JP2008069274A - Polyarylene sulfide composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyarylene sulfide composition, excellent in adhesiveness to epoxy resins, etc., and also excellent in toughness, impact resistance, weld strength, resistance to heat cycle and mechanical strength and particularly useful for component applications such as electric/electronic components or equipment components for automobiles. <P>SOLUTION: The polyarylene sulfide composition is composed of (A) 67-98.9 wt.% polyarylene sulfide, (B) 1-30 wt.% at least one kind of polyethylene-based copolymer selected from the group consisting of specific modified polyethylene-based copolymers and (C) 0.1-5 wt.% modified polysiloxane compounds each having at least one kind of functional group selected from the group consisting of an amino group, an epoxy group and a carboxy group at both ends. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is excellent in adhesiveness with epoxy resin, etc. without impairing heat resistance, chemical resistance, dimensional stability, etc. inherent in polyarylene sulfide, and at the same time, toughness, impact resistance, weld strength, heat cycle resistance More particularly, the present invention relates to a polyarylene sulfide composition that is particularly useful for applications such as electric / electronic parts or automobile equipment members.

  Polyarylene sulfide is a resin that exhibits excellent properties such as heat resistance, chemical resistance, and dimensional stability. Utilizing these excellent properties, it is widely used in electrical and electronic equipment members, automotive equipment members, OA equipment members, etc. Has been.

  However, polyarylene sulfide has many applications because it is significantly inferior in adhesiveness, toughness, impact resistance, etc. with epoxy resin compared to other engineering plastics such as polyamide, polycarbonate, polybutylene terephthalate, polyacetal, etc. The use was limited.

  Several attempts have been made to improve the adhesiveness of polyarylene sulfide, and for example, it consists of (a) polyarylene sulfide, (b) polyester copolymer, and (c) olefin copolymer. Resin composition (for example, refer to Patent Document 2), (a) polyarylene sulfide, (b) bisphenol A type epoxy resin, (c) oxazoline group-containing amorphous polymer. ) Etc. have been proposed.

  Further, with regard to attempts to improve the toughness, impact resistance, etc. of polyarylene sulfide, for example, a resin composition comprising (a) polyarylene sulfide, (b) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer Product (for example, see Patent Document 3), (a) a composition obtained by melt-kneading polyphenylene sulfide and a non-blocking polyfunctional isocyanate compound, and (b) an ethylene-α, β-unsaturated carboxylic acid alkyl ester system. (A) polyarylene sulfide, (b) ethylene-α, β-unsaturated carboxylic acid alkyl ester copolymer, and (a) a resin composition containing the copolymer (for example, see Patent Document 4). c) A resin composition composed of a specific type of alkoxysilane compound (see, for example, Patent Document 5) has been proposed.

Japanese Patent Laid-Open No. 11-228828 JP 2000-103964 A Japanese Patent Laid-Open No. 62-151460 Japanese Patent Laid-Open No. 02-255862 Japanese Patent Laid-Open No. 05-202245

  However, the resin compositions proposed in Patent Documents 1 and 2 have insufficient adhesiveness, while the resin compositions proposed in Patent Documents 3 to 5 still have toughness, impact resistance, etc. There was a problem that it was not satisfactory enough. In addition, these proposals cannot satisfy the problems of improving adhesion with epoxy resin and the like and the problems of improving toughness, impact resistance, weld strength, heat cycle resistance, etc. at the same time. there were.

  Therefore, the present invention is excellent in adhesion without impairing the heat resistance, chemical resistance, dimensional stability, etc. inherent in polyarylene sulfide, and at the same time, toughness, impact resistance, weld strength, heat cycle resistance, mechanical It is an object of the present invention to provide a polyarylene sulfide composition that is also excellent in mechanical strength, and more specifically, to provide a polyarylene sulfide composition that is particularly useful for electrical parts such as electrical / electronic parts or automobile electrical parts. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyarylene sulfide composition comprising a polyarylene sulfide, a specific polyethylene copolymer, and a modified polysiloxane compound having specific functional groups at both ends. However, the present inventors have found that it is excellent in adhesiveness with an epoxy resin and the like and at the same time is excellent in toughness, impact resistance, weld strength, heat cycle resistance, and mechanical strength, and has completed the present invention.

  That is, the present invention relates to polyarylene sulfide (A) 67-98.9% by weight, maleic anhydride graft-modified ethylene-α-olefin copolymer (b1), ethylene-α, β-unsaturated carboxylic acid alkyl ester Maleic anhydride copolymer (b2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4) , Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5) at least one polyethylene copolymer (B) 1 to 30% by weight and at least one functional group selected from the group consisting of an amino group, an epoxy group and a carboxyl group at both ends The modified polysiloxane compound (C) is a polyarylene sulfide composition comprising 0.1 to 5% by weight.

  Hereinafter, the present invention will be described in detail.

  The polyarylene sulfide composition of the present invention has a polyarylene sulfide (A) of 67 to 98.9% by weight, a polyethylene copolymer (B) of 1 to 30% by weight, and a modified polysiloxane compound (C) of 0.1 to 0.1%. It consists of 5% by weight.

  As the polyarylene sulfide (A) constituting the polyarylene sulfide composition of the present invention, any polyarylene sulfide may be used as long as it belongs to the category called polyarylene sulfide. Since the composition is excellent in mechanical strength, toughness, impact resistance, weld strength, heat cycle resistance and molding processability, the measurement temperature is 315 ° C., the load is 10 kg, the diameter is 1 mm, and the length is 2 mm. A polyarylene sulfide having a melt viscosity of 100 to 30000 poise measured by a Koka flow tester equipped with a die is preferred, and a polyarylene sulfide having a melt viscosity of 200 to 20000 poise is particularly preferred.

  The polyarylene sulfide (A) preferably contains 70 mol% or more, particularly 90 mol% or more of a p-phenylene sulfide unit represented by the following general formula (1) as a structural unit.

そして、他の構成成分としては、例えば下記の一般式（２）に示されるｍ−フェニレンスルフィド単位、一般式（３）に示されるｏ−フェニレンスルフィド単位、一般式（４）に示されるフェニレンスルフィドスルホン単位、一般式（５）に示されるフェニレンスルフィドケトン単位、一般式（６）に示されるフェニレンスルフィドエーテル単位、一般式（７）に示されるジフェニレンスルフィド単位、一般式（８）に示される置換基含有フェニレンスルフィド単位、一般式（９）に示される分岐構造含有フェニレンスルフィド単位等を挙げることができ、その中でも接着性、靭性、耐衝撃性、ウェルド強度、耐ヒートサイクル性、機械的強度のバランスに優れたポリアリーレンスルフィド組成物となることからポリ（ｐ−フェニレンスルフィド）が好ましい。

Examples of other constituent components include m-phenylene sulfide units represented by the following general formula (2), o-phenylene sulfide units represented by the general formula (3), and phenylene sulfides represented by the general formula (4). A sulfone unit, a phenylene sulfide ketone unit represented by general formula (5), a phenylene sulfide ether unit represented by general formula (6), a diphenylene sulfide unit represented by general formula (7), and a general formula (8) Substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units represented by the general formula (9), and the like can be mentioned. Among them, adhesiveness, toughness, impact resistance, weld strength, heat cycle resistance, mechanical strength Since the polyarylene sulfide composition has an excellent balance of poly (p-phenylenesulfur) De) is preferred.

（ここで、ＲはＯＨ、ＮＨ_２、ＣＯＯＨ、ＣＨ_３を示し、ｎは１又は２を示す。）

(Here, R represents OH, NH ₂ , COOH, CH ₃ , and n represents 1 or 2)

該ポリアリーレンスルフィド（Ａ）の製造方法としては、特に制限はなく、一般的にポリアリーレンスルフィドの製造方法として知られている方法により製造すればよく、例えば重合溶媒中で、アルカリ金属硫化物とジハロ芳香族化合物とを反応する方法により製造することが可能である。アルカリ金属硫化物としては、例えば硫化リチウム、硫化ナトリウム、硫化カリウム、硫化ルビジウム、硫化セシウム及びそれらの混合物が挙げられ、これらは水和物の形で使用しても差し支えない。また、これらアルカリ金属硫化物は、水硫化アルカリ金属とアルカリ金属塩基とを反応させることによって得られるが、ジハロ芳香族化合物の重合系内への添加に先立ってその場で調整されても、また系外で調整されたものを用いても差し支えない。また、ジハロ芳香族化合物としては、例えばｐ−ジクロロベンゼン、ｐ−ジブロモベンゼン、ｐ−ジヨードベンゼン、ｍ−ジクロロベンゼン、ｍ−ジブロモベンゼン、ｍ−ジヨードベンゼン、１−クロロ−４−ブロモベンゼン、４，４’−ジクロロジフェニルスルフォン、４，４’−ジクロロジフェニルエーテル、４，４’−ジクロロベンゾフェノン、４，４’−ジクロロジフェニル等が挙げられる。また、アルカリ金属硫化物とジハロ芳香族化合物との仕込み比は、アルカリ金属硫化物／ジハロ芳香族化合物＝１／０．９〜１．１（モル比）の範囲とすることが好ましい。

The method for producing the polyarylene sulfide (A) is not particularly limited, and may be produced by a method generally known as a method for producing polyarylene sulfide. For example, in a polymerization solvent, an alkali metal sulfide and It can be produced by a method of reacting with a dihaloaromatic compound. Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture thereof, and these may be used in the form of hydrate. These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base, and can be prepared in situ prior to addition of the dihaloaromatic compound into the polymerization system. It is possible to use one adjusted outside the system. Examples of the dihaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 1-chloro-4-bromobenzene. 4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl ether, 4,4′-dichlorobenzophenone, 4,4′-dichlorodiphenyl, and the like. The charging ratio of the alkali metal sulfide and the dihaloaromatic compound is preferably in the range of alkali metal sulfide / dihaloaromatic compound = 1 / 0.9 to 1.1 (molar ratio).

  As the polymerization solvent, a polar solvent is preferable, and an organic amide which is aprotic and stable to alkali at high temperature is particularly preferable. Examples of the organic amide include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, and N-methyl-2-pyrrolidone. 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethylurea and mixtures thereof. Moreover, it is preferable to use this polymerization solvent in 150-3500 weight% with respect to the polymer produced | generated by superposition | polymerization, and it is preferable to use especially in the range used as 250-1500 weight%. The polymerization is preferably carried out at 200 to 300 ° C., particularly 220 to 280 ° C. for 0.5 to 30 hours, particularly 1 to 15 hours with stirring.

  Further, the polyarylene sulfide (A) may be a straight-chain one or a one obtained by treatment at high temperature in the presence of oxygen and crosslinked, and a slight amount of a polyhalo compound of trihalo or higher may be added to slightly crosslink or Even if it introduces a branched structure, it may be heat-treated in a non-oxidizing inert gas such as nitrogen, or may be a mixture of these structures. Above all, as the polyarylene sulfide (A), the resulting polyarylene sulfide composition should have an excellent balance of adhesion, toughness, impact resistance, weld strength, and heat cycle resistance, especially with epoxy resins and the like. Therefore, the functional group-containing polyarylene sulfide (a1) and / or the linear polyarylene sulfide (a2) having a functional group corresponding to 0.05 to 5 mol% per arylene sulfide unit is preferable.

  Examples of the functional group-containing polyarylene sulfide (a1) include amino group-containing polyarylene sulfide, carboxyl group-containing polyarylene sulfide, thiol group-containing polyarylene sulfide, and hydroxyl group-containing polyarylene sulfide. From the viewpoint of easiness, it is preferably an amino group-containing polyarylene sulfide.

  The functional group-containing polyarylene sulfide (a1) can be produced by a method in which, for example, when an alkali metal sulfide and a dihaloaromatic compound are reacted, polymerization is performed in the presence of the functional group-containing aromatic halogen compound. is there.

  Examples of the functional group-containing aromatic halogen compound include amino group-containing polyarylene sulfides such as 2,5-dichloroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, and 3,5-diamino. Chlorobenzene, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino-2-chlorotoluene, 3-chloro-m-phenylenediamine, 2,5-dibromoaniline, 2,6-dibromo Examples include aniline, 3,5-dibromoaniline, and mixtures thereof, and 3,5-dichloroaniline and 3,5-diaminochlorobenzene are particularly preferable. Examples of the carboxyl group-containing polyarylene sulfide include 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,5-dibromobenzoic acid, and 2,6-dibromo. Examples include benzoic acid, 3,5-dibromobenzoic acid, and mixtures thereof, and 3,5-dichlorobenzoic acid is particularly preferable. When a thiol group-containing polyarylene sulfide is used, for example, 2,5-dichlorothiophenol, 2,6-dichlorothiophenol, 3,5-dichlorothiophenol, 2,5-dibromothiophenol, 2,6-dibromo Examples thereof include thiophenol, 3,5-dibromothiophenol, and mixtures thereof, and 3,5-dichlorothiophenol is particularly preferable. When the hydroxyl group-containing polyarylene sulfide is used, for example, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, 2,5-dibromophenol, 2,6-dibromophenol, 3,5 -Dibromophenol and a mixture thereof are mentioned, and 3,5-dichlorophenol is particularly preferable.

  On the other hand, any linear polyarylene sulfide (a2) may be used as long as it belongs to the category called linear polyarylene sulfide. For example, it is described in JP-B-52-12240. It is possible to manufacture by this method.

  The polyarylene sulfide composition of the present invention comprises 67 to 98.9% by weight of polyarylene sulfide (A). Here, when the polyarylene sulfide (A) is less than 67% by weight, the resulting polyarylene sulfide composition has a significant decrease in mechanical strength. On the other hand, when it exceeds 98.9% by weight, the resulting polyarylene sulfide composition has poor adhesion, toughness, impact resistance, weld strength, and heat cycle resistance.

  The polyethylene-based copolymer (B) constituting the polyarylene sulfide composition of the present invention improves the adhesiveness of the polyarylene sulfide composition by combining with the modified polysiloxane compound (C), as well as toughness and impact resistance. , Weld strength, heat cycle resistance, maleic anhydride graft-modified ethylene-α-olefin copolymer (b1), ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer Polymer (b2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4) and ethylene-α , Β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5 At least one selected from the group consisting of:

  Any maleic anhydride graft-modified ethylene-α-olefin copolymer (b1) may be used as long as it belongs to this category. Among them, the polyarylene sulfide composition obtained has adhesiveness, toughness, Since it is excellent in impact resistance and the like, it is composed of ethylene residue unit: α-olefin residue unit: maleic anhydride residue unit (weight ratio) = 50 to 98:45 to 1: 5 to 1. Specifically, maleic anhydride graft-modified linear low-density polyethylene, maleic anhydride graft-modified ethylene-propylene rubber and the like can be mentioned. The maleic anhydride graft-modified ethylene-α-olefin copolymer (b1) is obtained, for example, by coexisting an ethylene-α-olefin copolymer, a peroxide, and maleic anhydride and proceeding with the grafting reaction. It is possible.

  Any ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b2) may be used as long as it belongs to this category, and polyarylene sulfide composition obtained among them may be used. Is excellent in adhesion, toughness, impact resistance and the like, ethylene residue unit: α, β-unsaturated carboxylic acid alkyl ester residue unit: maleic anhydride residue unit (weight ratio) = 50 to 98:40 It is preferable to be in the range of ˜1: 10-1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b2) include (trade name) Bondine LX4110 (manufactured by Arkema), (trade name) Bondine TX8030 (Arkema). (Trade name) Bondine AX8390 (manufactured by Arkema) and the like.

  As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), any copolymer belonging to this category may be used. Among them, the polyarylene sulfide composition obtained is adhesive, Since it is excellent in toughness, impact resistance and the like, the ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit (weight ratio) is preferably in the range of 85 to 99: 15-1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3) include (trade name) Bond Fast 2C (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) Bond Fast E ( Sumitomo Chemical Co., Ltd.).

  Any ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4) may be used as long as it belongs to this category. Because of excellent adhesion, toughness, impact resistance, etc., ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: vinyl acetate residue unit (weight ratio) = 50 to 98:15 to 1 : It is preferable that it is the range of 35-1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4) include (trade name) Bond Fast 2B (manufactured by Sumitomo Chemical Co., Ltd.), (trade name) bond. Fast 7B (Sumitomo Chemical Co., Ltd.) etc. are mentioned.

  As the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5), any copolymer belonging to this category may be used. Since the resulting polyarylene sulfide composition is excellent in adhesiveness, toughness, impact resistance, etc., ethylene residue unit: α, β-unsaturated carboxylic acid glycidyl ester residue unit: α, β-unsaturated carboxylic acid alkyl The ester residue unit (weight ratio) is preferably in the range of 50 to 98:10 to 1:40 to 1. Specific examples of the ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5) include (trade name) Bondfast 7L (Sumitomo Chemical Co., Ltd.) Manufactured), (trade name) Bond Fast 7M (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Here, the α-olefin constituting the polyethylene copolymer (B) refers to an α-olefin having 3 or more carbon atoms, such as propylene, butene-1, 4-methyl-pentene-1, and hexene-1. And octene-1 and the like. Examples of the α, β-unsaturated carboxylic acid alkyl ester include alkyl esters such as acrylic acid and methacrylic acid, and specifically include methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate. , N-butyl acrylate, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate Etc. Examples of the α, β-unsaturated carboxylic acid glycidyl ester include acrylic acid glycidyl ester and methacrylic acid glycidyl ester.

  The polyarylene sulfide composition of the present invention comprises 1 to 30% by weight of a polyethylene copolymer (B), and is obtained when the blending amount of the polyethylene copolymer (B) is less than 1% by weight. The resulting polyarylene sulfide composition has poor adhesion, toughness, impact resistance, weld strength, and heat cycle resistance. On the other hand, when it exceeds 30% by weight, the resulting polyarylene sulfide composition has a significant decrease in mechanical strength.

  The modified polysiloxane compound (C) constituting the polyarylene sulfide composition of the present invention is blended in combination with the polyethylene copolymer (B), so that the adhesion of the polyarylene sulfide composition to an epoxy resin or the like is improved. In addition to improving toughness, impact resistance, weld strength and heat cycle resistance, at least one functional group selected from the group consisting of an amino group, an epoxy group, and a carboxyl group at both ends It is a modified polysiloxane compound having.

  Here, as the polysiloxane compound modified with a functional group, in addition to the both-end functional group-modified polysiloxane constituting the polyarylene sulfide composition of the present invention, one-end functional group-modified polysiloxane, side chain-modified As a result of investigation by the present inventor, when a polyarylene sulfide composition is formed using a single-end functional group-modified polysiloxane or a side chain-modified polysiloxane, a polyethylene copolymer is used. Even if blended in combination with (B), a polyarylene sulfide composition excellent in adhesiveness, toughness, impact resistance, weld strength and heat cycle resistance cannot be obtained, and a modified poly having functional groups at both ends. It has been found that it is impossible to achieve the object of the present invention other than the siloxane compound (C). In addition, when a polyarylene sulfide composition is formed using a polysiloxane compound that is not modified with at least one functional group selected from the group consisting of an amino group, an epoxy group, and a carboxyl group, it is excellent in toughness and impact resistance. Not only was the polyarylene sulfide composition not obtained, but the polysiloxane compound bleeds onto the surface of the molded product, resulting in a marked deterioration in adhesion.

  On the other hand, as a compound in which both ends are modified with a functional group, for example, an epoxy resin is known, and in particular, a bisphenol A type epoxy resin is widely known as a compound having an epoxy group at both ends. However, according to the study of the present inventor, even if a bisphenol A type epoxy resin is used instead of the modified polysiloxane compound (C) having functional groups at both ends, the resulting polyarylene sulfide composition has toughness, The object of the present invention is that it is inferior in impact resistance, weld strength and heat cycle resistance, and satisfies the adhesiveness with epoxy resin etc. and toughness, impact resistance, weld strength and heat cycle resistance at the same time. Turned out to be unable to achieve.

  The modified polysiloxane compound (C) is a compound that belongs to the category of modified polysiloxane compounds having at least one functional group selected from the group consisting of an amino group, an epoxy group, and a carboxyl group at both ends. Any compound can be used, and in particular, the polyarylene sulfide composition is excellent in the balance of adhesiveness, toughness, impact resistance and the like with an epoxy resin and the like. It is preferable that it is a both-ends modified polysiloxane compound shown by this.

（ここで、Ｒ_１，Ｒ_２はそれぞれ独立してアルキレン基を示し、Ｘ_１，Ｘ_２はそれぞれ独立してアミノ基，グリシドキシ基，３，４−エポキシシクロヘキシル基，カルボキシル基を示し、ｎ≧１である。）
本発明のポリアリーレンスルフィド組成物は、変性ポリシロキサン化合物（Ｃ）０．１〜５重量％からなるものであり、変性ポリシロキサン化合物（Ｃ）の配合量が０．１重量％未満である場合、得られるポリアリーレンスルフィド組成物は接着性、靭性、耐衝撃性、ウェルド強度、耐ヒートサイクル性が劣るものとなる。一方、配合量が５重量％を越える場合、得られるポリアリーレンスルフィド組成物は機械的強度が著しく低下するものとなる。

(Here, R ₁ and R ₂ each independently represent an alkylene group, X ₁ and X ₂ each independently represent an amino group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a carboxyl group, and n ≧ 1)
The polyarylene sulfide composition of the present invention is composed of 0.1 to 5% by weight of the modified polysiloxane compound (C), and the blending amount of the modified polysiloxane compound (C) is less than 0.1% by weight. The resulting polyarylene sulfide composition has poor adhesion, toughness, impact resistance, weld strength, and heat cycle resistance. On the other hand, when the blending amount exceeds 5% by weight, the resulting polyarylene sulfide composition has a significant decrease in mechanical strength.

  The polyarylene sulfide composition of the present invention may be formed by blending a filler (D) blended in a general resin composition, and the filler (D) is a fibrous filler. Examples of the material include glass fiber (d1), carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, asbestos fiber, stone koji fiber, metal fiber and the like. Among them, glass fiber is preferable because it becomes a polyarylene sulfide composition having particularly excellent mechanical strength. Examples of non-fibrous fillers include wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, talc, alumina silicate, and other silicates, aluminum oxide, silicon oxide, magnesium oxide, Oxides such as zirconium oxide, titanium oxide, zinc oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, nitrides such as silicon nitride, boron nitride and aluminum nitride Glass flakes, glass beads, and the like can be exemplified, and among these, mica, clay, talc, calcium carbonate, glass flakes, and glass beads are preferable because the polyarylene sulfide composition is particularly excellent in dimensional stability. In addition, the filler (D) is surface-treated with an isocyanate compound, a silane coupling agent, a titanate coupling agent, an epoxy compound, etc. because the polyarylene sulfide composition has high mechanical strength. It may be what you did.

  Since the blending amount of the filler (D) is a polyarylene sulfide composition having particularly excellent mechanical strength and dimensional stability, the polyarylene sulfide (A), the polyethylene copolymer (B), the modified poly It is preferable that it is 10-150 weight part with respect to a total of 100 weight part of a siloxane compound (C).

  The polyarylene sulfide composition of the present invention is preferably formed by blending a lubricant (E) in order to improve mold releasability and appearance when forming a molded article. Examples of the lubricant (E) include: Carnauba wax (e1) and carboxylic acid amide wax (e2) may be mentioned. As the carnauba wax (e1), a general commercial product can be used, and examples thereof include (trade name) purified carnauba No. 1 powder (manufactured by Nikko Fine Products). The carboxylic acid amide wax (e2) is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine, and any one belonging to this category can be used. Examples thereof include (trade name) LIGHT AMIDE WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), which is a polycondensate composed of stearic acid, sebacic acid, and ethylenediamine.

  The blending amount of the lubricant (E) is less likely to cause problems such as mold contamination especially during molding, and it becomes a polyarylene sulfide composition having excellent mold releasability and appearance of the molded product. It is preferable that it is 0.05-5 weight part with respect to a total of 100 weight part of an arylene sulfide (A), a polyethylene-type copolymer (B), and a modified polysiloxane compound (C).

  As a method for producing the polyarylene sulfide composition of the present invention, a conventionally used hot melt kneading method can be used. For example, a heat melt kneading method using a single screw or twin screw extruder, a kneader, a mill, a Brabender or the like can be mentioned, and a melt kneading method using a twin screw extruder excellent in kneading ability is particularly preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 280-400 degreeC. Moreover, the polyarylene sulfide composition of the present invention can be molded into an arbitrary shape using an injection molding machine, an extrusion molding machine, a transfer molding machine, a compression molding machine, or the like.

  Further, the polyarylene sulfide composition of the present invention is a conventionally known heat stabilizer, antioxidant, ultraviolet absorber, crystal nucleating agent, foaming agent, mold corrosion inhibitor, and the like within a range not departing from the object of the present invention. One or more additives such as flame retardants, flame retardant aids, colorants such as dyes and pigments, and antistatic agents may be used in combination.

  The polyarylene sulfide composition of the present invention is excellent in adhesiveness with an epoxy resin and the like, and at the same time has high toughness, high impact resistance, high weld strength, excellent heat cycle resistance, and high mechanical strength. It can be used as a resin composition raw material for various molded articles, and can be widely used for, for example, electrical / electronic equipment members, automobile equipment members, OA equipment members and the like.

  The present invention is excellent in adhesiveness with epoxy resin, etc. without impairing heat resistance, chemical resistance, dimensional stability, etc. inherent in polyarylene sulfide, and at the same time, toughness, impact resistance, weld strength, heat cycle resistance It provides a polyarylene sulfide composition having excellent properties and mechanical strength, and the polyarylene sulfide composition is particularly useful for applications such as electric / electronic parts or automobile equipment members.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention, this invention is not restrict | limited at all to these examples.

  Polyarylene sulfide (A), polyethylene copolymer (B), modified polysiloxane compound (C), filler (D), carnauba wax (e1), carboxylic acid amide wax used in Examples and Comparative Examples (E2) and other additives are shown below.

<Polyarylene sulfide (A)>
Amino group-containing poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a1-2)): Melt viscosity 1600 poise, amino group content 0.1 mol% per phenylene sulfide unit.

  Linear poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a2-1)): Melt viscosity 350 poise.

  Poly (p-phenylene sulfide) (hereinafter simply referred to as PPS (a-2)): melt viscosity of 3000 poise.

<Polyethylene copolymer (B)>
Maleic anhydride graft-modified ethylene-α-olefin copolymer (b1-1) (hereinafter, simply referred to as PE copolymer (b1-1)): maleic anhydride graft-modified directly obtained according to Synthesis Example 4 Chain low density polyethylene; maleic anhydride content 1.4% by weight, MFR = 0.7 g / 10 min.

  Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b2-1) (hereinafter, simply referred to as PE copolymer (b2-1)): manufactured by Arkema, Inc. ) Bondine TX8030; ethyl acrylate residue unit 12% by weight, maleic anhydride residue unit 3% by weight, MFR = 3 g / 10 min.

  Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (b2-2) (hereinafter simply referred to as PE copolymer (b2-2)): manufactured by Arkema, Inc. ) Bondine AX8390; ethyl acrylate residue unit 30.5% by weight, maleic anhydride residue unit 1.5% by weight, MFR = 7 g / 10 min.

  Ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3-1) (hereinafter simply referred to as PE copolymer (b3-1)): manufactured by Sumitomo Chemical Co., Ltd. (trade name) Bond Fast E; glycidyl methacrylate residue unit 12% by weight, MFR = 3 g / 10 min.

<Modified polysiloxane compound (C)>
Polysiloxane compound (C-1): Shin-Etsu Chemical Co., Ltd., (trade name) KF-105; glycidoxypropyl modified at both ends.

  Polysiloxane compound (C-2): Shin-Etsu Chemical Co., Ltd., (trade name) KF-8010;

  Polysiloxane compound (C′-1): manufactured by Shin-Etsu Chemical Co., Ltd. (trade name) X-22-173BX; one-terminal glycidoxypropyl modified type.

  Polysiloxane compound (C′-2): Shin-Etsu Chemical Co., Ltd., (trade name) KF-101; side chain glycidoxypropyl modified type.

  Polysiloxane compound (C′-3): manufactured by Shin-Etsu Chemical Co., Ltd., (trade name) KF96-100; functional group unmodified type.

<Filler (D)>
Glass fiber (d1-1); manufactured by NSG Vetrotex Co., Ltd. (trade name) RES03-TP91; fiber diameter 9 μm, fiber length 3 mm.

  Calcium carbonate (d2-1); manufactured by Shiraishi Kogyo Co., Ltd. (trade name) Whiten P-30; average particle size 4.3 μm.

<Lubricant (E)>
Carnauba wax (e1-1); (trade name) purified carnauba No. 1 powder manufactured by Nikko Fine Products.

  Carboxylic acid amide wax (e2-1) (hereinafter simply referred to as acid amide wax (e2-1)); manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Light Amide WH-255; stearic acid, sebacic acid, Ethylenediamine polycondensate.

<Other additives (F)>
Epoxy resin (f-1): Dainippon Ink & Chemicals, Inc. (trade name) Epicron 3050; Bisphenol A type epoxy resin.

<Synthesis Example 1 (Synthesis of PPS (a1-2))>
A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flaky sodium sulfide (Na ₂ S · 2.9H ₂ O) and 17000 g of N-methyl-2-pyrrolidone, and gradually heated to 205 ° C. while stirring under a nitrogen stream. 1355 g of water was distilled off. After cooling the system to 140 ° C., 7278 g of p-dichlorobenzene, 11.7 g of 3,5-dichloroaniline and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer is repeatedly washed with warm water and dried at 100 ° C. for a whole day and night, whereby an amino group-containing poly (p-phenylene sulfide) having a melt viscosity of 400 poise (hereinafter referred to as PPS (a1-1)) is obtained. Obtained. This PPS (a1-1) was further cured at 250 ° C. for 2 hours in an oxygen atmosphere to obtain PPS (a1-2).

  The melt viscosity of the obtained PPS (a1-2) was 1600 poise, and the amino group content per phenylene sulfide unit was 0.1 mol%.

<Synthesis Example 2 (Synthesis of PPS (a2-1))>
A 50-liter titanium autoclave equipped with a stirrer was charged with 10773 g of N-methyl-2-pyrrolidone, 5607 g of 47% sodium hydrogen sulfide aqueous solution and 3807 g of 48% sodium hydroxide aqueous solution, and gradually heated to 200 ° C. while stirring under a nitrogen stream. Then, 4533 g of water was distilled off. The system was cooled to 170 ° C., 7060 g of p-dichlorobenzene and 5943 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225 ° C., polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. and polymerized at 250 ° C. for 2 hours. Further, 1503 g of water was injected at 250 ° C., the temperature was raised again to 255 ° C., and polymerization was performed at 225 ° C. for 2 hours. After completion of the polymerization, the mixture was cooled to room temperature, and the polymerization slurry was subjected to solid-liquid separation. The polymer was washed successively with N-methyl-2-pyrrolidone, acetone and water and dried overnight at 100 ° C. to obtain PPS (a2-1).

  The obtained PPS (a2-1) was linear, and its melt viscosity was 350 poise.

<Synthesis Example 3 (Synthesis of PPS (a-2))>
A 50-liter autoclave equipped with a stirrer was charged with 6214 g of flaky sodium sulfide (Na ₂ S · 2.9H ₂ O) and 17000 g of N-methyl-2-pyrrolidone, and gradually heated to 205 ° C. while stirring under a nitrogen stream. 1355 g of water was distilled off. After the system was cooled to 140 ° C., 7160 g of p-dichlorobenzene and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer was repeatedly washed with warm water and dried at 100 ° C. for 24 hours to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (a-1)) having a melt viscosity of 280 poise. This PPS (a-1) was further cured at 250 ° C. for 4 hours in an oxygen atmosphere to obtain PPS (a-2).

  The melt viscosity of the obtained PPS (a-2) was 3000 poise.

  A method for evaluating and measuring polyarylene sulfides obtained in Synthesis Examples 1 to 3 is shown below.

~ Measurement of amino group content ~
Using an infrared absorption spectrum measuring apparatus, the absorption at 1900 cm ⁻¹ (C—H out-of-plane vibration of the benzene ring) and the absorption at 3387 cm ⁻¹ (NH stretching vibration of an amino group) are measured. The amino group content was obtained. The calibration curve at that time was prepared from a mixture of benzene and aniline.

~ Measurement of melt viscosity ~
The melt viscosity was measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg using a Koka type flow tester (trade name: CFT-500, manufactured by Shimadzu Corporation) equipped with a die having a diameter of 1 mm and a length of 2 mm. It was.

<Synthesis Example 4 (Synthesis of PE Copolymer (b1-1))>
250 g of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and dialkyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd., trade name) for 10 kg of linear low density polyethylene (manufactured by Tosoh Corporation, trade name Nipolon Z 1P53A) 10 g of Perhexa 25B) was uniformly mixed with a hexchel mixer. Then, it extruded at the cylinder temperature of 220 degreeC with the twin-screw extruder (Toshiba machine Co., Ltd., brand name TEM-35-102B), and obtained the PE-type copolymer (b1-1). The maleic anhydride content obtained from a calibration curve prepared separately by measuring absorption by a carbonyl group by infrared absorption spectrum was 1.4 wt%. The melt flow rate (MFR) was 0.7 g / 10 min (measuring temperature 190 ° C., load 21.18 N).

  The evaluation / measurement methods used in Examples and Comparative Examples are shown below.

~ Measurement of adhesive strength ~
An ASTM D638 No. 1 dumbbell test piece was produced by an injection molding machine (trade name SE-75S, manufactured by Sumitomo Heavy Industries, Ltd.). The test piece was cut into two at the center of the dumbbell parallel part, and an adhesive area of 1.27 cm ² (test piece width of 1. The epoxy adhesive was cured at 100 ° C. × 1 hr followed by 150 ° C. × 3 hr. The cured test piece was pulled at 5 mm / min with a tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph AG-5000B), and the breaking strength was measured. The breaking strength was divided by the bonding area to obtain the bonding strength. Moreover, the form of adhesion failure was classified into the following three.

  Aggregation (destruction); high adhesive strength, destruction with adhesive.

  Base material (fracture): The test piece of polyarylene sulfide composition was broken with medium adhesive strength.

  Interface (Fracture): Low adhesive strength, fracture at the interface between the test piece of the polyarylene sulfide composition and the adhesive.

~ Measurement of tensile strength and tensile elongation ~
No. 1 test piece of ASTM D-638 was produced by injection molding, and tensile strength and tensile elongation were measured using the test piece according to ASTM D-638. Using a measuring device (manufactured by Shimadzu Corporation, (trade name) Autograph AG-5000B), the test was performed under the test conditions of a distance between chucks of 110 mm and a measurement speed of 5 mm / min. The higher the tensile strength, the better the mechanical strength, and the higher the tensile elongation, the better the toughness.

~ Charpy impact strength ~
A test piece for measuring Charpy impact strength was prepared by an injection molding machine (trade name SE-75S, manufactured by Sumitomo Heavy Industries, Ltd.), and a notching machine (trade name: A-3 type, manufactured by Toyo Seiki Seisakusho Co., Ltd.). A notch was added and measurement was performed in accordance with ISO 179 using a Charpy impact tester (trade name DG-CB, manufactured by Toyo Seiki Seisakusho Co., Ltd.).

~ Measurement of weld strength ~
A test piece was prepared by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name SE-75S), and ASTM was used using a tensile tester (manufactured by Shimadzu Corporation, trade name Autograph AG-5000B). Measurement was performed in accordance with D638.

~ Heat cycle resistance ~
Using an injection molding machine (product name SE-75S, manufactured by Sumitomo Heavy Industries, Ltd.), insert molding for inserting a 30 mm × 20 mm × 10 mm rectangular steel material (carbon steel) is performed, and a polyarylene sulfide composition having a wall thickness of 1 mm. A test piece for heat cycle resistance coated with an object was prepared. After the obtained test piece is held at 150 ° C. for 30 minutes, it is subjected to a cooling and heating cycle in which holding at −40 ° C. for 30 minutes is one cycle. The number of cold cycle treatments in which was observed was evaluated as heat cycle resistance. It was judged that the larger the number of heat cycle treatments, the better the heat cycle resistance.

Example 1
Twin screw extrusion blended in a proportion of 84 wt% PPS (a1-2), 15 wt% PE copolymer (b1-1) and 1 wt% polysiloxane compound (C-1) and heated to 290 ° C Into a hopper (made by TOSHIBA MACHINE, (trade name) TEM-35-102B), melted and kneaded at a screw speed of 200 rpm, the molten composition flowing out from the die was cooled and cut, and pelletized polyarylene A sulfide composition was made.

  A test piece for measuring the adhesive strength, tensile strength, and tensile elongation by introducing the polyarylene sulfide composition into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75) heated to 290 ° C. Each test piece for measuring Charpy impact strength was molded. Using these test pieces, adhesive strength, tensile strength, tensile elongation, and Charpy impact strength were each evaluated. These results are shown in Table 1.

  The obtained polyarylene sulfide composition had high adhesive strength, and the form of adhesive failure was cohesive failure. Moreover, both tensile strength and Charpy impact strength were high, and tensile elongation was also large. That is, it was excellent in adhesiveness and mechanical strength, toughness, and impact resistance.

Examples 2-10
Table 1 shows PPS (a1-2, a2-1, a-2), PE copolymers (b1-1, b2-1, b3-1), and polysiloxane compounds (C-1, 2). A polyarylene sulfide composition was prepared in the same manner as in Example 1 except that the blending ratio shown in FIG. The evaluation results are shown in Table 1.

  All the obtained polyarylene sulfide compositions had high adhesive strength, and the form of adhesion failure was cohesive failure. Moreover, both tensile strength and Charpy impact strength were high, and tensile elongation was also large.

比較例１〜８
ＰＰＳ（ａ１−２）、ＰＥ系共重合体（ｂ２−１）及びポリシロキサン化合物（Ｃ−１、Ｃ’−１，２，３）、エポキシ樹脂（ｆ−１）を表２に示す配合割合とした以外は、実施例１と同様の方法によりポリアリーレンスルフィド組成物を作製し、実施例１と同様の方法により評価した。評価結果を表２に示す。

Comparative Examples 1-8
PPS (a1-2), PE copolymer (b2-1), polysiloxane compound (C-1, C′-1,2,3), and epoxy resin (f-1) are shown in Table 2. A polyarylene sulfide composition was prepared in the same manner as in Example 1 except that the above was evaluated, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

  Each of the obtained polyarylene sulfide compositions is one in which the amount of polyarylene sulfide (A) falls outside the scope of claims, and the amount of polyethylene-based copolymer (B) falls outside the scope of claims, The compounding amount of the modified polysiloxane compound (C) is not within the scope of the claims, the polysiloxane compound is a one-terminal functional group modified type, a side chain functional group modified type, or a functional group unmodified type, and poly An epoxy resin was blended in place of the siloxane compound, and a material having excellent adhesive strength, tensile strength, tensile elongation, and Charpy impact strength was not obtained.

実施例１１
ＰＰＳ（ａ１−２）８４重量％、ＰＥ系共重合体（ｂ１−１）１５重量％及びポリシロキサン化合物（Ｃ−１）１重量％からなる合計量１００重量部に対し、滑剤（ｅ１−１）０．５重量の割合で配合し、３１０℃に加熱した二軸押出機（東芝機械製、（商品名）ＴＥＭ−３５−１０２Ｂ）のホッパーに投入した。一方、ガラス繊維（ｄ１−１）が５０重量部となるように該二軸押出機のサイドフィーダーから供給し、スクリュー回転数２００ｒｐｍにて溶融混練し、ダイより流出する溶融組成物を冷却後裁断し、ペレット状のポリアリーレンスルフィド組成物を作製した。

Example 11
Lubricant (e1-1) with respect to a total amount of 100 parts by weight consisting of 84% by weight of PPS (a1-2), 15% by weight of PE copolymer (b1-1) and 1% by weight of polysiloxane compound (C-1) ) Compounded at a ratio of 0.5 wt. And charged into a hopper of a twin screw extruder (manufactured by Toshiba Machine, (trade name) TEM-35-102B) heated to 310 ° C. On the other hand, the glass fiber (d1-1) is supplied from the side feeder of the twin screw extruder so as to be 50 parts by weight, melt kneaded at a screw rotation speed of 200 rpm, and the molten composition flowing out from the die is cooled and cut. Thus, a pellet-like polyarylene sulfide composition was produced.

  A test piece for measuring the adhesive strength, tensile strength, and tensile elongation by introducing the polyarylene sulfide composition into a hopper of an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75) heated to 310 ° C. A test piece for measuring Charpy impact strength, a test piece for measuring weld strength, and a test piece for evaluating heat cycle resistance were formed. Using these test pieces and test pieces, adhesive strength, tensile strength, tensile elongation, Charpy impact strength, weld strength, and heat cycle resistance were evaluated. These results are shown in Table 3.

  The obtained polyarylene sulfide composition had high adhesive strength, and the form of adhesive failure was cohesive failure. Moreover, tensile strength, Charpy impact strength, and weld strength were all high, and tensile elongation was also large. Furthermore, it was excellent in heat cycle resistance.

実施例１２〜１８
ＰＰＳ（ａ１−２、ａ２−１、ａ−２）、ＰＥ系共重合体（ｂ１−１、ｂ２−１，２、ｂ３−１）、ポリシロキサン化合物（Ｃ−１、２）、ガラス繊維（ｄ１−１）、炭酸カルシウム（ｄ２−１）及び滑剤（ｅ１−１、ｅ２−１）を表３に示す配合割合とした以外は、実施例１１と同様の方法によりポリアリーレンスルフィド組成物を作製し、実施例１１と同様の方法により評価した。評価結果を表３に示す。

Examples 12-18
PPS (a1-2, a2-1, a-2), PE copolymer (b1-1, b2-1, b3-1), polysiloxane compound (C-1,2), glass fiber ( A polyarylene sulfide composition was prepared in the same manner as in Example 11 except that d1-1), calcium carbonate (d2-1), and lubricants (e1-1, e2-1) were mixed in the proportions shown in Table 3. Then, it was evaluated by the same method as in Example 11. The evaluation results are shown in Table 3.

  All the obtained polyarylene sulfide compositions had high adhesive strength, and the form of adhesion failure was cohesive failure. Moreover, tensile strength, Charpy impact strength, and weld strength were all high, and tensile elongation was also large. Furthermore, it was excellent in heat cycle resistance.

Comparative Examples 9-14
PPS (a1-2), PE copolymer (b2-1), polysiloxane compound (C-1, C′-1, 2), glass fiber (d1-1), calcium carbonate (d2-1), A polyarylene sulfide composition was prepared in the same manner as in Example 11 except that the lubricants (e1-1, e2-1) and the epoxy resin (f-1) were mixed in the proportions shown in Table 4, and Example 11 was prepared. It evaluated by the same method. The evaluation results are shown in Table 4.

  Each of the obtained polyarylene sulfide compositions has a polyarylene sulfide (A) blending amount deviating from the claims, a modified polysiloxane compound (C) blending amount deviating from the claims, poly The siloxane compound is one-end functional group-modified type or side-chain functional group-modified type, and an epoxy resin is blended in place of the polysiloxane compound. Adhesive strength, tensile strength, tensile elongation, Charpy impact strength No weld strength was obtained at the same time. In addition, all the polyarylene sulfide compositions obtained had poor heat cycle resistance.

Claims (6)

  67-98.9% by weight of polyarylene sulfide (A), maleic anhydride graft-modified ethylene-α-olefin copolymer (b1), ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B2), ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer (b3), ethylene-α, β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer (b4), ethylene-α, β -At least one polyethylene copolymer (B) selected from the group consisting of an unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (b5), 1 to 30% by weight, And modified polysiloxane having at least one functional group selected from the group consisting of an amino group, an epoxy group, and a carboxyl group at both ends. A polyarylene sulfide composition comprising 0.1 to 5% by weight of a xylene compound (C).   The polyarylene sulfide (A) is a functional group-containing polyarylene sulfide (a1) and / or a linear polyarylene sulfide (a2) having a functional group corresponding to 0.05 to 5 mol% per arylene sulfide unit. The polyarylene sulfide composition according to claim 1.   The polyarylene sulfide (A) is at least one polyarylene sulfide selected from the group consisting of an amino group-containing polyarylene sulfide, a carboxyl group-containing polyarylene sulfide, a thiol group-containing polyarylene sulfide, and a hydroxyl group-containing polyarylene sulfide. The polyarylene sulfide composition according to claim 1, wherein the polyarylene sulfide composition is present. The polyarylene sulfide composition according to any one of claims 1 to 3, wherein the modified polysiloxane compound (C) is a modified polysiloxane compound represented by the following general formula (1).

(Here, R ₁ and R ₂ each independently represent an alkylene group, X ₁ and X ₂ each independently represent an amino group, a glycidoxy group, a 3,4-epoxycyclohexyl group, and a carboxyl group, and n ≧ 1)   Further, 10 to 150 parts by weight of the filler (D) and / or the lubricant (E) are added to 100 parts by weight of the total of the polyarylene sulfide (A), the polyethylene copolymer (B) and the modified polysiloxane (C). The polyarylene sulfide composition according to any one of claims 1 to 4, wherein 05 to 5 parts by weight are blended. The polyarylene sulfide composition according to claim 5, wherein the filler (D) is glass fiber (d1), and the lubricant (E) is carnauba wax (e1) or carboxylic acid amide wax (e2).