JP2018100365A - 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 low in recrystallization temperature (Tc2) and is also excellent in heat resistance when formed into a molded article; a polyarylene sulfide resin molded article obtained by molding the same; and a method for producing them.SOLUTION: There are provided a polyarylene sulfide resin composition which is obtained by blending a polyarylene sulfide resin (A), polyvinyl pyrrolidone (B) and phosphate (C) containing metal belonging to 2 or 12 group of the periodic table as essential components, where the polyvinyl pyrrolidone (B) is in a range of 0.01-100 pts.mass and the phosphate (C) is in a range of 0.001-50 pts.mass with respect to 100 pts.mass of the polyarylene sulfide resin (A); a molded article; and a method for producing them.SELECTED DRAWING: None

Description

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

  A polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin typified by a polyphenylene sulfide (hereinafter abbreviated as PPS) resin has a high melting point and excellent heat resistance, as well as mechanical strength, chemical resistance, It is known that it is excellent in molding processability and dimensional stability. In general, therefore, additives such as fillers and elastomers are blended into the PAS resin, melted and kneaded so that these are dispersed in the matrix made of the PAS resin, and then the PAS resin composition is melted. Molded and processed into molded products used as electrical / electronic equipment parts, automobile parts, etc.

  Various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding are employed for melt molding of thermoplastic resins such as polyarylene sulfide resins. When the thermoplastic resin is melt-processed, the resin composition is heated to a temperature equal to or higher than the melting point to improve fluidity and then processed. For example, in the injection molding method, a molten resin is injected and filled into a mold heated to an appropriate temperature, and cooled and solidified to obtain a molded product. However, since the PAS resin composition has a high temperature (recrystallization temperature: Tc2) at which it is solidified (crystallized) from a molten state, there is a problem that it is solidified (crystallized) before filling the mold. These problems are not limited to injection molding, but are found in general melt processing. For molded products with complex shapes, shapes with different wall thicknesses, and larger (with a large amount of resin) molded products, The percentage of defective moldings increases due to solidification (crystallization), and the yield (the ratio of the actual number of products produced (quantity) to the production expected from the amount of resin composition input) is It was low. Therefore, development of a resin composition containing a polyarylene sulfide resin having a lower recrystallization temperature (Tc2) has been desired.

  Thus, a method of copolymerizing paradichlorobenzene and metadichlorobenzene has been proposed for the purpose of lowering the recrystallization temperature of the polyarylene sulfide resin (see Patent Document 1). However, since the PAS resin is a method in which a meta isomer is inserted into a part of the skeleton, the recrystallization temperature of the PAS resin itself to be used is lowered and the melting point (heat resistance) is also lowered. It was. As a result, while the resin material using the PAS resin is excellent in low-temperature moldability, the obtained molded product also has a property that the melting point (heat resistance) is remarkably lowered. Furthermore, the change in the skeleton of the PAS resin has led to a decrease in productivity because a great amount of energy is required for cleaning the polymer production line from the viewpoint of preventing contamination.

JP 2014-051655 A

  Therefore, the problem to be solved by the present invention is a polyarylene sulfide resin composition having a low recrystallization temperature (Tc2) and excellent heat resistance when formed into a molded product, and a polyarylene sulfide obtained by molding the same. It is in providing a resin molded product and a manufacturing method thereof.

  As a result of diligent research to solve the above problems, the present inventor has blended polyarylene sulfide resin with polyvinylpyrrolidone and a phosphate containing a metal belonging to Group 2 or Group 12 of the periodic table as essential components. It has been found that the resin composition obtained by smelting has a low recrystallization temperature (Tc2) without changing the skeleton of the polyarylene sulfide resin used, and is excellent in heat resistance when formed into a molded product. The above problems have been solved.

That is, the present invention comprises polyarylene sulfide resin (A), polyvinylpyrrolidone (B), and phosphate (C) containing a metal belonging to Group 2 or Group 12 of the periodic table as essential components. ,
The polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass and the phosphate (C) is in the range of 0.001 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is related with the polyarylene sulfide resin composition characterized by the above-mentioned.

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

  Furthermore, the present invention provides a polyarylene sulfide resin comprising, as essential components, a polyarylene sulfide resin (A), a polyvinylpyrrolidone (B), and a phosphate (C) containing a metal belonging to Group 2 or Group 12 of the periodic table. The present invention relates to a method for producing a polyarylene sulfide resin composition, characterized by melting and kneading at a melting point of (A) 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.

  According to the present invention, a polyarylene sulfide resin composition having a low recrystallization temperature (Tc2) and excellent heat resistance when formed into a molded product, a polyarylene sulfide resin molded product obtained by molding the same, and Their manufacturing method can be provided.

  The polyarylene sulfide resin composition of the present invention is essentially composed of polyarylene sulfide resin (A), polyvinylpyrrolidone (B), and phosphate (C) containing a metal belonging to Group 2 or Group 12 of the periodic table. 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), and the phosphate (C) is 0.001. It is the range of -50 mass parts, It is characterized by the above-mentioned.

  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.

(Melting point (Tm) and recrystallization temperature (Tc2))
The melting point (Tm) of the resin (A) is preferably in the range of 270 ° C. or more, and more preferably in the range of 270 to 300 ° C., since it becomes a polyarylene sulfide resin composition excellent in heat resistance and mechanical strength. More preferably. Moreover, since it becomes a polyarylene sulfide resin composition excellent in heat resistance and mechanical strength, it is preferable that the recrystallization temperature (Tc2) of the resin (A) is in the range of 200 to 260 ° C.

(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 comprises polyvinyl pyrrolidone (B) as an essential component. The average molecular weight of the polyvinyl pyrrolidone is not particularly limited, but preferably the weight average molecular weight is in the range of 3,000 to 2,000,000, more preferably in the range of 500,000 to 1,500,000, The range is 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 is in the above range, but preferably n is in the range of 30 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. In addition, the mass average molecular weight prepared the tetrahydrofuran solution (0.1 wt%) of polyvinylpyrrolidone, and the GPC apparatus (made by Tosoh Corporation) equipped with the TSKGelGHxl series 5000, 3000, 2000, 1000 column and a differential refractometer (RI) detector. HLC-8220GPC) was used, and the measurement was performed at 40 ° C. using a sample solution injection amount of 50 μl and tetrahydrofuran as a mobile phase (1 ml / min). The mass average molecular weight was calculated from a calibration curve composed of standard styrene. However, the measurement conditions can be appropriately changed within a range that does not substantially affect the measurement value of the mass average molecular weight.

  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、好ましくは３０〜１８，０００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, Preferably it is the range of 30-18,000. 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 proportion of the polyvinylpyrrolidone (B) is preferably in the range of 0.01 to 100 parts by mass, and 0.1 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). 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 such a range, the polyarylene sulfide resin composition of the present invention is preferable because it exhibits a low recrystallization temperature and the obtained molded article exhibits good heat resistance.

  The polyarylene sulfide resin composition of the present invention comprises a phosphate (C) containing a metal belonging to Group 2 or Group 12 of the periodic table as an essential component. Examples of the phosphate include metal salts such as phosphoric acid (orthophosphoric acid), phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, polyphosphoric acid, metaphosphoric acid, acidic metaphosphoric acid, hexametaphosphoric acid, pyrophosphoric acid, and acidic pyrophosphoric acid. In addition, the metal element of the metal salt includes a metal belonging to Group 2 or Group 12 of the periodic table. Further, as the metal belonging to Group 2 or Group 12 of the periodic table, magnesium, calcium, barium, and zinc are preferable. Specifically, magnesium phosphate, calcium phosphate, barium phosphate, zinc phosphate, magnesium phosphite, calcium phosphite, barium phosphite, zinc phosphite, magnesium hypophosphite, calcium hypophosphite, hypophosphorous acid Barium phosphate, aluminum hypophosphite, zinc hypophosphite, magnesium tripolyphosphate, calcium tripolyphosphate, barium tripolyphosphate, zinc tripolyphosphate, magnesium polyphosphate, calcium polyphosphate, barium polyphosphate, zinc polyphosphate, magnesium metaphosphate, meta Calcium phosphate, barium metaphosphate, zinc metaphosphate, acidic magnesium metaphosphate, acidic calcium metaphosphate, acidic barium metaphosphate, acidic zinc metaphosphate, magnesium hexametaphosphate, hexametaphosphate potassium Cium, barium hexametaphosphate, zinc hexametaphosphate, magnesium pyrophosphate, calcium pyrophosphate, barium pyrophosphate, zinc pyrophosphate, magnesium acid pyrophosphate, calcium calcine pyrophosphate, acid barium pyrophosphate, acid zinc pyrophosphate, etc. Of these, calcium polyphosphate, zinc polyphosphate, calcium tripolyphosphate, and zinc tripolyphosphate are preferable.

  In the present invention, the proportion of the phosphate (C) is preferably in the range of 0.001 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A), and 0.05 to 30 The range is more preferably in the range of parts by mass, even more preferably in the range of 0.01 to 20 parts by mass, and most preferably in the range of 0.05 to 15 parts by mass. Within such a range, the polyarylene sulfide resin composition of the present invention is preferable because it exhibits a low recrystallization temperature and the obtained molded article exhibits good heat resistance.

  The polyarylene sulfide resin composition of the present invention comprises a silane coupling agent (D) having a functional group that reacts with a carboxy group as an optional component, if necessary. The silane coupling agent is not particularly limited as long as it has a functional group that reacts with a carboxy group and does not impair the effects of the present invention. For example, a silane coupling agent having an epoxy group, an isocyanato group, an amino group, or a hydroxyl group A preferable example is an agent. 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 blending ratio of the silane coupling agent is not particularly limited as long as the effects of the present invention are not impaired, but 0.01 to 30 with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is preferably in the range of parts by mass, more preferably in the range of 0.05 to 10 parts by mass, and most preferably in the range of 0.1 to 5 parts by mass. Within such a range, the polyarylene sulfide resin composition of the present invention is preferable because it exhibits a low recrystallization temperature and the obtained molded article exhibits good heat resistance.

  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, but when blended, the proportion of the blend is not particularly limited as long as it does not impair the effects of the present invention, and differs depending on the purpose and is generally specified. Although it cannot do, 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. In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.

  If necessary, the polyarylene sulfide resin composition of the present invention can be blended with a thermoplastic elastomer as an optional component. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. Among these, polyolefin-based elastomers are preferable. When blending these elastomers, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and it varies depending on each purpose and cannot be specified in general. (A) It is preferable that it is the range of 0.01-10 mass parts with respect to 100 mass parts, and it is more preferable that it is the range of 0.1-5 mass parts. 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 blended as optional components. In the present invention, the synthetic resin is not an essential component, but when blended, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and it varies depending on each purpose and is generally specified. The total of the polyarylene sulfide resin and the polyvinyl pyrrolidone as a proportion of the resin component (the total of the polyarylene sulfide resin, the polyvinyl pyrrolidone and the synthetic resin) to be blended in the polyarylene sulfide resin composition of the present invention. Is in the range of 75.0% by mass or more, preferably in the range of 80 to 99.99% by mass, in other words, the synthetic resin is in the range of 25.0% by mass or less, preferably 0.01 to 20. What is necessary is just to adjust suitably according to the objective and use in the range of 0 mass% so that the effect of this invention may not be impaired.

  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 mix | blend 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, but when blended, the proportion of the blend is not particularly limited as long as the effect of the present invention is not impaired, and differs depending on each purpose, and is generally defined. However, for example, with respect to 100 parts by mass of the polyarylene sulfide resin (A), preferably in the range of 0.01 to 1,000 parts by mass, appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention. Can be used.

  The method for producing the polyarylene sulfide resin composition of the present invention comprises a polyarylene sulfide resin (A), the polyvinyl pyrrolidone (B) and the phosphate (C) as essential components, and a polyarylene sulfide resin ( Melt-knead at a melting point of A) or higher.

  A preferable method for producing the polyarylene sulfide resin composition of the present invention is that each of the polyarylene sulfide resin (A), the polyvinylpyrrolidone (B), and the phosphate (C) is essential so as to achieve the above-described blending ratio. Ingredients and optional ingredients such as fillers in various forms such as powders, pellets, strips, etc. are put into ribbon blenders, Henschel mixers, V blenders, etc., dry blended, then Banbury mixers, mixing Put into a known melt-kneader such as a roll, single-screw or twin-screw extruder, kneader, etc. The temperature range is preferably a melting point + 10 ° C to a melting point + 100 ° C, more preferably a melting point +20 to a melting point +50. It can be manufactured through a step of melt-kneading at a temperature range of a. 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 the polyarylene sulfide resin (A) which is an essential component, the polyvinylpyrrolidone (B), the phosphate (C), It is a molten mixture containing optional components to be added as necessary and components derived therefrom, and after the melt-kneading, it is processed into a form of pellets, chips, granules, powders, etc. by a known method, and then 100 to 100 as necessary. It is preferable to perform preliminary drying at a temperature of 150 ° C. and use for various moldings.

  The polyarylene sulfide resin composition of the present invention produced by the above production method has a polyarylene sulfide resin as a matrix, and the polyvinylpyrrolidone (B) and the phosphate (C) as essential components in the matrix. In addition, a morphology in which components derived from them and optional components added as necessary are dispersed is formed. As a result, the polyarylene sulfide resin composition exhibits a low recrystallization temperature, and the obtained molded product is excellent in heat resistance, chemical resistance, and the like. Polyvinyl pyrrolidone that has excellent compatibility with the polyarylene sulfide resin due to the pyrrolidone skeleton is considered to have delayed the crystallization of the polyarylene sulfide resin during melt kneading. It is considered that the crystallization was further delayed by the effect that the chains formed a mercaptide bond with the metal element derived from the phosphate of the sulfur atom at the molecular end and the molecular chain was extended.

  The melting point (Tm) of the polyarylene sulfide resin composition or molded product of the present invention is maintained at the melting point (Tm) of the resin (A), while the polyarylene sulfide resin composition or molded product thereof is reused. The crystallization temperature (Tc2) can be further lowered from the recrystallization temperature (Tc2) of the resin (A). Regarding the specific range of decrease in recrystallization temperature (Tc2), the blending of essential components and optional components is determined based on the relationship with other properties such as mechanical properties according to the use and purpose of the molded product. However, in the preferred case, the recrystallization temperature (Tc2) of the polyarylene sulfide resin composition or the molded product thereof is preferably the recrystallization temperature of the resin (A) ( Tc2) can be lowered in the range of 20 to 100 ° C, and more preferably in the range of 30 to 80 ° C. That is, the difference ΔT between the melting point (Tm) and the recrystallization temperature (Tc2) of the polyarylene sulfide resin composition and molded product of the present invention is preferably 50 ° C. or more, more preferably in the range of 50 to 130 ° C. Preferably it can also be set as the range of 60-80 degreeC. Accordingly, the polyarylene sulfide resin composition of the present invention and the recrystallization temperature (Tm) of the molded article are preferably in the range of 270 to 300 ° C. Tc2) is preferably in the range of 240 ° C. or lower, more preferably in the range of 120 to 240 ° C., and still more preferably in the range of 160 to 200 ° C. The melting point (Tm) of the polyarylene sulfide resin composition of the present invention or its molded product maintains the melting point (Tm) of the resin (A), and the melting point is substantially the same. Preferably, the temperature difference between the Tm (° C.) of the polyarylene sulfide resin composition or molded product thereof and the Tm (° C.) of the polyarylene sulfide resin (A) blended as an essential component is within 10 ° C., more preferably It means that it is within 5 ° C.

  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 can also be set to a known temperature range, for example, a room temperature (23 ° C.) to 300 ° C., preferably a range of 40 to 180 ° C. The polyarylene sulfide resin composition of the present invention can be set to a preferable temperature range of 120 to 180 ° C. as a normal molding temperature, and has a low recrystallization temperature (Tc2) as described above and excellent low temperature moldability. Since it also has characteristics, a molded product excellent in moldability such as appearance and filling properties, mechanical properties, and chemical resistance can be obtained even at a relatively low mold temperature range of 40 ° C or higher and lower than 120 ° C. be able to.

  A molded product formed by molding the polyarylene sulfide resin composition of the present invention is excellent in the mechanical strength in the TD direction at the time of injection molding while being excellent in adhesiveness with a silicone resin, and further, the polyvinyl pyrrolidone (B) When a material having a mass average molecular weight in the range of 50,000 to 2,000,000 is used, the adhesion to the silicone resin and the mechanical strength in the TD direction during injection molding are particularly excellent. 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.

(Measurement of melt viscosity of polyphenylene sulfide resin)
Using the polyphenylene sulfide resin produced in the reference example, a flow tester manufactured by Shimadzu Corporation, CFT-500D, at 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 (mm) / 1 (mm), Measurements were taken after holding for 6 minutes.

(Measurement of melting point (Tm) and recrystallization temperature (Tc2) of PPS resin and PPS resin composition)
The melting point (Tm) and the recrystallization temperature (Tc2) of the polyarylene sulfide resin obtained in the reference examples and comparative reference examples and the examples and the polyarylene sulfide resin compositions obtained in the comparative examples are the resin or resin composition. The product was melted at 350 ° C. and then rapidly cooled to prepare an amorphous film. Approximately 4 mg was weighed from this film and measured using a differential scanning calorimeter (“DSC8500” manufactured by Perkin Elmer).

Reference Example 1 Production of Carboxy Group-Containing Polyphenylene Sulfide Resin (PPS-1) p-Dichlorobenzene (hereinafter referred to as “p”) in a 150 liter autoclave with stirring blades connected with a pressure gauge, thermometer, condenser, decanter, and rectifying tower. -DCB ") 33.222 kg (226 mol), NMP 2.280 kg (23 mol), 47.23 wt% NaSH aqueous solution 27.300 kg (230 mol as NaSH), and 49.21 wt% NaOH aqueous solution 18 .533 g (228 mol as NaOH) was charged, and the temperature was raised to 173 ° C. over 5 hours under stirring in a nitrogen atmosphere to distill 27.300 kg of water, and then the autoclave was sealed. The p-DCB distilled azeotropically during dehydration was separated with a decanter and returned to the autoclave as needed. In the autoclave after the completion of the dehydration, the finely divided anhydrous sodium sulfide composition was dispersed in p-DCB. Since the NMP content in this composition was 0.069 kg (0.7 mol), 97 mol% (22.3 mol) of the charged NMP was a ring-opened product of NMP (4- (methylamino) It was shown to be hydrolyzed to the sodium salt of butyric acid (hereinafter abbreviated as “SMAB”). The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave. When the total amount of NaSH and NaOH charged is changed to anhydrous Na ₂ S, the theoretical dehydration amount is 27.921 g. Therefore, 401 g (22.3 mol) out of the remaining water amount 621 g (34.5 mol) in the autoclave. Is consumed in the hydrolysis reaction of NMP and NaOH and does not exist in the autoclave as water, and the remaining 220 g (12.2 mol) remains in the autoclave in the form of water or crystal water. Was showing. The amount of water in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.

  After completion of the dehydration step, the internal temperature was cooled to 160 ° C., a solution containing 47.492 kg (479 mol) of NMP was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per 1 mol of NMP charged in step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectifying column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, the cooling and the valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled vapor of p-DCB and water was condensed by a condenser and separated by a decanter, and p-DCB was returned to the autoclave. The amount of distilled water was 179 g (9.9 mol), the water content in the autoclave was 41 g (2.3 mol), 0.005 mol per 1 mol of NMP charged after dehydration, and 1 mol of sulfur atoms present in the autoclave. It was 0.010 mol. The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave, as in dehydration.

  Next, the temperature was raised from an internal temperature of 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 1 hour, then heated to 250 ° C. and stirred for 1 hour. The gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.30 MPa. After cooling, 6.5 kg of the obtained slurry was poured into 30 liters of 80 ° C. warm water and stirred for 1 hour, followed by filtration. The cake was again stirred with 30 liters of warm water for 1 hour, washed and filtered. Next, 30 liters of water was added to the obtained cake, the pH was adjusted to 4.5 with acetic acid, the mixture was stirred at room temperature for 1 hour, and then filtered. Further, 30 liters of warm water was added to the obtained cake, and the mixture was stirred for 1 hour, followed by filtration twice, followed by drying overnight at 120 ° C. using a hot air circulating dryer, and the carboxy group-containing PPS on the white powder. A resin (hereinafter referred to as PPS-1) was obtained. The obtained polymer had a melt viscosity of 98 Pa · s. The melting point (Tm) was 282 ° C., and the recrystallization temperature (Tc 2) was 203 ° C.

Reference Example 2 Production of Carboxy Group-Containing Polyphenylene Sulfide Resin (PPS-2) 45% sodium hydrosulfide (47.55% by mass) was added to a 150-liter autoclave equipped with a pressure gauge, thermometer, condenser and a stirring blade and a bottom valve. NaSH) 14.148 kg, 48% caustic soda (48.7 mass% NaOH) 9.474 kg, and N-methyl-2-pyrrolidone 38.0 kg were charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 12.150 kg of water (the amount of water remaining was 1.13 mol per 1 mol of NaSH). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 17.129 kg of paradichlorobenzene and 16.0 kg of N-methyl-2-pyrrolidone were charged. The temperature was raised by pressurizing to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. After stirring at a liquid temperature of 220 ° C. for 4 hours, when the temperature was raised to 260 ° C., the reaction was carried out at 260 ° C. for 3 hours while cooling by sprinkling the upper part of the autoclave. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The maximum pressure during the reaction was 0.87 MPa. After the reaction, the reaction mixture was cooled, the bottom valve was opened at 100 ° C., the reaction slurry was transferred to a 150 liter flat plate filter and pressure filtered at 120 ° C. To the obtained cake, 50 kg of 70 ° C. warm water was added and stirred, followed by filtration. Further, 25 kg of warm water was added and filtered. Next, 25 kg of warm water was added, the pH was adjusted to 4.5 with acetic acid, the mixture was stirred for 1 hour, filtered, and then 25 kg of warm water was added and filtered. Furthermore, after adding 25 kg of warm water and stirring for 1 hour and filtering, the operation of adding 25 kg of warm water and filtering was repeated twice. The obtained cake was dried at 120 ° C. for 15 hours using a hot air circulating dryer to obtain PPS-2. The melt viscosity of the obtained polymer was 108 Pa · s. The melting point (Tm) was 278 ° C., and the recrystallization temperature (Tc 2) was 240 ° C.

Reference Example 3 Production of Carboxy Group-Containing Polyphenylene Sulfide Resin (PPS-3) “Next, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 1 hour, and then raised to 250 ° C. Then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, stirred at 230 ° C. for 3 hours, then heated to 250 ° C. and stirred for 1 hour. "Next, 30 liters of water was added to the obtained cake, the pH was adjusted to 4.5 with acetic acid, and the mixture was stirred at room temperature for 1 hour and then filtered." In addition, 30 liters of water was added to the obtained cake, the pH was adjusted to 6.0 with carbonated water, and the mixture was stirred for 1 hour at room temperature and then filtered. In the same manner, PPS-3 was obtained. The obtained polymer had a melt viscosity of 171 Pa · s. The melting point (Tm) was 280 ° C., and the recrystallization temperature (Tc 2) was 211 ° C.

(Reference Example 4)
Carboxy group-containing polyphenylene sulfide resin (PPS-4), except that 65.3 g of 1,3,5-trichlorobenzene (0.3 mol% relative to 1 mol of NaSH) was added simultaneously with paradichlorobenzene. Got. The obtained polymer had a melt viscosity of 2840 Pa · s and a carboxy group concentration of 66.9 μmol / g. The melting point (Tm) was 284 ° C., and the recrystallization temperature (Tc 2) was 230 ° C.

(Reference Example 5)
A polyphenylene sulfide resin (PPS-5) was obtained in the same manner as in Reference Example 2 except that acetic acid was not added. The obtained polymer had a melt viscosity of 110 Pa · s. The melting point (Tm) was 279 ° C., and the recrystallization temperature (Tc 2) was 242 ° C.

(Comparative Reference Example 1)
Carboxy group-containing polyphenylene sulfide resin (PPS-C1) was obtained in the same manner as in Reference Example 2 except that 14.559 kg of paradichlorobenzene and 2.569 kg of metadichlorobenzene were added instead of 17.129 kg of paradichlorobenzene. The obtained polymer had a melt viscosity of 10 Pa · s. The melting point (Tm) was 242 ° C., and the recrystallization temperature (Tc 2) was 146 ° C.

<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. Using this pellet, the melting point (Tm) and the recrystallization temperature (Tc2) were measured, and the difference ΔT between them was calculated. The results are shown in Tables 1-2.

なお、表１、２中の組成の数値は質量部を示す。以下の表も同じ。
※１ ΔＴｃ２は、各実施例で得られた試験片（ＰＰＳ樹脂成形品）のＴｃ２（℃）から、各実施例で原料の用いたＰＰＳ樹脂のＴｃ２（℃）を差し引いた値。
また、表中の各原料は以下の通り。

In addition, the numerical value of the composition in Table 1, 2 shows a mass part. The following table is the same.
* 1 ΔTc2 is a value obtained by subtracting Tc2 (° C.) of the PPS resin used as the raw material from Tc2 (° C.) of the test piece (PPS resin molded product) obtained in each example.
In addition, each raw material in the table is as follows.

Vinylpyrrolidone-based additive PVP-1 Polyvinylpyrrolidone resin “K-90” manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 1050000 to 1200000)
PVP-2 polyvinyl pyrrolidone resin “K-85” manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 900,000 to 1050000)
PVP-3 Polyvinylpyrrolidone resin “K-30” manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 80000-120000)
PVP-4 polyvinyl pyrrolidone resin “Pitzkor K-17L” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (mass average molecular weight: 9000 to 120,000)

Zinc-polyphosphate “ZP-SB” manufactured by Kikuchi Color Co., Ltd.

Epoxysilane 3-glycidoxypropyltrimethoxysilane "SH-6040" manufactured by Dow Corning

Claims (15)

A polyarylene sulfide resin (A), polyvinylpyrrolidone (B), and a phosphate (C) containing a metal belonging to Group 2 or Group 12 of the periodic table are blended as essential components,
The polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass and the phosphate (C) is in the range of 0.001 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). A polyarylene sulfide resin composition characterized by the above.   The polyarylene sulfide resin composition according to claim 1, wherein the polyvinyl pyrrolidone (B) has a mass average molecular weight in the range of 3,000 to 2,000,000. The polyvinylpyrrolidone (B) is represented by the following general formula (1)

(Wherein n represents a repeating unit and is in the range of 30 to 18,000. R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group.) The polyarylene sulfide resin composition according to claim 1 or 2, wherein:   Furthermore, the silane coupling agent (D) which has a functional group which reacts with a carboxy group is mix | blended in the range of 0.001-30 mass parts with respect to 100 mass parts of polyarylene sulfide resins. The polyarylene sulfide resin composition according to any one of the above.   It is a melt-kneaded material, The polyarylene sulfide resin composition as described in any one of Claims 1-4.   The polyarylene sulfide resin composition according to any one of claims 1 to 5, which has a melting point (Tm) of 270 ° C or higher and a recrystallization temperature (Tc2) of 240 ° C or lower.   The polyarylene sulfide resin composition according to claim 1, wherein a difference ΔT between the melting point (Tm) and the recrystallization temperature (Tc2) is 50 ° C. or more.   The molded article formed by shape | molding the polyarylene sulfide resin composition as described in any one of the said Claims 1-7.   The polyarylene sulfide resin (A), the polyvinyl pyrrolidone (B), and the phosphate (C) containing a metal belonging to Group 2 or Group 12 of the periodic table as essential components, the melting point of the polyarylene sulfide resin (A) A method for producing a polyarylene sulfide resin composition, comprising melt-kneading as described above.   The method for producing a polyarylene sulfide resin composition according to claim 9, wherein the polyvinyl pyrrolidone (B) has a mass average molecular weight in the range of 3,000 to 2,000,000.   The polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass and the phosphate (C) is in the range of 0.001 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). The method for producing a polyarylene sulfide resin composition according to claim 9 or 10. The polyvinylpyrrolidone (B) is represented by the following general formula (1)

(Wherein n represents a repeating unit and is in the range of 30 to 18,000. R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group.) The manufacturing method of the polyarylene sulfide resin composition as described in any one of Claims 9-11 which has these.   Furthermore, the manufacturing method of the polyarylene sulfide resin composition as described in any one of Claims 9-12 formed by mix | blending the silane coupling agent (D) which has a functional group which reacts with a carboxy group.   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 9-13.   The method for producing a molded article according to claim 14, comprising a step of molding the polyarylene sulfide resin composition in a mold, and the mold temperature is in the range of 40 to 180 ° C.