JP2018065965A - Polyarylene sulfide resin composition, molded article and production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin composition which is a molded article having excellent silicone resin adhesion, and a molded article having excellent silicone resin adhesion obtained by molding the composition, and further the molded article and silicone To provide a composite molded product obtained by bonding a cured product of a curable resin composition containing a resin, and to provide a method for producing them. SOLUTION: Polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 are contained as essential components, and polyarylene sulfide resin (A). A polyarylene sulfide resin composition, a molded article, and a composite molded article with a cured silicone resin, wherein the polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass. And their manufacturing methods. [Selection figure] None

Description

  The present invention relates to a polyarylene sulfide resin composition, a molded article, and a method for producing them.

  Polyarylene sulfide (hereinafter abbreviated as PAS) resin, represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin, has excellent heat resistance and mechanical strength, chemical resistance, and moldability. They are also excellent in dimensional stability, and are used as electrical / electronic equipment parts, automobile parts materials, etc. by utilizing these characteristics.

  In many cases, these parts are bonded to a part material made of silicone resin or the like as the secondary processing. However, polyarylene sulfide resins have relatively poor adhesion to other resins, in particular, adhesion to an adhesive made of a curable resin composition containing a silicone resin or a silicone resin (hereinafter referred to as a silicone resin adhesive). . Therefore, for example, when polyarylene sulfides are bonded with silicone resin adhesives, polyarylene sulfide resins are bonded to other materials, or when electrical / electronic components are sealed with silicone adhesives, polyarylene sulfide resins are used. Inadequate adhesion between the resin and the curable resin composition containing silicone resin or silicone resin (hereinafter sometimes referred to as silicone resin adhesion) has been a problem.

  Therefore, it is known that a molded article of a polyarylene sulfide resin composition containing a polyarylene sulfide resin and magnesium oxide improves the silicone resin adhesion (see Patent Document 1). However, although magnesium oxide is a relatively stable compound, when it is left in the air, it easily absorbs carbon dioxide due to the presence of moisture, changes to magnesium hydroxide due to moisture absorption, or absorbs carbon dioxide and moisture to carbonate. Change to magnesium. For this reason, since strict management is required as a manufacturing raw material, a manufacturing raw material that can be stored more stably even in the air has been desired. Furthermore, it cannot be said that the effect of the silicone resin adhesiveness by magnesium oxide is yet sufficient, and it is difficult to say that it has been improved to a practical level.

JP 2003-96299 A

  The problem to be solved by the present invention is to provide a polyarylene sulfide resin composition that is a molded article excellent in silicone resin adhesion, and a molded article excellent in silicone resin adhesion obtained by molding it. It is another object of the present invention to provide a composite molded product obtained by bonding the molded product and a cured product of a curable resin composition containing a silicone resin, and to provide a method for producing them.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a molded product of a resin composition obtained by blending and kneading high molecular weight polyvinyl pyrrolidone with polyarylene sulfide resin is a silicone resin. It has been found that the adhesiveness is excellent, and the present invention has been completed.

That is, the present invention contains polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components,
The polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A).
The present invention relates to a polyarylene sulfide resin composition characterized in that the polyarylene sulfide resin (A) is used as a matrix, and a morphology in which the polyvinylpyrrolidone (B) is dispersed is formed in the matrix.

  In addition, the present invention relates to a molded article obtained by molding the polyarylene sulfide resin composition.

  Furthermore, the present invention relates to a composite molded product formed by bonding a molded product formed by molding the polyarylene sulfide resin composition and a cured product of a silicone resin or a curable resin composition containing silicone.

  In addition, the present invention provides the polyarylene sulfide resin (A) and the polyarylene sulfide resin (A) having as essential components a polyarylene sulfide resin (A) and a polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000. The present invention relates to a method for producing a polyarylene sulfide resin composition characterized by melting and kneading at a melting point or higher.

  Moreover, this invention relates to the manufacturing method of a molded article which shape | molds the polyarylene sulfide resin composition obtained by the said manufacturing method.

  Further, the present invention is a composite molded article characterized by contacting a molded article obtained by the above-described production method with a curable resin composition containing a silicone resin, and then curing the curable resin composition. The manufacturing method.

  According to the present invention, a polyarylene sulfide resin composition that is a molded article having excellent silicone resin adhesion, and a molded article having excellent silicone resin adhesion, which is obtained by molding the polyarylene sulfide resin composition, are further provided. And a cured product of a curable resin composition containing a silicone resin can be provided, and a production method thereof can be provided.

The polyarylene sulfide resin composition of the present invention contains the polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components,
The polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A).

  The polyarylene sulfide resin composition of the present invention contains the polyarylene sulfide resin (A) as an essential component. The polyarylene sulfide resin used in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the polyarylene sulfide resin has the following general formula (2).

（式中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１〜４の範囲のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、エトキシ基を表す。）で表される構造部位と、必要に応じてさらに下記一般式（２）

(Wherein R ¹ and R ² each independently represent 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). And, if necessary, the following general formula (2)

で表される３官能性の構造部位と、を繰り返し単位とする樹脂である。式（３）で表される３官能性の構造部位は、他の構造部位との合計モル数に対して０．００１〜３モル％の範囲が好ましく、特に０．０１〜１モル％の範囲であることが好ましい。

And a trifunctional structural moiety represented by formula (1). The trifunctional structural site represented by the formula (3) is preferably in the range of 0.001 to 3 mol%, particularly in the range of 0.01 to 1 mol%, based on the total number of moles with other structural sites. It is preferable that

Here, in the structural part represented by the general formula (2), R ¹ and R ² in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. In this case, those bonded at the para position represented by the following formula (4) and those bonded at the meta position represented by the following formula (5) are exemplified.

これらの中でも、特に繰り返し単位中の芳香族環に対する硫黄原子の結合は前記一般式（４）で表されるパラ位で結合した構造であることが前記ポリアリーレンスルフィド樹脂の耐熱性や結晶性の面で好ましい。

Among these, in particular, the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para-position represented by the general formula (4). In terms of surface.

  Further, the polyarylene sulfide resin is not limited to the structural portion represented by the general formulas (2) and (3), but also includes the following structural formulas (6) to (9).

で表される構造部位を、前記一般式（２）と一般式（３）で表される構造部位との合計の３０モル％以下で含んでいてもよい。特に本発明では上記一般式（６）〜（９）で表される構造部位は１０モル％以下であることが、ポリアリーレンスルフィド樹脂の耐熱性、機械的強度の点から好ましい。前記ポリアリーレンスルフィド樹脂中に、上記一般式（６）〜（９）で表される構造部位を含む場合、それらの結合様式としては、ランダム共重合体、ブロック共重合体の何れであってもよい。

The structural site represented by the formula (2) and the structural site represented by the general formula (3) may be included at 30 mol% or less. In particular, in the present invention, the structural sites represented by the general formulas (6) to (9) are preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin. When the polyarylene sulfide resin contains a structural moiety represented by the general formulas (6) to (9), the bonding mode may be either a random copolymer or a block copolymer. Good.

  Further, the polyarylene sulfide resin may have a naphthyl sulfide bond or the like in its molecular structure, but is preferably 3 mol% or less with respect to the total number of moles with other structural sites, particularly 1 It is preferable that it is below mol%.

  The physical properties of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.

(Melt viscosity)
The polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300 ° C. in the range of 2 to 1000 [Pa · s], and has a good balance between fluidity and mechanical strength. Therefore, the range of 10 to 500 [Pa · s] is more preferable, and the range of 60 to 200 [Pa · s] is particularly preferable. However, in the present invention, the melt viscosity (V6) is as follows: polyarylene sulfide resin is flow tester manufactured by Shimadzu Corporation, CFT-500D, 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 (mm ) / 1 (mm), and the melt viscosity is measured after holding for 6 minutes.

(Non-Newtonian index)
The non-Newtonian index of the polyarylene sulfide resin (A) used in the present invention is not particularly limited as long as the effect of the present invention is not impaired, but is preferably in the range of 0.90 to 2.00. When the linear polyarylene sulfide resin is used, the non-Newton index is preferably in the range of 0.90 to 1.50, and more preferably in the range of 0.95 to 1.20. Such a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, the non-Newtonian index (N value) is measured by measuring the shear rate and shear stress using a capillograph at 300 ° C, the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40. These are values calculated using the following formula.

［ただし、ＳＲは剪断速度（秒^−１）、ＳＳは剪断応力（ダイン／ｃｍ^２）、そしてＫは定数を示す。］Ｎ値は１に近いほどＰＰＳは線状に近い構造であり、Ｎ値が高いほど分岐が進んだ構造であることを示す。

[Wherein SR represents a shear rate (second ⁻¹ ), SS represents a shear stress (dyne / cm ² ), and K represents a constant. The closer the N value is to 1, the closer the PPS is to a linear structure, and the higher the N value is, the more branched the structure is.

(Production method)
The method for producing the polyarylene sulfide resin (A) is not particularly limited. For example, 1) dihalogenoaromatic compound in the presence of sulfur and sodium carbonate, and if necessary polyhalogenoaromatic compound or other copolymerization component. In addition, a polymerization method, 2) a dihalogenoaromatic compound in a polar solvent in the presence of a sulfidizing agent, and a polyhalogenoaromatic compound or other copolymerization component, if necessary, and polymerization, 3) Examples of the method include self-condensation of p-chlorothiophenol by adding another copolymer component if necessary. Among these methods, the method 2) is versatile and preferable. In the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above methods 2), a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound in the organic polar solvent. And a sulfidizing agent, if necessary, with a polyhalogenoaromatic compound and reacting, and the amount of water in the reaction system is in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. If necessary, a method for producing a polyarylene sulfide resin by controlling (see JP 07-228699 A), a dihalogenoaromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent, if necessary Polyhalogenoaromatic compound or other copolymerization component is added, and alkali metal hydrosulfide and organic acid alkali metal salt are added to sulfur source 1 While controlling the organic acid alkali metal salt in the range of 0.01 to 0.9 mol and the amount of water in the reaction system to 0.02 mol or less with respect to 1 mol of the aprotic polar organic solvent, What is obtained by the method of making it react (refer pamphlet of WO2010 / 058713) is especially preferable. Specific examples of the dihalogenoaromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and each of the above compounds A compound having an alkyl group having 1 to 18 carbon atoms in the aromatic ring, and 1,2,3-trimethyl as a polyhalogenoaromatic compound. Lobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6- And trihalonaphthalene. Moreover, it is desirable that the halogen atom contained in each compound is a chlorine atom or a bromine atom.

  The post-treatment method of the reaction mixture containing the polyarylene sulfide resin obtained by the polymerization step is not particularly limited. For example, (1) after the completion of the polymerization reaction, the reaction mixture is left as it is, or an acid or a base is used. After adding the solvent, the solvent is distilled off under reduced pressure or normal pressure, and then the solid after the solvent is distilled off is water, a reaction solvent (or an organic solvent having an equivalent solubility in a low molecular weight polymer), acetone, methyl ethyl ketone. , A method of washing once or twice with a solvent such as alcohols, and further neutralizing, washing with water, filtering and drying, or (2) after completion of the polymerization reaction, water, acetone, methyl ethyl ketone, alcohols, Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (soluble in the polymerization solvent used, and at least A solvent which is a poor solvent for the arylene sulfide) is added as a precipitating agent to precipitate solid products such as polyarylene sulfide and inorganic salts, and these are filtered, washed and dried, or (3) After the completion of the polymerization reaction, the reaction mixture (or an organic solvent having an equivalent solubility with respect to the low molecular polymer) is added to the reaction mixture and stirred, and then filtered to remove the low molecular weight polymer. A method of washing once or twice with a solvent such as acetone, methyl ethyl ketone, alcohol, etc., followed by neutralization, washing with water, filtration and drying. (4) After completion of the polymerization reaction, water is added to the reaction mixture to wash with water. Filtration, if necessary, acid treatment at the time of washing with water, acid treatment and drying, (5) after completion of the polymerization reaction, the reaction mixture is filtered, and if necessary, once or twice or more with a reaction solvent Wash Further washing with water, a method of filtering and drying, and the like.

   In the post-treatment methods exemplified in the above (1) to (5), the polyarylene sulfide resin may be dried in a vacuum or in an inert gas atmosphere such as air or nitrogen. May be.

  The polyarylene sulfide resin composition of the present invention contains polyvinylpyrrolidone (B) as an essential component. The polyvinyl pyrrolidone has a mass average molecular weight in the range of 50,000 to 2,000,000, preferably in the range of 500,000 to 1,500,000, more preferably 1,000,000 to 1. , 200,000. The degree of polymerization n is not particularly limited as long as the mass average molecular weight falls within the above range, but preferably n is in the range of 450 to 18,000, preferably in the range of 4,500 to 13,500. Is more preferable, and the range of 9,000 to 108,000 is particularly preferable. Polyvinyl pyrrolidone may be either a linear type or a crosslinked type.

  As polyvinylpyrrolidone (B), for example, the following general formula (1)

で表される構造を有するものが好ましく挙げられる。ただし、式（１）中、ｎは繰り返し単位を表し、４５０〜１８，０００の範囲である。また、Ｒ^１は水素原子、炭素原子数１〜６の範囲のアルキル基またはアルコキシ基で、好ましくはメチル基、ｉ−またはｎ−プロピル基、ブチル基であり、このうち、水素原子が好ましい。

Those having a structure represented by the formula are preferred. However, in Formula (1), n represents a repeating unit and is in the range of 450 to 18,000. R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, preferably a methyl group, i- or n-propyl group or butyl group, and among these, a hydrogen atom is preferred.

  The method for producing the polyvinyl pyrrolidone can be a known method and is not particularly limited as long as the effects of the present invention are not impaired. For example, a method of reacting 2-pyrrolidone, acetylene and raw materials (Repe method) In addition to the method using a dehydration reaction of N-hydroxyethylpyrrolidone, preferably, N-hydroxyethylpyrrolidone obtained by subjecting N-hydroxyethylpyrrolidone to a gas-phase dehydration reaction and having a γ-butyrolactone content reduced to, for example, 500 ppm or less -A method in which vinyl pyrrolidone is radically polymerized by appropriately adding a known polymerization initiator or a basic pH adjuster.

  Here, the N-vinylpyrrolidone has the following general formula (10)

で示されるピロリジニル基を含有する重合性不飽和モノマーである。ここでＲ^１は前記式（１）と同様である。

It is a polymerizable unsaturated monomer containing a pyrrolidinyl group represented by: Here, R ¹ is the same as the formula (1).

  The polyvinyl pyrrolidone used in the present invention is preferably a homopolymer obtained from the N-vinyl pyrrolidone as a raw material, but N-vinyl represented by the general formula (10) as long as the effects of the present invention are not impaired. It may be a copolymer using pyrrolidone or other monomer as a raw material. In this case, the amount of the other monomer used is preferably 10% by mass or less, more preferably 1% by mass or less. More preferably, it is 1% by mass or less.

  Other monomers include, for example, the following general formula (11)

で示されるピロリジニル基を含有する重合性不飽和モノマーが挙げられる。ここでＸは、ラジカル重合可能な二重結合を有する置換基であり、次の一般式（１２）〜（１７）

The polymerizable unsaturated monomer containing the pyrrolidinyl group shown by these is mentioned. Here, X is a substituent having a double bond capable of radical polymerization, and is represented by the following general formulas (12) to (17).

（式（１２）〜（１７）中、Ｒ^１は水素原子、炭素原子数１〜６の範囲のアルキル基またはアルコキシ基で、好ましくはメチル基、ｉ−またはｎ−プロピル基、ブチル基である。）で表される置換基が挙げられる。

(In the formulas (12) to (17), R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, preferably a methyl group, i- or n-propyl group or butyl group. )).

As the polyvinylpyrrolidone used in the present invention, commercially available products such as “K-90”, “K-85”, and “K-30” manufactured by Nippon Shokubai Co., Ltd. can be used.

  In the present invention, the polyvinyl pyrrolidone (B) is preferably in the range of 0.01 to 100 parts by mass and in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). More preferably, it is more preferably in the range of 1 to 30 parts by mass, and most preferably in the range of 2 to 25 parts by mass. Within this range, the polyarylene sulfide resin molded article of the present invention is preferable because it exhibits good silicone resin adhesion.

  The polyarylene sulfide resin composition of the present invention can contain a filler as an optional component, if necessary. As these fillers, known and commonly used materials can be used as long as they do not impair the effects of the present invention. For example, various fillers such as fibrous ones and non-fibrous ones such as granular and plate shapes can be used. A filler etc. are mentioned. Specifically, fiber fillers such as glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium silicate, wollastonite, etc., natural fiber, etc. Glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber Non-fibrous fillers such as calcium sulfate can also be used.

  In the present invention, the filler is not an essential component, and when added, the content is not particularly limited as long as the effects of the present invention are not impaired. As content of a filler, it is preferable that it is the range of 1-600 mass parts with respect to 100 mass parts of polyarylene sulfide resin (A), for example, and it is more preferable that it is the range of 10-200 mass parts. preferable. In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.

  The polyarylene sulfide resin composition of the present invention can contain a silane coupling agent as an optional component, if necessary. The silane coupling agent is not particularly limited as long as the effects of the present invention are not impaired, but a silane coupling agent having a functional group that reacts with a carboxy group, for example, an epoxy group, an isocyanato group, an amino group, or a hydroxyl group is preferable. Can be mentioned. Examples of such silane coupling agents include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , Γ-isocyanatopropylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- ( -Aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. It is done. In the present invention, the silane coupling agent is not an essential component, but when it is added, the amount added is not particularly limited as long as the effects of the present invention are not impaired, but the polyarylene sulfide resin (A) is 100 parts by mass. Is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.1 to 5 parts by mass. Within such a range, the resin composition is preferable because it has good corona resistance and moldability, in particular, releasability, and the molded product exhibits excellent adhesiveness with the epoxy resin and further improves the mechanical strength.

  The polyarylene sulfide resin composition of the present invention can contain a thermoplastic elastomer as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. Among these, polyolefin-based elastomers are preferable. When these elastomers are added, the content is not particularly limited as long as the effects of the present invention are not impaired, but in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is preferable that it is in the range of 0.1 to 5 parts by mass. Within such a range, the resulting polyarylene sulfide resin composition is preferred because the impact resistance is improved.

  When the polyolefin-based elastomer further imparts a functional group, for example, by homopolymerization of α-olefin or copolymerization of different α-olefins, the α-olefin and a vinyl polymerizable compound having a functional group It can be obtained by copolymerization. Examples of the α-olefin include those having 2 to 8 carbon atoms such as ethylene, propylene, and butene-1. In addition, as the functional group, a carboxy group, an acid anhydride group represented by the formula-(CO) O (CO)-, an ester, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group Etc.

  Specific examples of the vinyl polymerizable compound having such a functional group include, for example, α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid. Examples thereof include acids, itaconic acid and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters and acid anhydrides thereof), and glycidyl (meth) acrylate. Among these, an ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the above-described epoxy group, carboxy group, and acid anhydride group are mechanical. It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.

  Furthermore, in addition to the above components, the polyarylene sulfide resin composition of the present invention may further include other synthetic resins excluding the polyarylene sulfide resin and the polyvinyl pyrrolidone, depending on the application, for example, a polyester resin, a polyamide resin, Polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene Resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenol resin, urethane resin, liquid crystal polymer and the like (hereinafter simply referred to as synthetic resin) can be contained as optional components. In addition, the content of these synthetic resins varies depending on the purpose and cannot be generally specified. However, the resin components in the polyarylene sulfide resin composition of the present invention (the polyarylene sulfide resin, the polyvinyl In other words, the total of the polyarylene sulfide resin and the polyvinyl pyrrolidone is in the range of 75.0% by mass or more, preferably in the range of 80 to 99.99% by mass. The synthetic resin may be used in a range of 25.0% by mass or less, preferably in the range of 0.01 to 20.0% by mass, appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention.

  In addition, the polyarylene sulfide resin composition of the present invention includes other colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant aids, You may contain well-known and usual additives, such as a rust agent and a coupling agent, as an arbitrary component as needed. These additives are not essential components. For example, with respect to 100 parts by mass of the polyarylene sulfide resin (A), preferably in the range of 0.01 to 1000 parts by mass, the purpose and application are not impaired. It may be adjusted as appropriate according to the conditions.

  In the method for producing the polyarylene sulfide resin composition of the present invention, the polyarylene sulfide resin (A) and the polyvinyl pyrrolidone (B) are essential components and melt kneaded at a melting point or higher of the polyarylene sulfide resin (A).

  A preferred method for producing the polyarylene sulfide resin composition of the present invention is to fill the polyarylene sulfide resin (A) and each of the essential components of the polyvinyl pyrrolidone (B), if necessary, so as to have the above-described content. Arbitrary ingredients such as agents are put into ribbon blenders, Henschel mixers, V blenders, etc. in various forms such as powders, pellets, and strips, dry blended, and then banbury mixers, mixing rolls, single or twin screw extrusions In a known melt kneader such as a kneader and a kneader, and a temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably a temperature range in which the melting point is + 10 ° C or higher, more preferably a melting point + 10 ° C to a melting point + 100 ° C. In the temperature range of melting point +20 to melting point + 50 ° C. It can be manufactured through a step of. Addition and mixing of each component to the melt kneader may be performed simultaneously or may be performed separately.

  The melt kneader is preferably a biaxial kneader / extruder from the viewpoint of dispersibility and productivity. For example, the resin component discharge rate is in the range of 5 to 500 kg / hr, and the screw rotation speed is 50 to 500 (rpm). It is preferable to perform melt kneading while appropriately adjusting the range of the above, and melt kneading under the condition that the ratio (discharge amount / screw rotation number) is in the range of 0.02 to 5 (kg / hr / rpm). Is more preferable. Moreover, when adding a filler and an additive among the said components, it is preferable from a dispersible viewpoint to throw in into this extruder from the side feeder of the said biaxial kneading extruder. The position of the side feeder is preferably such that the ratio of the distance from the extruder resin charging part to the side feeder with respect to the total screw length of the twin-screw kneading extruder is in the range of 0.1 to 0.9. In particular, a range of 0.3 to 0.7 is particularly preferable.

  Thus, the polyarylene sulfide resin composition of the present invention obtained by melt-kneading comprises the polyarylene sulfide resin (A) which is an essential component, the polyvinyl pyrrolidone (B), optional components added as necessary, and those After the melt-kneading, it is processed into a form of pellets, chips, granules, powder, etc. by a known method, and then pre-dried at a temperature of 100 to 150 ° C. as necessary. Thus, it is preferably used for various moldings.

  The polyarylene sulfide resin composition of the present invention produced by the above production method uses the polyarylene sulfide resin as a matrix, and the polyvinyl pyrrolidone (B), which is an essential component, in the matrix, components derived therefrom, and necessary According to this, a morphology in which optional components to be added are dispersed is formed. As a result, a molded article of the polyarylene sulfide resin composition is preferable because it has excellent silicone resin adhesion.

  The polyarylene sulfide resin composition of the present invention can be subjected to various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. It is suitable for injection molding because of its excellent properties. In the case of molding by injection molding, various molding conditions are not particularly limited, and can be usually molded by a general method. For example, in an injection molding machine, the resin temperature is a temperature range above the melting point of the polyarylene sulfide resin, preferably the temperature range above the melting point + 10 ° C., more preferably the temperature range from the melting point + 10 ° C. to the melting point + 100 ° C., more preferably the melting point. After passing through the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to melting point + 50 ° C., the resin discharge port may be injected into the mold and molded. At that time, the mold temperature may be set to a known temperature range, for example, room temperature (23 ° C.) to 300 ° C., preferably 120 to 180 ° C.

  A molded product obtained by molding the polyarylene sulfide resin composition of the present invention is excellent in mechanical strength in the TD direction during injection molding while being excellent in adhesiveness with a silicone resin. Therefore, it can be suitably used as a composite molded article in which a polyarylene sulfide resin and a cured product made of a silicone resin are bonded. The silicone resin used in producing the composite molded article may be any silicone resin that is commonly used by those skilled in the art as an adhesive, and may be either a condensation type silicone resin or an addition type silicone resin. However, it is preferable to use an addition-type silicone resin because it can be uniformly cured. As the method for producing the composite molded product, a method of producing a composite molded product by bringing a silicone resin into contact with a polyarylene sulfide resin molded product molded by various molding methods and then curing the silicone resin can be used. .

  Examples of main applications of the composite molded body include various home appliances, mobile phones, and casings of electronic devices such as PCs (Personal Computers), protective / support members for box-shaped electrical / electronic component integrated modules, Individual semiconductor or module, sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker , Microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts and other electrical and electronic parts; VTR parts , TV parts, iron, hair dry , Rice cooker parts, microwave oven parts, acoustic parts, audio / video equipment parts such as audio / laser disc / compact disc / DVD disc / Blu-ray disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, or Household appliances such as water heaters, bath water volume, temperature sensors, etc., office electrical appliance parts; office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs Mechanical parts such as motor parts, writers, typewriters, etc .: Optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machine parts; Alternator terminals, alternator connectors, brush holders, slip rings, ICs Regulator and light dial Various valves such as a nichiometer base, relay block, inhibitor switch, exhaust gas valve, various pipes related to fuel, exhaust system and intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor Spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, radiator motor Brush holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, Ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, electrical component insulation It can also be applied to automotive and vehicle related parts such as plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and other various applications.

<Examples 1-5 and Comparative Examples 1-2>
According to the composition components and blending amounts (all parts by mass) described in Tables 1 and 2, each material was uniformly mixed with a tumbler. Thereafter, the blended material is put into a twin-screw extruder “TEM-35B” manufactured by Toshiba Machine Co., Ltd., and the resin component discharge rate is 25 kg / hr, the screw rotation speed is 250 rpm, and the resin component discharge rate (kg / hr). The ratio of the screw rotation speed (rpm) (discharge amount / screw rotation speed) = 0.1 (kg / hr · rpm) was melt kneaded at a set resin temperature of 330 ° C. to obtain resin composition pellets. The following various evaluation tests were performed using this pellet. The result of a test and evaluation is shown to Tables 1-2.

[Adhesive strength of PAS resin molded product with silicone resin]
The obtained pellets were supplied to an injection molding machine (SE-75D) manufactured by Sumitomo Heavy Industries, Ltd., which was set to a cylinder temperature of 320 ° C., and injected using an ASTM No. 1 dumbbell piece molding die whose temperature was adjusted to 140 ° C. Molding was performed to obtain ASTM No. 1 dumbbell pieces. The obtained ASTM No. 1 dumbbell piece was divided into two equal parts from the center, and the contact area with a silicon adhesive (Toray Dow Corning, SE-1714, one liquid, heating / addition curing type) was 25 mm × 12.5 mm = 312. The molded products were overlapped so as to be 5 mm ² and fixed by using a clip, and then heated and cured / adhered in a hot air dryer set at 150 ° C. for 0.5 hours. The clip was removed after cooling at 23 ° C for 1 day, and the tensile strength at break was measured using an Instron tensile tester at 23 ° C with a strain rate of 1 mm / min and a fulcrum distance of 65 mm. The value obtained by dividing by the adhesion area was defined as the silicon adhesion strength.

The compounded resins and materials in Tables 1 and 2 are as follows.
PPS
A1 “MA-520” manufactured by linear type PPS DIC Corporation (peak molecular weight 35000, melt viscosity (V6) 160 Pa · s)
Vinylpyrrolidone-based additive B1 Polyvinylpyrrolidone resin “K-90” manufactured by Nippon Shokubai Co., Ltd.
(Weight average molecular weight: 1,050,000 to 1,200,000)
B2 Polyvinylpyrrolidone resin “K-85” manufactured by Nippon Shokubai Co., Ltd.
(Weight average molecular weight: 900,000 to 1,050,000)
B3 Polyvinylpyrrolidone resin “K-30” manufactured by Nippon Shokubai Co., Ltd.
(Weight average molecular weight: 80,000 to 120,000)
b4 Polyvinylpyrrolidone resin Daiichi Kogyo Seiyaku Co., Ltd. “Pitzkor K-17L”
(Weight average molecular weight: 9,000)

Inorganic filler C1 Glass fiber “T-717H” manufactured by Nippon Electric Glass Co., Ltd. (diameter 10 μm chopped strand)
C2 Magnesium oxide (“Pyroxuma (registered trademark) 500-04R” manufactured by Kyowa Chemical Industry Co., Ltd.)
C3 calcium carbonate (Maruo Calcium Co., Ltd., “Caltex 5” (powder, average particle size 1.2 μm)

Claims (10)

Containing polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components;
The polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A).
A polyarylene sulfide resin composition, wherein the polyarylene sulfide resin (A) is used as a matrix, and a morphology in which the polyvinylpyrrolidone (B) is dispersed is formed in the matrix. The polyvinylpyrrolidone (B) is represented by the following general formula (1)

(Wherein n represents a repeating unit and is in the range of 450 to 18,000. R ¹ is a hydrogen atom, an alkyl group or an alkoxy group having 1 to 6 carbon atoms). The polyarylene sulfide resin composition according to claim 1, comprising:   The polyarylene sulfide resin composition according to claim 1, which is a melt-kneaded product.   The molded article formed by shape | molding the polyarylene sulfide resin composition as described in any one of the said Claims 1-3.   A composite molded article obtained by bonding the molded article according to claim 4 and a cured product of a silicone resin or a curable resin composition containing the silicone resin.   Using polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) having a mass average molecular weight in the range of 50,000 to 2,000,000 as essential components, melt kneading is performed at a melting point or higher of polyarylene sulfide resin (A). A process for producing a polyarylene sulfide resin composition characterized by the above.   The manufacturing method of the polyarylene sulfide resin composition of Claim 6 whose said polyvinyl pyrrolidone (B) is the range of 0.01-100 mass parts with respect to 100 mass parts of polyarylene sulfide resins (A). The polyvinylpyrrolidone (B) is represented by the following general formula (1)

(Wherein, n represents a repeating unit, is in the range of 450~18,000 .R ¹ is a hydrogen atom, an alkyl group or an alkoxy group ranging from 1 to 6 carbon atoms.) Structure represented by A process for producing a polyarylene sulfide resin composition according to claim 6 or 7, wherein:   The manufacturing method of a molded article which shape | molds the polyarylene sulfide resin composition obtained by the manufacturing method as described in any one of the said Claims 6-8.   A molded article obtained by the production method according to claim 9 and a curable resin composition containing a silicone resin are brought into contact with each other, and then the curable resin composition is cured. Production method.