JP2000063669A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin compsn. excellent in toughness and resistances to heat and gasoline permeation and to provide a blow molded article and a multilayered blow molded article prepd. from the compsn. SOLUTION: This compsn. contains (A) 100 pts.wt. polyphenylene sulfide, (B) 1-100 pts.wt. conductive filler, and (C) 1-100 pts.wt. elastomer having at least one kind of functional groups selected from epoxy, acid anhydride, carboxyl and its salt, and carboxylic ester groups and exhibits a variation in vol. resistance lower than 1,000 times when treated in a gasoline model liquid (the vol. ratio of toluene/isooctane = 50/50) at 60 deg.C for 72 hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition having excellent heat resistance, gasoline permeation resistance, toughness, and stable conductivity, and a hollow molded article and a multi-layer hollow molded article using the same. Is.

[0002]

2. Description of the Related Art Hollow molded articles of thermoplastic resins are manufactured, for example, by blow molding using a polyamide resin, mainly in ducts in the engine room of automobiles, and saturated polyester resins and polyamides for tubes. A technique of manufacturing by extrusion molding using a resin, a polyolefin resin, and a thermoplastic polyurethane has become widespread.

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 therefore, products having further improved heat resistance, hot water resistance, chemical resistance, etc. are required.

Polyamide resins, particularly flexible polyamide resins such as polyamide 11 and polyamide 12, are widely used especially for automobile fuel tubes, but when polyamide resins are used alone, they are required from the viewpoint of environmental pollution and improvement of fuel consumption. It has been pointed out that there is a concern that it is not sufficient for the permeation preventing property of alcohol gasoline, which has been proposed, and its improvement is desired.

Further, in applications where a non-conductive liquid such as a fuel flows in a blow hollow molded body or a tube molded body, the molded body may be charged, and it is also required to suppress this.

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 and electric characteristics, and is used for electric / electronic parts and automobiles. Demand is increasing for applications such as parts.

As an example of a tubular hollow molded article which makes use of the features of this PPS resin, Japanese Patent Laid-Open No. 2004-200415 discloses:
A PPS-based tubular body excellent in toughness and the like, which is composed of a composition in which a specific elastomer is mixed with PPS, is disclosed.

On the other hand, many studies have been made so far on making the PPS resin conductive, for example, JP-A-60-53.
No. 560, there is disclosed a conductive PPS resin composition in which a conductive carbon black is mixed with a PPS resin.
Japanese Patent No. 272665 discloses an electrically conductive PPS mixture in which electrically conductive carbon black and graphite are mixed with a PPS resin.

By using a hollow molded article made of PPS resin whose toughness is improved and made conductive by such an elastomer, there is a possibility that the above-mentioned concerns such as heat resistance, alcohol gasoline permeation preventive property, and electrification can be solved.

[0010]

Therefore, based on the above idea, a study is made to obtain a PPS resin composition excellent in heat resistance, gasoline permeation resistance, toughness and conductivity by blending a PPS resin with a conductive filler and an elastomer. At the start, it was found that even if the initial conductivity is improved, the conductivity may be reduced when treated with gasoline or gasoline containing peroxide used in some areas. That is, an object of the present invention is to obtain a PPS resin composition having excellent heat resistance, gasoline resistance, permeability, toughness, and electrical conductivity, and maintaining excellent electrical conductivity even when treated with gasoline or the like. Furthermore, it is an object to obtain a hollow molded article and a multilayer hollow molded article using the same.

[0011]

Means for Solving the Problems That is, the present invention is (1)
(A) 100 parts by weight of polyphenylene sulfide,
(B) 1 to 100 parts by weight of a conductive filler and (C)
Epoxy group, acid anhydride group, carboxyl group and salts thereof,
What is claimed is: 1. A resin composition containing 1 to 100 parts by weight of an elastomer containing at least one functional group selected from carboxylic acid esters, wherein the composition is a melt indexer (temperature = 315.5 ° C, residence time 5 minutes). , Load 15.5
kg, orifice diameter 0.0825 inch, length 0.31
5 inch) and extruded to obtain a gut, and the gut is a gasoline model liquid (toluene: isooctane = 5).
A polyphenylene sulfide resin composition characterized in that the volume resistance variation when treated at 60 ° C. for 72 hours in a volume ratio of 0:50 satisfies the following formula: Y / X <1,000 (where X: Volume resistance before treatment (Ω · cm) Y: Volume resistance after treatment with gasoline model liquid (Ω · c)
m)) (2) 1 to 100 parts by weight of a conductive filler (B) and (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, a carboxylic acid ester, relative to 100 parts by weight of (A) polyphenylene sulfide. A resin composition containing 1 to 100 parts by weight of an elastomer containing at least one functional group selected from the group consisting of a melt indexer (temperature = 315.5 ° C, residence time 5 minutes, load 1
5.5 kg, orifice diameter 0.0825 inch, length 0.315 inch) and extruded to obtain gut,
When the gut was treated in a peroxide-containing gasoline model liquid (toluene: isooctane = 50: 50 volume ratio with 5% by weight of lauroyl peroxide added) at 60 ° C. for 72 hours, the volume resistance variation was The polyphenylene sulfide resin composition as described in 1 above, which satisfies the following formula: Y '/ X <1,000 (where X: volume resistance value (Ω · cm) before treatment Y': peroxide gasoline Volume resistance value (Ω · cm) after treatment with model solution (3) (C) Elastomer containing at least one functional group selected from epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester 3. The polyphenylene according to any one of 1 to 2 above, wherein (C) is an epoxy group-containing olefin-based copolymer mainly composed of α-olefin and glycidyl ester of α, β-unsaturated acid. The sulfide resin composition, (4) (C) epoxy group-containing olefin copolymer, is further represented by the following general formula with α-olefin (1) and glycidyl ester (2) of α, β-unsaturated acid. The polyphenylene sulfide resin composition according to the above 3, which is an olefin-based copolymer obtained by copolymerizing a monomer containing the monomer (3) as an essential component.

[0012]

[Chemical 2]

(Wherein R ¹ represents hydrogen or a lower alkyl group, X represents one or more groups selected from a --COOR ² group, a --CN group or an aromatic group, and R ² represents a carbon atom. (5) (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and an elastomer containing at least one functional group selected from carboxylic acid esters (C1). ) A polyphenylene sulfide resin composition containing at least two functional group-containing elastomers, an epoxy group-containing elastomer and a (C2) acid anhydride group-containing elastomer, wherein the weight percentage of (C1) and (C2) is Is (C
1): (C2) = 1 to 99:99 to 1 (total 100% by weight), the polyphenylene sulfide resin composition according to any one of the above 1 to 4, (6) further (D) epoxy group, acid anhydride group An elastomer containing neither a carboxyl group, a salt thereof, nor a carboxylic acid ester group, (A)
1 to 100 parts by weight of polyphenylene sulfide resin
The polyphenylene sulfide resin composition according to any one of 1 to 5 above, which contains 99 parts by weight and the total amount of the components (C) and (D) is 100 parts by weight or less based on 100 parts by weight of the (A) polyphenylene sulfide resin. And (7) the alkoxysilane compound (E) with respect to 100 parts by weight of the polyphenylene sulfide resin (A) in an amount of 0.05 to 5
7. The polyphenylene sulfide resin composition according to any one of 1 to 6 above, wherein (8) (A) the polyphenylene sulfide resin is added by weight, and is deionized. 1 to 8, wherein the polyphenylene sulfide resin composition and (9) (B) the conductive filler are carbon blacks
A polyphenylene sulfide resin composition according to any one of
(10) Gut volume resistance before gasoline treatment is 100Ω
・ The polyphenylene sulfide resin composition according to any one of 1 to 9 above, which is not more than cm.
(A) polyphenylene sulfide and (C) epoxy group,
An elastomer containing at least one functional group selected from an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester, and (D) an epoxy group, an acid anhydride group,
In the case of blending an elastomer containing neither a carboxyl group nor its salt nor a carboxylic acid ester group, the component (D) is melt-kneaded and then the component (B) is blended with a conductive filler and melt-kneaded. Any one of the polyphenylene sulfide resin composition, (12) (A) polyphenylene sulfide and (B) conductive filler are melt-kneaded, and then (C) an epoxy group, an acid anhydride group, a carboxyl group and its salt, a carboxylic acid ester. When an elastomer containing at least one functional group selected from the group (D) and an elastomer containing neither (D) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, nor a carboxylic acid ester group is added ( (D) The polyphenylene sulfide resin composition according to any one of 1 to 10 above, which is prepared by mixing and melting and kneading the components. 3) (A) polyphenylene sulfide and (C) an epoxy group, acid anhydride group, carboxyl group and its salts, elastomers containing at least one functional group selected from carboxylic acid ester, further (D)
Epoxy group, acid anhydride group, carboxyl group and salts thereof,
In the case of blending an elastomer containing neither carboxylic acid ester group, after melt-kneading the component (D),
(B) A method for producing a polyphenylene sulfide resin composition, which comprises producing a polyphenylene sulfide resin composition according to any one of 1 to 10 by blending a conductive filler and melt-kneading, (14) (A ) After melt-kneading polyphenylene sulfide and (B) conductive filler, (C) an elastomer containing at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester, and (D)
Epoxy group, acid anhydride group, carboxyl group and salts thereof,
When an elastomer not containing any of carboxylic acid ester groups is blended, the component (D) is blended and melt-kneaded to produce the polyphenylene sulfide resin composition according to any one of 1 to 10 above. A method for producing a polyphenylene sulfide resin composition, (1
5) A hollow molded article made of the polyphenylene sulfide resin composition described in any one of 1 to 12 above, and (16) a layer made of the polyphenylene sulfide resin composition described in any one of 1 to 12 above and a resin composition other than that. And a multi-layer hollow molded article having layers.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The (A) polyphenylene sulfide resin (PPS resin) used in the present invention is a repeating unit represented by the following structural formula.

[0015]

[Chemical 3]

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, particularly 90 mol% or more of the repeating unit is preferable. Further, the PPS resin can comprise 30 mol% or less of its repeating unit with a repeating unit having the following structural formula.

[0017]

[Chemical 4]

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded, but in order to obtain more excellent toughness and tube moldability, the melt flow rate (temperature = 315.5). ℃, retention time 5 minutes after sample introduction until the start of measurement, orifice diameter 0.0825 inches, length 0.315 inches, 5000g load) 400
It is preferably g / 10 min or less, more preferably 150 g / 10 min or less.

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

A specific method for crosslinking / polymerizing the PPS resin by heating is as follows: in an atmosphere of an oxidizing gas such as air or oxygen, or in a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. An example is a method of heating in a heating container at a predetermined temperature in an atmosphere until a desired melt viscosity is obtained. The heat treatment temperature is usually
170-280 degreeC is selected, Preferably it is 200-27.
The temperature is 0 ° C., and the time is usually selected from 0.5 to 100 hours, preferably 2 to 50 hours, but it is possible to obtain a target viscosity level by controlling both the heat treatment temperature and time. it can. The heat treatment apparatus may be a normal hot air dryer or a rotary type or a heating apparatus with a stirring blade, but for efficient and more uniform treatment, a heating type with a rotation type or a stirring blade is used. Is more preferable.

A specific method for heat-treating the PPS resin in an atmosphere of an inert gas such as nitrogen or under a reduced pressure is as follows:
Heat treatment temperature 150 to 280 ° C., preferably 200 to 2
70 ° C., heating time 0.5 to 100 hours, preferably 2
A method of heat treatment for up to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air dryer or a rotary type or a heating apparatus with a stirring blade, but for efficient and more uniform treatment, a heating type with a rotation type or a stirring blade is used. Is more preferable.

The PPS resin used in the present invention is preferably a deionized PPS resin in order to obtain more excellent toughness and to further suppress resistance fluctuation due to gasoline treatment. Specific examples of such deionization treatment include 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.

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, but is, for example, a nitrogen-containing polar solvent such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl. Sulfoxide / sulfone type solvents such as sulfone, acetone, methyl ethyl ketone, diethyl ketone, ketone type solvents such as acetophenone, dimethyl ether, dipropyl ether, ether type solvents such as tetrahydrofuran, chloroform, methylene chloride,
Halogen-based solvents such as trichlorethylene, ethylene dichloride, dichloroethane, tetrachloroethane, chlorobenzene, alcohol / phenolic solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol. And aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, it is preferable to use N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like. Further, these organic solvents are used alone or as a mixture of two or more kinds.
As a method of washing with an organic solvent, PP in an organic solvent is used.
There is a method of immersing the S resin, and if necessary, it is possible to appropriately stir or heat. P in organic solvent
There is no particular limitation on the washing temperature when washing the PS resin, and any temperature from room temperature to about 300 ° C. can be selected.
The higher the cleaning temperature, the higher the cleaning efficiency tends to be. However, normally, a sufficient cleaning effect can be obtained at a cleaning temperature of room temperature to 150 ° C. The PPS resin that has been washed with an organic solvent 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, it is preferable that the water used is distilled water or deionized water in order to exert the effect of preferable chemical modification of the PPS resin by washing with hot water. The operation of hot water treatment is usually carried out by adding a predetermined amount of PPS resin to a predetermined amount of water and heating and stirring at normal pressure or in a pressure vessel. The ratio of the PPS resin to water is preferably such that the amount of water is large, but normally, a bath ratio of 200 g or less of PPS resin to 1 liter of water is 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 the acid, and it is also possible to appropriately stir or heat as necessary. The acid used is not particularly limited as long as it does not have the action of degrading PPS, and aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted aliphatic saturated acids such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acids such as carboxylic acid, acrylic acid, crotonic acid, benzoic acid, aromatic carboxylic acids such as salicylic acid, oxalic acid, malonic acid, dicarboxylic acids such as succinic acid, phthalic acid and fumaric acid, sulfuric acid, Examples thereof include inorganic acid compounds such as phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The acid-treated PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the preferred chemical modification effect of the PPS resin by acid treatment is not impaired.

Next, the conductive filler (B) will be described. The conductive filler is not particularly limited as long as it is a conductive filler usually used for making a resin conductive, and specific examples thereof include metal powder, metal flakes, metal ribbons, metal fibers, metal oxides, and conductive substances. Examples thereof include coated inorganic fillers, carbon black, graphite, carbon fibers, carbon flakes, and scaly carbon.

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

As a specific example of the metal species of the metal fiber, iron,
Examples include copper, stainless steel, aluminum, brass and the like.

The metal powder, metal flakes, metal ribbons, and metal fibers may be surface-treated with a surface-treating agent such as titanate, aluminum, or silane.

Specific examples of metal oxides include SnO ₂ (antimony-doped), In ₂ O ₃ (antimony-doped),
Examples thereof include ZnO (aluminum dope), and these may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based, or silane-based.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony-doped), I
Examples thereof include n ₂ O ₃ (antimony-doped). Further, as the inorganic filler to be coated, mica, glass beads, glass fiber, carbon fiber, potassium whisker titanate,
Examples thereof include barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide type whiskers, titanic acid type whiskers, and silicon carbide whiskers. Examples of the coating method include a vacuum vapor deposition method, a sputtering method, an electroless plating method and a baking method. Further, these may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based or silane-based.

Carbon black is acetylene black, gas black, oil black, depending on its raw material and manufacturing method.
It is classified into naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black and so on. Carbon black that can be used in the present invention, its raw material,
The production method is not particularly limited, but acetylene black and furnace black are particularly preferably used. As for carbon black, various carbon blacks having different characteristics such as particle size, surface area, DBP oil absorption, and ash are manufactured. The carbon black that can be used in the present invention is not particularly limited in these characteristics, but from the viewpoint of the balance between toughness and conductivity, the average particle diameter is 500 nm or less, especially 5
It is preferably -100 nm, more preferably 10-70 nm. The surface area (BET method) is 10 m ² / g or more, and further 301
0 m ² / g or more, particularly 500 to 1500 ² / g are preferred. The DBP oil absorption is 50 ml / 100 g or more, particularly 100 ml / 100 g, and more preferably 370 ml / 100 g or more. Ash content is 0.5% or less, especially 0.3%
The following are preferred.

Such carbon black is a titanate type,
It may be surface-treated with a surface-treating agent such as aluminum-based or silane-based. It is also possible to use a granulated product in order to improve the workability of melt-kneading.

From the viewpoint of obtaining excellent surface smoothness, the conductive filler used in the present invention has a powdery, granular, plate-like, scale-like or resin composition rather than a fibrous filler having a high aspect ratio. It is preferable that any of the fibrous forms having a length / diameter ratio of 200 or less is used.

The conductive fillers may be used in combination of two or more kinds. Among these conductive fillers, carbon black is particularly preferably used in terms of strength and cost.

Since the content of the conductive filler used in the present invention varies depending on the type of the conductive filler used,
Although it cannot be specified unconditionally, from the viewpoint of the balance between conductivity, fluidity, mechanical strength, etc., (A) thermoplastic resin 100
1 to 100 parts by weight, preferably 2 to 50 parts by weight
A range of 3 to 10 parts by weight, more preferably 3 to 10 parts by weight, is preferably selected.

Next, in the present invention, compounding an elastomer containing (C) at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester has excellent toughness. , Is essential for obtaining extrusion moldability.

As the elastomer containing such a functional group, an olefin (co) polymer containing at least one selected from an epoxy group, an acid anhydride group, a carboxyl group and its salt, and a carboxylic acid ester, a fluorine type ( Both)
Examples thereof include polymers.

As the epoxy group-containing polyolefin polymer, an olefin copolymer having glycidyl ester, glycidyl ether, glycidyl diamine or the like in the side chain, or a double bond portion of an olefin copolymer having a double bond is used. , Epoxidized, and the like. Among them, an olefin-based copolymer in which a monomer having an epoxy group is copolymerized is preferable, and particularly a glycidyl ester of α-olefin and α, β-unsaturated acid is a main constituent component. The olefin-based copolymer is preferably used.

Specific examples of such α-olefins include:
Examples thereof include ethylene, propylene, butene-1, 4-methylpentene-1, hexene-1, decene-1, octene-1, and among them, ethylene is preferably used. Also, two or more of these may be used at the same time.

On the other hand, the glycidyl ester of α, β-unsaturated acid has the general formula

[0042]

[Chemical 5]

(Wherein R represents a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, and the like, of which glycidyl methacrylate is preferable. Used.

The olefin copolymer mainly composed of the α-olefin and the glycidyl ester of the α, β-unsaturated acid is a random copolymer of the α-olefin and the glycidyl ester of the α, β-unsaturated acid, Any of alternating, block and graft copolymers may be used.

The copolymerization amount of the glycidyl ester of the α, β-unsaturated acid in the olefin copolymer mainly composed of the glycidyl ester of the α-olefin and the α, β-unsaturated acid has a desired effect. From the viewpoints of influence of, polymerizability, gelation, heat resistance, fluidity, influence on strength, etc.,
0.5 to 40% by weight, particularly 3 to 30% by weight is preferable.

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

[0047]

[Chemical 6]

(Wherein R ¹ represents hydrogen or a lower alkyl group, X represents a group selected from a --COOR ² group, a --CN group or 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 (2) of the α, β-unsaturated acid used in the olefin copolymer are the same as those of the (B) 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. These can be used in combination of two or more.

Such an olefin copolymer is a random, alternating, block of α-olefin (1), glycidyl ester of α, β-unsaturated acid (2) and monomer (3).
The graft copolymer may be any copolymerization mode, for example, a monomer (3) with respect to a random copolymer of α-olefin (1) and glycidyl ester of α, β-unsaturated acid (2). It may be a copolymer in which two or more types of copolymerization modes are combined, such as graft copolymerization.

The copolymerization ratio of the olefin-based copolymer is such that α-olefin (1) / (α) -olefin (1) / from the viewpoints of influence on desired effects, polymerizability, gelation, heat resistance, fluidity and strength. Glycidyl ester of α, β-unsaturated acid (2)
= 60 to 99% by weight / 40 to 1% by weight is preferably selected. The copolymerization ratio of the monomer (3) is 95 to 40% by weight of the total amount of the α-olefin (1) and the glycidyl ester (2) of the α, β-unsaturated acid, and the monomer (3) is used. The range of 5 to 60% by weight is preferably selected.

Examples of the elastomer containing a carboxyl group and a salt thereof, a carboxylic acid ester group and an acid anhydride group which are preferably used in the present invention include ethylene-butene copolymer, ethylene-octene copolymer and ethylene. −
Copolymer of ethylene and α-olefin such as hexene copolymer, polyethylene, polypropylene, polystyrene, ethylene-propylene 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,
Polyolefin resins such as butene-isoprene copolymer, styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), and maleic anhydride, succinic anhydride , Fumaric anhydride, acrylic acid, methacrylic acid, vinyl acetate and its Na, Zn,
Salts of K, Ca, Mg, etc., methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
Examples include olefin-based copolymers obtained by copolymerizing propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, and the like, and 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-acrylic acid Isobutyl copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer,
Ethylene-n-propyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-t-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer Such as olefin- (meth) acrylic acid ester copolymer, methyl acrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, propyl acrylate-acrylonitrile copolymer, propyl methacrylate-acrylonitrile copolymer (Meth) acrylic acid ester-acrylonitrile copolymer, ethylene- (meth) acrylic acid copolymer and Na, Zn thereof, such as a combination, a butyl acrylate-acrylonitrile copolymer, a butyl methacrylic acid-acrylonitrile copolymer , K Metal salts such as Ca and Mg, ethylene-maleic anhydride copolymer, ethylene-butene-maleic anhydride copolymer, ethylene-propylene-maleic anhydride copolymer, ethylene-hexene-maleic anhydride Copolymer, ethylene-octene-maleic anhydride copolymer, propylene-maleic anhydride copolymer or maleic anhydride modified SBS, maleic anhydride modified SIS, maleic anhydride modified SEBS, maleic anhydride modified SEPS, Examples include maleic anhydride-modified ethylene-ethyl acrylate copolymer.

The copolymerization mode of such an olefinic copolymer is not particularly limited, and any copolymer mode such as a random copolymer, a graft copolymer or a block copolymer may be used.

The amount of the (C) elastomer containing at least one functional group selected from the epoxy group, the acid anhydride group, the carboxyl group and its salt, and the carboxylic acid ester group is such that the toughness, surface smoothness, and extrusion are From the viewpoints of moldability, electric resistance stability, etc., the range of 1 to 100 parts by weight, preferably the range of 5 to 50 parts by weight is selected with respect to 100 parts by weight of the (A) PPS resin, but peroxide is particularly preferable. A range of 5 to 20 parts by weight is particularly preferably selected in the sense of obtaining excellent electric resistance stability after treating the contained gasoline.

The above (C) epoxy group, acid anhydride group,
Two or more kinds of elastomers 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. In particular, the combined use of the functional group-containing elastomer of the (C1) epoxy group-containing elastomer and the (C2) acid anhydride group-containing elastomer is more preferable in order to obtain excellent toughness with an excellent smaller amount of elastomer. At that time, (C1) and (C
The weight ratio of 2) is (C1) :( C2) = 1 to 99:
The range of 99-1 (weight ratio) is selected.

Further, an elastomer containing at least one functional group selected from the above-mentioned (C) epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester group, and (D) functional group It is also effective to use a non-use elastomer together in order to obtain excellent toughness.

Examples of the (D) functional group-free elastomer include ethylene-α-butene copolymers, ethylene-octene copolymers, ethylene-propylene copolymers and ethylene-hexene copolymers.
Olefin copolymer, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, SBS, SIS, SEBS, SEPS And so on.

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

Two or more kinds of the (D) elastomers having no functional group may be used in combination. Further, when (D) an elastomer not containing a functional group is used, its preferable blending amount is 100 parts by weight of (A) PPS resin from the viewpoints of gasoline permeation preventive property, toughness, tube moldability, electric resistance stability and the like. On the other hand, the range of 1 to 99 parts by weight is selected, preferably the range of 5 to 50 parts by weight,
In particular, the range of 5 to 30 parts by weight is particularly preferably selected in the sense of obtaining excellent electrical resistance stability after the treatment of gasoline containing peroxide.

From the viewpoints of gasoline permeation resistance and electric resistance stability, the total amount of the (C) functional group-containing elastomer and the (D) functional group-free elastomer is 100 parts by weight of the (A) PPS resin. It is preferably 100 parts by weight or less. A particularly preferred range is (A) P
With respect to 100 parts by weight of the PS resin, 3 to 15 parts by weight of the (C) functional group-containing elastomer and 3 to 20 parts by weight of the (D) functional group-free elastomer.

The composition of the present invention further comprises (E) an alkoxysilane compound, and (A) a polyphenylene sulfide resin 1.
Addition of 0.05 to 5 parts by weight with respect to 00 parts by weight is more effective in terms of improving toughness and tube moldability. The (E) alkoxysilane is preferably 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 ureido group, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
Epoxy group-containing alkoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
-Mercapto group-containing alkoxysilane compound such as mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, etc. Alkoxysilane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane, γ- (2
-Aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and other amino group-containing alkoxysilane compounds, γ-hydroxypropyltrimethoxysilane, γ- Examples thereof include a hydroxyl group-containing alkoxysilane compound such as hydroxypropyltriethoxysilane, and among them, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl. Epoxy group-containing alkoxysilane compounds such as trimethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, etc. Amino group-containing alkoxysilane compounds such as ureido group-containing alkoxysilane compounds, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane , Γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ
-Isocyanatopropylmethyldimethoxysilane, γ-
Isocyanato group-containing alkoxysilane compounds such as isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane are particularly preferable.

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

The resin composition of the present invention is usually prepared by subjecting the resin composition to a melt indexer (temperature = 315.5 ° C., a residence time of 5 minutes from sample introduction to start of melt extrusion gut collection,
Load 15.5 kg, orifice diameter 0.0825 inch,
It was put into a length of 0.315 inch) and extruded to obtain a gut, and the gut was treated in a gasoline model liquid (toluene: isooctane = 50: 50 volume ratio) at 60 ° C. for 72 hours to change volume resistance. Satisfies the following formula.

Y / X <1,000 (where X: volume resistance before treatment (Ω · cm) Y: volume resistance after treatment with gasoline model liquid (Ω · c)
m)) Moreover, Y / X <100 is more preferable.

The resin composition of the present invention further has a melt indexer (temperature = 315.5 ° C., a residence time of 5 minutes from the sample introduction to the start of melt extrusion gut collection, and a load of 15.5 k).
g, orifice diameter 0.0825 inch, length 0.31
(5 inches) and extruded to obtain a gut, and the gut was mixed with 60 parts in a peroxide-containing gasoline model liquid (toluene: isooctane = 50: 50 volume ratio added with 5% by weight of lauroyl peroxide). It is preferable that the volume resistance variation when treated at 72 ° C. for 72 hours satisfies the following formula.

Y ′ / X <1,000 (where X: volume resistance value before treatment (Ω · cm) Y ′: volume resistance value after treatment of peroxide-containing gasoline model liquid (Ω · cm)) Y '/ X <100 is more preferable.

The resistance fluctuation measuring method will be described in more detail. The gut extruded from the melt indexer is rapidly cooled in water. Next, to make the crystal state constant,
The gut is heat treated at 130 ° C. for 30 minutes. The diameter of the gut thus obtained is about 2 mm. Using this gut, the volume resistance value (X) before gasoline treatment is measured. Next, the gut heat-treated at 130 ° C. for 30 minutes was immersed in a gasoline model liquid or a peroxide-containing gasoline model liquid, and treated in a sealed state at 60 ° C. for 72 hours. Using this gut (peroxide-containing) gasoline treatment The subsequent volume resistance value (Y) or (Y ′) is measured.

When measuring the resistance, a conductive paste (“dotite”) is applied around the gut and the resistance value is measured using this as an electrode. The distance between the electrodes is about 5 cm, and the volume resistance value (Ω · cm) is converted using the Gut cross-sectional area and the distance between the electrodes. Since the conductive paste may dissolve in the gasoline model liquid, the measurement of the volume resistance value before and after the gasoline treatment is performed using different guts.

In order to suppress the resistance fluctuation due to the gasoline treatment (containing peroxide), it is selected from (A) polyphenylene sulfide and (C) epoxy group, acid anhydride group, carboxyl group and its salt, and carboxylic acid ester. When an elastomer containing at least one functional group and, if necessary, an elastomer containing neither (D) an epoxy group, an acid anhydride group, a carboxyl group and its salt, nor a carboxylic acid ester group are blended, The method of melt-kneading the component (D), then blending the conductive filler (B) and melt-kneading is effective. Further, after (A) polyphenylene sulfide and (B) conductive filler are melt-kneaded, (C) at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and its salt, and a carboxylic acid ester is contained. In the case of blending an elastomer which does not contain (D) an epoxy group, an acid anhydride group, a carboxyl group and its salt, or a carboxylic acid ester group, the component (D) is blended and melted. The method of kneading is also effective. In order to express particularly excellent toughness, the former method is more effective. Further, as a method of adding the conductive filler (B), it is possible to apply a master pellet made of a conductive filler and a PPS resin, which is prepared in advance.

The reason why the resistance fluctuation due to the gasoline treatment is suppressed by the above method is not clear, but it is considered that the above method influences the proper control of the dispersed state of the conductive filler. Presumed.

As the melt-kneading method, the mixture of the raw materials is fed to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixin-gall, and the mixture is heated at 280 to 380. A typical example is a method of kneading at a temperature of ° C. Further, as a method of controlling the kneading order, a method in which a part of the raw materials are mixed and then melt-kneaded by the above method, and then the remaining raw materials are mixed and melt-kneaded, or a part of the raw materials are mixed and melted by the above method Examples include a method of mixing the remaining raw materials with a side feeder during kneading. In addition, the small amount additive component may be added before kneading after kneading and pelletizing the other components by the above method or the like.

The PPS resin composition of the present invention contains a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic phosphorus compound, talc, kaolin, and an organic compound as long as the effects of the present invention are not impaired. Crystal nucleating agents such as phosphorus compounds, release agents such as polyolefin compounds, silicone compounds, long-chain aliphatic ester compounds, antioxidants, heat stabilizers, lubricants such as calcium stearate, aluminum stearate and lithium stearate. Ordinary additives such as a UV inhibitor, a colorant, a flame retardant, and a foaming agent can be added. Further, the PPS resin composition of the present invention is a polyamide, polyester, polyphenylene oxide, polysulfone, tetrafluoropolyethylene, polyethylene imide, polyamide imide, polyimide, polycarbonate, polyether, as long as the effect of the present invention is not impaired. -Tersulphone, polyetheretherketone, polythioetherketone, polyetheretherketone, epoxy resin, phenol resin, polyethylene, polystyrene, polypropylene, ABS resin, polyamide elastomer, polyester elastomer,
A resin such as polyalkylene oxide may be included.

Further, in the present invention, a filler may be blended within the range not impairing the scope of the present invention depending on the purpose and application. The shape of the filler may be fibrous or non-fibrous, and both may be used in combination. Specific examples of such fillers include glass fiber, glass milled fiber,
Carbon fiber, potassium titanate whisker, zinc oxide whisker,
Fibrous fillers such as aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, wollastonite,
Zeolite, sericite, kaolin, mica, clay,
Pyrophyllite, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, metal compounds such as iron oxide, calcium carbonate, magnesium carbonate, carbonates such as dolomite, Sulfates such as calcium sulfate and barium sulfate, magnesium hydroxide,
Calcium hydroxide, hydroxides such as aluminum hydroxide, glass beads, ceramic beads, boron nitride, non-fibrous fillers such as silicon carbide and silica, and the like.
These may be hollow, and it is also possible to use two or more kinds of these fillers in combination. In addition, using these fibrous and / or non-fibrous fillers after pretreatment 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 in the sense of obtaining better mechanical strength.

The polyphenylene sulfide resin composition of the present invention is particularly suitable for hollow moldings such as tubes and hoses in which gasoline flows, and suitable molding methods include extrusion molding and blow molding. The extrusion molding method is particularly suitable.

The hollow molded body may be not only a single layer but also a multi-layer hollow molded body.
For example, a multi-layer hollow molded article having a layer made of a polyphenylene sulfide resin composition and a layer made of a resin composition other than that can be mentioned.

Among them, a multilayer hollow molded article having an outer layer made of a resin other than the polyphenylene sulfide resin composition of the present invention and an inner layer or an intermediate layer made of the resin composition of the present invention has particularly excellent toughness. This is effective in obtaining a hollow molded article having Examples of suitable molding methods include a coextrusion molding method and a blow molding method.
The coextrusion method is particularly suitable.

Specific examples of the resin of the present invention which can be used in the outer layer in the case of such a multi-layer hollow molded article include saturated polyester resin, polysulfone resin, tetrafluoroethylene resin, polyetherimide resin, polyamideimide resin,
Polyamide resin, polyimide resin, polycarbonate resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, thermoplastic polyurethane resin, polyolefin resin, ABS resin, polyamide elastomer, polyester elastomer and the like. Among them, polyamide resin, saturated polyester resin, thermoplastic polyurethane resin, and polyolefin resin are particularly preferable. It is also possible to use a PPS resin composition outside the scope of the present invention.

Here, the polyamide resin is an amino acid,
It is a polyamide containing lactam or diamine and dicarboxylic acid as main raw materials. As typical examples of the main raw materials, amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and para-aminomethylbenzoic acid, ε-caprolactam, lactams such as ω-laurolactam, tetramethylenediamine, 2-
Methylpentamethylenediamine, hexamerenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine Amine, 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-
Aliphatic, alicyclic, aromatic diamines such as bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, and aminoethylpiperazine, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, Aliphatic, alicyclic, aromatic such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Examples thereof include dicarboxylic acids of the group, and in the present invention, polyamide homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

Particularly useful polyamide resins applicable to the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46) and polyhexamethylene sene. Bacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydodecane amide (nylon 12), polyundecane amide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide ( Nylon XD
6) and mixtures or copolymers thereof.

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 (polymer 1 g, concentrated sulfuric acid 100 ml) is 1.5.
The preferable range is from 1.0 to 7.0, particularly from 2.0 to 6.5, or the relative viscosity measured at 25 ° C. in metacresol (polymer concentration: 0.5% by weight) is 1. A polyamide resin in the range of 0 to 7.0, particularly in the range of 1.5 to 5.0 can be exemplified.

The saturated polyester resin means a polyester obtained from a dicarboxylic acid having at least 60 mol% terephthalic acid and an aliphatic diol. As dicarboxylic acids other than terephthalic acid, azelaic acid,
C2-C20 aliphatic dicarboxylic acids such as sebacic acid, adipic acid, dodecanedicarboxylic acid and isophthalic acid, aromatic dicarboxylic acids such as isophthalic acid and naphthalenedicarboxylic acid, or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid Or a mixture thereof. Examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, 1,4-cyclohexanedimethanol and hexamethylene glycol.

Examples of preferred saturated polyesters which can be used in the present invention include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, etc. Copolymerization of a dicarboxylic acid component containing polybutylene terephthalate or terephthalic acid having mechanical strength of 60 mol% or more, preferably 70 mol% or more and dodecanedicarboxylic acid and / or isophthalic acid, and a 1,4-butanediol component. Polyester is particularly preferably used.

Of these saturated polyester resins, polybutylene terephthalate (hereinafter referred to as PB) is preferably used.
The degree of polymerization of the copolyester is not particularly limited, and the relative viscosity of 0.5% orthochlorophenol solution measured at 25 ° C. is in the range of 0.5 to 2.5, particularly 0.8. Those in the range of to 2.0 are preferable. Further, polyethylene terephthalate is also not particularly limited in the degree of polymerization, and has an intrinsic viscosity of 0.54 to 1.5 in a 0.5% orthochlorophenol solution measured at 25 ° C.
Particularly, those in the range of 0.6 to 1.2 are preferable.

The thermoplastic polyurethane resin is a chain polymer composed of polyisocyanate and diol, and specific examples of the polyisocyanate include 2,4-tolylene diisocyanate, hexamethylene diisocyanate and metaxylene. Diisocyanate, and 4,4 '
-Diphenylmethane diisocyanate and the like. There are polyester type and polyether type in diol, and specific examples of the former include phthalic acid, adipic acid, dimerized linoic acid, maleic acid and other organic acids, and ethylene, propylene, butylene, diethylene and other glycols. Examples of the latter include polyoxypropylene glycol, poly (oxypropylene) poly (oxymethylene) glycol, poly (oxybutylene) glycol, and poly (oxytetramethylene) glycol. Used for.

The degree of polymerization of these thermoplastic polyurethanes is not particularly limited, but usually 220 ° C., shear rate 10 / s.
Those having a melt viscosity in ec of 1000 to 100000 poise are used.

Examples of the polyolefin resin include polyethylene, polypropylene, chlorinated polyethylene, chlorinated polypropylene, and polymethylpentene.

Further, in order to bond the outer layer and the resin composition of the present invention, it is possible to dispose a resin composition containing both the outer layer resin and PPS between both layers. Further, another resin having adhesiveness may be arranged on both the outer layer and the resin composition of the present invention, and in order to bond the layers, sandblast treatment, ultraviolet irradiation treatment, plasma discharge treatment, corona discharge treatment, etc. May be applied.

The PPS resin composition obtained according to the present invention is particularly suitable for use in the above hollow molded article, but other applications such as a sensor, an LED lamp, a connector,
Sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, Electric / electronic parts such as power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave ovens Parts, audio parts, audio equipment parts such as audio / laser disk / compact disk, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Parts; office computer-related parts, telephone-related parts, facsimile-related parts, copying machine-related parts, cleaning jig, motor parts, lighters,
Machine-related parts such as typewriters: optical devices such as microscopes, binoculars, cameras, watches, precision machine-related parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light deer, exhaust Various valves such as gas valves, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature Sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, air conditioner thermostat bases , Heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, detributor, starter switch, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, Fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulating plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, etc. Of course, it can be applied to related parts and other various uses.

[0089]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the description of these examples. [Measurement of Volume Resistance Value] The details of the measuring method are as described above. For electrical resistance measurement, Takeda Riken Industry Co., Ltd.
A TR6877 Computing Digital Multimeter manufactured by Mitsui Chemicals, Inc. was used.

[IZOD Impact Strength with Notch] An IZOD impact test piece with a mold notch was prepared by injection molding.
The measurement was performed according to the ASTM D256 method.

[Gut Surface Property] The gut surface was visually observed and judged according to the following criteria. ◯: Almost no protrusions are observed on the surface and the gloss is excellent. Δ: Almost no protrusions are observed on the surface, but the gloss is poor. X: A protrusion is clearly recognized on the surface, and the gloss is inferior.

Reference Example 1 (Polymerization of PPS Resin) Sodium sulfide nonahydrate 6.005 was added to an autoclave equipped with a stirrer.
kg (25 mol), sodium acetate 0.656 kg (8
Mol) and N-methyl-2-pyrrolidone (hereinafter NMP
Abbreviated) 5kg is charged, and gradually 20 while passing nitrogen.
The temperature was raised to 5 ° C., and 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C., 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and NMP3.
7 kg was added, the mixture was sealed under nitrogen, heated to 270 ° C., and reacted at 270 ° C. for 4.5 hours. After cooling, the reaction product was washed 5 times with warm water and dried under reduced pressure at 80 ° C. for 24 hours to obtain 2.45 kg of PPS (P-1).

Polymerization was carried out in the same manner as above, and after cooling, the reaction product was washed 5 times with warm water, then heated to 100 ° C. and put into 10 kg of NMP, and after stirring for about 1 hour, filtration was carried out. Then, it was washed several times with hot water. 90 ° C
Pour into 25 liters of pH 4 acetic acid aqueous solution heated to 1, and continue stirring for about 1 hour, then filter and wash with deionized water at about 90 ° C until the pH of the filtrate becomes 7, and then at 80 ° C.
And dried under reduced pressure for 24 hours to obtain a melt flow rate of 120 g
/ 10 minutes of PPS (PPS-2), 2.45 kg was obtained.

[Blending materials used in Examples and Comparative Examples] (B) Conductive filler B-1: carbon black (EC600JD manufactured by Ketjen Black International Co., Ltd., DBP oil absorption 495 ml / 100 g, BET surface area) 1270m
² / g, average particle diameter 30 nm, ash content 0.2% (C) Elastomer C-1 containing functional group: α-olefin and olefin-based copolymer mainly containing glycidyl ester of α, β-unsaturated acid Polymer ethylene / glycidyl methacrylate = 88/12 (wt%) copolymer C-2: maleic anhydride (0.5 wt%) graft modified ethylene-butene copolymer C-3: ethylene / glycidyl methacrylate -To (E / G
MA) = 85/15 (wt%) as the main skeleton, and acrylonitrile / styrene (AS) = 30/70 (wt%) graft-copolymerized, wherein (E / GMA) /
(AS) = 70/30 (wt%) Copolymer (D) Epoxy group, acid anhydride group, carboxyl group and salt thereof, carboxylic acid ester group-free elastomer D-1: ethylene / butene-1 = 82 / 18 (wt%)
Copolymer D-2: Ethylene / propylene copolymer (E) Alkoxysilane compound β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was used.

[Melting and kneading method] For the melting and kneading, a twin-screw extruder (30 mm) having a cylinder set temperature of 290 ° C was used. Method 1: All materials were blended in predetermined amounts, dry-blended, melt-kneaded, and pelletized with a pelletizer.
The pellets were melt-kneaded again and re-pelletized. Method 2: (A) PPS and (C) functional group-containing elastomer and (D) functional group-free elastomer were blended in a predetermined amount, dry-blended, melt-kneaded, and pelletized by a pelletizer. A predetermined amount of the conductive filler (B) was blended with the pellets, melt-kneaded, and pelletized. The pellets were melt-kneaded again and re-pelletized. Method 3: (A) PPS and (C1) epoxy group-containing elastomer were blended in a predetermined amount, dry-blended, melt-kneaded, and pelletized by a pelletizer. A predetermined amount of (C2) acid anhydride group-containing elastomer and (D) functional group-free elastomer were blended in the pellets, dry blended, melt-kneaded, and pelletized by a pelletizer. A predetermined amount of the conductive filler (B) was blended with the pellets, melt-kneaded, and pelletized. The pellets were melt-kneaded again and re-pelletized. Method 4: (A) PPS and (B) conductive filler were blended in predetermined amounts, melt-kneaded, and pelletized. A predetermined amount of (C) functional group-containing elastomer and (D) functional group-free elastomer were blended in the pellets, dry blended, melt-kneaded, and pelletized by a pelletizer. The pellets were melt-kneaded again and re-pelletized.

Examples 1 to 10 and Comparative Example 1 The materials shown in Table 1 were used and pelletized by the melt-kneading method shown in Table 1. Using this pellet, a test piece for measuring impact strength and a gut for measuring electric resistance were prepared and each characteristic was evaluated. The results are shown in Table 1.

[0097]

[Table 1]

It can be seen that the material of Comparative Example 1 is inferior in resistance stability. By changing the melt-kneading method as shown in Examples 1 and 2, the resistance fluctuation due to the gasoline model liquid treatment can be remarkably suppressed. In addition, by reducing the amount of elastomer as shown in Examples 3 to 8, the resistance fluctuation due to the peroxide-containing gasoline model substance can be further suppressed.

[Tube preparation] Nylon 11 (Toray Industries, Ltd. "Rilsan" BESNBKP20TL was used for the outer layer,
The pellet obtained in Example 5 was used for the inner layer with the intermediate adhesive layer sandwiched, and the outer diameter was 8 mm, the inner diameter was 6 mm, and the outer layer thickness was:
0.7 mm, middle layer thickness 0.1 mm, inner layer thickness: 0.2
mm 3 layer tube was molded. As a molding device, three 30 mm single-screw extruders set to a resin temperature of 210 to 290 ° C., and resins discharged from these three extruders are collected by an adapter (temperature 270 to 290 ° C.) into a tube shape. A tube comprising a die to be molded, a sizing die for cooling and controlling the size of the tube, and a take-up machine was used, and the tube was formed at a take-up speed of 50 cm / min. As a result, a flexible conductive tube having excellent inner surface smoothness was obtained. In addition, as an adhesive layer, PPS (Toray Industries, Inc. M2
588, 50 parts by weight) and nylon 12 (Toray Industries, Inc. AE)
SNOTL, 25 parts by weight) and the functional group-containing elastomer ((B1, 10 parts by weight) and (B2, 15 parts by weight)) were also mixed.

[0100]

INDUSTRIAL APPLICABILITY According to the present invention, a PPS resin composition having excellent heat resistance, gasoline resistance, permeability, toughness, conductivity, and excellent conductivity even when treated with gasoline or the like, was used. Hollow molded articles and multilayer hollow molded articles can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 23/00 C08L 33/02 33/02 33/08 33/08 63/00 A 63/00 101/02 101/02 C08J 5/00 CEZ // C08J 5/00 CEZ C08K 5/54 B

Claims (16)

[Claims] 1. From 100 parts by weight of (A) polyphenylene sulfide, 1 to 100 parts by weight of a conductive filler (B) and (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, or a carboxylic acid ester. A resin composition containing 1 to 100 parts by weight of an elastomer containing at least one selected functional group, wherein the composition is a melt indexer (temperature = 315.5 ° C, residence time 5 minutes,
Load 15.5 kg, orifice diameter 0.0825 inch,
It was put into a length of 0.315 inch) and extruded to obtain a gut, and the gut was treated in a gasoline model liquid (toluene: isooctane = 50: 50 volume ratio) at 60 ° C. for 72 hours to change volume resistance. Satisfies the following formula: 1. A polyphenylene sulfide resin composition. Y / X <1,000 (where X: volume resistance value before treatment (Ω · cm) Y: volume resistance value after gasoline model liquid treatment (Ω · c)
m)) 2. From 100 parts by weight of (A) polyphenylene sulfide, 1 to 100 parts by weight of a conductive filler (B) and (C) an epoxy group, an acid anhydride group, a carboxyl group and its salt, or a carboxylic acid ester. A resin composition containing 1 to 100 parts by weight of an elastomer containing at least one selected functional group, wherein the composition is a melt indexer (temperature = 315.5 ° C, residence time 5 minutes,
Load 15.5 kg, orifice diameter 0.0825 inch,
It is charged into a length of 0.315 inch) and extruded to obtain a gut, and the gut is a peroxide-containing gasoline model liquid (toluene: isooctane = 50: 50 volume ratio added with 5% by weight of lauroyl peroxide). In 72 at 60 ℃
The polyphenylene sulfide resin composition according to claim 1, wherein the change in volume resistance upon time treatment satisfies the following formula. Y ′ / X <1,000 (where X: volume resistance value before treatment (Ω · cm) Y ′: volume resistance value after treatment of peroxide-containing gasoline model liquid (Ω · cm)) 3. An (C) elastomer containing at least one functional group selected from epoxy groups, acid anhydride groups, carboxyl groups and salts thereof, and carboxylic acid esters is an α-olefin and an α, β-unsaturated acid. The polyphenylene sulfide resin composition according to claim 1, which is (C) an epoxy group-containing olefin-based copolymer having the glycidyl ester as a main constituent. 4. An epoxy group-containing olefin copolymer (C) comprising an α-olefin (1), a glycidyl ester of an α, β-unsaturated acid (2) and a monomer represented by the following general formula ( The polyphenylene sulfide resin composition according to claim 3, which is an olefin-based copolymer obtained by copolymerizing a monomer having 3) as an essential component. [Chemical 1] (Wherein R ¹ represents hydrogen or a lower alkyl group, X 1
Is one or more groups selected from a -COOR ² group, a -CN group or an aromatic group. R ² has 1 to 10 carbon atoms
Represents the alkyl group of 5. An elastomer containing (C) at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester is (C).
1) A polyphenylene sulfide resin composition containing at least two functional group-containing elastomers, an epoxy group-containing elastomer and a (C2) acid anhydride group-containing elastomer, the weight of (C1) and (C2) % Is (C1) :( C2) = 1 to 99:99 to 1 (total 100
% By weight). The polyphenylene sulfide resin composition according to claim 1. 6. An elastomer containing neither (D) an epoxy group, an acid anhydride group, a carboxyl group and its salt nor a carboxylic acid ester group is added to 1 to 99 parts by weight of (A) polyphenylene sulfide resin. 100 parts by weight based on 100 parts by weight of the (A) polyphenylene sulfide resin, and the total amount of the (C) component and the (D) component is 100 parts by weight.
The polyphenylene sulfide resin composition according to any one of claims 1 to 5, which is less than or equal to parts by weight. 7. An (E) alkoxysilane compound is further added,
The polyphenylene sulfide resin composition according to claim 1, which is added in an amount of 0.05 to 5 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. 8. The (A) polyphenylene sulfide resin comprises:
The polyphenylene sulfide resin composition according to any one of claims 1 to 7, which has been deionized. 9. The polyphenylene sulfide resin composition according to claim 1, wherein the conductive filler (B) is carbon black. 10. The gut volume resistance value before gasoline treatment is 1
It is less than or equal to 00 Ω · cm.
The polyphenylene sulfide resin composition according to any one of the above. 11. An elastomer containing (A) polyphenylene sulfide and (C) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and at least one functional group selected from a carboxylic acid ester, and (D) an epoxy. When blending an elastomer that does not contain any of a group, an acid anhydride group, a carboxyl group and its salt, and a carboxylic acid ester group, after melt-kneading the component (D), (B) a conductive filler is blended and melt-kneaded. The polyphenylene sulfide resin composition according to any one of claims 1 to 10. 12. After melt-kneading (A) polyphenylene sulfide and (B) conductive filler, at least one functional group selected from (C) epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester. In the case of blending an elastomer containing a group, and (D) an elastomer containing neither an epoxy group, an acid anhydride group, a carboxyl group and its salt nor a carboxylic acid ester group, the component (D) is blended and melt-kneaded. Claims 1 to 10
The polyphenylene sulfide resin composition according to any one of the above. 13. An elastomer containing (A) polyphenylene sulfide and (C) an epoxy group, an acid anhydride group, a carboxyl group and salts thereof, and at least one functional group selected from carboxylic acid esters, and (D) an epoxy. When blending an elastomer that does not contain any of a group, an acid anhydride group, a carboxyl group and its salt, and a carboxylic acid ester group, after melt-kneading the component (D), (B) a conductive filler is blended and melt-kneaded. Claim 1 by
11. A method for producing a polyphenylene sulfide resin composition, which comprises producing the polyphenylene sulfide resin composition according to any one of 10 above. 14. After melt-kneading (A) polyphenylene sulfide and (B) conductive filler, at least one function selected from (C) epoxy group, acid anhydride group, carboxyl group and salt thereof, and carboxylic acid ester. In the case of blending an elastomer containing a group, and (D) an elastomer containing neither an epoxy group, an acid anhydride group, a carboxyl group and its salt nor a carboxylic acid ester group, the component (D) is blended and melt-kneaded. Claim 1 by
10. A method for producing a polyphenylene sulfide resin composition, which comprises producing the polyphenylene sulfide resin composition according to any one of items 10 to 10. 15. A hollow molded article comprising the polyphenylene sulfide resin composition according to claim 1. 16. A multi-layer hollow molded article having a layer made of the polyphenylene sulfide resin composition according to claim 1 and a layer made of a resin composition other than that.