阅读说明：本技术 聚芳硫醚树脂组合物和其成形体、聚芳硫醚树脂组合物的制造方法以及成形体的制造方法 (Polyarylene sulfide resin composition and molded article thereof, method for producing polyarylene sulfide resin composition, and method for producing molded article ) 是由 西田卓哉 于 2020-02-20 设计创作，主要内容包括：提供：成为冷热冲击性优异的成形体、以及熔接部的机械强度和TD方向上的弯曲韧性优异的成形体的原料的聚芳硫醚树脂组合物和该聚芳硫醚树脂组合物的成形体、该聚芳硫醚树脂组合物的制造方法以及该成形体的制造方法。进而详细地,提供：聚芳硫醚树脂组合物和成形品以及其制造方法,所述聚芳硫醚树脂组合物含有：聚芳硫醚树脂(A)、烯烃系聚合物(B)、沸石(C)、玻璃纤维(D1)和玻璃鳞片(D2),玻璃鳞片(D2)的重均粒径为100μm以下的范围。(Providing: a polyarylene sulfide resin composition which is a raw material for a molded article having excellent cold and heat shock properties and a molded article having excellent mechanical strength of a weld and excellent bending toughness in the TD direction, a molded article of the polyarylene sulfide resin composition, a method for producing the polyarylene sulfide resin composition, and a method for producing the molded article. Further specifically, provided are: a polyarylene sulfide resin composition containing: polyarylene sulfide resin (A), olefin polymer (B), zeolite (C), glass fiber (D1), and glass flake (D2), wherein the weight average particle diameter of the glass flake (D2) is in the range of 100 [ mu ] m or less.)

1. A polyarylene sulfide resin composition, characterized by comprising: a polyarylene sulfide resin (A), an olefin polymer (B), zeolite (C), glass fibers (D1), and glass flakes (D2), wherein the weight-average particle diameter of the glass flakes (D2) is in the range of 100 [ mu ] m or less.

2. The polyarylene sulfide resin composition according to claim 1, wherein the content of the zeolite (C) is in a range of 20 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide resin (A).

3. The polyarylene sulfide resin composition according to claim 1 or 2, wherein the olefin-based resin (B) comprises a copolymer of an olefin, an alkyl acrylate, and a glycidyl acrylate.

4. The polyarylene sulfide resin composition according to any one of claims 1 to 3, which is a melt-kneaded product.

5. The polyarylene sulfide resin composition according to any one of claims 1 to 4, which is in the form of pellets.

6. A molded article obtained by molding the polyarylene sulfide resin composition according to any one of claims 1 to 5.

7. A method for producing a polyarylene sulfide resin composition, comprising the steps of: the polyarylene sulfide resin (A), the olefin polymer (B), the zeolite (C), the glass fiber (D1), and the glass flake (D2) are melt-kneaded at a temperature not lower than the melting point of the polyarylene sulfide resin (A), and the weight-average particle diameter of the glass flake (D2) is in the range of not more than 100 [ mu ] m.

8. A method for producing a molded body, comprising the steps of: a step of producing a polyarylene sulfide resin composition by the production method according to claim 7; and a step of melt-molding the polyarylene sulfide resin composition obtained.

Technical Field

The present invention relates to: a polyarylene sulfide resin-containing resin composition (hereinafter referred to as polyarylene sulfide resin composition), a molded article obtained by molding the polyarylene sulfide resin composition, a method for producing the polyarylene sulfide resin composition, and a method for producing the molded article.

Background

Polyarylene sulfide (hereinafter, also referred to as "PAS") resins represented by polyphenylene sulfide (hereinafter, also referred to as "PPS") resins are known as engineering plastics exhibiting excellent heat resistance while maintaining a melting point of 270 ℃ or higher. However, it is known that toughness is generally inferior to other engineering plastics, and there is room for improvement in molding flowability, cold and hot impact properties, and the like in consideration of the end product use and the shape thereof.

For example, patent document 1 below describes a technique for improving low gas properties at the time of injection molding, the cold heat property of a molded article, and the like, by using a resin composition containing: the polyphenylene sulfide resin, the glass flake as the inorganic filler, the inorganic filler other than the glass flake, and the olefin polymer are added in such a manner that the amount of the glass flake and the inorganic filler other than the glass flake is within a constant range.

Patent document 2 below describes a technique for improving toughness, adhesive strength, dimensional accuracy, and molding processability of a molded article with a resin composition containing: polyarylene sulfide, maleic anhydride-containing olefin copolymer, alkoxysilane coupling agent, glass flake, and glass fiber.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2002-129014

Patent document 2: japanese patent laid-open publication No. 2010-13515

Disclosure of Invention

Problems to be solved by the invention

However, in recent years, in various technical fields, the component structure is complicated, and the cold and heat shock properties required for a molded article of a resin composition are increasing, and the conventional structural techniques including the techniques described in the above patent documents are becoming unable to meet the market requirements. In particular, when a molded body is molded by injection molding or the like, breakage of a material at a welded portion which is the weakest part in structure is often a problem, and in order to improve this, it is necessary to improve the mechanical strength of the welded portion of the molded body. Further, it is necessary to prevent deterioration of bending toughness in the TD direction of the molded article, which is caused by anisotropy at the time of molding. In the present invention, the "TD Direction" refers to a Direction (Transverse Direction) perpendicular to the "MD Direction (Machine Direction)" which is the resin flow Direction during molding.

The present invention has been made in view of the above circumstances, and an object thereof is to provide: a polyarylene sulfide resin composition which is a raw material for a molded article having excellent mechanical strength of a weld and excellent bending toughness in the TD direction, a molded article of the polyarylene sulfide resin composition, a method for producing the polyarylene sulfide resin composition, and a method for producing the molded article. In addition, there is provided: a polyarylene sulfide resin composition which is a raw material for a molded article having excellent cold and heat shock properties, a molded article of the polyarylene sulfide resin composition, a method for producing the polyarylene sulfide resin composition, and a method for producing the molded article.

Means for solving the problems

The present inventors have focused attention on crystallization behavior of a molten PAS resin during molding to solve the above problems, and as a result, have found that: the present inventors have found that the mechanical strength of a weld of a molded article can be significantly improved by adding a predetermined amount of zeolite as a crystal nucleating agent of a PAS resin to a polyarylene sulfide resin composition, and further that: the present inventors have found that the bending toughness in the TD direction can be improved by making the particle size of the glass flakes to be blended small, and the thermal shock resistance of the molded article can be improved, and have completed the present invention.

That is, the present invention relates to a polyarylene sulfide resin composition containing: a polyarylene sulfide resin (A), an olefin polymer (B), zeolite (C), glass fibers (D1), and glass flakes (D2), wherein the weight average particle diameter of the glass flakes (D2) is 30 to 100 [ mu ] m.

The present invention also relates to a molded article obtained by molding the polyarylene sulfide resin composition according to any of the above.

The present invention also relates to a method for producing a polyarylene sulfide resin composition, comprising the steps of: the polyarylene sulfide resin (A), the olefin polymer (B), the zeolite (C), the glass fiber (D1), and the glass flake (D2) are melt-kneaded at a temperature not lower than the melting point of the polyarylene sulfide resin (A), and the weight-average particle diameter of the glass flake (D2) is 30 to 100 [ mu ] m.

Further, the present invention relates to a method for producing a molded body, comprising the steps of: a step of producing a polyarylene sulfide resin composition by the production method; and a step of melt-molding the polyarylene sulfide resin composition thus obtained.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: a polyarylene sulfide resin composition which is a raw material for a molded article having excellent mechanical strength of a weld and excellent bending toughness in the TD direction, a molded article of the polyarylene sulfide resin composition, a method for producing the polyarylene sulfide resin composition, and a method for producing the molded article. Further, according to the present invention, there can be provided: a polyarylene sulfide resin composition which is a raw material for a molded article having excellent cold and heat shock properties, a molded article of the polyarylene sulfide resin composition, a method for producing the polyarylene sulfide resin composition, and a method for producing the molded article.

Drawings

FIG. 1 is a schematic view of a rectangular parallelepiped SUS steel material used in the method for evaluating thermal shock resistance in examples.

Detailed Description

The polyarylene sulfide resin composition of the present invention contains: PAS resin (A), olefin polymer (B), zeolite (C), glass fiber (D1) and glass flake (D2). Hereinafter, each configuration will be described.

The polyarylene sulfide resin composition of the present invention contains a PAS resin (a) as an essential component. The PAS resin (A) used in the present invention has a resin structure having a structure in which an aromatic ring is bonded to a sulfur atom as a repeating unit, specifically, a resin having a structural site represented by the following general formula (1) and, if necessary, a 3-functional structural site represented by the following general formula (2) as repeating units,

(in the formula, R¹And R²Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group. )

The 3-functional structural site represented by the formula (2) is preferably in the range of 0.001 to 3 mol%, particularly preferably in the range of 0.01 to 1 mol%, based on the total mole number with respect to other structural sites.

Here, with respect to the structural site represented by the general formula (1), R in the formula is R in the PAS resin (A) from the viewpoint of mechanical strength¹And R²Particularly, a hydrogen atom is preferable, and in this case, a para-type bond represented by the following formula (3) and a meta-type bond represented by the following formula (4) are mentioned.

Among these, in terms of heat resistance and crystallinity of the PAS resin (a), the bond of the sulfur atom in the repeating unit to the aromatic ring is particularly preferably a structure bonded at the para position as shown in the general formula (3).

Further, the PAS resin (A) may contain not only the structural sites represented by the general formulae (1) and (2) but also the structural sites represented by the following structural formulae (5) to (8) in an amount of 30 mol% or less of the total of the structural sites represented by the general formulae (1) and (2),

in the present invention, it is particularly preferable that the structural sites represented by the general formulae (5) to (8) are 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the PAS resin (A). When the PAS resin (a) contains the structural sites represented by the general formulae (5) to (8), the bonding system may be any of a random copolymer and a block copolymer.

The PAS resin (a) may have a naphthalene thioether bond or the like in its molecular structure, and is preferably 3 mol% or less, particularly preferably 1 mol% or less, based on the total mole number with respect to other structural sites.

The production method of the PAS resin (a) is not particularly limited, and examples thereof include the following methods: (preparation method 1) a method of polymerizing a dihalo-aromatic compound by adding a polyhaloaromatic compound and/or other copolymerizable components as needed in the presence of sulfur and sodium carbonate; (preparation method 2) a method of polymerizing a dihalo-aromatic compound by adding a polyhaloaromatic compound and/or other copolymerizable components as necessary in a polar solvent in the presence of a thioether reagent or the like; (preparation method 3) a method of self-condensing p-chlorothiophenol by adding other copolymerization components as required; (preparation method 4) A method of melt-polymerizing a diiodo aromatic compound and elemental sulfur in the presence of a polymerization inhibitor optionally having a functional group such as a carboxyl group or an amino group, while reducing the pressure. Of these methods, the method of (preparation method 2) is general and preferred. In the reaction, an alkali metal salt or an alkali metal hydroxide of a carboxylic acid or a sulfonic acid may be added to adjust the degree of polymerization. Among the above (production method 2), those obtained by the following method are particularly preferred: a method for producing a PAS, which comprises introducing a water-containing thioether agent into a heated mixture comprising an organic polar solvent and a dihalo-aromatic compound at a rate allowing water to be removed from the reaction mixture, adding a polyhaloaromatic compound to the organic polar solvent if necessary, reacting the dihalo-aromatic compound with the thioether agent, and controlling the water content in the reaction system to be in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent (see Japanese patent application laid-open No. H07-228699); a method of adding a dihalo-aromatic compound and, if necessary, a polyhaloaromatic compound and/or other copolymerizable components to a solid alkali metal sulfide and an aprotic polar organic solvent in the presence of a sulfur source, and reacting the dihalo-aromatic compound and the polyhaloaromatic compound while controlling the amount of the alkali metal sulfide and the organic acid alkali metal salt to be in the range of 0.01 to 0.9 mol relative to the sulfur source and the amount of water in the reaction system to be in the range of 0.02 mol or less relative to 1 mol of the aprotic polar organic solvent (see WO2010/058713 pamphlet). Specific examples of the dihalogenated aromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2, 5-dihalotoluene, 1, 4-dihalonaphthalene, 1-methoxy-2, 5-dihalobenzene, 4 '-dihalobiphenyl, 3, 5-dihalobenzoic acid, 2, 4-dihalobenzoic acid, 2, 5-dihalonitrobenzene, 2, 4-dihaloanisole, p' -dihalodiphenyl ether, 4 '-dihalobenzophenone, 4' -dihalodiphenylsulfone, 4 '-dihalodiphenylsulfoxide, 4' -dihalodiphenylsulfide, and compounds having an alkyl group having 1 to 18 carbon atoms in the aromatic ring of each of the above-mentioned compounds, examples of the polyhalogenated aromatic compound include 1,2, 3-trihalobenzene, 1,2, 4-trihalobenzene, 1,3, 5-trihalobenzene, 1,2,3, 5-tetrahalobenzene, 1,2,4, 5-tetrahalobenzene, 1,4, 6-trihalonaphthalene and the like. The halogen atom contained in each of the compounds is preferably a chlorine atom or a bromine atom.

The post-treatment method of the reaction mixture containing the PAS resin obtained in the polymerization step is not particularly limited, and examples thereof include the following methods: (post-treatment 1) after completion of the polymerization reaction, a method comprising distilling the reaction mixture to remove the solvent, or adding an acid or an alkali thereto, and distilling the solvent under reduced pressure or normal pressure, washing the solid obtained after the solvent distillation with a solvent such as water, a reaction solvent (or an organic solvent having a solubility equivalent to that of a low-molecular polymer), acetone, methyl ethyl ketone, or alcohols 1 or 2 or more times, and further neutralizing, washing with water, filtering, and drying; or (post-treatment 2) a method comprising adding a solvent (a solvent which is soluble in the polymerization solvent used and is a poor solvent for at least PAS) such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, etc. as a settling agent to the reaction mixture after the completion of the polymerization reaction, settling the solid product such as PAS and inorganic salts, filtering, washing, and drying the solid product; or (post-treatment 3) a method comprising adding a reaction solvent (or an organic solvent having a solubility equivalent to that of the low-molecular polymer) to the reaction mixture after completion of the polymerization reaction, stirring the mixture, filtering the mixture to remove the low-molecular polymer, washing the mixture with a solvent such as water, acetone, methyl ethyl ketone or alcohols 1 or 2 times or more, and then neutralizing the mixture, washing the washed mixture with water, filtering the washed mixture, and drying the washed mixture; (post-treatment 4) a method comprising adding water to the reaction mixture after completion of the polymerization reaction, washing with water, filtering, adding an acid when washing with water as required, carrying out an acid treatment, and drying; (post-treatment 5) after completion of the polymerization reaction, the reaction mixture is filtered, washed with the reaction solvent 1 or 2 times or more as necessary, and further washed with water, filtered and dried.

In the post-treatment methods exemplified in the above (post-treatment 1) to (post-treatment 5), the drying of the PAS resin (a) may be performed in vacuum, or may be performed in an inert gas atmosphere such as air or nitrogen.

The polyarylene sulfide resin composition of the present invention contains an olefin polymer (B) as an essential component. Examples of the raw materials for the olefin-based polymer (B) include: a polymer obtained by polymerizing an α -olefin such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, isobutylene or 2 or more kinds thereof alone, or a copolymer of the α -olefin with an α, β -unsaturated acid such as (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, or butyl (meth) acrylate, or an alkyl ester thereof. In the present invention, the term (meth) acrylic acid means acrylic acid and/or methacrylic acid.

The olefin-based polymer (B) is preferably used as a raw material, from the viewpoint of improving compatibility with other components in the polyarylene sulfide resin composition. This improves the cold and heat shock properties of the molded article. Examples of the functional group include an epoxy group, a carboxyl group, an isocyanate group, an oxazoline group, and a functional group represented by the formula: r (CO) O (CO) -or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms). The olefin polymer having the functional group can be obtained, for example, by copolymerization of an α -olefin and a vinyl polymerizable compound having the functional group. The vinyl polymerizable compound having the functional group includes, in addition to the α, β -unsaturated acid and its alkyl ester, maleic acid, fumaric acid, itaconic acid, an α, β -unsaturated dicarboxylic acid having 4 to 10 carbon atoms thereof, other derivatives (monoester or diester, anhydride thereof, and the like), glycidyl (meth) acrylate, and the like. Among the olefin-based polymers, the olefin-based polymer (B) preferably has a structure selected from the group consisting of an epoxy group, a carboxyl group, and a formula: r (CO) O (CO) -or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms), and the olefin resin is particularly preferably a copolymer comprising an olefin, an alkyl acrylate and a glycidyl acrylate.

The lower limit of the range of the content of the olefin polymer (B) in the polyarylene sulfide resin composition of the present invention is preferably 5 parts by mass, more preferably 7 parts by mass, assuming that the total amount of the PAS resin (a) is 100 parts by mass. On the other hand, the upper limit of the range of the content is preferably 15 parts by mass, more preferably 13 parts by mass. By setting the content of the olefin-based polymer (B) within the above range, the molding flowability and the cold-heat shock property of the molded article can be improved in a well-balanced manner.

The polyarylene sulfide resin composition of the present invention contains zeolite (C) as an essential component. As the raw material of the zeolite (C) used in the present invention, any known material to those skilled in the art can be used as long as it is a crystalline aluminosilicate, and examples thereof include known materials represented by the following general formula.

x(M^I ₂，M^II)O·Al₂O₃·nSiO₂·mH₂O

Here, M^IA metal having a valence of 1, for example, an alkali metal such as Li, Na or K, or ammonium, alkylammonium, pyridinium, anilinium ion or hydrogen ion, M^IIRepresents a 2-valent metal, for example, an alkaline earth metal such as Ca, Mg, Ba, Sr, etc. From the viewpoint of effectively adjusting the melt crystallization temperature, M is preferred^IIIs Ca, M^IIs substantially absent.

As the zeolite (C) used in the present invention, any natural or synthetic zeolite can be used. Examples of the natural zeolite include borolite, clinoptilolite, natrolite, mesolite, thomson zeolite, chrysotile, scolecite, barite, clinoptilolite, laumontite, mordenite, thogawaralite, erionite, offretite, heulandite, clinoptilolite, stilbite, epistilbite, phillipsite, gmelinite, chabazite, and faujasite. Examples of the synthetic zeolite include a-type, X-type, Y-type, L-type, mordenite, chabazite, etc., preferably a-type zeolite, and more preferably, among them, one containing calcium as a metal atom, particularly preferably one containing calcium as a metal atom, and substantially no alkali metal. Among the above zeolites, synthetic zeolites are preferably used. As the synthetic zeolite, commercially available products can be used, and examples thereof include A-type zeolite A-4 powder, A-type zeolite A-5 powder (both trade marks, manufactured by Tosoh corporation), CS-100K, CS-100S (both trade marks, manufactured by Toyota chemical Co., Ltd.), AMT-25 (both trade marks, manufactured by Mizukalizzer chemical Co., Ltd.), and Mizukalizer ES (both trade marks, manufactured by Mizu chemical Co., Ltd.).

From the viewpoint of increasing the melt crystallization temperature of the resin composition, the zeolite (C) is preferably in the form of powder particles, and the upper limit of the range of the average particle diameter is preferably 3 μm, and particularly preferably 2 μm. Here, the average particle diameter is a value (D50) determined by the coulter counter method. The lower limit of the range of the average particle diameter of the zeolite (C) is preferably 0.1. mu.m. By appropriately raising the melt crystallization temperature of the resin composition, solidification by resin crystals in the mold at the time of injection molding becomes faster, and the molding cycle can be shortened.

In the polyarylene sulfide resin composition of the present invention, zeolite (C) acts as a crystal nucleating agent when the molten PAS resin (a) is crystallized, and is greatly advantageous in improving the mechanical strength of the weld of the molded article. In order to optimize the crystallization rate of the PAS resin (a) and improve the mechanical strength of the weld zone of the molded article, the upper limit of the range of the content of the zeolite (C) in the polyarylene sulfide resin composition of the present invention is preferably 20 parts by mass, more preferably 15 parts by mass, even more preferably 10 parts by mass, and most preferably 7 parts by mass, when the total amount of the PAS resin (a) is 100 parts by mass. In order to effectively function as a crystal nucleating agent for the PAS resin (a), the lower limit of the content range is preferably set to a range of 1 part by mass.

The polyarylene sulfide resin composition of the present invention contains glass fibers (D1) as an essential component. As a raw material of the glass fiber (D1) used in the present invention, those known to those skilled in the art can be used, and the fiber diameter, the fiber length, the aspect ratio, and the like thereof can be adjusted as appropriate depending on the use of the molded article and the like. In order to improve the dispersibility in the PAS resin (a), for example, the glass fibers (D1) may be subjected to a surface treatment with a known coupling agent, a known binder, or the like. The lower limit of the range of the content of the glass fiber (D1) in the polyarylene sulfide resin composition of the present invention is preferably 32 parts by mass, and more preferably 48 parts by mass, assuming that the total amount of the PAS resin (a) is 100 parts by mass. On the other hand, the upper limit of the range of the content is preferably 120 parts by mass, more preferably 100 parts by mass. By setting the content of the glass fiber (D1) within the above range, the molding flowability and the mechanical strength of the molded article can be improved in a well-balanced manner.

The polyarylene sulfide resin composition of the present invention contains glass flake (D2) as an essential component. The weight average particle diameter of the glass flake (D2) is preferably in the range of 100 μm or less, more preferably in the range of 30 μm to 100 μm. In the present invention, glass flakes having a weight average particle diameter of preferably 100 μm or less, more preferably 30 μm or more and 100 μm or less are used as a raw material. The weight average particle diameter of glass flakes circulating in the market is generally much more than 100 μm. The polyarylene sulfide resin composition of the present invention is preferably obtained by blending glass flakes having a weight average particle diameter of preferably 100 μm or less, more preferably 30 to 100 μm, in addition to the PAS resin (a), the olefin polymer (B), the zeolite (C), and the glass fibers (D1), because the fusion-bonded portion of a molded article obtained by using the composition as a raw material has excellent mechanical strength and bending toughness in the TD direction. The method for measuring the weight average particle diameter of the glass flake (D2) is as follows.

The weight average particle diameter of the glass flake (D2) is not the value of the glass flake raw material itself but the value of the polyarylene sulfide resin composition which is a raw material of the molded body and may have a shape such as a pellet shape or a strand shape. The glass flake (D2) can be used as a glass flake adjusted so that the weight average particle diameter of the polyarylene sulfide resin composition before compounding is within a range of preferably 100 μm or less, more preferably 30 μm or more and 100 μm or less. In addition, the weight average particle size may be adjusted so that the weight average particle size in the final polyarylene sulfide resin composition is preferably in the range of 100 μm or less, more preferably in the range of 30 μm to 100 μm by being larger than 100 μm in the pre-compounding stage and being pulverized at the time of compounding.

The lower limit of the range of the content of the glass flake (D2) in the polyarylene sulfide resin composition of the present invention is preferably 4 parts by mass, more preferably 6 parts by mass, assuming that the total amount of the PAS resin (a) is 100 parts by mass. On the other hand, the upper limit of the range of the content is preferably 70 parts by mass, more preferably 50 parts by mass. By setting the content of the glass flake (D2) within the above range, the molding flowability and the amount of reduction in warpage of the molded article can be improved in a well-balanced manner.

In the polyarylene sulfide resin composition of the present invention, the mass ratio ((D1)/(D2)) of the glass fibers (D1) to the glass flakes (D2) is preferably 8 or less, more preferably 5 or less, and still more preferably 2 or less. By setting the range of (D1)/(D2) to the above range, the reduction in the mechanical strength and warpage of the weld of the molded article can be improved in a well-balanced manner. (D1) The lower limit of the range of/(D2) is not particularly limited, and may be, for example, 1 or more.

Further, the polyarylene sulfide resin composition of the present invention may further contain, in addition to the above components, according to the use: other synthetic resins than the PAS resin (a) and the olefin-based polymer (B), for example, epoxy resin, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polyvinylidene fluoride resin, polystyrene resin, ABS resin, phenol resin, polyurethane resin, liquid crystal polymer, and the like (hereinafter, simply referred to as synthetic resin) are used as an arbitrary component. In the present invention, the synthetic resin is not an essential component, and when it is compounded, the compounding ratio is not particularly limited as long as the effect of the present invention is not impaired, and is different depending on the purpose, and cannot be generally limited, and as the ratio of the synthetic resin compounded in the polyarylene sulfide resin composition of the present invention, for example, a range of preferably 5 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 15 parts by mass or less with respect to 100 parts by mass of the PAS resin (a), in other words, a range of preferably (100/115) or more, more preferably (100/110) or more with respect to the total amount of the PAS resin (a) and the synthetic resin can be cited.

The polyarylene sulfide resin composition of the present invention may further contain, as optional components, known and commonly used additives such as a colorant, an antistatic agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant aid, a rust inhibitor, and a coupling agent, if necessary. These additives are not essential components, but in the case of blending, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and is different depending on the purpose, and cannot be generally limited, and for example, may be appropriately adjusted and used in accordance with the purpose and use so as not to impair the effect of the present invention with respect to 100 parts by mass of the PAS resin (a), preferably in the range of 0.01 to 1000 parts by mass.

The method for producing a polyarylene sulfide resin composition of the present invention comprises the steps of: the polyarylene sulfide resin (a), the olefin polymer (B), the zeolite (C), the glass fiber (D1), and the glass flake (D2) are each essentially composed of a raw material, and other optional raw materials are blended as necessary, and melt-kneaded at a temperature equal to or higher than the melting point of the PAS resin.

The preferred method for producing the polyarylene sulfide resin composition of the present invention can be produced through the following steps: the raw materials of the essential components and the raw materials of the optional components are put in various forms such as powder, pellet, and chip into a ribbon mixer, henschel mixer, V-type blender, etc. and dry-blended, and then put into a known melt-kneading machine such as a banbury mixer, a mixing roll, a single-screw or twin-screw extruder, and a kneader, and melt-kneaded at a temperature in a range where the resin temperature is not less than the melting point of the PAS resin, preferably not less than the melting point +10 ℃, more preferably not less than the melting point +10 ℃ and not less than the melting point +100 ℃, and further preferably not less than the melting point +20 and not more than the melting point +50 ℃.

The melt kneading machine is preferably a twin-screw kneading extruder from the viewpoint of dispersibility and productivity, and for example, the melt kneading is preferably carried out while appropriately adjusting the discharge amount of the resin component to a range of 5 to 500 (kg/hour) and the screw rotation speed to a range of 50 to 500(rpm), and further preferably carried out under the condition that the ratio (discharge amount/screw rotation speed) thereof is in a range of 0.02 to 5 (kg/hour/rpm). In addition, when a filler or an additive is added to the above components, it is preferable to feed the components into the twin-screw kneading extruder from a side feeder of the extruder from the viewpoint of dispersibility. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin input portion to the side feeder to the total screw length of the twin-screw kneading extruder is in the range of 0.1 or more, more preferably in the range of 0.3 or more, and preferably in the range of 0.9 or less, more preferably in the range of 0.3 or less. Therefore, the range of 0.1 to 0.9 is preferable. Among them, the range of 0.3 to 0.7 is particularly preferable.

As described above, the following method can be mentioned as a method for optimizing the weight average particle diameter of the glass flake (D2). Examples thereof include: a step of molding a melt-kneaded product (polyarylene sulfide resin composition) into a pellet shape or the like by introducing glass flakes from a top feeder of the melt kneader together with the PAS resin (a) other than the glass fibers (D1), the olefin polymer (B), and the zeolite (C) and kneading the mixture; and a method of charging the polyarylene sulfide resin composition into the extruder from a side feeder, kneading the mixture, and molding the molten and kneaded product (polyarylene sulfide resin composition) into a pellet shape.

In addition, there can be mentioned: a method of treating the glass flakes while adjusting shearing of the glass flakes in melt kneading (melt mixing). Examples of the method for treating the glass flakes under conditions that are not easily sheared include the following methods: the method includes a step of mixing and/or kneading using a full-flight type single screw, a single screw having a mixing mechanism such as a dullmadge type, a Maddock type, or a pin type as a screw form, and a method using only this step is preferable. In this case, a single screw having a compression ratio of 2 or less is preferably used, a single screw having a compression ratio of 2 or less and 1 or more is more preferably used, and a fully-threaded single screw having a compression ratio of 2 or less is particularly preferably used. On the other hand, as conditions under which the glass flakes are easily sheared, for example, the following methods can be mentioned: comprises a step of kneading the mixture using a forward (conveying-ability) kneading screw, a reverse (recovery-ability) kneading screw, or the like as a screw form. In this case, the lower limit of the angle of any kneading disk is preferably 30 degrees or more, more preferably 45 degrees or more. On the other hand, the upper limit value is preferably 90 degrees or less. In the case where the weight average particle diameter of the glass flakes in the polyarylene sulfide resin composition is adjusted by the above-mentioned treatment method so that the weight average particle diameter of the glass flakes in the polyarylene sulfide resin composition falls within the above-mentioned range, it is preferable to use a condition under which the glass flakes are easily sheared when the glass flakes of the raw material tend to be larger than the weight average particle diameter, and it is preferable to use a condition under which the glass flakes are not easily sheared when the glass flakes of the raw material tend to fall within the above-mentioned range.

The effective length (L/D) is not particularly limited as long as it is a value used in molding a general polyarylene sulfide resin, and is, for example, preferably in the range of 1 or more, more preferably in the range of 5 or more, preferably in the range of 100 or less, and more preferably in the range of 50 or less. Thus, the range of 1 to 100 is preferable, and the range of 5 to 50 is more preferable.

The polyarylene sulfide resin composition of the present invention obtained by melt-kneading in this manner is a melt-kneaded product (melt mixture) containing the essential components, optional components added as needed, and their source components, and is preferably processed into a form of pellets, chips, granules, powder, etc. by a known method after the melt-kneading, and then predried at a temperature of 100 to 150 ℃ as needed, and subjected to various molding.

The polyarylene sulfide resin composition of the present invention produced by the above production method is in the form of: the PAS resin (a) is used as a matrix, and the olefin polymer (B), the glass fiber (D1), and the glass flake (D2) are dispersed therein. Therefore, the polyarylene sulfide resin composition is excellent in molding flowability and cold and heat shock properties of a molded article. Further, the presence of the zeolite (C) makes it possible to optimize the crystallization behavior when the PAS resin (a) is crystallized, and as a result, the mechanical strength of the welded portion of the molded article is greatly improved.

The molded article of the present invention is obtained by molding the polyarylene sulfide resin composition. The method for producing a molded article of the present invention includes, for example: and a step of melt-molding the polyarylene sulfide resin composition. The melt molding may be a known method, and various molding methods such as injection molding, compression molding, extrusion molding of a composite, a sheet, a tube, and the like, drawing molding, blow molding, transfer molding, and the like can be applied, and injection molding is particularly suitable. When melt molding is performed, various molding conditions are not particularly limited, and molding can be performed by a general method. For example, the method may include the following steps: after the step of melting the polyarylene sulfide resin composition in a melt molding machine in a temperature range in which the resin temperature is not less than the melting point of the polyarylene sulfide resin, preferably not less than +10 ℃ of the melting point, more preferably not less than +10 ℃ and not more than +100 ℃ of the melting point, and further preferably not less than +20 ℃ and not more than +50 ℃, various types of molding are performed, for example, injection molding can be performed by injecting the polyarylene sulfide resin composition into a mold through a resin discharge port and molding the composition. In this case, the mold temperature is preferably in a known temperature range, for example, in a range of room temperature (23 ℃) or higher, more preferably in a range of 40 ℃ or higher, further preferably in a range of 120 ℃ or higher, and further preferably in a range of 300 ℃ or lower, more preferably in a range of 200 ℃ or lower, and most preferably in a temperature range of 180 ℃ or lower. The pressure maintaining step in the mold requires a time for completing the gate sealing by the curing of the resin. The pressure holding time is not generally determined because it is affected by the size, shape, etc. of the molded article, but it is preferable to set the temperature range described above because the temperature range is set to a temperature range that is faster, the molding cycle can be shortened, and the crystallization of the resin sufficiently progresses, whereby the physical properties as the molded article can be expressed.

In addition, in melt molding, for example, the melt mixing can be performed under the condition that the breakage of the glass flakes by shearing when the resin is melted is suppressed, and the glass flakes in the molded body can be maintained in the range of the weight average particle size of the glass flakes in the polyarylene sulfide resin composition.

As examples of main applications of the molded article of the present invention, the following may be used: electric/electronic parts represented by housings of various electronic devices such as home electric appliances, mobile phones, and pcs (personal computers), protection/support members for box-type electric/electronic part integrated modules, a plurality of individual semiconductors or components, sensors, LED lamps, connectors, sockets, resistors, relay boxes, switches, bobbins, capacitors, variable capacitor housings, optical pickups, vibrators, various terminal plates, transformers, pistons, printed circuit boards, tuners, speakers, microphones, headphones, small-sized engines, magnetic head sockets, power components, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD racks, engine brush holders, parabolic antennas, computer-related parts, and the like; home and office electric appliance parts typified by VTR parts, television parts, irons, hair dryers, electric rice cooker parts, induction cooker parts, audio/video equipment parts such as audio equipment, laser disks, optical disks, DVD disks, and blu-ray disks, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and bathroom equipment parts such as water heaters, hot water amounts in bathtubs, and temperature sensors; machine-related parts typified by office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, engine parts, lighters, typewriters, and the like: optical devices and precision machine-related parts typified by microscopes, telescopes, cameras, clocks, and the like; for housing terminals of an alternator, connectors of the alternator, brush holders, slip rings, IC regulators, effect meter bases for a dimmer, relay parts, inhibitor switches, exhaust gas valves, various valves such as fuel-related/exhaust/intake pipes, air intake nozzle snorkels, intake manifolds, fuel pumps, engine cooling water connectors, carburetor bodies, carburetor pads, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crank position sensors, air flow meters, brake pad wear sensors, thermostat bases for an air conditioner, hot air flow control valves, brush holders for a radiator engine, water pump impellers, turbofan fans, related parts of the scraper engine, distributors, bobbin starter switches, ignition coils, and the like, An engine insulator, an engine rotor, an engine core, a starter relay, a transmission wiring, a window washer nozzle, an air conditioner panel switch substrate, a fuel-related solenoid valve coil, a fuse connector, a horn terminal, an electric component insulating plate, a step engine rotor, a lamp socket, a lamp reflector, a lamp housing, a brake cylinder piston, an electromagnetic coil, an engine oil filter, an ignition device housing, a power module, an inverter, a power device, an intelligent power module, an insulated gate bipolar transistor, a power control unit, a reactor, a converter, a capacitor, an insulator, an engine terminal block, a battery, an electric compressor, a battery current sensor, a junction block, a housing that houses a DLI system ignition coil, and the like, and other various uses.

Examples

The present invention will be described in further detail below with reference to specific examples. The parts and% are by mass unless otherwise specified.

(measurement of melt viscosity of PPS resin)

Using a rheometer of the Koka type (Shimadzu Corp., CFT-500D), the load was measured at 300 ℃ under a load: 1.96X 10⁶The PPS resins produced in the following production examples were held at Pa and L/D of 10(mm)/1(mm) for 6 minutes, and then the melt viscosity was measured.

(production example)

Production of PPS resin

[ Process 1]

A150-liter autoclave equipped with a stirring blade and connected to a pressure gauge, a thermometer, a condenser, a decanter, and a rectifying column was charged with 33.075 parts by mass (225 parts by mol) of p-dichlorobenzene (hereinafter, abbreviated as "p-DCB"), 3.420 parts by mass (34.5 parts by mol) of NMP, 27.300 parts by mass (230 parts by mol in terms of NaSH) of 47.23% by mass of NaSH aqueous solution, and 18.533 parts by mass (228 parts by mol in terms of NaOH) of 49.21% by mass of NaOH aqueous solution, and the temperature was raised to 173 ℃ for 5 hours under a nitrogen atmosphere while stirring to distill off 27.300 parts by mass of water, and the autoclave was then sealed. The p-DCB distilled off by azeotropy during the dehydration was separated in a decanter and returned to the autoclave as needed. The anhydrous sodium sulfide composition in the form of fine particles in the autoclave after the dehydration was completed was dispersed in p-DCB. Since the NMP content in this composition was 0.079 parts by mass (0.8 parts by mole), it was revealed that 98% by mole (33.7 parts by mole) of the NMP charged was hydrolyzed into the ring-opened body (4- (methylammonium) of NMPMesityl) butyric acid) (hereinafter, abbreviated as "SMAB"). The amount of SMAB in the autoclave was 0.147 mole parts per 1 mole of sulfur atoms present in the autoclave. The total amount of the added NaSH and NaOH is changed into anhydrous Na₂The theoretical dehydration amount at S was 27.921 parts by mass, indicating that 0.878 parts by mass (48.8 parts by mol) and 0.609 parts by mass (33.8 parts by mol) of the residual water in the autoclave were consumed by the hydrolysis reaction between NMP and NaOH and were not present in the autoclave as water, and the remaining 0.269 parts by mass (14.9 parts by mol) remained in the autoclave as water or crystal water. The amount of water in the autoclave was 0.065 mol per 1 mol of sulfur atom present in the autoclave.

[ Process 2]

After the completion of the dehydration step, the internal temperature was cooled to 160 ℃ and NMP46.343 parts by mass (467.5 parts by mol) was added thereto, and the temperature was raised to 185 ℃. The amount of water in the autoclave was 0.025 mol based on 1 mol of NMP charged in step 2. When the gauge pressure reached 0.00MPa, the valve connected to the rectifying column was opened, and the internal temperature was raised to 200 ℃ over 1 hour. At this time, the outlet temperature of the rectifying column is controlled to 110 ℃ or lower by cooling and valve opening degree. The mixed vapor of distilled p-DCB and water was condensed in a condenser, separated in a decanter, and the p-DCB was returned to the autoclave. The amount of distillate water was 0.228 parts by mass (12.7 parts by mol).

[ Process 3]

The amount of water in the autoclave at the start of step 3 was 0.041 parts by mass (2.3 parts by mole), 0.005 moles per 1 mole of NMP charged in step 2, and 0.010 moles per 1 mole of sulfur atoms present in the autoclave. The amount of SMAB in the autoclave was 0.147 mol based on 1 mol of sulfur atom present in the autoclave, as in the case of step 1. Then, the internal temperature was raised from 200 ℃ to 230 ℃ over 3 hours, and after stirring at 230 ℃ for 1 hour, the temperature was raised to 250 ℃ and stirring was carried out for 1 hour. The gauge pressure at the time of 200 ℃ of the internal temperature was 0.03MPa, and the final gauge pressure was 0.40 MPa. After cooling, 0.650 parts by mass of the resulting slurry was poured into 3 parts by mass (3 liters) of water, stirred at 80 ℃ for 1 hour, and then filtered. The cake was stirred again in 3 parts by mass (3 liters) of hot water for 1 hour, washed, and filtered. This operation was repeated 4 times. To the cake, 3 parts by mass (3 liters) of hot water and acetic acid were added again, the pH was adjusted to 4.0, and then the mixture was stirred for 1 hour, washed and filtered. The cake was stirred again in 3 parts by mass (3 liters) of hot water for 1 hour, washed, and filtered. This operation was repeated 2 times. Then, the obtained mixture was dried at 120 ℃ overnight in a hot air dryer to obtain a white powdery PPS resin (A). The melt viscosity of the polymer at 300 ℃ was 56 pas. The non-newtonian index is 1.07.

(use of raw materials)

Hereinafter, each component to be a raw material of the polyarylene sulfide resin composition is shown.

PAS resin (A); using the PPS resin produced in the above production example

Olefin polymer (B)

Olefin polymer (B-1) (ethylene-maleic anhydride-glycidyl methacrylate copolymer); trade name "BONDFAST 7L", manufactured by Sumitomo chemical Co., Ltd

Olefin polymer (B-2) (ethylene-maleic anhydride-glycidyl methacrylate copolymer); trade name "BONDFAST 7M", manufactured by Sumitomo chemical Co., Ltd

Olefin polymer (B-3) (ethylene-alpha-olefin polymer); trade name "Engage 8842", manufactured by Dow Inc

Silicate minerals

Zeolite (C-1); trade name "Zeorum A type A-5", manufactured by Tosoh corporation

Talc (C-2); trade name "HF 5000 PJ", manufactured by Sonmura industries, Ltd

Mica (C-3); trade name "A-21S", Yamaguchi Mica Co., Ltd

Calcium carbonate (C-4); trade name "grade 1 calcium carbonate", manufactured by Sanko Co., Ltd

Glass fibers (D1); a fiber length of 3mm, an average diameter of 10 μm, a trade name of "T-717H", manufactured by Nippon electric Nitri K.K

Glass flake (D2)

Glass flakes (D2-1); an average thickness of 5 μm, a weight-average particle diameter of 160 μm, a trade name "REFG-301", manufactured by NIPPHI KOKAI

Glass flakes (D2-2); an average thickness of 5 μm, a weight-average particle diameter of 160 μm, a trade name "REFG-315", manufactured by NIPPHI KOKAI

Glass flakes (D2-3); an average thickness of 5 μm, a weight-average particle diameter of 600 μm, a trade name "REFG-112", manufactured by NIPPHI KOKAI

(production of polyarylene sulfide resin composition)

The respective materials were uniformly mixed in a tumbler according to the composition components and the compounding amounts (all in parts by mass) described in tables 1 and 2. Then, together with the PAS resin (A), the olefin polymer (B) and the zeolite (C), glass flakes (D2) were fed from the inlet of a top feeder of a vented twin-screw extruder (TEX 30 α, Japan Steel works, Ltd.), the resin component discharge amount was set to 30 kg/hr, the screw rotation speed was set to 220rpm, the screw shape was set to a fully-threaded type, and the resin temperature was set to 320 ℃ to carry out melt-kneading, thereby obtaining pellets of the polyarylene sulfide resin compositions of examples 1 to 9 and comparative examples 1 to 6.

(method of measuring weight-average particle diameter of glass flake)

Pellets of the polyarylene sulfide resin composition were baked at 550 ℃ for 3 hours, and the particle size distribution of the obtained Ash was measured by a sonic/vibrating sieve method. The following shows the apparatus used, the measurement method, and the measurement conditions.

The use equipment comprises the following steps: RPS-85(Seishin Enterprise Co., Ltd.)

The determination method comprises the following steps: 1. will be provided withThe screen is mounted to the apparatus.

2. An appropriate amount of the sample was placed in the sample cup.

3. With the screen apertures stored in the device.

4. The sieving (metering and sieving automation) is performed using a sonic/vibratory sieving apparatus.

The measurement conditions were as follows: the measurement range is 20 to 1400 mu m

Intensity of Acoustic wave 5

Sieving time 5 minutes

Vibration interval 1 time/second

(measurement of melt crystallization temperature of polyarylene sulfide resin composition)

The melt crystallization temperature (. degree. C.) was measured as follows: the polyarylene sulfide resin composition was melted at 350 ℃ and then quenched to prepare an amorphous film, and approximately 10mg of the amorphous film was measured from the amorphous film by a differential scanning calorimeter ("DSC 8500" manufactured by Perkin Elmer Co.).

The measurement conditions were as follows: after the melt was held at 350 ℃ for 3 minutes, the temperature was decreased at a rate of 20 ℃ per minute, and the exothermic peak temperature accompanying the crystallization was measured as the melt crystallization temperature.

(method of evaluating weld Strength)

(production of molded article)

Pellets of the polyarylene sulfide resin compositions of examples 1 to 9 and comparative examples 1 to 6 were fed to a Sumitomo weight injection molding machine (SE75D-HP) having a cylinder temperature of 310 ℃ and injection-molded using a mold for molding ISO type A1 dumbbell sheets having a weld at the center of the molded article at a mold temperature of 140 ℃ to obtain ISO type A1 dumbbell sheets having a weld at the center of the molded article.

The dwell time at the time of molding is determined by measuring the gate sealing time until the mold internal pressure at the time of dwell becomes zero. Examples 1 to 9 were carried out with a dwell time of 12 seconds, and comparative examples 1 to 6 were carried out with a dwell time of 13 seconds.

(measurement of weld Strength of molded article)

The tensile breaking strength of the test piece thus obtained was measured at a strain rate of 5 mm/min, a fulcrum distance of 115mm and 23 ℃ by a tensile tester manufactured by Instron corporation.

(method of evaluating bending toughness in TD direction)

(production of molded article)

Pellets of the polyarylene sulfide resin compositions of examples 1 to 9 and comparative examples 1 to 6 were fed to a Sumitomo weight injection molding machine (SE75D-HP) having a cylinder temperature of 310 ℃ and melt-mixed at a melting temperature of 310 ℃ in a screw-shaped full-screw type, and then injection-molded using a 60X 2mm flat plate molding die having a die temperature of 140 ℃ to obtain a 60X 2mm flat plate-shaped molded article. Thereafter, the resin was cut into a shape of 25X 60X 2mm so that the resin flow direction became a short side, and subjected to a bending test.

(measurement of flexural elongation in TD direction)

The flexural elongation (%) in the TD direction of the test piece obtained was measured in accordance with JIS-K7171. The larger the elongation, the more excellent the bending toughness in the TD direction.

[ Table 1]

[ Table 2]

From the results in tables 1 and 2, it is understood that the polyarylene sulfide resin compositions of examples 1 to 9 have significantly improved mechanical strength of the weld as compared with the molded article of comparative example 1. On the other hand, it is found that in the molded article of the polyarylene sulfide resin compositions of comparative examples 2 to 5 in which talc, mica and calcium carbonate, which are silicate minerals similar to zeolite (C), were blended, the crystallization rate of the PPS resin could not be optimized as in zeolite (C), and in particular, the weld strength of the molded article was deteriorated.

Further, it was found that the molded articles of the polyarylene sulfide resin compositions of examples 1 to 9 had improved weld strength and also improved flexural toughness in the TD direction, as compared with the molded article of comparative example 6 using glass flakes (D2) having a large weight average particle diameter.

(method of evaluating thermal shock resistance)

(production of molded article)

After arranging a rectangular parallelepiped steel material in a cavity prepared so as to cover the entire surface with a resin thickness of 1mm with respect to a rectangular parallelepiped SUS steel material (hereinafter referred to as "rectangular parallelepiped steel material") shown in fig. 1, pellets of the polyarylene sulfide resin compositions of examples 1 to 9 and comparative examples 1 to 6 were supplied to a sumitomo-weight injection molding machine (SE75D-HP) having a cylinder temperature of 310 ℃, and injection molding was performed while adjusting the mold temperature to 140 ℃. At this time, the through-hole (2) was formed at 2 points from the upper surface of the rectangular parallelepiped steel material (L: 25mm, W: 40mm, H: 10mm) in FIG. 1, and injection molding was performed from the side surface (3) of the rectangular parallelepiped steel material at a pin gate so as to be fixed by a pin of the same diameter provided in the mold without inflow of resin, and the molded body evaluated had a plurality of weld points.

(measurement of Cold thermal shock resistance of molded article)

The obtained test piece was introduced into a thermal shock testing apparatus (ESPEC CORPORATION "TSA-103 EL") and subjected to a thermal cycle of-40 ℃/30 minutes → 150 ℃/30 minutes (1 cycle for 1 hour). The appearance of the molded article was observed after each heat cycle, and the number of heat cycles until cracking occurred was measured to obtain an average value of 5 measurements.

[ Table 3]

[ Table 4]

[ Table 5]

From the results in tables 3 to 5, it is clear that the molded articles using the polyarylene sulfide resin compositions of examples 1 to 9 have improved cold and heat shock properties as compared with the molded articles of comparative examples 1 to 6. It is considered that the presence of the olefin copolymer and zeolite, which are pulverized so that the glass flakes dispersed in the polyarylene sulfide resin composition fall within a specific range, can effectively disperse stress generated when exposed to a cold or hot environment, and therefore, the cold or hot impact property is improved.

Description of the reference numerals

Length of L-shaped rectangular steel material

Width of W rectangular steel material

Height of H-shaped rectangular steel

1 rectangular parallelepiped steel material

2 through hole

3 side face of rectangular parallelepiped steel material (resin inflow direction from 2 pin gates)