JP2017125215A - Polyarylene sulfide resin composition and molded body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin molded body containing a polyarylene sulfide resin, excellent in adhesiveness with an epoxy resin and a cold thermal impact property and less in burr amount and a polyarylene sulfide resin composition capable of molding the molded body.SOLUTION: There are provided a polyarylene sulfide resin composition containing a polyarylene sulfide resin (A), a polyamide ether resin (B) and an epoxy resin (C) as essential components, wherein flexure elastic modulus of the polyamide ether resin (B) is 100 (MPa) or less, and a molded body thereof.SELECTED DRAWING: None

Description

  The present invention includes a polyarylene sulfide resin, and in particular, a polyarylene sulfide resin molded article having excellent adhesion to an epoxy resin and thermal shock resistance and having a small amount of burr, and a polyarylene sulfide resin composition capable of providing the molded article Related to things.

  Polyarylene sulfide (hereinafter abbreviated as PAS) resin, represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin, has excellent mechanical strength, heat resistance, chemical resistance, molding processability, and dimensional stability. Using these characteristics, they are used as electrical / electronic equipment parts, automobile parts materials, and the like.

  In many cases, these parts are bonded to a part material made of epoxy resin or the like as the secondary processing. However, PAS resins have relatively poor adhesion to other resins, especially adhesion to epoxy resins. Therefore, for example, when bonding PASs with epoxy adhesives, bonding PAS resins with other materials, or sealing electrical / electronic parts with epoxy resins, the adhesion between PAS resins and epoxy resins (hereinafter referred to as “bonding”) , Epoxy adhesion or simply adhesion) is a problem.

  For this reason, several studies have been made so far for the purpose of improving the epoxy adhesiveness of PAS resin. For example, a PAS resin composition in which an epoxy resin is blended with a polyarylene sulfide resin, or a glass fiber with a polyarylene sulfide resin. PAS resin compositions containing olefin polymers, epoxy resins, and glass flakes have been proposed (see Patent Documents 1 and 2). However, since this method uses a bisphenol A type epoxy resin as an epoxy resin, although it has excellent epoxy adhesion and fluidity, it is difficult to say that thermal shock resistance is practically sufficient, and furthermore, there is a large amount of burrs during molding. There was room for improvement.

Japanese Examined Patent Publication No. 6-104773 JP-A-2005-306926

  Therefore, the problem to be solved by the present invention is a polyarylene sulfide resin molded article containing a polyarylene sulfide resin, excellent in adhesion to an epoxy resin and thermal shock resistance, and having a small amount of burrs, and a mold capable of molding the molded article. The object is to provide an arylene sulfide resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a polyamide ether resin (B) having a specific flexural modulus in combination with a PAS resin and an epoxy resin. The present invention has been completed.

  That is, the present invention is a polyarylene sulfide resin composition comprising polyarylene sulfide resin (A), polyamide ether resin (B), and epoxy resin (C) as essential components, wherein the polyamide ether resin (B) The present invention relates to a polyarylene sulfide resin composition having a flexural modulus of 100 (MPa) or less.

  Furthermore, this invention relates to the molded object formed by shape | molding the said polyarylene sulfide resin composition.

  INDUSTRIAL APPLICABILITY According to the present invention, a polyarylene sulfide resin molded article containing a polyarylene sulfide resin, particularly excellent in adhesion to an epoxy resin and thermal shock resistance and having a small amount of burr, and a polyarylene sulfide resin composition capable of molding the molded article Can be provided.

  The polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin (A), a polyamide ether resin (B) having a flexural modulus of 100 (MPa) or less, and an epoxy resin (C) as essential components. . Details will be described below.

・ Polyarylene sulfide resin (A)
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 formula (1):

（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を繰り返し単位とする樹脂である。

(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). It is a resin having a structural site as a repeating unit.

Here, in the structural site represented by the formula (1), R ¹ and R ² in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. A compound bonded at the para position represented by the following formula (2) is preferable.

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構造式（２）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 structural formula (2). In terms of surface.

  Further, the polyarylene sulfide resin is not only the structural portion represented by the formula (1), but also the following structural formulas (3) to (6).

で表される構造部位を、前記式（１）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式（３）〜（６）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、上記式（３）〜（６）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 (1) may be included at 30 mol% or less of the total with the structural site represented by the formula (1). In particular, in the present invention, the structural portion represented by the above formulas (3) to (6) is preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin. In the case where the polyarylene sulfide resin contains a structural portion represented by the above formulas (3) to (6), the bonding mode thereof may be either a random copolymer or a block copolymer. .

  The polyarylene sulfide resin has the following formula (7) in its molecular structure.

で表される３官能性の構造部位、或いは、ナフチルスルフィド結合などを有していてもよいが、他の構造部位との合計モル数に対して、３モル％以下が好ましく、特に１モル％以下であることが好ましい。

May have a trifunctional structural site represented by the formula (1) or a naphthyl sulfide bond, but is preferably 3 mol% or less, particularly 1 mol%, based on the total number of moles with other structural sites. The following is preferable.

  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 5 to 1000 [Pa · s], and has a good balance between fluidity and mechanical strength. Therefore, the range of 5 to 100 [Pa · s] is more preferable, and the range of 5 to 50 [Pa · s] is particularly preferable.

(Non-Newtonian index)
The non-Newtonian index of the polyarylene sulfide resin used in the present invention is not particularly limited as long as the effects of the present invention are 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. During the reaction, or by adding an alkali metal salt of a carboxylic acid or sulfonic acid to adjust the degree of polymerization, it may be added alkali hydroxide. 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 0.01-0.9 mol of an organic acid alkali metal salt with respect to the catalyst and a method of reacting while controlling the amount of water in the reaction system within a range of 0.02 mol with respect to 1 mol of the aprotic polar organic solvent (See the pamphlet of WO2010 / 058713). 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 include compounds having an aromatic ring in the alkyl group having 1 to 18 carbon atoms. Examples of the Poriharogeno aromatics 1,2,3 Toriharobe Zen, 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.

・ Polyamide ether resin (B)
As the polyamide ether resin (B) used in the present invention, a resin having a flexural modulus of 100 MPa or less measured by a measuring method based on ISO 178 is used alone. Further, the elastic modulus is preferably in the range of 10 to 100 (MPa), and preferably in the range of 20 to 90 (MPa) because it has excellent thermal shock resistance and can reduce the amount of burrs. It is more preferable that

  As such a polyamide ether resin (B), a block copolymer resin having a polyoxyalkylene block and a polyamide block can be mentioned as a preferred resin. Specific examples of the monomer constituting the polyoxyalkylene block include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Specific examples of monomers that form polyamide blocks include polycondensed polyamides such as ε-caprolactam, 11-aminoundecanoic acid, and 12-aminolauric acid, and dicarboxylic acids such as adipic acid, sebacic acid, terephthalic acid, and isophthalic acid. And copolycondensation polyamides of diamines such as hexamethylenediamine, nonanediamine, and methylpentadiamine. The production method is not particularly limited. For example, a monomer that forms a polyamide block is reacted with a dicarboxylic acid such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, decanediic acid, and dodecanediic acid to form a carboxy terminal. Then, it may be subjected to condensation polymerization with the monomer constituting the polyoxyalkylene block.

  Examples of the commercially available polyamide ether resin (B) used in the present invention include Arkema “PEBAX 35R53” (flexural modulus 25 MPa), Arkema “PEBAX 4033” (flexural modulus 84 MPa), and the like.

  The ratio of the polyamide ether resin (B) to the polyarylene sulfide resin (A) may be appropriately adjusted according to the purpose and use so as not to impair the effects of the present invention. From the viewpoint of excellent adhesiveness and thermal shock resistance and capable of reducing the amount of burrs, the polyamide ether resin (B) is in the range of 0.5 to 40 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 1 to 20 parts by mass.

・ Epoxy resin (C)
The resin composition of the present invention further contains an epoxy resin (C) as an essential component from the viewpoint of improving the adhesion with other resins such as an epoxy resin.

  The epoxy resin (C) is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include bisphenol-type epoxy resins and novolac-type epoxy resins. Among these, epoxy adhesiveness and thermal shock resistance are excellent. In addition, a bisphenol-type epoxy resin is preferred because it can reduce the amount of burrs.

  Examples of the epoxy resin of the bisphenol type epoxy resin include glycidyl ethers of bisphenols, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, bisphenol. S-type epoxy resin, bisphenol AD-type epoxy resin, tetrabromobisphenol A-type epoxy resin, dihydroxynaphthalene-type epoxy resin, etc. are mentioned, and among these, bisphenol A-type epoxy resin is preferable. When a bisphenol type epoxy resin is used, the epoxy equivalent is 400 to 5000 [g / eq. It is preferable to use the thing of the range of 450-4000 [g / eq. It is more preferable to use the thing of the range of]. 400 [g / eq. ] The above is preferable because the amount of gas generated can be reduced, and the fluidity and adhesion with an epoxy resin or metal are improved. On the other hand, 5000 [g / eq. The following is preferable because the thermal shock resistance is improved. Moreover, when using a bisphenol type | mold epoxy resin, it is preferable to use the thing of the range whose softening point is 60-150 degreeC, and it is more preferable to use the thing whose softening point is the range of 65-130 degreeC. When the temperature is 60 ° C. or higher, the amount of gas generated can be reduced, and fluidity and adhesion with an epoxy resin or a metal are improved. On the other hand, when the temperature is 150 ° C. or lower, thermal shock resistance is improved.

  The novolac type epoxy resin includes novolac type epoxy resins obtained by reacting novolak type phenol resins obtained by condensation reaction of phenols and aldehydes with epihalohydrin. Specific examples include phenol novolac type epoxy resins. Resin, cresol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, brominated phenol novolak type epoxy resin, and among these, phenol novolac Type epoxy resin and cresol novolac epoxy resin are preferable. When a novolac type epoxy resin is used, the epoxy equivalent is 170 to 300 [g / eq. It is preferable to use the thing of the range of 190-250 [g / eq. It is more preferable to use the thing of the range of]. 170 [g / eq. ] The above is preferable because the thermal shock resistance is improved, while 300 [g / eq. ] The following is preferable because the fluidity and the adhesion to epoxy resin and metal are improved. Moreover, when using a novolak-type epoxy resin, it is preferable to use the thing of the range whose softening point is 55-90 degreeC, and it is more preferable to use the thing of the range of 60-80 degreeC. If it is 55 degreeC or more, since a thermal-thermal impact property improves, it is preferable, on the other hand, if it is 90 degrees C or less, since fluidity | liquidity and adhesiveness with an epoxy resin or a metal improve, it is preferable.

  The ratio of the epoxy resin (C) to the polyarylene sulfide resin (A) may be appropriately adjusted according to the purpose and use so as not to impair the effects of the present invention. From the viewpoint of improving the properties, the epoxy resin (C) is preferably in the range of 0.5 to 40 parts by mass, and more preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). More preferably.

  The resin composition of the present invention may further contain a filler (D) in addition to the above components in order to further improve the mechanical strength, in particular, the thermal shock strength, heat resistance, dimensional stability, and the like. preferable. The filler used in the present invention is not an essential component, but is more than 0 parts by weight, usually 1 part by weight or more, more preferably 10 parts by weight or more and 600 parts by weight or less with respect to 100 parts by weight of the polyarylene sulfide resin. By adding in this range, various performances can be improved according to the purpose of the filler to be added, such as strength, rigidity, heat resistance, heat dissipation and dimensional stability.

  As the filler, known and conventional materials can be used as long as they do not impair the effects of the present invention, and various shapes such as a fibrous material and a non-fibrous material such as a granular shape or a plate shape can be used. And the like. Specifically, fibers such as glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and natural fibers such as wollastonite. Can be used, and glass beads, glass flakes, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, talc, attapulgite, ferrite, calcium silicate, carbonic acid Non-fibrous fillers (D2) such as calcium, magnesium carbonate and glass beads can also be used.

  Of these, as the filler (D), it is more preferable to use glass fiber (D1) in combination with at least one (D2) selected from the group consisting of glass beads, glass flakes, and calcium carbonate. The blending ratio is 10 to 200 in total of at least one (D2) selected from the group consisting of glass fibers (D1), glass beads, glass flakes, and calcium carbonate with respect to 100 parts by mass of the polyarylene sulfide resin. It is preferable that it is the range of a mass part. Furthermore, the blending ratio of the glass fiber (D1) and at least one (D2) selected from the group consisting of glass beads, glass flakes, and calcium carbonate is 20:80 to 80:20 on a mass basis. Is preferred.

  As such a glass fiber, known ones can be used as long as the effects of the present invention are not impaired.For example, chopped strands used for injection molding compounds can be preferably used, and in particular, The diameter is in the range of 3 to 20 μm, preferably in the range of 6 to 13 μm, and the strand length is preferably in the range of 3 to 6 mm.

  As the glass flakes, known ones can be used as long as the effects of the present invention are not impaired. For example, glass flakes having an average particle size in the range of 10 to 4000 μm can be preferably used. What is the glass flakes having a thickness in the range of 0.1 to 20 μm can be preferably used. As a glass bead, a well-known thing can be used in the range which does not impair the effect of this invention, For example, the thing whose average particle diameter is the range of 1-100 micrometers can be used preferably. Specific examples include soda lime glass beads, low alkali glass beads, potash glass beads, and quartz glass beads. As calcium carbonate, known ones can be used as long as the effects of the present invention are not impaired. For example, those having an average particle diameter in the range of 0.1 to 300 μm can be preferably used. Specific examples include precipitated calcium carbonate, heavy calcium carbonate, and calcium carbonate whisker. However, the average particle diameter and the average thickness mean a particle size of 50% cumulative degree obtained from a cumulative particle size distribution curve measured by a laser light diffraction method.

  Furthermore, in addition to the above components, the polyarylene sulfide resin composition of the present invention may further comprise a polyester resin, a polyamide resin, a polyimide resin, a polyetherimide resin, a polycarbonate resin, a polyphenylene ether resin, a polysulfone, depending on the intended use. 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, silicone resin Further, it may be used as a polyarylene sulfide resin composition containing a synthetic resin such as a phenol resin, a urethane resin, or a liquid crystal polymer, or an elastomer such as fluorine rubber or silicone rubber. In addition, the amount of these resins used varies depending on the purpose and cannot be specified in general, but in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). In order not to impair the effects of the present invention, it may be appropriately adjusted according to the purpose and application.

  Furthermore, if the polyarylene sulfide resin composition of the present invention is within a range that does not impair the effects of the present invention, a coupling agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent are used as additives during molding. Various additives such as an agent, a rust inhibitor, a flame retardant, and a lubricant can be contained.

  The amount of these additives used varies depending on the purpose and cannot be generally defined, but in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A), What is necessary is just to adjust suitably according to the objective and the use so that the effect of this invention may not be impaired. In addition, the method of using these additives varies depending on the purpose and cannot be specified in general. For example, the coupling agent may be used after being pretreated in a filler in advance. However, it is preferable to use it alone as an additive.

  As such a coupling agent, a coupling agent such as silane or titanium is used. Among these, a silane coupling agent is preferable, and 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. 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. The usage-amount of a coupling agent is 0.01-1.0 mass part with respect to 100 mass parts of polyarylene sulfide resin (A), More preferably, it is the range of 0.1-0.4 mass part.

The production method of the PAS resin composition of the present invention is not particularly limited, and the raw material polyarylene sulfide resin (A), polyamide ether resin (B), epoxy resin (C), and filler (D ) And coupling agent (E) in various forms such as powders, berets, strips, ribbon blenders, Henschel mixers, V blenders, etc., dry blended, and then a banbury mixer mixing roll And a melt kneading method using a single-screw or twin-screw extruder and a neater. Among them, a typical method is melt-kneading using a single-screw or twin-screw extruder having a sufficient kneading force.
The PAS resin composition of the present invention can be used for various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. Because it is excellent, it is suitable for injection molding.

  The PAS resin composition of the present invention has various performances such as mechanical strength, heat resistance, and dimensional stability inherent to the PAS resin. For this reason, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers, microphones , Headphones, small motors, magnetic head bases, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts, VTR parts, TV parts, irons, hair dryers Home appliances such as rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs, motor parts, writers, typewriters and other machine related parts, microscopes, binoculars, Optical equipment such as cameras and watches, precision machine related parts, water faucet tops, mixing faucets, pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter housings, etc. Water-related parts, valve alternator terminal, alternator connector, IC regulator, light meter potentiometer base, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel Pump, engine cooling water joy , Carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioning thermostat base, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse Connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp It is widely useful as a material for various applications such as housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, HEV condenser cases, vehicle speed sensors, cable liners and other automobile / vehicle-related parts, or fibers or films.

EXAMPLES Hereinafter, although this invention is demonstrated using an Example, this invention is not limited to a following example.
[Peak molecular weight of PAS resin]
The conditions for measuring the peak molecular weight of the PPS resin are as follows: apparatus: SSC-7000 (manufactured by Senshu Kagaku), column: UT-805L (manufactured by Showa Denko), solvent: 1-chloronaphthalene, column temperature: 210 ° C., detector: UV Using a detector (360 nm), the molecular weight distribution was measured using six types of monodisperse polystyrene for calibration, the vertical axis was d (weight) / dLog (molecular weight), and the horizontal axis was differential weight molecular weight distribution with Log (molecular weight). The peak molecular weight was read from the horizontal axis.

[Melt viscosity of PAS resin]
Using a flow tester (Shimadzu Corporation Koka-type flow tester “CFT-500D type”), the temperature / 300 ° C., the load 1.96 MPa, the orifice length / orifice diameter ratio is 10/1. The melt viscosity after holding for 6 minutes was measured using an orifice.

[Measurement of flexural modulus of polyamide ether resin]
In accordance with the method described in ISO 178, the flexural modulus of the thermoplastic polyamide-based elastomer was measured.

<Examples 1-8 and Comparative Examples 1-6>
According to the composition components and blending amounts 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 results of the test and evaluation are shown in Tables 1 and 2.

[Adhesive strength of PAS resin composition to epoxy resin]
Next, the obtained pellets were supplied to an injection molding machine (SG75-HIPRO · MIII) manufactured by Sumitomo-Nestal Co., Ltd., which was set at a cylinder temperature of 320 ° C., and the mold for molding ASTM No. 1 dumbbell piece was adjusted to a mold temperature of 130 ° C. Was used for injection molding 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 spacer was prepared so that the contact area with the epoxy adhesive was 50 mm 2 (thickness: 1.8 to 2.2 mm, opening: 5 mm × 10 mm) Is sandwiched between two pieces of ASTM No. 1 dumbbell pieces, and fixed with a clip, and then an epoxy resin (two-part epoxy resin manufactured by Nagase ChemteX Corporation, main agent: XNR5002, curing agent: XNH5002, The main component: curing agent = 100: 90) was injected, and the mixture was heated and cured for 3 hours in a hot air dryer set at 135 ° C. for curing and adhesion. After cooling at 23 ° C. for 1 day, the spacer was removed, and using the obtained test piece, the strain rate was 1 mm / min, the distance between fulcrums was 80 mm, and the tensile strength at break was measured using an Instron tensile tester at 23 ° C. The value obtained by dividing by the adhesion area was defined as the epoxy adhesion strength.

(Cool thermal shock test)
A steel insert block member having a length of 25 mm, a width of 40 mm, and a thickness of 10 mm connects the midpoints of the sides in the vertical direction of the member, and has a thickness of 3.55 mm on a straight line parallel to the side in the horizontal direction of the member. Preparing an insert block member having a diameter center of two through-holes parallel to the vertical direction, the diameter centers of the through-holes being arranged 20 mm apart from each other about the midpoint of the straight line; The insert block member is held inside the injection mold by using the two through holes and the two steel cylindrical pins installed in the injection mold. After the installation and the injection molding of the pellets of the polyphenylene sulfide resin composition, the entire outer periphery of the insert block member is designed to be coated with the polyphenylene sulfide resin composition having a thickness of 1 mm. Using an injection molding die was to obtain the polyphenylene sulfide resin composition pellets were injection-molded moldings. Using the obtained molded product of the polyphenylene sulfide resin composition encapsulating the insert block member, a thermal shock test in which a thermal cycle from −40 ° C. to 150 ° C. is performed in a gas-phase type thermal shock tester as one cycle. , And the number of cycles until a crack was generated and broken was measured.

[Burr test]
A 20 mm wide, 100 mm long, 3 mm thick connector with 20 pin holes and a pin hole size of 2 × 2 mm was formed, and the burr length [μm] generated in the pin hole (gap 20 μm) was measured and evaluated. did.

The compounded resins and materials in Tables 1 and 2 are as follows.
PPS
A1 “MA-501” made by linear PPS DIC Corporation (peak molecular weight 28000, melt viscosity (V6) 150 poise)
Polyamide ether resin B1 Arkema Co., Ltd. “PEBAX35R53” Flexural modulus 25 MPa
B2 Arkema Co., Ltd. “PEBAX4033” Flexural modulus 84 MPa
B3 Arkema Co., Ltd. “PEBAX55R53” Flexural modulus 160 MPa
Epoxy resin C1 Bisphenol A type epoxy resin “Epiclon 7050” manufactured by DIC Corporation
C2 Cresol novolac type epoxy resin “Epiclon N-695” manufactured by DIC Corporation
Inorganic filler D1 Glass fiber “T-717H” manufactured by Nippon Electric Glass Co., Ltd. (diameter 10 μm chopped strand)
D2 Calcium carbonate Maruo Calcium Co., Ltd. “Calcium carbonate grade 1” (powder, average particle size 13 μm)
Additive E1 3-Glycidoxypropyltrimethoxysilane “OFS-6040” manufactured by Dow Corning

Claims (6)

A polyarylene sulfide resin composition comprising the polyarylene sulfide resin (A), the polyamide ether resin (B), and the epoxy resin (C) as essential components,
A polyarylene sulfide resin composition, wherein the polyamide ether resin (B) has a flexural modulus of 100 (MPa) or less. The polyarylene sulfide resin composition according to claim 1, wherein the polyamide ether resin (B) is a block copolymer resin having a polyether block and a polyamide block. With respect to 100 parts by mass of the polyarylene sulfide resin (A), the polyamide ether resin (B) is in the range of 0.5 to 40 parts by mass, and the epoxy resin (C) is in the range of 0.5 to 40 parts by mass. The polyarylene sulfide resin composition according to claim 1 or 2. The polyarylene sulfide resin composition according to any one of claims 1 to 3, wherein the epoxy resin (C) is a bisphenol A type epoxy resin. The polyarylene sulfide resin composition according to any one of claims 1 to 4, which is a melt-kneaded product. The molded object formed by shape | molding the polyarylene sulfide resin composition as described in any one of Claims 1-5.