JP6701610B2 - Polyarylene sulfide resin composition, molded article and manufacturing method - Google Patents

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 represented by a polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin has excellent heat resistance and mechanical strength, chemical resistance, and molding processing. It has excellent properties and dimensional stability, and by utilizing these characteristics, it is used as a material for electric/electronic device parts, automobile parts, etc.

  In many cases, these parts are bonded and joined to a part material made of a curable resin such as an epoxy resin or a silicone resin or a metal as a secondary processing. However, the polyarylene sulfide resin is relatively poor in adhesiveness with other resins, particularly with epoxy resin or silicone resin, and in bondability with metals. Therefore, for example, when joining polyarylene sulfides with an epoxy adhesive or silicone resin, or when sealing electrical/electronic parts with epoxy resin or silicone resin, etc., curability including polyarylene sulfide resin and epoxy resin or silicone resin Poor adhesiveness with the resin composition or bondability between the polyarylene sulfide resin and other materials such as metal has been a problem.

  Therefore, in order to improve the decrease in adhesiveness with a curable resin composition containing an epoxy resin (hereinafter sometimes referred to as epoxy resin adhesiveness), a polyarylene sulfide resin composition containing a polyarylene sulfide resin and a filler. There is also proposed a method of improving the balance between the epoxy resin adhesiveness, the releasability and the mechanical properties of a molded article by adding an oxidized polyethylene wax as a release agent (see Patent Document 1). However, also in this case, the epoxy resin adhesiveness of the polyarylene sulfide resin molded product was low, and it was at a level that was not practically sufficient.

  Further, a resin composition in which a non-crystalline α-olefin copolymer and a fatty acid metal salt are blended with a polyphenylene sulfide-based resin composition has also been investigated for the purpose of enhancing mold releasability (see Patent Document 2). .. However, even in this case, it could not be said that sufficient epoxy resin adhesiveness was obtained.

  Further, it is obtained by molding a polyarylene sulfide resin composition containing a polyarylene sulfide resin and an olefin wax having an acid value in the range of 65 to 150 mgKOH/g and having a carboxy group and a carboxylic acid anhydride group. It is known that the molded product has excellent epoxy resin adhesiveness while maintaining the mechanical properties inherent in the polyarylene sulfide resin molded product (see Patent Document 3). However, even in this case, it cannot be said that sufficient adhesiveness with the epoxy resin is obtained, and there is room for further improvement.

  On the other hand, in order to improve the decrease in the adhesiveness with a curable resin composition containing a silicone resin (hereinafter sometimes referred to as the silicone resin adhesiveness), a polyarylene sulfide resin is added to dimethylpolysiloxane, a fatty acid ester and a silane cup. It is known that a polyarylene sulfide resin molded product obtained by blending and kneading a ring agent as an essential component is excellent in silicone adhesiveness and releasability while maintaining the mechanical properties originally possessed. (For example, see Patent Document 4). However, even in this molded product, further improvement in silicone resin adhesiveness has been desired.

JP, 2002-012762, A JP 2004-35635 A International publication 2013/141364 pamphlet International Publication No. 2016/093309 Pamphlet

  Therefore, the present inventors have proposed a method utilizing physical interaction, that is, irradiating the surface of a polyarylene sulfide resin molded article with an active energy ray in order to improve the adhesiveness or the bondability regardless of the type of material. Then, a method of increasing the contact area with the material to be bonded or joined by roughening the surface was tried, but even if the polyarylene sulfide resin molded product surface was irradiated with active energy rays, the surface smoothness was improved. It was high, and it became clear that surface roughening was difficult.

  Therefore, the problem to be solved by the present invention is to provide a polyarylene sulfide resin composition capable of surface roughening when the surface of the molded product is irradiated with active energy rays, the molded product thereof, and a method for producing them, A method of subjecting a molded article obtained by molding the polyarylene sulfide resin composition to surface roughening by irradiating active energy rays, and a molded article obtained by surface roughening containing an epoxy resin or a silicone resin. It is intended to provide a polyarylene sulfide resin composite molded article in which a curable resin composition or another material such as a metal is bonded with good adhesiveness, and a method for producing the same.

  The present inventor has conducted extensive studies in order to solve the above problems. The inventors have found that surface irradiation can be roughened by irradiation, and have completed the present invention.

That is, the present invention provides (1) a polyarylene sulfide resin composition containing a polyarylene sulfide resin, a glass fiber, a metal oxide, and a layered and cleavable clay mineral,
Polyarylene sulfide resin, glass fiber, metal oxide, and a layered and cleavable clay mineral to a total of 100 parts by mass, a range of 10 to 35 parts by mass of glass fiber and 1 to 30 parts by mass of metal oxide. And the range of 1 to 20 parts by mass of clay mineral, and the balance is polyarylene sulfide resin,
The Mohs hardness of the metal oxide is smaller than the Mohs hardness of the glass fiber, and the difference is less than 1.5.
The metal oxide contains at least one selected from the group consisting of copper and chromium,
And a polyarylene sulfide resin composition.

  The present invention also relates to (2) a polyarylene sulfide resin molded product obtained by molding the polyarylene sulfide resin composition described above.

The present invention also provides (3) a polyarylene sulfide in which a polyarylene sulfide resin, glass fibers, a metal oxide, and a layered and cleavable clay mineral are melt-kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide resin. A method for producing a resin composition,
Polyarylene sulfide resin, glass fiber, metal oxide, and a layered and cleavable clay mineral with respect to a total of 100 parts by mass, the range of 10 to 35 parts by mass of glass fiber and 1 to 30 parts by mass of metal oxide. And the range of 1 to 20 parts by mass of clay minerals, and the balance is polyarylene sulfide resin,
The Mohs hardness of the metal oxide is smaller than the Mohs hardness of the glass fiber, and the difference is less than 1.5.
The method for producing a polyarylene sulfide resin composition, wherein the metal oxide contains at least one selected from the group consisting of copper and chromium.

  The present invention also relates to (4) a method for producing a polyarylene sulfide resin molded article, which comprises molding the polyarylene sulfide resin composition obtained by the production method described in (3) above.

  The present invention also relates to (5) a method for roughening the surface of a polyarylene sulfide resin molded article, which comprises irradiating the surface of the polyarylene sulfide resin molded article according to (2) above with active energy rays or ionizing radiation.

  In addition, the present invention provides (6) the surface of the polyarylene sulfide resin molded article according to (2) above, which is irradiated with active energy rays or ionizing radiation, and has an arithmetic average roughness (Ra) of 2 on the surface roughened surface. The present invention relates to a method for producing a polyarylene sulfide resin molded product in the range of 8 to 5.0 (μm).

  The present invention also provides (7) the arithmetic average roughness of the surface roughened surface obtained by irradiating the surface of the polyarylene sulfide resin molded article according to (2) above with active energy rays or ionizing radiation. A curable resin composition or a metal is brought into contact with a polyarylene sulfide resin molded product having (Ra) in the range of 2.8 to 5.0 (μm) in a liquid state at least at the time of bonding, and then the curing is performed. TECHNICAL FIELD The present invention relates to a method for producing a polyarylene sulfide resin composite molded article having a solid resin composition or a metal.

The present invention also provides (8) a polyarylene sulfide resin molded article as described in (2) above, and a cured product of a curable resin composition or a metal-bonded polyarylene sulfide resin composite molded article,
The surface of the polyarylene sulfide resin molded product which comes into contact with the cured product of the curable resin composition or the metal is in the range of 2.8 to 5.0 (μm) of the arithmetic average roughness (Ra) of the surface roughened surface. The present invention relates to a polyarylene sulfide resin composite molded article characterized by the above.

  According to the present invention, when the surface of a polyarylene sulfide resin molded article is irradiated with active energy rays, a polyarylene sulfide resin composition capable of surface roughening, a molded article thereof, and a method for producing them, and the poly Method of irradiating a molded product obtained by molding an arylene sulfide resin composition with an active energy ray to roughen the surface, and a molded product obtained by roughening the surface, a curable resin containing an epoxy resin or a silicone resin It is possible to provide a polyarylene sulfide resin composite molded article in which another material such as a composition or metal is bonded with good adhesiveness, and a method for producing the same.

  The polyarylene sulfide resin composition of the present invention contains the polyarylene sulfide resin 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, and specifically, the following general 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）

(In the formula, 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.) Structure part 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（２）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。

A resin having a trifunctional structural site represented by and a repeating unit. The trifunctional structural moiety represented by the formula (2) is preferably in the range of 0.001 to 3 mol% and particularly in the range of 0.01 to 1 mol% with respect to the total number of moles with other structural sites. Is preferred.

Here, in the structural moiety represented by the general formula (2), R ¹ and R ² in the formula are preferably hydrogen atoms from the viewpoint of mechanical strength of the polyarylene sulfide resin. In this case, those which bond at the para position represented by the following formula (3) and those which bond at the meta position represented by the following formula (4) are mentioned.

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（３）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, it is particularly preferable that the bond of the sulfur atom to the aromatic ring in the repeating unit has a structure in which it is bonded at the para position represented by the general formula (3) so that the polyarylene sulfide resin has good heat resistance and crystallinity. It is preferable from the aspect.

  Further, the polyarylene sulfide resin is not limited to the structural moieties represented by the general formulas (1) and (2), but also the following structural formulas (5) to (8).

で表される構造部位を、前記一般式（１）と一般式（２）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（５）〜（８）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（５）〜（８）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 part represented by may be contained in an amount of 30 mol% or less of the total of the structural parts represented by the general formula (1) and the general formula (2). Particularly in the present invention, it is preferable that the structural portion represented by the general formulas (5) to (8) is 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin. When the polyarylene sulfide resin contains the structural moieties represented by the general formulas (5) to (8), the bonding mode thereof 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 it is preferably 3 mol% or less, particularly preferably 1 mol% with respect to the total number of moles with other structural sites. It is preferably not more than mol %.

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

(Melt viscosity)
The polyarylene sulfide resin used in the present invention preferably has a melt viscosity (V6) measured at 300° C. in the range of 2 to 1000 [Pa·s], and has a good balance of 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) was obtained by using a polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500D, at 300° C., load: 1.96×10 ⁶ Pa, L/D=10 (mm. )/1 (mm), the melt viscosity is measured after being held for 6 minutes.

(Non-Newton index)
The non-Newtonian index of the polyarylene sulfide resin (A) used in the present invention is not particularly limited as long as it does not impair the effects of the present invention, but it is preferably in the range of 0.90 to 2.00. When a linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.90 to 1.50, more preferably 0.95 to 1.20. Such a polyarylene sulfide resin has excellent mechanical properties, fluidity and abrasion resistance. However, the non-Newtonian index (N value) was measured at 300° C., the ratio of the orifice length (L) and the orifice diameter (D), and the shear rate and the shear stress under the conditions of L/D=40 using a capillograph. , A value calculated using the following equation (9).

［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。

[However, SR shows a shear rate (second ^-1 ), SS shows a shear stress (dyne/cm< ² >), and K shows a constant. The closer the N value is to 1, the more linear the PPS structure is, and the higher the N value is, the more branched the structure is.

(Production method)
The method for producing the polyarylene sulfide resin is not particularly limited, but for example, 1) adding a dihalogeno aromatic compound in the presence of sulfur and sodium carbonate, and if necessary adding a polyhalogeno aromatic compound or other copolymerization component, Polymerization method, 2) dihalogenoaromatic compound in a polar solvent in the presence of a sulfidizing agent, etc., and if necessary, a polyhalogenoaromatic compound or other copolymerization component is added, and 3) p-chloro Examples include a method of self-condensing ruthiophenol by adding other copolymerization components if necessary. Among these methods, the method 2) is versatile and preferable. During the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide may be added to control the degree of polymerization. Among the above 2) methods, a hydrous sulfidizing agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at such a rate that water can be removed from the reaction mixture, and the dihalogenoaromatic compound is introduced in the organic polar solvent. And a sulfidizing agent are added to the polyhalogenoaromatic compound as the case requires, and the reaction is carried out, and the amount of water in the reaction system is set within the range of 0.02 to 0.5 mol per mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by controlling (see JP-A-07-228699), a dihalogenoaromatic compound, if necessary, in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent. A polyhalogeno aromatic compound or other copolymerization component is added, and an alkali metal hydrosulfide and an organic acid alkali metal salt are added in an amount of 0.01 to 0.9 mol of organic acid alkali metal salt and 1 mol of a sulfur source. What is obtained by the method (refer to WO 2010/058713 pamphlet) in which the reaction is carried out while controlling the amount of water in the reaction system within the range of 0.02 mol or less relative to 1 mol of the aprotic polar organic solvent is particularly preferable. Specific examples of the dihalogeno aromatic 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 the above compounds Examples of the compound having an alkyl group having 1 to 18 carbon atoms in its aromatic ring include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3, as the polyhalogeno aromatic compound. Examples thereof include 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, and 1,4,6-trihalonaphthalene. The halogen atom contained in each of the above compounds is preferably a chlorine atom or a bromine atom.

  The method for post-treating the reaction mixture containing the polyarylene sulfide resin obtained by the polymerization step is not particularly limited, but, 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 matter after the solvent is distilled off is water, a reaction solvent (or an organic solvent having an equivalent solubility to the low molecular weight polymer), acetone, methyl ethyl ketone. , A method of washing once or twice or more with a solvent such as alcohols, and further neutralizing, washing with water, filtration and drying, or (2) after completion of the polymerization reaction, water, acetone, methyl ethyl ketone, alcohols, Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons (solvents that are soluble in the used polymerization solvent and are poor solvents for at least polyarylene sulfide) as a precipitant A method in which a solid product such as polyarylene sulfide or an inorganic salt is precipitated and then filtered, washed and dried, or (3) after completion of the polymerization reaction, a reaction solvent (or a low molecular weight compound) is added to the reaction mixture. After adding an organic solvent having an equivalent solubility to the polymer and stirring, filtering to remove the low molecular weight polymer, washing with a solvent such as water, acetone, methyl ethyl ketone, alcohols once or twice or more And then neutralizing, washing with water, filtering and drying. (4) After completion of the polymerization reaction, water is added to the reaction mixture to wash with water, filter, and if necessary, acid is added to the reaction mixture for acid treatment. , A method of drying, (5) a method of filtering the reaction mixture after completion of the polymerization reaction, optionally washing once or twice or more with a reaction solvent, and further washing with water, filtration and drying. ..

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

  The content of the polyarylene sulfide resin in the polyarylene sulfide resin composition of the present invention is 100 in total of the essential components of the polyarylene sulfide resin, the glass fiber, the metal oxide, and the layered and cleavable clay mineral. It is a range (residual part) excluding the total mass part of the glass fiber, the metal oxide, and the layered and cleavable clay mineral, relative to the mass part, but it may be 15 to 88 mass parts. It is more preferably in the range of 45 to 70 parts by mass.

  The polyarylene sulfide resin composition of the present invention contains glass fiber as an essential component.

  The glass fibers used in the present invention preferably have an average diameter of 20 μm or less, and those having an average diameter of 1 to 15 μm further enhance the physical property balance (strength, rigidity, heat resistant rigidity, impact strength) and molding warpage. It is preferable in that it is further reduced. Although glass fibers having a circular cross section are generally used in many cases, they are not particularly limited in the present invention, and may be similarly used in, for example, eyebrows, ellipses, and rectangles in cross section.

  The length of the glass fiber is not specified and can be selected from long fiber type (roving), short fiber type (chopped strand) and the like. In this case, the number of bundles is preferably about 100 to 5000. Further, if the length of the glass fiber in the thermoplastic resin composition after kneading the thermoplastic resin composition is obtained with an average of 0.1 mm or more, so-called milled fiber, a crushed product of strands called glass powder may be used, Further, a continuous single fiber sliver may be used. The composition of the raw material glass is also preferably alkali-free, and examples thereof include E glass, C glass, and S glass. In the present invention, E glass is preferably used.

  The glass fiber is preferably surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-aminopropyltriethoxysilane. The amount of adhesion is usually 0.01 to 1% by mass of the glass fiber mass. Further, if necessary, a fatty acid amide compound, a lubricant such as silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin and a urethane resin, a resin having a film forming ability and a heat treatment. It is also possible to use those surface-treated with a mixture of a stabilizer, a flame retardant and the like.

The content of the glass fiber in the polyarylene sulfide resin composition of the present invention is 100 parts by mass in total of the polyarylene sulfide resin, the glass fiber, the metal oxide, and each of the essential components of the layered and cleavable clay mineral. On the other hand, it is in the range of 10 to 35 parts by mass, preferably 12 to 30 parts by mass.
In the polyarylene sulfide resin composition of the present invention, it is generally preferable that the polyarylene sulfide resin and the glass fiber account for 60% by mass or more of all components.

The polyarylene sulfide resin composition of the present invention contains a metal oxide as an essential component. The metal atom preferably contains at least one selected from the group consisting of copper and chromium, and more preferably contains copper and chromium. Specific examples of the metal oxide that can be used in the present invention include CuFe _0.5 B _0.5 O _2.5 , CuAl _0.5 B _0.5 O _2.5 , and CuGa _0.5 B _{0. .5} O _2.5 , CuB ₂ O ₄ , CuB _0.7 O ₂ , CuMo _0.7 O ₃ , CuMo _0.5 O _2.5 , CuMoO ₄ , CuWO ₄ , CuSeO ₄ , CuCr ₂ O _4. Be done.

  The number average particle diameter of the metal oxide is not particularly limited as long as the effect of the present invention is not impaired, but since the surface roughness of the molded product progresses, a larger particle diameter of the metal oxide tends to be preferable. ˜50 μm, more preferably 0.05 to 30 μm. If it is too soft, it will be broken by contact with glass fibers during melt-kneading and the particle size cannot be maintained. Therefore, it is preferable to have a smaller Mohs hardness within the range of less than 1.5 relative to the Mohs hardness of the glass fibers. . The glass fiber preferably has a Mohs hardness in the range of 5.5 or more, more preferably in the range of 5.5 to 8, and still more preferably in the range of 5.5 to 7.5. As the metal oxide, the Mohs hardness of the glass fiber is preferably in the range of 4.0 to 6.5, and more preferably in the range of 4.0 to 6.0. On the other hand, it is preferable to use a combination of metal oxides having a smaller Mohs hardness within the range of less than 1.5.

  In the polyarylene sulfide resin composition of the present invention, the content of the metal oxide is 100 in total of each essential component of the polyarylene sulfide resin, the glass fiber, the metal oxide, and the layered and cleavable clay mineral. The range is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass, and further preferably 3 to 18 parts by mass with respect to parts by mass. Further, by combining with a clay mineral described later, surface roughening proceeds even with a small content, which is preferable.

  The polyarylene sulfide resin composition of the present invention contains a layered and cleavable clay mineral as an essential component. In the present invention, the addition of the clay mineral is preferable because it enables appropriate surface roughening even if the content of the metal oxide is reduced.

  Examples of the clay minerals include talc, hydrotalcite, smectite, mica, dik stone, nakuru stone, halloy stone, antigorite, monoclinic chrysotile stone, orthoclinic chrysotile stone, parachrysotile stone, lizard stone, ames Examples thereof include kaolinites such as stones, kelly stones, bercherin, greena stones, and nupore stones. Of these, talc, hydrotalcite, and smectite are preferable, and talc and hydrotalcite are more preferable.

  In the polyarylene sulfide resin composition of the present invention, the content of the clay mineral is 100 masses of the polyarylene sulfide resin, the glass fiber, the metal oxide, and the essential components of the layered and cleavable clay mineral. It is preferably in the range of 1 to 20 parts by mass, more preferably in the range of 2 to 15 parts by mass, and even more preferably in the range of 2 to 10 parts by mass.

  The clay mineral used in the present invention preferably has a Mohs hardness smaller than that of the metal oxide, specifically, a range of 2.5 or less is preferable, and a range of 2 or less is more preferable. It is preferable to use a clay mineral having a Mohs hardness within the above range from the viewpoint of suppressing the destruction of the metal oxide during melt-kneading. Although it is not a definite theory, we believe that this effect is due to the role of a cushioning material.

  The polyarylene sulfide resin composition of the present invention can optionally contain a filler other than the above-mentioned essential components (hereinafter simply referred to as a filler) as an optional component. As these fillers, known and commonly used materials may be used as long as they do not impair the effects of the present invention. Examples include fillers. Specifically, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, fibers such as wollastonite, fibrous fillers such as natural fibers can be used, In addition, non-fibrous fillers such as glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, attapulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite and calcium sulfate are also used. it can.

  In the present invention, the filler is not an essential component, and when added, the content thereof is not particularly limited as long as the effect of the present invention is not impaired. The content of the filler is, for example, preferably in the range of 0.01 to 10 mass% in the polyarylene sulfide resin composition, and more preferably in the range of 0.1 to 5 mass %. Within such a range, good mechanical strength and moldability can be imparted to the resin composition, which is preferable.

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

  The polyarylene sulfide resin composition of the present invention can optionally contain a thermoplastic elastomer as an optional component. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers and silicone-based elastomers, and among these, polyolefin-based elastomers are preferable. When these elastomers are added, the content thereof is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably in the range of 0.01 to 10 mass% in the polyarylene sulfide resin composition, More preferably, it is in the range of 0.1 to 5 mass %. In such a range, impact resistance of the obtained polyarylene sulfide resin composition is improved, which is preferable.

  The polyolefin-based elastomer is, for example, by homopolymerization of α-olefins or copolymerization of different α-olefins with each other, and in the case of imparting a functional group, with a vinyl polymerizable compound having an α-olefin and 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. As the functional group, a carboxy group, an acid anhydride group represented by the formula —(CO)O(CO)—, an ester thereof, an epoxy group, an amino group, a hydroxyl group, a mercapto group, an isocyanate group, or an oxazoline group. And so on.

  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 ester, and their alkyl esters, maleic acid, fumaric acid. Examples thereof include acids, itaconic acid, other α,β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their derivatives (mono- or diesters, their acid anhydrides, etc.), and glycidyl (meth)acrylate. Among these, the above-mentioned epoxy group, carboxy group, and ethylene-propylene copolymer and ethylene-butene copolymer having at least one functional group selected from the group consisting of the acid anhydride group are mechanical It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.

  Furthermore, the polyarylene sulfide resin composition of the present invention is, in addition to the above-mentioned components, further depending on the application, polyester resin, polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone. Resin, polyethersulfone resin, polyetheretherketone resin, polyetherketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenol resin , A urethane resin, a synthetic resin such as a liquid crystal polymer, or the like can be contained as an optional component. Further, the contents of these resins differ depending on their respective purposes and cannot be unconditionally specified, but the effect of the present invention is in the range of 0.01 to 20% by mass in the polyarylene sulfide resin composition. It may be appropriately adjusted and used according to the purpose and application so as not to impair the above.

  Further, the polyarylene sulfide resin composition of the present invention is also a colorant, an antistatic agent, an antioxidant, a heat resistance stabilizer, a UV stabilizer, a UV absorber, a foaming agent, a flame retardant, a flame retardant auxiliary agent, and a protective agent. A known and commonly used additive such as a rusting agent and a coupling agent may be contained as an optional component, if necessary. These additives are not essential components, for example, in the polyarylene sulfide resin composition, preferably in the range of 0.01 to 20 mass%, appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention And use it.

  The method for producing a polyarylene sulfide resin composition of the present invention includes a polyarylene sulfide resin, the glass fiber, the metal oxide, each essential component of the clay mineral, and, if necessary, an optional filler such as a filler. Melting and kneading the components as essential components at a melting point of the polyarylene sulfide resin or higher.

  A preferred method for producing the polyarylene sulfide resin composition of the present invention is to have the above-mentioned content, and the polyarylene sulfide resin, each of the glass fiber, the metal oxide, and each of the essential components of the clay mineral, and if necessary. Then, optional components such as a filler are put into a ribbon blender, a Henschel mixer, a V blender, etc. in various forms such as powder, pellets, and fine particles, and dry blended, and then a Banbury mixer, a mixing roll, a single shaft or 2 It is charged in a known melt-kneading machine such as a shaft extruder and a kneader, and the temperature range in which the resin temperature is the melting point of the polyarylene sulfide resin or higher, preferably the melting point +10°C or higher, more preferably the melting point +10°C- It can be produced through a step of melt-kneading in a temperature range of melting point +100°C, more preferably in a temperature range of melting point +20 to melting point +50°C. The addition and mixing of the respective components to the melt-kneader may be carried out simultaneously or in a divided manner.

  As the melt kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity, and for example, the discharge amount of the resin component is in the range of 5 to 500 (kg/hr), and the screw rotation speed is 50 to 500 (rpm). It is preferable to melt-knead while appropriately adjusting the above range, and to perform melt-kneading under the condition that the ratio (discharging amount/screw rotation speed) is in the range of 0.02 to 5 (kg/hr/rpm). Is more preferable. Further, in the case of adding a filler or an additive among the above components, it is preferable to add the filler or the additive into the extruder from the side feeder of the twin-screw kneading extruder, from the viewpoint of good shape retention and good dispersibility. With respect to the position of the side feeder, the ratio of the distance from the extruder resin feeding portion to the side feeder to the entire screw length of the twin-screw kneading extruder is preferably in the range of 0.1 to 0.9. Above all, the range of 0.3 to 0.7 is particularly preferable.

  The polyarylene sulfide resin composition of the present invention obtained by melt-kneading in this manner is a polyarylene sulfide resin which is an essential component, the glass fiber, the metal oxide and the clay mineral, and an optional component added as necessary. And a melt mixture containing the components derived therefrom, and after the melt-kneading, processed into a form of pellets, chips, granules, powders and the like by a known method, and then pre-dried at a temperature of 100 to 150° C. if necessary. It is preferable to subject it to various moldings.

  The polyarylene sulfide resin composition of the present invention produced by the above production method uses a polyarylene sulfide resin as a matrix, and in the matrix, the glass fiber, the metal oxide, and the clay mineral, which are essential components, are derived from it. A morphology is formed in which the components and optional components added as necessary are dispersed. As a result, the surface of the polyarylene sulfide resin molded article is roughened by irradiation with active energy rays, which is preferable.

  The polyarylene sulfide resin composition of the present invention can be molded by melt molding by various molding methods such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. Although it is possible to manufacture the resin, it is suitable for injection molding because of its excellent releasability. Various molding conditions in the melt molding are not particularly limited, and the molding can be performed by a general method. Melt molding may be carried out, for example, in a molding machine in which the resin temperature is at or above the melting point of the polyarylene sulfide resin, preferably at the melting point+10° C. or higher, more preferably at the melting point+10° C. to melting point+100° C. Preferably, after the step of melting the polyarylene sulfide resin composition in the temperature range of melting point +20 to melting point +50° C., the resin is discharged from the resin discharge port and injected into a mold or the like for molding. When injecting into a mold and molding, the mold temperature may be set within a known temperature range, for example, room temperature (23° C.) to 300° C., preferably 120 to 180° C.

  The molded product obtained by molding the polyarylene sulfide resin composition of the present invention obtained as described above is treated with an active energy ray, and the surface thereof has, for example, an arithmetic mean roughness (Ra) of 2.8. To 5.0 (μm), more preferably 3.0 to 4.0 (μm).

  Roughening of the surface of the molded product is carried out using a known method as long as it is a method capable of roughening the surface of the polyarylene sulfide resin molded product in a non-contact manner by physical action of atoms, electrons, active energy rays, etc. Examples of the treatment include irradiation with active energy rays such as ultraviolet rays, infrared rays to far infrared rays, laser beams, microwaves, corona discharge, arc discharge, and plasma treatment. The irradiation output of the active energy ray is not particularly limited as long as it does not impair the effects of the present invention, and may be adjusted by preliminary experiments or the like performed as appropriate, but it is preferably in the range of 1 to 20 W, and further 5 to 12 W. The range is more preferably. The area to be surface-roughened of the polyarylene sulfide resin molded article is not particularly limited as long as it does not impair the effects of the present invention, but the polyarylene sulfide resin molded article in the finally obtained composite molded article and other materials The area ratio is preferably 1% or more, but more preferably 10% or more, still more preferably 50% or more, since more excellent adhesive strength can be imparted. % Is particularly preferable, and 100% is the most preferable.

  As described above, the molded article obtained by molding the polyarylene sulfide resin composition of the present invention is preferably subjected to non-contact surface roughening treatment (etching treatment) by irradiation with active energy rays to suitably roughen the surface. You can As a result, since it becomes possible to manufacture a composite molded article by a joining method based on a physical action, at least the contact surface at the time of joining is in a liquid state, and if the material becomes a solid state thereafter, regardless of its type Any of these can exhibit excellent adhesiveness. Examples of such a material include, but are not limited to, a curable resin composition containing an epoxy resin and a silicone resin, and other materials such as metal.

  Therefore, the polyarylene sulfide resin composite molded article of the present invention is a molded article obtained by molding the polyarylene sulfide resin composition of the present invention. It can be produced by contacting with a material whose contact surface with the surface of the molded product is in a liquid state, for example, a curable resin composition containing an epoxy resin or a silicone resin, or another material such as a metal, and then curing or solidifying. it can.

  The curable resin composition containing an epoxy resin, a silicone resin, or the like mentioned herein preferably contains a curing agent or a curing catalyst. The epoxy resin is not particularly limited as long as it is a polymer compound containing two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type Epoxy resin, bisphenol type epoxy resin typified by tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin typified by biphenyl type epoxy resin or tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, Cresol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-contracted novolac type epoxy resin, brominated phenol novolac type epoxy resin, and other novolac type epoxy resins are listed. Be done. These epoxy resins are used as a curable resin composition containing a curing agent, and are preferably used by causing a curing reaction by giving heat energy or light energy. At that time, the use ratio of the epoxy resin and the curing agent is not particularly limited as long as it is a known ratio within a range that does not impair the effects of the present invention, but the curability is excellent, and the heat resistance and resistance of the cured product are high. From the viewpoint that a cured product having excellent chemical properties can be obtained, it is preferable that the amount of the active groups in the curing agent is 0.7 to 1.5 equivalents based on 1 equivalent of the total of epoxy groups in the epoxy resin component. In addition, the curing agent is not particularly limited as long as it is generally used as a curing agent for epoxy resins, and examples thereof include amine type curing agents, phenol resin type curing agents, acid anhydride type curing agents, and latent potentials. A hardening agent etc. are mentioned.

  On the other hand, as the silicone resin, in addition to a polyorganosiloxane having a linear structure, a polyorganosiloxane having a three-dimensional network structure containing a trifunctional siloxane unit, a tetrafunctional siloxane unit, and the like is used in combination, if necessary. May be The polyorganosiloxane usually refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the following general formula (10) and a mixture thereof.

ここで、上記式（１０）において、Ｒ^１からＲ^６は独立して、有機官能基、水酸基、水素原子から選択される。またＭ、Ｄ、ＴおよびＱは０以上１未満であり、Ｍ＋Ｄ＋Ｔ＋Ｑ＝１を満足する数である。
一般式（１０）に示す通り、ポリオルガノシロキサンを構成する主な単位は、１官能型［Ｒ^１Ｒ^２Ｒ^３ＳｉＯ_１／２］(トリオルガノシルヘミオキサン)、２官能型［Ｒ^４Ｒ^５ＳｉＯ_２／２］（ジオルガノシロキサン）、３官能型［Ｒ^６ＳｉＯ_３／２］（オルガノシルセスキオキサン）、４官能型［ＳｉＯ_４／２］（シリケート）であり、これら４種の単位の構成比率を変えることにより、ポリオルガノシロキサンの性状の違いが出てくるため、所望の特性が得られるように適宜選択すればよい。シリコーン樹脂は、公知の硬化触媒の存在下で、熱エネルギーや光エネルギー等を与えることにより硬化させることができる。

Here, in the above formula (10), R ¹ to R ⁶ are independently selected from an organic functional group, a hydroxyl group, and a hydrogen atom. Further, M, D, T and Q are 0 or more and less than 1 and are numbers satisfying M+D+T+Q=1.
As shown in the general formula (10), the main units constituting the polyorganosiloxane are monofunctional [R ¹ R ² R ³ SiO _1/2 ](triorganosylhemioxane) and difunctional [R ⁴ R ⁵ SiO _2/2 ] (diorganosiloxane), trifunctional [R ⁶ SiO _3/2 ] (organosilsesquioxane), and tetrafunctional [SiO _4/2 ] (silicate), and these four types. Since the property of the polyorganosiloxane varies depending on the composition ratio of the unit, it may be appropriately selected so as to obtain desired characteristics. The silicone resin can be cured by applying heat energy or light energy in the presence of a known curing catalyst.

  On the other hand, examples of the metal material include copper, nickel, gold, silver, palladium, and aluminum, and one or a mixture of two or more thereof may be used. Of these, copper is more preferable. When these metal materials are in a solid state in the manufacturing process, the surface is kept in a molten state by the treatment with the active energy ray irradiation, and the surface is bonded to the surface-roughened surface of the polyarylene sulfide resin molded article. Then, a method of cooling and solidifying and adhering, and a method of applying to the surface of the surface-roughened polyarylene sulfide resin molded article when melted and in a liquid state are mentioned.

  Main applications of the composite are box-shaped electric/electronic component integrated module protection/support members, plural individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, Capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, electronic circuits, LSIs, ICs, tuners, speakers, 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 electric and electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, Audio parts, audio/video devices such as audio/laser discs/compact discs/DVD discs/Blu-ray discs, lighting components, refrigerator components, air conditioner components, typewriter components, word processor components, or the amount of water in a water heater or bath, temperature sensor Household and office electric product parts such as water supply equipment parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, writers, typewriters, etc. Machine-related parts such as: Microscopes, binoculars, cameras, optical devices such as watches, precision machine-related parts; alternator terminals, alternator connectors, IC regulators, potentiometer bases for light deya, relay blocks, inhibitor switches , Various valves such as exhaust gas valve, fuel related/exhaust system/intake system various pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil Temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane , Wiper motor related parts, dust distributor, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor Cores, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings. It is also applicable to automobile/vehicle-related parts such as a brake piston, a solenoid bobbin, an engine oil filter, and an ignition device case, and various other uses.

<Examples 1 to 10 and Comparative Examples 1 to 6>
Each material was uniformly mixed with a tumbler according to the composition components and blending amounts (all parts by mass) described in Tables 1 to 4. Then, the compounding material was charged into a twin-screw extruder with a vent made by Toshiba Machine Co., Ltd. "TEM-35B", and the resin component discharge rate was 25 kg/hr, the screw rotation speed was 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 preset resin temperature of 330° C. to obtain pellets of the resin composition.

  Next, the pellets thus obtained were supplied to an injection molding machine (SG75-HIPRO MIII) manufactured by Sumitomo-Nestal Co., Ltd. in which the cylinder temperature was set to 320° C., and the temperature of the mold was adjusted to 130° C. to mold ASTM No. 1 dumbbell piece. Injection molding was performed using a mold to obtain ASTM No. 1 dumbbell pieces.

The obtained ASTM No. 1 dumbbell piece was subjected to irradiation with active energy rays (spot diameter 70 μm, moving speed 4 m/s, output 7 W) to roughen the surface of length 10 mm×width 5 m.
The following various evaluation tests were performed using this test piece. The results of the tests and evaluations are shown in Tables 1-4.

[Method of measuring roughness of laser-irradiated surface]
The arithmetic average roughness Ra was measured according to JIS B 0601:2013. That is, the roughened surface of the ASTM No. 1 dumbbell piece was measured using a surface roughness measuring instrument (Mitutoyo Corporation, contour profile measuring instrument Surftest SV-3000CNC). For the measurement, only the reference length is extracted from the roughness curve in the direction of the average line, the x-axis is taken in the direction of the average line of the extracted portion, the y-axis is taken in the direction of longitudinal magnification, and the roughness curve is taken as y=f( The value obtained by the following equation when represented by x) is represented by micrometers (μm).

ここで、Ｌ＝３００μｍとし、ダンベル片１体につき、１００点の測定を、ダンベル片３体について行った。各測定結果を平均して、算術平均粗さ（Ｒａ）を求めた。

Here, L=300 μm, and 100 points were measured for one dumbbell piece and three dumbbell pieces were measured. The respective measurement results were averaged to obtain the arithmetic mean roughness (Ra).

  In Comparative Example 1 in which the PPS resin was mixed with carbon black for absorbing active energy rays, a PPS skin layer having good surface smoothness was formed at the irradiation mark.

  In Comparative Example 2, the metal oxide was not contained and the absorption of the active energy ray was insufficient, so that a sufficient surface roughening (etching) effect was not obtained.

  In Comparative Example 3, since the glass fiber was small, the surface irregularities were small and the surface smoothness was good. On the other hand, in Comparative Example 4, a large amount of glass fiber was reflected by the active energy rays, so that a sufficient surface roughening (etching) effect was not obtained.

  In Comparative Examples 5 and 6, the absorption of active energy rays was insufficient and a sufficient surface roughening (etching) effect was not obtained.

Numerical values in Tables 1 to 4 represent parts by mass, and each material is as follows.
PPS(A-1) "MA-520" manufactured by Linear PPS DIC Co., Ltd. (peak molecular weight 35000, melt viscosity (V6) 160 Pa·s)
GF(B-1) glass fiber "T-717H" manufactured by Nippon Electric Glass Co., Ltd. (chopped strand having an average fiber length of 200 µm and an average diameter of 10 µm, Mohs hardness of 6.5)
Metal oxide _{(C-1) CuCr 2 O} 4 ( Mohs hardness 5.5-6.0)
Metal oxide _{(c-2) Cu 3 (} PO 4) 2 Cu (OH) 2 ( Mohs hardness 4.0-5.0)
Metal oxide (c-3) A mixture of Bi ₂ O ₃ (98 to 99% by mass) and Nd ₂ O ₃ (0.3 to 1.0% by mass) (Mohs hardness: 4.0 to 5.0).
Clay Mineral (D-1) Talc Matsumura Sangyo Co., Ltd. “HF5000PJ” (aspect ratio <20, D ₅₀ /20 (μm), Mohs hardness 1.0)
Clay Mineral (D-2) Hydrotalcite Kyowa Chemical Industry Co., Ltd. “DHT-4A” (Aspect ratio 2.6, D ₅₀ /0.4 (μm), Mohs hardness 1.0)
Additive (E-1) Amino group-containing alkoxysilane additive (E-2) Epoxy group-containing alkoxysilane additive (e-3) Carbon black ("Denka black granular product" manufactured by Denki Kagaku Kogyo Co., Ltd. average particle diameter 35 nm) )
As the Mohs hardness, 10-step Mohs hardness generally used as an index of hardness of minerals was used.

Claims (9)

The surface of the polyarylene sulfide resin molded product obtained by molding the polyarylene sulfide resin composition is irradiated with active energy rays or ionizing radiation, and the arithmetic average roughness (Ra) of the surface roughened surface is 2.8 to A method for producing a polyarylene sulfide resin molded article having a range of 5.0 (μm), comprising:
The polyarylene sulfide resin composition,
Polyarylene sulfide resin, glass fiber, a metal oxide, containing a layered and cleavable clay mineral as an essential component,
Polyarylene sulfide resin, glass fiber, metal oxide, and a layered and cleavable clay mineral with respect to a total of 100 parts by mass, the range of 10 to 35 parts by mass of glass fiber and 1 to 30 parts by mass of metal oxide. And the range of 1 to 20 parts by mass of clay mineral, and the balance is polyarylene sulfide resin,
The Mohs hardness of the metal oxide is smaller than the Mohs hardness of the glass fiber, and the difference is less than 1.5, and the metal oxide is at least one selected from the group consisting of copper and chromium. A method for producing a polyarylene sulfide resin molded article, comprising: The method for producing a polyarylene sulfide resin molded article according to claim 1, wherein the clay mineral is talc. The method for producing a polyarylene sulfide resin molded article according to claim 1, wherein the clay mineral is hydrotalcite. Arithmetic average roughness (Ra) of the surface roughened surface obtained by performing irradiation with active energy rays or ionizing radiation on the surface of a polyarylene sulfide resin molded product obtained by molding a polyarylene sulfide resin composition. Is in the range of 2.8 to 5.0 (μm), the curable resin composition or the metal is brought into contact with at least the contact surface in a liquid state at the time of joining, and then the curable resin composition. A method for producing a polyarylene sulfide resin composite molded article in which an object or a metal is in a solid state ,
The polyarylene sulfide resin composition,
Polyarylene sulfide resin, glass fiber, a metal oxide, containing a layered and cleavable clay mineral as an essential component,
Polyarylene sulfide resin, glass fiber, metal oxide, and a layered and cleavable clay mineral to a total of 100 parts by mass, a range of 10 to 35 parts by mass of glass fiber and 1 to 30 parts by mass of metal oxide. And the range of 1 to 20 parts by mass of clay mineral, and the balance is polyarylene sulfide resin,
The Mohs hardness of the metal oxide is smaller than the Mohs hardness of the glass fiber, and the difference is less than 1.5, and the metal oxide is at least one selected from the group consisting of copper and chromium. A method for producing a polyarylene sulfide resin composite molded article, which comprises: The method for producing a polyarylene sulfide resin composite molded article according to claim 4 , wherein the clay mineral is talc. The method for producing a polyarylene sulfide resin composite molded article according to claim 4 , wherein the clay mineral is hydrotalcite. A polyarylene sulfide resin molded article obtained by molding a polyarylene sulfide resin composition, and a polyarylene sulfide resin composite molded article in which a cured product of a curable resin composition or a metal is bonded,
The surface of the polyarylene sulfide resin molded article that comes into contact with the cured product of the curable resin composition or the metal is in the range of arithmetic average roughness (Ra) of 2.8 to 5.0 (μm),
The polyarylene sulfide resin composition,
Contains polyarylene sulfide resin, glass fiber, metal oxide, and a layered and cleavable clay mineral as essential components
Polyarylene sulfide resin, glass fiber, metal oxide, and a layered and cleavable clay mineral to a total of 100 parts by mass, a range of 10 to 35 parts by mass of glass fiber and 1 to 30 parts by mass of metal oxide. And the range of 1 to 20 parts by mass of clay mineral, and the balance is polyarylene sulfide resin,
The Mohs hardness of the metal oxide is smaller than the Mohs hardness of the glass fiber, and the difference is less than 1.5, and the metal oxide is at least one selected from the group consisting of copper and chromium. A polyarylene sulfide resin composite molded article characterized by containing . The polyarylene sulfide resin composite molded article according to claim 7 , wherein the clay mineral is talc. The polyarylene sulfide resin composite molded article according to claim 7 , wherein the clay mineral is hydrotalcite.