JPH11228827A - Polyphenylene sulfide resin composition and molded form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition (PPS resin composition) for multilayer blow-molded form, excellent in film thickness controllability, moldability, hot water resistance, hot antifreeze resistance, chemical resistance, heat resistance, surface smoothness and adhesivity, and to obtain a multilayer blow-molded form by the use of this composition. SOLUTION: This PPS resin composition is obtained by compounding (A) 100 pts.wt. of a polyphenylene sulfide resin with (B) 20-80 pts.wt. of a polyamide resin and (C) 20-80 pts.wt. of an olefin-based polymer. This composition has an MFR of <=100 g/10 min which is determined in accordance with the procedure specified in the JIS K-7210 at 315.5 deg.C under a load of 5 kg for a residence time of 5 min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyphenylene sulfide resin composition for a multilayer hollow molded article having excellent film thickness controllability, moldability, hot water resistance, heat resistant antifreeze, chemical resistance, heat resistance, surface smoothness and adhesiveness. More specifically, the present invention relates to a multilayer hollow molded article suitable for a heat medium circulation pipe such as a cooling system pipe for automobiles or a heating system for snow melting or heating, and more specifically, a polyphenylene sulfide resin composition having at least one inner layer side. The present invention relates to a multilayer hollow molded article having a nylon resin composition as at least one outer layer.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter referred to as P
Abbreviated as PS resin. ) Has excellent properties such as excellent heat resistance, hot water resistance, chemical resistance, and flame retardancy, and is suitable for engineering plastics. Therefore, various electric parts, machine parts, and automobile parts mainly for injection molding It is used for In recent years, studies have been made on hollow molding of tubes, blows, and the like.

[0003] Under such circumstances, recently, utilizing the characteristics of PPS resin, the cost is higher and the toughness is inferior to, for example, a hollow molded article of PPS resin (Japanese Patent Publication No. 6-98673) or a general-purpose engineer plastic. Because of its drawbacks, PP is used to improve the drawbacks of PPS resin.
Numerous studies have been made, such as compounding S resins with nylon resins and elastomers. For example, there is a composition comprising a PPS resin and a nylon 66 resin, an epoxy copolymer and an ethylene copolymer (JP-A-3-37263).

However, the use of a single-layer hollow molded article of a PPS resin composition containing glass fibers is expensive, is not economical, and has insufficient surface smoothness, so its application is limited. Further, for the purpose of improving the above-mentioned drawbacks, multilayer hollow molded articles using a PPS resin composition on the inner layer side and a nylon resin composition on the outer layer side have been studied. Since the melt viscosity is too low, PP
It is difficult to control the film thickness of the S-resin composition, the film is liable to be cut, or the surface is apt to have irregularities, sufficient surface smoothness cannot be obtained, the molding condition width is narrow, and there are restrictions on the extrusion molding model. A problem arose. In particular, the film thickness of the exchange part when obtaining a multilayer hollow molded body by blow molding cannot be controlled, and the characteristics cannot be said to be sufficient as a multilayer hollow molded body such as a cooling pipe for an automobile. It turned out to be inapplicable.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a multilayer hollow molded article having a polyphenylene sulfide resin composition having at least one inner layer and a nylon resin composition having at least one outer layer. In particular, it has been achieved as a result of examining the problem of improving the controllability of the film thickness of the exchange part when obtaining a multilayer hollow molded article by blow molding. That is, the present invention provides a PPS resin composition for a multilayer hollow molded article excellent in film thickness controllability, moldability, hot water resistance, heat resistance antifreeze property, chemical resistance, heat resistance, surface smoothness, adhesiveness and the like, and a cooling system for automobiles. The present invention relates to a multilayer hollow molded article having at least one inner layer side of a polyphenylene sulfide resin composition for a heat medium circulation pipe such as a pipe or a snow melting or heating system for heating, and at least one outer layer side of a nylon resin composition. .

[0006]

That is, the present invention provides:
(1) 100 parts by weight of (A) polyphenylene sulfide resin, (B) 20 to 80 parts by weight of polyamide resin,
(C) A polyphenylene sulfide resin composition comprising 20 to 80 parts by weight of an olefin polymer, the composition being subjected to a method of JIS K7210 under the conditions of a temperature of 315.5 ° C., a load of 5 kg, and a residence time of 5 minutes. A polyphenylene sulfide resin composition having an MFR of 100 (g / 10 minutes) or less, (2) (A) a polyphenylene sulfide resin in which the polyphenylene sulfide resin has a linear structure and / or a polyphenylene sulfide resin having a branched structure (3) The polyphenylene sulfide resin composition according to (1) or (2), wherein the polyamide resin has a relative viscosity of at least 2.4. ) (C) at least one of the olefin polymers is (C1) an epoxy group,
(5) The polyphenylene sulfide resin composition according to the above (1) to (3), which is an olefin polymer containing at least one functional group selected from an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester. (C1) an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof,
The polyphenylene sulfide resin composition according to the above (4), wherein the olefin polymer containing at least one functional group selected from carboxylic acid esters is an olefin copolymer containing an epoxy group, and (6) the polyphenylene sulfide resin is The polyphenylene sulfide resin composition according to any one of the above (1) to (5), which is for hollow molding.
(7) The polyphenylene sulfide resin composition according to the above (6), wherein the polyphenylene sulfide resin is for multi-layer hollow molding, and (8) the polyphenylene sulfide resin composition is produced using the polyphenylene sulfide resin composition according to any one of the above (1) to (5). (9) at least one layer is formed of the above-mentioned (1) to
(5) The multilayer hollow molded article comprising the polyphenylene sulfide resin composition according to any one of (10), (10) above,
(5) a multilayer hollow molded article, characterized in that the polyphenylene sulfide resin composition according to any one of the above is at least one layer on the inner layer side, and (D) the thermoplastic resin or the thermoplastic resin composition is at least one layer on the outer layer side. (11)
(D) The multilayer hollow molded article according to the above (10), wherein the thermoplastic resin or the thermoplastic resin composition is a nylon resin or a nylon resin composition obtained by mixing 0 to 100 parts by weight of a filler with respect to 100 parts by weight of the nylon resin. (12) The multilayer hollow molded article according to any one of the above (8) to (11), wherein the multilayer hollow molded article is a part for water supply, and (13) an engine cooling system pipe for an automobile. Alternatively, the multi-layer hollow molded article for water circulation according to the above (12), which is a heat medium circulation pipe for a heating system for snow melting or heating.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula (I),

Embedded image From the viewpoint of heat resistance, it is preferably a polymer containing at least 70 mol%, more preferably at least 90 mol%, of a polymer containing a repeating unit represented by the above structural formula. In the PPS resin, less than about 30 mol% of the repeating unit may be composed of a repeating unit having the following structure.

[0008]

Embedded image

[0009] The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
2,000 Pa · s (320 ° C, shear rate 1000s
ec ^-1 ), preferably 10 to 200 Pa · s.

The PPS resin is a polymer having a relatively small molecular weight obtained by a generally known method, that is, a production method typified by JP-B-45-3368.
An essentially linear, relatively high molecular weight polymer obtained by the production method represented by JP-A-2240
No. 332, a method for obtaining a polymer having a relatively large molecular weight, and under a oxygen atmosphere described in JP-B-57-334, or without a crosslinking step of adding a crosslinking agent such as peroxide and heating. It can be produced by a method for obtaining a polymer having a branched structure.

In the present invention, the PPS obtained as described above is used.
The resin may be used after cross-linking / high molecular weight by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, and washing with an organic solvent, hot water, acid aqueous solution, etc. It is possible. When washing with an organic solvent, the organic solvent to be used is not particularly limited as long as it does not have an action of decomposing PPS. For example, N-methylpyrrolidone, dimethylformaldehyde, dimethylacetamide, 1,3-dimethylimidazolidinone , Hexamethylphosphoramide, nitrogen-containing polar solvents such as piperazinones, dimethyl sulfoxide, dimethyl sulfone, sulfoxide-sulfone solvents such as sulfolane, acetone,
Ketone solvents such as methyl ethyl ketone, diethyl ketone and acetophenone; ether solvents such as dimethyl ether, dipropyl ether, dioxane and tetrahydrofuran; chloroform, methylene chloride, trichloroethylene, ethylene chloride, perchlorethylene, monochloroethane; Halogen solvents such as dichloroethane, tetrachloroethane, perchloroethane, and chlorobenzene, methanol, ethanol, propanol, and butanol
Alcohols such as phenol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol and polypropylene glycol.
Phenol solvents and aromatic hydrocarbon solvents such as benzene, toluene and xylene. The washing temperature is not particularly limited, and is usually selected from a room temperature to about 300 ° C. When washing with an acid aqueous solution, the acid to be used is not particularly limited as long as it does not have an action of decomposing PPS, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. It is also possible to use the product after performing various treatments such as activation with a compound containing a functional group such as an acid anhydride group, an epoxy group and an isocyanate group.

In the present invention, it is possible to use a PPS resin obtained by any method. However, it is possible to use a PPS having a linear structure with the nylon resin composition on the outer layer side, adhesiveness, heat-resistant antifreeze solution, It is preferable from the viewpoint of obtaining chemical properties and surface smoothness. Further, in order to control the film thickness of the exchange part, it is more preferable to use a PPS having a linear structure and a PPS having a branched structure in combination.

The term "PPS having a branched structure" as used herein refers to a branched structure obtained by copolymerizing 1,2,4-trichlorobenzene with a repeating unit represented by the above structural formula (I) as a main structural unit. It has. Among them, the copolymerization amount of 1,2,4-trichlorobenzene is 0.01 to
Those having 3 mol% are preferred. In the PPS having a linear structure, the main structural unit is mainly composed of a repeating unit represented by the above structural formula (I).

The polyamide resin (B) used in the present invention is a polyamide (nylon) mainly composed of units formed from amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the monomer capable of forming the main component include 6-aminocaproic acid,
11-aminoundecanoic acid, 12-aminododecanoic acid,
Amino acids such as paraaminomethylbenzoic acid, lactams such as ε-aminocaprolactam, 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-
Such as trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine Aliphatic, cycloaliphatic, aromatic diamines, and adipic, spearic, azelaic, sebacic, dodecandioic, terephthalic,
Aliphatic, alicyclic and aromatic dicarboxylic acids such as isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid and hexahydroisophthalic acid In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, particularly useful polyamide resins (nylon resins) are polycaproamide (nylon 6) and polyhexamethylene adipamide (nylon 6).
6), polydodecaneamide (nylon 12), polyundecaneamide (nylon 11), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612) , Polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide /
Polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T /
6I), polyxylylene adipamide (nylon XD6)
And mixtures or copolymers thereof.

Particularly preferred examples include nylon 6, nylon 66, nylon 12, nylon 11, and the like.

The degree of polymerization of these nylon resins is not particularly limited, and the relative viscosity is 1.5 to 7.0 (1 g of the polymer is dissolved in 100 ml of 98% concentrated sulfuric acid and measured at 25 ° C. according to JIS K6810). , Especially 2.4 to 6.5
And more preferably in the range of 4.0 to 6.0 for obtaining the film thickness controllability.

In the present invention, it is preferable to mix a nylon resin with the PPS resin composition on the inner layer side of the multilayer molded hollow body in order to obtain adhesiveness with the nylon resin composition on the outer layer side of the multilayer molded hollow body. If the nylon resin is not blended with the PPS resin composition on the inner layer side of the multilayer molded hollow body, it will not adhere at all to the nylon resin composition on the outer layer side of the multilayer molded hollow body, so the heat resistance antifreeze property, chemical resistance, etc. are insufficient. This is not applicable.

The blending amount of the above (B) nylon resin is determined based on (A) 100 parts by weight of the PPS resin from the viewpoints of adhesiveness to the nylon resin composition on the outer layer side, heat and antifreeze properties, and chemical resistance. A range of 20 to 80 parts by weight is selected, preferably a range of 40 to 60 parts by weight. 20 blended amounts
If the amount is less than 10 parts by weight, the adhesiveness of the nylon resin on the outer layer side is insufficient, which is not preferable. If the amount exceeds 80 parts by weight, the heat-resistant antifreeze solution and the chemical resistance are insufficient, which is not preferable.

The olefin polymer (C) used in the present invention may be any of an unmodified olefin polymer and a modified olefin polymer, among which an unmodified olefin elastomer, an unmodified diene elastomer, Modified olefin-based elastomers can be mentioned. In addition,
The elastomer in the present invention has a glass transition temperature of-
Polymers having a temperature of 20 ° C. or lower are exemplified.

In the present invention, one or more olefin polymers can be used.

Suitable unmodified olefin polymers include ethylene, propylene, butene-1 and pentene-
Α- such as 1,4-methylpentene-1 and isobutylene
Olefins, 1,4-hexadiene dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5-
Examples thereof include polyolefins obtained by radical polymerization of at least one non-conjugated diene such as (1-probenyl) -2-norbornene.

A suitable unmodified diene-based elastomer is an AB-type or ABA'-type block copolymer elastic material composed of a vinyl-type aromatic hydrocarbon and a conjugated diene. And A ′ may be the same or different, and include a thermoplastic homopolymer or copolymer derived from a vinyl aromatic hydrocarbon in which the aromatic portion may be monocyclic or polycyclic. Examples of the aromatic hydrocarbon include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene,
And vinyl naphthalene and mixtures thereof. The intermediate polymerization block B is made of a conjugated diene hydrocarbon, and examples thereof include 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, and a polymer derived from a mixture thereof. The elastic block copolymer used in the present invention includes those obtained by subjecting the intermediate polymer block B of the above block copolymer to a hydrogenation treatment.

Preferred specific examples of the unmodified elastomer include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / ethyl acrylate copolymer,
Ethylene / methyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-
Ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated polybutadiene, unhydrogenated or hydrogenated styrene / isoprene / styrene triblock copolymer, unhydrogenated or hydrogenated styrene / butadiene / styrene triblock copolymer And the like.

Particularly preferred are ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / ethyl acrylate copolymer, and ethylene / propylene copolymer.
Examples include a methyl acrylate copolymer and an ethylene / butyl acrylate copolymer.

As the modified elastomer, a monomer component having at least one functional group such as a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid metal base, a carboxylic acid anhydride group, and an imide group in the unmodified elastomer is used. (Hereinafter, abbreviated as a functional group-containing component).

Examples of the functional group-containing component include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid,
Mesaconic acid, citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride , Itaconic anhydride, citraconic anhydride, endobicyclo-
(2,2,1) -5-heptene-2,3-dicarboxylic acid,
Endobicyclo- (2,2,1) -5-heptene-2,3
-Dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate,
Glycidyl ethacrylate, glycidyl itaconate, glycidyl citracone and the like.

The method for introducing these functional group-containing components is not particularly limited, and a method such as copolymerization or graft introduction to an unmodified elastomer using a radical initiator can be used. The amount of the functional group-containing component to be introduced is suitably in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on the entire modified elastomer.

Specific examples of the modified elastomer particularly useful in the present invention include ethylene / acrylic acid copolymer and ethylene / acrylic acid copolymer.
Methacrylic acid copolymers and those in which some or all of the carboxylic acid moieties in these copolymers are salts with sodium, lithium, potassium, zinc, calcium, ethylene / methyl acrylate copolymer, ethylene / acrylic acid Ethyl copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer,
(“G” represents a graft, the same applies hereinafter), ethylene /
Methyl methacrylate-g-maleic anhydride copolymer, ethylene / ethyl acrylate-g-maleimide copolymer,
Ethylene / ethyl acrylate-g-N-phenylmaleimide copolymers and partially saponified products of these copolymers, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / Glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer, ethylene / glycidyl ether copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene- 1-g-maleic anhydride copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer, ethylene / propylene Len / 2,5-norbornadiene-g-maleic anhydride copolymer, ethylene / propylene-g-N-phenylmaleimide copolymer, ethylene / butene-1-g-N-phenylmaleimide copolymer, hydrogenated styrene / Butadiene / styrene-g-maleic anhydride copolymer, hydrogenated styrene / isoprene / styrene-g-
Maleic anhydride copolymer, ethylene / propylene-g-
Glycidyl methacrylate copolymer, ethylene / butene
1-g-glycidyl methacrylate copolymer, ethylene /
Propylene / 1,4-hexadiene-g-glycidyl methacrylate copolymer, ethylene / propylene / dicyclopentadiene-g-glycidyl methacrylate copolymer,
Examples include hydrogenated styrene / butadiene / styrene-g-glycidyl methacrylate copolymer.

Particularly preferred are ethylene / ethyl acrylate-g-maleic anhydride copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / butene-1- g-maleic anhydride copolymer and the like.

Particularly, the combined use of the ethylene / butene-1 copolymer and the ethylene / glycidyl methacrylate copolymer is more preferable in terms of obtaining moldability, surface smoothness, toughness, and compatibility between the PPS resin and the nylon resin. .

The compounding amount of the olefin polymer (C) is determined based on 100 parts by weight of the (A) PPS resin in view of moldability, surface smoothness, toughness, and compatibility of the PPS resin and the nylon resin. A range of 20 to 80 parts by weight is selected, preferably a range of 40 to 60 parts by weight. If the amount is less than 20 parts by weight, the melt viscosity, moldability and toughness are insufficient, which is not preferable. If it exceeds 80 parts by weight, the adhesiveness to the outer layer side nylon resin is insufficient, which is not preferable.

Further, a filler may be added to the PPS resin composition of the present invention depending on the purpose and application within a range not to impair the effects of the present invention. It may be fibrous. Specific examples of such a fibrous and / or non-fibrous filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, Fibrous fillers such as ceramic fibers, asbestos fibers, masonry fibers, metal fibers, silicates such as walasteinite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, and 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; sulfates such as calcium sulfate and barium sulfate; magnesium hydroxide; calcium hydroxide Umm,
Non-fibrous fillers such as hydroxides such as aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, carbon black, metal powders and silica, which may be hollow, Two or more of these fillers can 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.

Further, the PPS resin composition of the present invention includes:
Coupling agents such as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, epoxy compounds, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds , Nucleating agents such as talc, kaolin, organic phosphorus compounds, polyetheretherketone, anti-coloring agents such as hypophosphite, antioxidants, heat stabilizers, lubricants, UV inhibitors, coloring agents, flame retardants,
Conventional additives such as a foaming agent can be added.

The PPS resin composition of the present invention further includes a polysulfone resin, a polyethylene tetrafluoride resin, a polyetherimide resin, a polyamideimide resin, a polyimide resin, a polyethersulfone resin, as long as the effects of the present invention are not impaired. Other resins such as polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, thermoplastic polyurethane resin, ABS resin, polyamide elastomer, polyester elastomer, epoxy resin, and phenol resin may be added and blended.

In the present invention, the PP constituting the composition
The MFR of the S resin composition is 100 (g / 10 minutes) or less, preferably in the range of 0.5 to 50 (g / 10 minutes), more preferably 1 to 30 (g / 10 minutes). Is in the range, the film thickness controllability at the time of molding the multilayer molded hollow body using the nylon resin composition on the outer layer side and the PPS resin composition on the inner layer side, particularly, the multilayer hollow molded body is obtained by blow molding. It is preferable to obtain the film thickness controllability of the exchange part at the time. When the MFR of the PPS resin composition constituting the composition exceeds 100 (g / 10 minutes), the multilayer moldability and the controllability of the film thickness of the PPS resin composition are insufficient, which is not preferable. The MF of the PPS resin composition
R is measured by the method of JIS K7210 under the conditions of a temperature of 315.5 ° C., a load of 5 kg, and a residence time of 5 minutes.

Furthermore, in order to obtain an MFR of 100 (g / 10 min) or less of the PPS resin composition constituting the composition of the present invention, (A) PPS having a linear structure is selected as the PPS resin. More preferably, PPS having a branched structure is used in combination with PPS having a linear structure. (B)
The polyamide resin preferably has a higher relative viscosity.

The method for preparing the resin composition used in the present invention is not particularly limited, but the mixture of the raw materials is usually prepared by using a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixin gall. 280 to 3
A method of kneading at a temperature of 80 ° C. can be given as an example. Also, there is no particular limitation on the mixing order of the raw materials,
A method in which all the raw materials are blended and then melt-kneaded by the above method, a method in which some raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded. Any method may be used, such as a method of mixing the remaining raw materials using a side feeder during melt-kneading with a twin-screw or twin-screw extruder. Further, as for the small amount of the additive component, it is of course possible to knead the other component by the above-mentioned method and the like to form a pellet, and then add it before molding to provide for molding.

The composition of the present invention is particularly suitable for producing hollow molded articles such as blow molded articles and tube molded articles.
When applied to the production of multi-layer hollow molded products by co-extrusion with other resins, especially nylon resins and saturated polyester resins, it improves hot water resistance, heat freezing resistance, chemical resistance, heat resistance, moldability, surface smoothness, and adhesion. It is effective for

Since the required properties of the hollow molded article of the present invention vary depending on the purpose and application, a single-layer hollow molded article or a multilayer hollow molded article can be selected. Heat-resistant antifreeze,
From the viewpoint of obtaining heat resistance and thermal rigidity, a multilayer hollow molded body is more preferable.

With respect to the materials used for the multilayer hollow molded article of the present invention, the PPS resin composition 2 of the present invention having a different composition is used.
A multilayer hollow molded article may be formed by using more than one kind. In addition, a thermoplastic resin or a thermoplastic resin composition other than the PPS resin composition of the present invention [(D) a thermoplastic resin or a thermoplastic resin is used as a material other than the layer composed of the PPS resin composition of the present invention. Shown as a composition. ] To form a multilayer hollow molded article. It is preferable to use a PPS resin composition for the inner layer side and a thermoplastic resin composition different from the PPS resin composition for the outer layer side, from the viewpoints of economy, heat-resistant antifreeze, heat resistance, and thermal rigidity.

The thermoplastic resin (D) or the thermoplastic resin composition used in the present invention is not particularly limited as long as the composition contains the thermoplastic resin or the thermoplastic resin. Examples of the thermoplastic resin (D) include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, nylon resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, modified polyphenylene ether resin, polysulfone resin, and polyallyl. Sulfone resin, polyketone resin, polyetherimide resin, polyarylate resin, polyphenylene sulfide resin, liquid crystal polymer, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyimide resin, polyamideimide Resin, polyethylene tetrafluoride resin, thermoplastic polyurethane resin, polyamide elastomer, polyester elastomer, etc. . Preferably,
Nylon resin is exemplified. Particularly, nylon 6, nylon 66, nylon 12, and nylon 11 are preferable.

Other thermoplastic resins (D) include unmodified elastomers and modified elastomers.

Suitable unmodified elastomers include ethylene / propylene copolymers, ethylene / butene-1 copolymers, ethylene / ethyl acrylate copolymers, and ethylene / propylene copolymers.
Methyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated polybutadiene, Examples include unhydrogenated or hydrogenated styrene / isoprene / styrene triblock copolymer, and unhydrogenated or hydrogenated styrene / butadiene / styrene triblock copolymer.

Preferred modified elastomers include ethylene / acrylic acid copolymers, ethylene / methacrylic acid copolymers, and carboxylic acid moieties in these copolymers which are partially or entirely sodium, lithium, potassium, zinc,
As a salt with calcium, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer,
Ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer, ethylene / methyl methacrylate-g-maleic anhydride copolymer, ethylene /
Ethyl acrylate-g-maleimide copolymer, ethylene / ethyl acrylate-g-N-phenylmaleimide copolymer and partially saponified products of these copolymers,
Glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer, ethylene / Glycidyl ether copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-maleic anhydride copolymer, ethylene / propylene / 1,4-hexadiene-g
-Maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g- Maleic anhydride copolymer, ethylene / propylene / 2,5-norbornadiene-g-
Maleic anhydride copolymer, ethylene / propylene-g-
N-phenylmaleimide copolymer, ethylene / butene-
1-g-N-phenylmaleimide copolymer, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymer, hydrogenated styrene / isoprene / styrene-g-maleic anhydride copolymer, ethylene / propylene- g-glycidyl methacrylate copolymer, ethylene / butene-1-g
-Glycidyl methacrylate copolymer, ethylene / propylene / 1,4-hexadiene-g-glycidyl methacrylate copolymer, ethylene / propylene / dicyclopentadiene-g-glycidyl methacrylate copolymer, hydrogenated styrene / butadiene / Styrene-g-glycidyl methacrylate copolymer and the like.

When such an unmodified elastomer and / or a modified elastomer is used, it is preferable to use it in combination with another thermoplastic resin. Examples of other thermoplastic resins that can be preferably used in combination therewith include nylon resins.

When these unmodified elastomers and / or modified elastomers and other thermoplastic resins are used in combination, the mixing ratio is based on the total amount of unmodified elastomers and / or modified elastomers and other thermoplastic resins. It is preferably in the range of 0 to 99% by weight of the modified elastomer and 100 to 1% by weight of the other thermoplastic resin.

Further, the thermoplastic resin composition (D) may contain a filler according to the purpose and application as long as the effects of the present invention are not impaired. The filler may be fibrous or non-fibrous. Either may be used. Specific examples of such a fibrous and / or non-fibrous filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, Fibrous fillers such as ceramic fibers, asbestos fibers, masonry fibers, metal fibers, silicates such as walasteinite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, and 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; sulfates such as calcium sulfate and barium sulfate; magnesium hydroxide; calcium hydroxide Umm,
Non-fibrous fillers such as hydroxides such as aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, carbon black, metal powders and silica, which may be hollow, Two or more of these fillers can 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.

The filler is preferably used in an amount of 0 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin.

A particularly preferred thermoplastic resin or thermoplastic resin composition (D) is a nylon resin or a nylon resin composition in which 0 to 100 parts by weight of a filler is blended with 100 parts by weight of a nylon resin.

Further, the thermoplastic resin composition (D) includes:
Coupling agents such as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, epoxy compounds, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds , Nucleating agents such as talc, kaolin, organic phosphorus compounds, polyetheretherketone, anti-coloring agents such as hypophosphite, antioxidants, heat stabilizers, lubricants, UV inhibitors, coloring agents, flame retardants,
Conventional additives such as a foaming agent can be added.

The thermoplastic resin composition (D) may contain an epoxy resin or an epoxy resin as long as the effects of the present invention are not impaired.
Other resins such as a phenol resin may be added and blended.

As a method for producing a multilayer hollow molded article in the present invention, a common coextrusion method can be employed. For example, a two-layer hollow molded article in which the inner layer is formed of a PPS resin composition and the outer layer is formed of a nylon resin composition In the case of the above, the PPS resin composition and the nylon resin composition are separately supplied to two extruders, and the separately extruded flows of these two types of molten resins are pressure-supplied into a common die. After each of the annular flows, they are joined in a die, and the PPS resin composition is placed on the inner layer side.
A two-layer hollow molded body can be obtained by forming a nylon resin composition on the outer layer side and then co-extrusion outside the die and performing a generally known tube molding method, blow molding method or the like. In the case of a three-layer hollow molded body, three extruders are used to form three layers by the same method as described above, or two extruders are used to form a two-layer, three-layer hollow molded body. It is also possible to get

The thus obtained hollow molded article of the present invention is excellent in hot water resistance, heat resistant antifreeze, chemical resistance, heat resistance, moldability, surface smoothness and adhesiveness. Blow molded products such as ducts, pipes,
As an extruded product such as a tube or a fuel tube, the present invention is particularly effective for a water supply part, particularly a heat medium circulation pipe such as a cooling system pipe for automobiles or a heating system for snow melting or heating.

The term “water in the vicinity of water” in the present invention means a concept including not only pure water but also a mixture containing water and other compounds, such as an aqueous solution mainly composed of water and ethylene glycol.

In the present invention, the present invention is not limited to the above-described hollow molding method, but may be applied to other molding methods such as a round bar, an injection molding method, a transfer molding method, and a welding method. , Connectors, coils, and other electrical and electronic parts, as well as sensors, LE
D, lamp socket, resistor, relay case, small switch, coil bobbin, condenser, variable condenser case,
Optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, Other electronic components such as parabolic antennas and computer-related components; generators, motors, transformers, current transformers,
Voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, other pole rods, electrical component applications such as electrical component cabinets, VTR components, TV components, irons, hair dryers, rice cookers Home and office electrical product parts such as parts, microwave 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 .; office Computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts,
Machine-related parts such as cleaning jigs, motor parts, lighters, and typewriters; optical equipment such as microscopes, binoculars, cameras, watches, etc., and precision machine-related parts;
Alternator terminal, alternator connector, I
C Regulator case, potentiometer base for light deer, various valves such as exhaust gas valve, 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 sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts,
Distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation board, step motor rotor, lamp socket, Lamp reflector,
The present invention can be applied to various applications such as a lamp housing, a brake piston, a solenoid bobbin, an engine oil filter, and an automobile / vehicle-related part such as an ignition device case.

[0057]

The present invention will be described in more detail with reference to the following examples.

The film thickness controllability, adhesiveness and antifreeze resistance described in Examples and Comparative Examples were determined according to the following methods.

The PPS resin composition and the nylon resin composition are each melt-kneaded inside the extruder by the above-described tube and blow molding method, supplied to the co-extrusion die, and melted in a multilayer at the joint in the co-extrusion die. They are joined and co-extruded from the die face at the tip as a multilayer hollow molded article or multilayer parison. This is blown into the blow mold with air,
A two-layer pipe having a length of 40 mm, a length of 300 mm and a thickness of 3 mm was formed. The evaluation of the obtained two-layer pipe was measured according to the following method.

[Thickness Controllability] When the molding temperature of the PPS resin composition is in the range of 280 to 300 ° C. and the molding temperature of the nylon resin composition is in the range of 230 to 290 ° C., the thickness of the PPS resin composition on the inner layer side is controlled. Is controlled to 0.5 (mm) to form a two-layer pipe, and the PPS resin composition on the inner layer side of the obtained two-layer pipe has a thickness of 0.5 to 0.1 mm.
で き る, 0.7 ~
Those that can be controlled within the range of 1.0 (mm)
Despite controlling the thickness of the PPS resin composition on the inner layer side to be 0.5 (mm), 1.0 (m)
Those exceeding m) were marked as x.

[Adhesiveness] The two-layer pipe obtained by the above method was cut into strips, and the PPS resin composition layer and the nylon resin composition layer at the ends of the strips were peeled off. , Tensile speed: 10 mm / min, test piece shape: 1 mm under conditions of 5 mm width × 100 mm length
80 degree peel strength (kg / 10mm) was measured, and
(Kg / 10mm) or more, ○, 1.0 (kg / 10m
Less than m) was rated x.

[Antifreeze solution resistance] A 50% ethylene glycol aqueous solution was sealed in a two-layer pipe obtained by the above method having a length of 30 cm, sealed, treated at a temperature of 130 ° C for 1000 hours, and a test piece was prepared from the pipe. , Tensile strength, and tensile elongation were measured, and the respective retentions were calculated by comparing with those of the untreated ones.

Reference Example 1 (Production of PPS) Production of PPS-1 Sodium sulfide nonahydrate was placed in an autoclave equipped with a stirrer.
005kg (25mol), sodium acetate 0.205k
g (2.5 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were gradually charged to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled off. Next, the reaction vessel was cooled to 180 ° C., and 3.719 kg (25.3 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added thereto.
After heating to 270 ° C, the reaction was carried out at 270 ° C for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water,
After drying under reduced pressure for 2 hours, 2.45 kg of PPS-1 was obtained.

Production of PPS-2 Polymerization was carried out in the same manner as above, and the reaction product was washed 5 times with warm water, then heated to 100 ° C. and charged into 10 kg of NMP, and stirred for about 1 hour. And then washed several times with boiling water. This was poured into 25 liters of an aqueous acetic acid solution of pH 4 heated to 90 ° C., and after stirring for about 1 hour, filtered, washed with ion-exchanged water at about 90 ° C. until the filtration pH reached 7, Dry under reduced pressure at 80 ° C for 24 hours
PS-2 was obtained. The number average molecular weight of this PPS is 920
0, the total ash content was 0.07% by weight.

Preparation of PPS-3 Sodium sulfide nonahydrate in an autoclave equipped with a stirrer.
005kg (25mol), sodium acetate 0.205k
g (2.5 mol) and NMP (5 kg) were charged, the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C.,
3.719 kg (25.3 mol) of 4-dichlorobenzene, 0.002 kg of 1,2,4-trichlorobenzene
(0.015 mol) and 3.7 kg of NMP were added, 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 5 times with warm water, and dried under reduced pressure at 80 ° C. for 24 hours to form PPS-3.
2.45 kg was obtained.

[Compounding Materials Used in Examples and Comparative Examples] (A) PPS resin PPS-4: PPS-2 / PPS-3 = 1/3 blend (B) Nylon resin Nylon-1: Nylon 6 (relative viscosity Nylon-2: Nylon 6 (Relative viscosity = 2.7) Nylon-3: Nylon 6 (Relative viscosity = 4.4) Nylon-4: Nylon 6 (Relative viscosity = 6.3) Nylon-5 : Nylon 66 (relative viscosity = 2.6) (C) Olefin polymer Olefin-1: Ethylene / glycidyl methacrylate = 88/12 (wt%) copolymer (Sumitomo Chemical Industries: B
FE) / ethylene / butene-1 = 82/18 (% by weight) copolymer (manufactured by Mitsui Chemicals: Tuffmer A4085) = 1
/ 4 blend olefin-2: ethylene / glycidyl methacrylate = 88/12 (wt%) copolymer (manufactured by Sumitomo Chemical Co., Ltd .: B
FE) / ethylene / butene-1 = 82/18 (% by weight) copolymer (manufactured by Mitsui Chemicals: Tuffmer A4085) = 1
/ 1 blend Examples 1 to 8 PPS resin, nylon resin and olefin polymer were dry-blended at the ratios shown in Table 1 and then melt-kneaded by a screw type extruder set at 320 ° C. and pelletized, and then PPS. A resin composition was obtained. After drying the obtained pellets, a two-layer pipe was formed by using a blow molding machine using the pellets of the nylon resin composition blended with the pellets in the ratio shown in Table 1, and the film thickness controllability, adhesiveness and resistance were improved. Antifreeze properties were measured. Table 1 shows the results.

The resin composition and the molded article obtained here are excellent in film thickness controllability, adhesiveness and antifreeze resistance,
It is suitable as a material for automotive cooling system pipes.

Comparative Example 1 Dry blending, melt kneading, pelletizing, molding and evaluation were performed in the same manner as in Example 1 at the ratios shown in Table 2. Table 2 shows the results.

The PFR resin composition has an MFR of 100 (g / g).
10 minutes), the film thickness cannot be controlled.
It was not a practical level.

Comparative Example 2 Dry blending, melt kneading, pelletizing, molding and evaluation were performed in the same manner as in Example 1 at the ratios shown in Table 2. Table 2 shows the results.

The relative viscosity of the polyamide resin is less than 2.4,
When the MFR of the composition exceeded 100 (g / 10 minutes), the film thickness could not be controlled and was not at a practical level.

Comparative Example 3 In the same manner as in Example 1, dry blending, melt kneading, pelletizing, molding, and evaluation were performed at the ratios shown in Table 2. Table 2 shows the results.

When the blending amount of the nylon resin was less than 20 parts by weight, no adhesion occurred at all and was not at a practical level.

Comparative Example 4 In the same manner as in Example 1, dry blending, melt kneading, pelletizing, molding, and evaluation were performed at the ratios shown in Table 2. Table 2 shows the results.

If the amount of the olefin polymer is less than 20 parts by weight, the film thickness cannot be controlled and the antifreeze resistance is low, which is not a practical level.

Comparative Example 5 Dry blending, melt kneading, pelletizing, molding and evaluation were performed in the same manner as in Example 1 at the ratios shown in Table 2. Table 2 shows the results.

When the amount of the nylon resin exceeds 80 parts by weight, the film thickness cannot be controlled, and the antifreeze resistance is low, which is not practical.

Comparative Example 6 Dry blending, melt kneading, pelletizing, molding and evaluation were performed in the same manner as in Example 1 at the ratios shown in Table 2. Table 2 shows the results.

When the amount of the olefin polymer was more than 80 parts by weight, no adhesion was observed, and it was not at a practical level.

[0080]

[Table 1]

[Table 2]

[0081]

Industrial Applicability The PPS resin composition and the multilayer hollow molded article of the present invention are excellent in film thickness controllability, adhesiveness, antifreeze resistance and the like, and particularly, a cooling pipe for automobiles or a heating system for snow melting or heating. It is particularly useful for heat medium circulation pipes and the like.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI F16L 11/04 F16L 11/04 // (C08L 81/02 77:00 23:00) B29K 77:00 81:00 B29L 23:00

Claims (13)

[Claims] 1. A polyphenylene sulfide resin (A)
A polyphenylene sulfide resin composition comprising (B) 20 to 80 parts by weight of a polyamide resin and (C) 20 to 80 parts by weight of an olefin polymer. A polyphenylene sulfide resin composition having an MFR of 100 (g / 10 minutes) or less measured by the method of JIS K7210 under the conditions of 5 ° C., a load of 5 kg, and a residence time of 5 minutes. 2. The polyphenylene sulfide resin having a linear structure (A) and / or a polyphenylene sulfide resin having a linear structure.
2. The polyphenylene sulfide resin composition according to claim 1, which is a polyphenylene sulfide resin having a branched structure. 3. The polyamide resin (B) has a relative viscosity of 2.4.
The polyphenylene sulfide resin composition according to claim 1 or 2, which is the above. (4) at least one of the olefin polymers (C)
The polyphenylene sulfide according to claim 1, wherein the species is (C1) an olefin polymer 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. Resin composition. 5. An olefin polymer 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. The polyphenylene sulfide resin composition according to claim 4, which is a polymer. 6. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin is for hollow molding. 7. The polyphenylene sulfide resin composition according to claim 6, wherein the polyphenylene sulfide resin is for multilayer hollow molding. 8. A hollow molded article produced by using the polyphenylene sulfide resin composition according to claim 1. 9. A multilayer hollow molded article comprising at least one layer comprising the polyphenylene sulfide resin composition according to claim 1. 10. A polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein at least one layer on the inner layer side is provided, and (D) a thermoplastic resin or a thermoplastic resin composition is provided on at least one layer on the outer layer side. Multi-layer hollow molded article. 11. A thermoplastic resin or a thermoplastic resin composition containing (D) 100 parts by weight of a nylon resin and fillers of 0 to 10 parts by weight.
The multilayer hollow molded article according to claim 10, which is a nylon resin or a nylon resin composition containing 100 parts by weight. 12. The multilayer hollow molded article according to claim 8, wherein the multilayer hollow molded article is a part for water circulation. 13. The multilayer hollow molded article according to claim 12, wherein the water-supplying part is an engine cooling pipe for an automobile or a heat medium circulation pipe for a snow melting or heating system for heating.