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber,
Fibrous filler such as alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone fiber, metal fiber,
Wollastenite, zeolite, sericite, kaolin,
Silicates such as mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate,
Metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite;
Non-fibrous fillers such as sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide and silica. These may be hollow, and two or more of these fillers may be used in combination. Further, the use of these fibrous and / or non-fibrous fillers after pre-treatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, It is preferable from the viewpoint of obtaining more excellent mechanical strength.

When such a fibrous and / or non-fibrous filler is used, the amount of the filler is usually 5 to the total composition.
It is in the range of ８０80 wt%.

Further, the thermoplastic resin composition for forming each layer used in the present invention includes a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic phosphorus compound, talc, kaolin, and the like.
Organic phosphorus compounds, crystal nucleating agents such as polyetheretherketone, coloring inhibitors such as hypophosphite, antioxidants,
Conventional additives such as heat stabilizers, lubricants, UV inhibitors, coloring agents, flame retardants, and foaming agents can be added.

The method for preparing each resin composition of the present invention is not particularly limited. The mixture of the raw materials is supplied to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. 10 from melting point
As a typical example, a method of kneading at a temperature higher by about 50 ° C. can be mentioned. The order of mixing the raw materials is also not particularly limited, and is a method in which all the raw materials are blended and then melt-kneaded by the above-mentioned method. Any method may be used, such as a method of mixing some raw materials and then mixing the remaining raw materials using a side feeder during melt-kneading by a single-screw or twin-screw extruder.
When a small amount of an additive component is used, it is of course possible to knead the other components into a pellet by the above-described method or the like and then add it before molding to provide the mixture for molding.

The multilayer structure of the multilayer hollow molded article of the present invention includes (a) outer layer (b) layer / adhesive layer / inner layer (a) layer,
(B) outer layer (b) layer / intermediate (b) layer / adhesive layer / inner layer (a) layer; (c) outer layer (b) layer / adhesive layer / inner layer conductive (a) layer; (d) outer layer (b) ) Layer / intermediate (b) layer / adhesive layer / inner layer conductive (a) layer, (e) outer layer (b) layer / adhesive layer /
Intermediate layer (a) layer / adhesive layer / inner conductive layer (b), (f) outer layer (b) layer / intermediate conductive (b) layer / adhesive layer / inner layer (a)
Examples include layers, but are not limited thereto. Note that the outer layer (b) layer in the above configurations (b) and (d),
The intermediate (b) layer means a layer made of a thermoplastic resin composition having a different composition and mainly containing a thermoplastic resin other than polyphenylene sulfide resin.

Next, an example of the method for producing a multilayer hollow molded article of the present invention will be described by taking a multilayer tubular molded article as an example, but is not limited to the following. That is, the molten resin extruded from the extruder of the number of layers or the number of materials is introduced into one multilayer tube die, and is adhered in the die or immediately after leaving the die, thereby producing a multilayer tube. Can be. Alternatively, a method may be used in which a single-layer tube is once manufactured, and another layer is laminated on the inside or outside of the tube to manufacture a multi-layer tube.

The conductive multilayer hollow molded article of the present invention has a total thickness of 0.2 mm or more and 3 m from the viewpoint of obtaining sufficient hot water resistance, chemical resistance, and flexibility particularly in the case of a tube.
m or less is preferably selected. In that case, in order to have sufficient conductivity and not to impair flexibility or the like, the thickness of the conductive layer is 1% to 50% of the total thickness,
In particular, it is preferably from 3% to 20%.

The multilayer hollow molded article of the present invention thus obtained is excellent in heat resistance, hot water resistance, chemical resistance, toughness and appearance of the molded article, and in particular, the PPS resin composition layer and the thermoplastic resin layer It has strong adhesion and excellent antistatic properties, and is used as a blow molded product such as bottles, tanks and ducts, and as an extruded product such as pipes and tubes, for automobile parts, electric / electronic parts, and chemical applications. In particular, the multilayer tubular molded article of the present invention is preferably applied to a fuel tube application exhibiting the above-mentioned properties sufficiently, particularly an internal combustion engine application such as an automobile, or an automobile engine coolant tube or pipe.

[0132]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the following examples, the electrical resistance, the interlayer adhesive strength, the alcohol gasoline permeability and the low-temperature tube toughness of the conductive layer in the multilayer hollow molded article were evaluated by the following methods.

[Electrical Resistance Value of Conductive Layer in Multilayer Hollow Molded Body] A conductive paste is applied to the conductive layer and used as an electrode, and TR6877 Computin manufactured by Takeda Riken Industry Co., Ltd.
g The resistance value was measured using a Digital Multimeter, and the resistance value per meter was calculated.

[Adhesive strength] A tube was cut into a strip having a width of 10 mm, and inner and outer layers sandwiching the adhesive layer (the adhesive layer was (B) PP
The adhesive strength per unit length was measured by pulling each of the thermoplastic resin compositions other than the S resin on the side of the layer made of a thermoplastic resin composition mainly composed of a thermoplastic resin in the direction of 180 degrees.

[Alcohol Gasoline Permeability] A tube cut into a length of 30 cm was sealed at one end, and commercially available regular gasoline and methyl alcohol were mixed at 85: 1.
An alcohol gasoline mixture mixed at a ratio of 5 (weight ratio) was added, and the other end was also sealed. Thereafter, the entire weight was measured, and the test tube was placed in an explosion-proof oven at 40 ° C., and the alcohol gasoline permeability was evaluated based on the change in weight.

[Evaluation of low-temperature toughness of tube] Ten tubes each having a length of 30 cm were prepared, and the tubes were allowed to stand in a cooling device at -40 ° C for 4 hours. Remove the tube from the cooling device,
A 0.454 kg weight was dropped onto the tube from a height of 304.8 mm, and the tube was observed for damage.

Reference Example 1 (Polymerization of PPS resin) Sodium sulfide nonahydrate 6.005 in an autoclave equipped with a stirrer.
kg (25 mol), 0.656 kg (8
Mol) and N-methyl-2-pyrrolidone (hereinafter NMP)
5 kg, and gradually feed through with nitrogen
The temperature was raised to 5 ° C., and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and NMP3.
After adding 7 kg, the mixture was sealed under nitrogen, heated to 270 ° C, and reacted at 270 ° C for 2.5 hours. After cooling, the reaction product was washed five times with warm water and dried under reduced pressure at 80 ° C. for 24 hours to obtain 2.45 kg of a PPS resin (P-1).

The polymerization was carried out in the same manner as described above, and the reaction product was washed five times with warm water.
After stirring for about 1 hour, the mixture was filtered and washed several times with hot water. This was poured into 25 liters of an aqueous acetic acid solution of pH 4 heated to 90 ° C.
After stirring was continued for a period of time, the mixture was filtered, washed with ion-exchanged water at about 90 ° C. until the pH of the filtrate became 7, and then dried under reduced pressure at 80 ° C. for 24 hours to obtain a PPS resin (P-2). This PP
The number average molecular weight of S was 10,500, and the total ash content was 0.07% by weight.

[Materials Used in Examples and Comparative Examples] (b)
B-1: Nylon 11 (Toray Co., Ltd. "Rilsan" BES
NBK P20TL) b-2: Nylon 12 (Toray Co., Ltd. "Rilsan" AES)
NBK P20TL) b-3: Polybutylene terephthalate (Toray PB)
T 1404X04) b-4: Polyurethane resin ("Elastolane" E598)
PNAT) b-5: Polyolefin resin (Mitsui Petrochemicals Co., Ltd. "HIZEX" 3000B) b-6: Nylon 6 (Toray Co., Ltd. "Amilan" CM10)
56)

(C) Adhesive layer C-1: ethylene / glycidyl methacrylate = 94 /
6 (wt%) copolymer C-2: ethylene / methyl acrylate / glycidyl methacrylate = 64/30/6 wt% copolymer C-3: ethylene / ethyl acrylate / maleic anhydride = 85/12/3 wt % Copolymer C-4: maleic anhydride (3 wt%) grafted low density polyethylene

(B) Olefin-based copolymer containing functional group B-1: Olefin-based copolymer having glycidyl ester of α-olefin and α, β-unsaturated acid as a main component ethylene / glycidyl methacrylate -B = 88/12 (wt%) copolymer B-2: ethylene / glycidyl methacrylate (E / G
MA) having a main skeleton of 85/15 (% by weight) and graft copolymerization of acrylonitrile / styrene (AS) = 30/70 (% by weight), wherein (E / GMA) /
(AS) = 70/30 (wt%) copolymer B-3: maleic anhydride (0.5 wt%) graft-modified ethylene propylene rubber

(C) Elastomer containing no epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylate group C-1: Ethylene / propylene copolymer

(D) Alkoxysilane compound D-1: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

(E) conductive filler and / or conductive polymer E-1: carbon black (Ketjen Black International Co., Ltd. EC600JD, DBP oil absorption 495 ml / 100 g, BET surface area 1270 m ² /
g, ash content 0.2% E-2: carbon black (Mitsubishi Chemical Industries, Ltd. Mitsubishi conductive carbon black # 3050, DBP oil absorption 18)
0 ml / 100 g, BET surface area 75 m ² / g, ash content 0.2%

Reference Example 2 (Preparation of Composition for Layer A) Table 1
After dry-blending each compounded material shown in Table 1 at the ratio shown in Table 1, pre-mixed for 2 minutes in a tumbler, melt-kneaded with a twin-screw extruder set at a cylinder temperature of 300 to 320 ° C, pelletized with a strand cutter, 130 ° C
And dried overnight.

Reference Example 3 (Preparation of material B-7) Nylon 11 ("Rilsan" BESN O TLSG, manufactured by Toray Industries, Inc.)
93 parts by weight of the conductive filler (E-1) was mixed in an amount of 7 parts by weight, preliminarily mixed in a tumbler for 2 minutes, and then melt-kneaded with a twin-screw extruder set at a cylinder temperature of 210 to 220 ° C. Pelletized by 80
Vacuum dried at 0 ° C overnight.

Examples 1 to 13 and Comparative Examples 1 to 3 Using the above-mentioned materials or resin compositions, a tube was formed from two to three thermoplastic resin composition layers and one adhesive layer.

The molding apparatus has three to four extruders, a die for collecting the resin discharged from the three extruders by an adapter and forming the same into a tube, and a sizing for cooling and controlling the dimensions of the tube. A die and a take-up machine were used.

The resulting three-layer tube had an outer diameter of 8 mm,
The inner diameter was 6 mm, the outer layer thickness was 0.75 mm, the adhesive layer thickness was 0.10 mm, and the inner layer thickness was 0.15 mm. The four-layer tube had an outer diameter of 8 mm, an inner diameter of 6 mm, an outer layer thickness of 0.2 mm, an intermediate layer thickness of 0.55 mm, an adhesive layer thickness of 0.10 mm, and an inner layer thickness of 0.15 mm. Tables 2 and 3 show the evaluation results of this multilayer tube.

[0151]

[Table 1]

[0152]

[Table 2]

[0153]

[Table 3]

As can be seen from the comparison between Comparative Example 1 and Example,
According to the constitution of the present invention, a tube molded article excellent in alcohol gasoline permeability and interlayer adhesion can be obtained. Comparative Example 3
Does not have a PPS composition layer. In this case, the tube is inferior in alcohol gasoline resistance.

From the comparison between Example 2 and Examples 3 and 4, (B
1) An olefin copolymer containing an epoxy group and (B)
2) It can be seen that the combined use of an olefin copolymer containing an acid anhydride group or the addition of an epoxysilane compound is effective in improving the low-temperature toughness of the tube and the interlayer adhesion.

Further, from the comparison between Example 3 and Example 5, it can be seen that the application of the deionized PPS is effective in improving the low-temperature toughness of the tube and the interlayer adhesion.

[0157]

As described above, the multilayer hollow molded article of the present invention has a good balance of heat resistance, hot water resistance, chemical resistance, gasohol resistance, toughness, adhesion between layers, and conductivity. Particularly, it is preferably applied to a fuel tube for an internal combustion engine such as an automobile or a coolant tube or a pipe for an automobile engine.

Claims (22)

[Claims] 1. A multilayer hollow molded article comprising at least two or more thermoplastic resin layers and at least one or more adhesive layers, wherein at least one of the thermoplastic resin layers comprises (a) polyphenylene sulfide. This is a layer composed of a composition mainly composed of a resin, and at least one of the thermoplastic resin layers is composed of a thermoplastic resin composition mainly composed of a thermoplastic resin other than (b) polyphenylene sulfide resin. Layer, and between the (a) and (b) layers,
A multilayer having (c) an adhesive layer having an adhesive property with both layers (provided that (c) the main constituent components of the adhesive layer are different from the main constituent components of the (a) and (b) layers) Hollow molded body. 2. The thermoplastic resin other than the polyphenylene sulfide resin constituting the layer (b) is at least one selected from a polyamide resin, a thermoplastic polyester resin, a thermoplastic polyurethane resin, and a polyolefin resin. The multilayer hollow molded article according to claim 1, wherein 3. The multilayer hollow molded article according to claim 2, wherein the thermoplastic resin other than the polyphenylene sulfide resin constituting the layer (b) is a polyamide resin. 4. The polyphenylene sulfide resin composition constituting the layer (a) is based on (B) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, based on 100 parts by weight of the polyphenylene sulfide resin. The multilayer hollow molded article according to claim 1, which is a polyphenylene sulfide resin composition containing 1 to 200 parts by weight of at least one kind of a copolymer containing at least one kind of functional group selected from acid esters. 5. The (B) functional group-containing copolymer in the polyphenylene sulfide resin composition constituting the layer comprises α-
The multilayer hollow molded article according to claim 4, which is an epoxy group-containing olefin-based copolymer (B) containing an olefin and a glycidyl ester of an α, β-unsaturated acid as main components. 6. The (B) functional group-containing copolymer in the polyphenylene sulfide resin composition constituting the layer is α-
The multilayer according to claim 4, which is an olefin-based copolymer comprising an olefin (1), a glycidyl ester of an α, β-unsaturated acid (2) and a monomer (3) represented by the following general formula. Hollow molded body. Embedded image (Where R ¹ represents hydrogen or a lower alkyl group;
Is -COOR ² group, groups selected from -CN group or an aromatic group, also R ² represents an alkyl group having 1 to 10 carbon atoms) 7. The polyphenylene sulfide resin composition constituting the layer (A) comprises: (B) a functional group-containing copolymer (B1) an olefin copolymer containing an epoxy group; and (B2) an acid anhydride group. Is a polyphenylene sulfide resin composition containing, as an essential component, at least two kinds of functional group-containing olefin copolymers with olefin copolymers containing (B1) and (B2), wherein the weight% of (B1) and (B2) is (B2).
1): (B2) = 1 to 99:99 to 1 (100% by weight in total), the multilayer hollow molded article according to any one of claims 5 to 6. 8. The polyphenylene sulfide resin composition constituting (a) a layer, wherein the polyphenylene sulfide resin further comprises (C) an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate group. A resin composition, wherein (C) at least one kind of an elastomer not containing an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is added to 100 parts by weight of a polyphenylene sulfide resin.
(B) a functional group-containing copolymer and (C) an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate group. 6.) 200 parts by weight or less based on 100 parts by weight of the polyphenylene sulfide resin.
8. The multilayer hollow molded article according to any one of claims 7 to 7. 9. The polyphenylene sulfide resin composition constituting the layer (A) further comprises (D) an epoxy group, an amino group,
At least one alkoxysilane compound having at least one functional group selected from an isocyanate group, a hydroxyl group, a mercapto group, and a ureide group is used in an amount of 0.04 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin (A).
9. A composition obtained by adding 5 to 5 parts by weight.
The multilayer hollow molded article according to any one of the above. 10. The multilayer according to any one of claims 1 to 9, wherein (A) the polyphenylene sulfide resin used in the polyphenylene sulfide resin composition constituting the layer has been deionized. Hollow molded body. (11) The adhesive layer comprises an epoxy group, an acid anhydride group, a carboxyl group or a salt thereof, an isocyanate group,
The multilayer hollow molded article according to any one of claims 1 to 10, comprising at least one compound containing at least one functional group selected from amino groups. (C) the adhesive layer comprises an epoxy group, an acid anhydride group, a carboxyl group or a salt thereof, an isocyanate group,
2. An olefin copolymer having at least one functional group selected from amino groups.
2. The multilayer hollow molded article according to 1. 13. The conductive multilayer hollow molded article according to claim 1, wherein at least one of the layers constituting the multilayer hollow molded article is made of a conductive thermoplastic resin composition. 14. The conductive multilayer hollow molded article according to claim 13, wherein the conductive layer is made of a conductive thermoplastic resin composition containing (E) a conductive filler or a conductive polymer. 15. The conductive filler or conductive polymer (E) is a non-fibrous conductive filler or a fibrous conductive filler having a length / diameter ratio of 200 or less. 15. The conductive multilayer hollow molded article according to 14. 16. The conductive multilayer hollow molded article according to claim 15, wherein (E) the conductive filler is carbon black. 17. The conductive multilayer hollow molded article according to any one of claims 13 to 16, wherein (a) a layer comprising a composition containing a polyphenylene sulfide resin as a main component is a conductive layer. 18. The conductive multilayer hollow molded article according to claim 13, wherein the resistance value of the conductive layer is 10 ⁷ Ω / m or less. 19. The conductive multilayer hollow molded article according to claim 1, wherein the multilayer hollow molded article is a multilayer tubular molded article produced by a coextrusion molding method. 20. The conductive multilayer hollow molded article has a total thickness of 0.2 mm or more and 3 mm or less, and a conductive layer has a thickness of 1% or more and 50% or less of the total thickness.
20. The multilayer hollow molded article according to any one of 3 to 19 above. 21. The multilayer hollow molded article according to claim 1, which is used as an automobile fuel tube. 22. The multilayer hollow molded article according to claim 1, which is used as an automobile engine coolant tube or pipe.