JP2018199250A - Polyarylene sulfide resin composition, molded product, metal/resin composite structure and production method - Google Patents

Abstract

[PROBLEMS] To provide a metal / resin composite structure having excellent adhesion, formed by joining a metal member and a molded product of a polyarylene sulfide resin composition, a polyarylene sulfide resin composition capable of providing the molded product, and the same Providing a manufacturing method of
A metal / resin composite structure formed by joining a metal member and a molded product of a polyarylene sulfide resin composition comprising polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components. , A polyarylene sulfide resin composition comprising the polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) used in the metal / resin composite structure as essential components, a molded product thereof, and a method for producing them.
[Selection figure] None

Description

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

  A polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by a polyphenylene sulfide (hereinafter abbreviated as PPS) resin can maintain a melting point of 270 ° C. or higher and exhibits excellent heat resistance, and It is also known that it has excellent mechanical strength, chemical resistance, molding processability, and dimensional stability. Therefore, generally, additives such as fillers and elastomers are blended into the polyarylene sulfide resin, and melt-kneaded so that these are dispersed in a matrix made of the polyarylene sulfide resin to obtain a PAS resin composition. Above, it is melt-molded and processed into various molded products as electrical / electronic equipment parts, automobile parts and the like.

  By the way, from the viewpoint of weight reduction of various parts, highly heat-resistant resin members are used as metal member substitutes. However, when it is difficult to replace all metal members with resin due to problems such as mechanical strength, a composite structure obtained by joining and integrating the metal member and the resin member (hereinafter referred to as a metal / resin composite structure) Is used). As such a metal / resin composite structure, for example, a method is known in which a metal member surface is roughened and bonded using a polyarylene sulfide resin due to an anchor effect. For example, an aluminum alloy or magnesium alloy having a recess having a number average inner diameter of 10 to 80 nm on the surface by a chemical treatment such as an erodible aqueous solution or an erodible suspension, or a surface having a number average inner diameter of 10 by treating with an anodic oxidation method. Aluminum alloy having recesses of ˜80 nm, polyphenylene sulfide and a specific proportion of maleic anhydride modified ethylene copolymer, glycidyl methacrylate modified ethylene copolymer, glycidyl ether modified ethylene copolymer and ethylene alkyl acrylate copolymer A composite is known which is formed by injection molding a resin composition containing at least one polyolefin resin selected from the group consisting of coalesced and fixed in a state in which the resin composition has entered a recess (Patent Document). 1). The minute recesses on the metal surface formed by the treatment method also have a very fine inner diameter, so that the resin composition is difficult to enter, and therefore the metal part and the molded product composed of the resin composition are in close contact with each other. The power was not enough.

  However, since the polyarylene sulfide resin composition has a high temperature (recrystallization temperature: Tc2) at which it is solidified (crystallized) from a molten state, the molten polyarylene sulfide resin composition is brought into contact with a metal member. At this time, the cause is that the resin composition is solidified (crystallized) before flowing into the fine irregularities on the surface of the metal member. Therefore, development of a resin composition containing a polyarylene sulfide resin having a lower recrystallization temperature (Tc2) has been desired.

  Therefore, a method of copolymerizing paradichlorobenzene and metadichlorobenzene has been proposed for the purpose of lowering the recrystallization temperature of the polyarylene sulfide resin (see Patent Document 2). However, since the polyarylene sulfide resin is a method in which a meta isomer is inserted into a part of the skeleton, the recrystallization temperature of the polyarylene sulfide resin itself used is lowered, and the melting point is much lower than 270 ° C. There was a property of lowering. As a result, the metal / resin composite structure produced using the metal / resin composite structure was excellent in adhesion between the metal member and the molded product of the polyarylene sulfide resin composition, but had a property that the heat resistance was remarkably reduced.

JP 2007-050630 A JP 2009-050630 A

  Therefore, the problem to be solved by the present invention is to provide a metal / resin composite structure having excellent heat resistance and adhesion, and a method for producing the same, in which a metal member and a molded article of a polyarylene sulfide resin composition are joined. There is to do. Furthermore, the present invention provides a polyarylene sulfide resin composition having excellent adhesion to metal parts and excellent in heat resistance, and excellent adhesion to metal parts formed by melt-molding it, and also in heat resistance. The object is to provide an excellent molded product.

  As a result of various studies, the present inventors have found that a polyarylene sulfide resin composition obtained by blending a polyvinyl pyrrolidone resin with a polyarylene sulfide resin exhibits excellent adhesion to a metal member, It has been found that the excellent heat resistance inherent in the arylene sulfide resin is maintained, and the present invention has been solved.

That is, the present invention is a metal / resin composite structure formed by joining a metal member and a molded product of a polyarylene sulfide resin composition,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). The metal / resin composite structure is characterized in that (B) is in the range of 0.01 to 100 parts by mass.

In addition, the present invention is a polyarylene sulfide resin composition used for a metal / resin composite structure in which a metal member and a molded article of a polyarylene sulfide resin composition are joined,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). The polyarylene sulfide resin composition is characterized in that (B) is in the range of 0.01 to 100 parts by mass.

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

Further, the present invention is a method for producing a metal / resin composite structure in which a metal member and a molded article of a polyarylene sulfide resin composition are joined,
(1) a step of joining the surface of the metal member by melt-molding the polyarylene sulfide resin composition, or (2) a step of joining the metal member and the molded product of the polyarylene sulfide resin composition. about,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). The present invention relates to a method for producing a metal / resin composite structure, wherein (B) is in the range of 0.01 to 100 parts by mass.

Further, the present invention is a method for producing a polyarylene sulfide resin composition used for a metal / resin composite structure in which a metal member and a molded product of a polyarylene sulfide resin composition are joined,
Having a step of melt-kneading polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and for 100 parts by mass of polyarylene sulfide resin (A), the polyvinylpyrrolidone (B) is 0.01 It is related with the manufacturing method of the polyarylene sulfide resin composition characterized by being in the range of -100 mass parts.

Further, the present invention is a method for producing the molded product used in a metal / resin composite structure formed by joining a metal member and a molded product of a polyarylene sulfide resin composition,
Having a step of molding the polyarylene sulfide resin composition in a mold,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). The present invention relates to a method for producing a molded product, wherein (B) is in the range of 0.01 to 100 parts by mass.

  According to the present invention, a metal member and a molded article of a polyarylene sulfide resin composition are joined, and an object of the present invention is to provide a metal / resin composite structure excellent in heat resistance and adhesion and a method for producing the same. Furthermore, the present invention provides a polyarylene sulfide resin composition having excellent adhesion to metal parts and excellent in heat resistance, and excellent adhesion to metal parts formed by melt-molding it, and also in heat resistance. An excellent molded product can be provided.

(Metal / resin composite structure)
The metal / resin composite structure of the present invention is formed by joining a metal member and a molded product of a polyarylene sulfide resin composition.
In the present invention, the bonding between the molded article and the metal member is considered to be mainly based on a physical bond or a chemical bond, although there is a contribution of mechanical bond. For this reason, the well-known joining method which can join a polyarylene sulfide resin composition thru | or its molded article to the metal member surface with fluidity | liquidity can be used. Hereinafter, (1) a step of joining the polyarylene sulfide resin composition to the metal member surface by melt molding (referred to as joining method 1), and (2) a molded product of the metal member and the polyarylene sulfide resin composition. And the process of joining (referred to as joining method 2).

  Examples of the joining method 1 include a so-called metal insert molding method in which a metal member is inserted into a mold of an injection molding machine and injection molding is performed using the polyarylene sulfide resin composition. Further, as another form of metal insert molding, a resin film-like product in which a metal member layer is laminated in a film shape is inserted into a mold, and a polyarylene sulfide resin composition is melt-molded on the metal member layer side, so-called Film insert molding may be used. The apparatus and manufacturing method in the metal insert molding method or the film insert molding method are not particularly limited, and a commercially available apparatus can be used or can be performed according to a conventional method. For example, in an injection molding machine, the resin temperature is in the temperature range above the melting point of the polyarylene sulfide resin composition, preferably in the temperature range above the melting point and the melting point plus 100 ° C., more preferably the melting point plus 20 ° C. and the melting point plus 50 ° C. After passing through the step of melting the polyarylene sulfide resin composition within a temperature range, the resin discharge port may be injected into the mold and molded. At that time, the mold temperature may also be in a known temperature range, but can be set from a lower temperature, for example, set in the range of room temperature (23 ° C.) to 300 ° C., preferably in the range of 40 to 180 ° C. Can do. As described above, the polyarylene sulfide resin composition of the present invention can be set to a temperature range of 120 to 180 ° C. which is preferable as a normal molding temperature, and has a low recrystallization temperature (Tc2) and excellent low temperature moldability. Since it also has characteristics, moldability such as appearance and filling properties and mechanical properties even at mold temperatures of relatively low temperature such as room temperature (23 ° C) or higher, preferably 40 ° C or higher and less than 120 ° C. A molded product having excellent chemical resistance can be obtained, which is preferable.

As the bonding method 2, the molded article of the polyarylene sulfide resin composition of the present invention is bonded by heating after being in contact with the metal member, or is bonded after being heated and then in contact with the metal member, Cooling. For example, hot plate welding method, vibration welding method, ultrasonic welding method, high frequency welding method, induction heating welding method, rotary welding method, laser welding method, hot press method, hot embossing method, etc. A commercially available apparatus can also be used for the apparatus and manufacturing method used for a method, and it can also carry out according to a conventional method. For example, in the hot plate welding method, the surface of a molded product to be welded to a metal member is melted. What is necessary is just to join by hold | maintaining in a pressure state. In vibration welding, ultrasonic welding, and high frequency welding, the surface of the molded product to be welded to the metal member is melted after the molded product is joined to the metal member. What is necessary is just to join by transmitting a sound wave and a high frequency to a molded article or a metal member, generating heat, melting the molded article by the generated heat, and holding in a pressurized state until it cools and hardens. The vibration, high frequency, and ultrasonic wave may be transmitted by bringing the molded product or the molded product into vibration by bringing a resonator or a vibration device into contact with the irradiated or molded product. The heat generation may be performed by frictional heat between the molded product and the metal member. On the other hand, in induction heating welding, after the molded product is joined to the metal member, the surface of the molded product to be welded to the metal member is melted, so that the metal member is heated by an induction heating device so as to satisfy the following temperature conditions. What is necessary is just to join by making the said molded article heat-dissipate and melt | dissolve and hold | maintain in a pressurized state until it cools and solidifies. In addition, in the rotary welding, after the molded product and the metal member are separately held, both of them are gradually brought close to each other while rotating at high speed within a range of 100 to 4,000 rotations, and the two contact each other. By the way, joining may be performed by generating frictional heat so as to satisfy the following temperature conditions, melting the resin, and then holding it in a pressurized state until it cools and hardens.

  The molded product of the polyarylene sulfide resin composition may be a film-like product. When the molded product of the polyarylene sulfide resin composition is a film-like product, from the viewpoint of maintaining the smoothness and surface appearance of the film-like product, in particular, the following hot press (thermocompression) method, melt extrusion method and A so-called joining method can also be used, and if the film-like material is a transparent material that can transmit a laser beam, a joining method called a laser welding method can also be used.

  That is, the hot press (thermocompression bonding) method and the hot embossing method are methods for thermocompression bonding of a film-like polyarylene sulfide resin composition film to a metal member under high temperature and high pressure. Although it is performed by a method or a hot plate press, a method using a heating roll is preferable from the viewpoint of the production process.

  In the case of the melt extrusion transfer method, the polyarylene sulfide resin composition is melted by a melt extruder and extruded into a film shape, and then it is pressed against a shaping roll and cooled and solidified while being pressed against a metal member. . The laser welding method can be applied when the molded product can transmit a laser beam. After joining the molded product to a metal member, a laser beam is applied from the molded product side to the metal member surface so that the following temperature condition is satisfied. What is necessary is just to join by making it generate | occur | produce by irradiation, melting a molded article, and hold | maintaining in a pressurized state until it cools and solidifies.

  On the other hand, the metal member may be a film-like material such as a metal foil. When the metal member is a film-like material, a so-called hot embossing method in which the metal member is joined by simultaneously embossing and foil pressing while heating the molded product of the polyarylene sulfide resin composition can be used. If the hot embossing method is used, a molded product having a three-dimensional shape and a fine pattern can be manufactured. If the fine pattern of the metal member is an electric circuit, the molded circuit component can be obtained. it can.

  In the present invention, the term film-like material is a generic term for so-called foils, films, sheets, and plates, and refers to those having a thickness in the range of 0.001 to 9 mm.

  Since the joining method 2 described above basically requires the molded product to be melted and pressure-bonded to a metal member, the heating conditions are such that the resin temperature is equal to or higher than the recrystallization temperature (Tc2) of the polyarylene sulfide resin. It may be adjusted as appropriate within the temperature range, but from the viewpoint of exhibiting sufficient adhesion, while maintaining excellent smoothness and appearance, such as a film-like material, the melting point is not less than the recrystallization temperature (Tc2). It is preferable to adjust appropriately within a temperature range of less than, while on the other hand, from the viewpoint of suppressing gas generation due to resin decomposition and preventing resin degradation and exhibiting better adhesion, it is appropriately adjusted in a temperature range above the melting point It is preferable to adjust, and it is more preferable to adjust appropriately within the temperature range of the melting point or higher and the melting point plus 100 ° C, and further appropriately adjusted within the temperature range of the melting point plus 20 ° C and the melting point plus 50 ° C. Rukoto is particularly preferred. In addition, the pressure condition for pressure bonding (pressing each other) the metal member and the molded product is not particularly limited as long as the bonded state can be maintained. For example, the metal member may be any one between the start of heating and the end of cooling. And in the direction in which the resin members are pressed against each other, a range of 0.01 [MPa] or more, preferably 0.01 to 100 [MPa], more preferably 0.05 to 10 [MPa] is sufficient. What is necessary is just to adjust suitably in the range from which the amount of burrs is small, exhibiting adhesive force. In the case of the laser welding method, it is not always necessary to press the metal member and the molded product against each other by external force before welding, and bonding is performed by using a pressure increase generated at the bonding interface due to volume expansion during melting. be able to.

(Metal member)
As a kind of metal which comprises the said metal member, aluminum, copper, magnesium, iron, titanium, or an alloy containing them is mentioned. More specifically, iron, for example, stainless steel, steel, and the like, in which iron is the main component, that is, 20% by mass or more, more preferably 50% by mass or more, and still more preferably 80% by mass, in addition to carbon, silicon , Manganese, chromium, tungsten, molybdenum, phosphor, titanium, vanadium, nickel, zirconium, boron, etc. Alloys containing zinc and nickel (hereinafter referred to as aluminum alloys), magnesium and magnesium as the main component, alloys containing zinc, aluminum and zirconium, etc. (hereinafter referred to as magnesium alloys), copper and copper as the main component As well as zinc, tin, phosphorus, nickel, magnesium, silicon, chromium (Hereinafter, copper alloy) or, or titanium, as a main component titanium, other copper, manganese, silicon, magnesium, zinc, alloys containing nickel (hereinafter, titanium alloy) and the like. Of these, iron, iron alloy, aluminum alloy, magnesium alloy, copper alloy, and titanium alloy are more preferable, and iron alloy, aluminum alloy, and magnesium alloy are more preferable.

  The surface of the metal member constituting the metal / resin composite structure of the present invention (hereinafter simply referred to as the metal member surface) preferably has a fine uneven surface (hereinafter simply referred to as the fine uneven surface). In the present invention, the bonding between the metal member and the molded article has excellent adhesion due to intermolecular force or chemical interaction that is considered to be due to the polyvinylpyrrolidone resin blended as an essential component in the polyarylene sulfide resin composition. In addition, the surface roughening treatment is performed, and the fine uneven surface is provided on the surface of the metal member, whereby the adhesive force can be further enhanced by the action of mechanical coupling.

  By subjecting the metal member surface of the metal / resin composite structure of the present invention to a surface roughening treatment and providing a fine irregular surface, the molten polyarylene sulfide resin composition enters the concave portion of the fine irregular surface with good fluidity. As a result of the solidification, an interface between the metal member and the resin member constituting the molded product (hereinafter simply referred to as a metal-resin interface) is formed, and the metal member and the molded product of the resin composition are strongly bonded. sell.

  The metal member used in the present invention preferably has a fine uneven surface formed on the surface of the metal part due to surface roughening, but the interval between the uneven parts is from the convex part to the adjacent convex part (hereinafter, convex part). Is preferably in the range of 5 nm or more, and more preferably in the range of 10 nm or more. The upper limit is not particularly limited because it can flow even if the fluidity is low, but it is preferably in the range of 700 μm or less, because the adhesion strength tends to be improved when the unevenness density is high, and more preferably 500 μm or less. A range is more preferable. When the length between the convex portions is within the above range, the polyarylene sulfide resin composition used in the present invention can enter the concave portion of the fine uneven surface with good adhesion, and has excellent adhesion at the metal-resin interface. It can be demonstrated. Furthermore, it is preferable that the interval between the concavo-convex portions has periodicity, since a better adhesion can be exhibited at the metal-resin interface.

  Further, the height difference of the concavo-convex portion is preferably in the range of 50 nm or more, and more preferably in the range of 100 nm or more. Since there is a tendency for the adhesion strength to improve as there is a difference in height with respect to the upper limit value, there is no particular limitation, but in consideration of filling the resin so as not to cause voids in the concavo-convex portion, the range is 500 μm or less. It is preferable.

  The length between the convex portions is adjacent to the top of the convex portion based on a photograph taken with an electron microscope or a laser microscope of a cross section cut in a direction perpendicular to the fine uneven surface of the metal member surface. After selecting at least 50 points between the two points up to the top of the convex part to be measured, the length of the component in the direction parallel to the fine uneven surface of the metal member surface can be measured and obtained as the number average value. Further, the height difference of the concavo-convex part is determined by selecting at least 50 points between two points from the top of the convex part to the bottom part of the adjacent concave part based on a photograph taken with an electron microscope or a laser microscope. Thus, the length of the component in the direction perpendicular to the fine uneven surface of the metal member surface can be measured and obtained as the number average value.

  Further, the uneven shape on the fine uneven surface is not particularly limited, and may be formed as a concave portion having a smaller pore diameter than the distance between the convex portions by surface roughening described later, and further the surface roughening is advanced. In addition, a rounded convex portion, that is, a column having a spherical shape, a smooth end portion, or a protrusion having a three-dimensional aspect such as a wart shape or a saccharide sugar shape may be used.

As the surface roughening method, a known method can be used without limitation, and for example, there are three kinds of methods.
(1) An immersion method using an erodible aqueous solution or an erodible suspension. It is preferable to have a shape in which fine uneven surfaces are formed on the metal surface, and it is more preferable that the metal surface has a shape in which a large number of recesses are formed, and the recesses have a number average inner diameter of 3 μm or less. Similarly, it is more preferable that the concave portion has a number average inner diameter of 10 nm to 3 μm.

(2) Anodizing method. It is preferable to form a metal oxide layer mainly on the surface to form a large number of openings having a number average inner diameter of 1 μm or less in the surface layer. Similarly, openings having a number average inner diameter of 1 nm to 1 μm. It is more preferable to form an opening, and it is more preferable to form an opening having a number average inner diameter of 10 to 200 nm.

(3) Forming irregularities on the metal surface by pressing a die punch with irregularities created by mechanical cutting, for example diamond abrasive grinding or blasting, or creating irregularities on the metal surface by sandblasting or laser processing how to. Mainly, it is preferable to process the surface into a large number of recesses, and when forming a recess having a continuous shape such as the number average inner diameter of the recesses or laser processing, the width is preferably in the range of 1 to 1000 μm, and more preferably 10 to 10 μm. A range of 800 μm is more preferable.

  Before forming the fine uneven surface, the metal member is processed into a predetermined shape by metal removal such as cutting, plastic working by stamping, punching, cutting, grinding, electric discharge machining, or the like. Is preferred.

  A primer layer may be formed on the surface of the metal member that has been subjected to metal surface treatment. Although the material which comprises a primer layer is not specifically limited, Usually, it consists of primer resin material containing a resin component. The primer resin material is not particularly limited, and known materials can be used. Specific examples include known polyolefin-based primers, epoxy-based primers, urethane-based primers, and the like. The method for forming the primer layer is not particularly limited. For example, the primer layer can be formed by applying a solution of the primer resin material or an emulsion of the primer resin material to the metal member subjected to the surface treatment. Examples of the solvent used for preparing the solution include toluene, methyl ethyl ketone (MEK), dimethylphosphamide (DMF) and the like. Examples of the medium for the emulsion include an aliphatic hydrocarbon medium and water.

  In the case of a film insert molding method, a molded product of a polyarylene sulfide resin composition is bonded to a resinous film-like product obtained by laminating a metal member layer in a film shape and the metal member layer. The body is obtained. Formation of the metal member layer on the resinous film-like material may be performed by transferring or printing a film-like material such as a metal foil, or by plating. At that time, as the resinous film-like material, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polyamide 6, polyamide 66 (PA6, PA66) and other polyamide resins, polyimide resin , A resin film having heat resistance such as a cured product of an active energy ray polymerizable resin composition mainly composed of a polyidimide resin, a polyvinyl alcohol resin, or a (meth) acrylic resin containing a radically polymerizable unsaturated group Are preferably used. Among them, a film made of PET resin is most preferably used because it is excellent in cost, beauty and transparency. In addition, the production of the resinous film-like product in which the metal member layers are laminated in a film shape is not particularly limited, and a commercially available apparatus can be used or can be performed according to a conventional method.

(Molded product of polyarylene sulfide resin composition)
The polyarylene sulfide resin composition of the present invention comprises a polyarylene sulfide resin (A) and a polyvinylpyrrolidone (B) as essential components, and is based on 100 parts by mass of the polyarylene sulfide resin (A). The polyvinyl pyrrolidone (B) is in the range of 0.01 to 100 parts by mass.

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

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

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). And, if necessary, the following general formula (2)

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(Polyvinylpyrrolidone)
The polyarylene sulfide resin composition of the present invention comprises polyvinyl pyrrolidone (B) as an essential component. The average molecular weight of the polyvinyl pyrrolidone is not particularly limited, but preferably the weight average molecular weight is in the range of 3,000 to 2,000,000, more preferably in the range of 500,000 to 1,500,000, The range is preferably 1,000,000 to 1,200,000. The degree of polymerization n is not particularly limited as long as the mass average molecular weight is in the above range, but preferably n is in the range of 30 to 18,000, preferably in the range of 4,500 to 13,500. Is more preferable, and the range of 9,000 to 108,000 is particularly preferable. In addition, the mass average molecular weight prepared the tetrahydrofuran solution (0.1 wt%) of polyvinylpyrrolidone, and the GPC apparatus (made by Tosoh Corporation) equipped with the TSKGelGHxl series 5000, 3000, 2000, 1000 column and a differential refractometer (RI) detector. HLC-8220GPC) was used, and the measurement was performed at 40 ° C. using a sample solution injection amount of 50 μl and tetrahydrofuran as a mobile phase (1 ml / min). The mass average molecular weight was calculated from a calibration curve composed of standard styrene. However, the measurement conditions can be appropriately changed within a range that does not substantially affect the measurement value of the mass average molecular weight.

  Polyvinyl pyrrolidone may be either a linear type or a crosslinked type. As polyvinylpyrrolidone (B), for example, the following general formula (1)

で表される構造を有するものが好ましく挙げられる。ただし、式（１）中、ｎは繰り返し単位を表し、好ましくは３０〜１８，０００の範囲である。また、Ｒ^１は水素原子、炭素原子数１〜６の範囲のアルキル基またはアルコキシ基で、好ましくはメチル基、ｉ−またはｎ−プロピル基、ブチル基であり、このうち、水素原子が好ましい。

Those having a structure represented by the formula are preferred. However, in Formula (1), n represents a repeating unit, Preferably it is the range of 30-18,000. R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group, preferably a methyl group, i- or n-propyl group or butyl group, and among these, a hydrogen atom is preferred.

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

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

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

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

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

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

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

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

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

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

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

  In the present invention, the proportion of the polyvinylpyrrolidone (B) is not particularly limited as long as the effects of the present invention are not impaired, but the range is 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). Preferably in the range of 0.1 to 50 parts by mass, more preferably in the range of 1 to 30 parts by mass, and most preferably in the range of 2 to 25 parts by mass. . Within such a range, the polyarylene sulfide resin composition of the present invention is preferable because it exhibits a low recrystallization temperature and the obtained molded article exhibits good heat resistance.

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

  In the present invention, the phosphate (C) is an optional component, but the proportion when blended is not particularly limited as long as the effects of the present invention are not impaired. For example, the polyarylene sulfide resin (A) is 100 parts by mass. On the other hand, the range is preferably 0.001 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and still more preferably 0.01 to 20 parts by mass. Most preferably, it is in the range of 0.05 to 15 parts by mass. In such a range, the polyarylene sulfide resin composition of the present invention exhibits a low recrystallization temperature, exhibits excellent adhesion with a metal member, and is preferable because the obtained molded article exhibits good heat resistance. .

  The polyarylene sulfide resin composition of the present invention may contain a silane coupling agent (D) as an optional component, if necessary. Although it will not specifically limit as long as the effect of this invention is not impaired as a silane coupling agent, For example, the silane coupling agent which has an epoxy group, an isocyanato group, an amino group, or a hydroxyl group is mentioned as a preferable thing. Examples of such silane coupling agents include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , Γ-isocyanatopropylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- ( -Aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. It is done. In the present invention, the silane coupling agent (D) is an optional component, but the ratio at the time of blending is not particularly limited as long as the effects of the present invention are not impaired. For example, 100 parts by mass of the polyarylene sulfide resin (A) Is preferably in the range of 0.01 to 30 parts by mass, more preferably in the range of 0.05 to 10 parts by mass, and further in the range of 0.1 to 5 parts by mass. Most preferred. In such a range, the polyarylene sulfide resin composition of the present invention exhibits a low recrystallization temperature, exhibits excellent adhesion with a metal member, and is preferable because the obtained molded article exhibits good heat resistance. .

  The polyarylene sulfide resin composition or molded product thereof according to the present invention is blended with at least one selected from the group consisting of the phosphate and the silane coupling agent, so that the resin (A On the other hand, the recrystallization temperature (Tc2) of the polyarylene sulfide resin composition or its molded product is maintained from the recrystallization temperature (Tc2) of the resin (A), while maintaining the melting point (Tm) of Can be reduced. Regarding the specific range of decrease in recrystallization temperature (Tc2), the blending of essential components and optional components is determined based on the relationship with other properties such as mechanical properties according to the use and purpose of the molded product. Since it is necessary, it is not possible to define it generally. However, it is preferable that the polyarylene sulfide resin composition of the present invention or a molded product thereof when the above phosphate or silane coupling agent is added. The crystallization temperature (Tc2) can be lowered in the range of 20 to 100 ° C. from the recrystallization temperature (Tc2) of the resin (A), and more preferably in the range of 30 to 80 ° C. it can. That is, the polyarylene sulfide resin composition and molded product of the present invention when the phosphate or silane coupling agent is blended have a difference ΔT between the melting point (Tm) and the recrystallization temperature (Tc2). , Preferably it is 90 degreeC or more, More preferably, it is the range of 90-130 degreeC, More preferably, it can also be set as the range of 100-120 degreeC. Therefore, when the phosphate or silane coupling agent is added, the melting point (Tm) of the polyarylene sulfide resin composition and the molded product of the present invention is preferably in the range of 270 to 300 ° C. The recrystallization temperature (Tc2) of the polyarylene sulfide resin composition and the molded product is preferably 200 ° C. or less, more preferably 120 to 200 ° C., and even more preferably 160 to 200 ° C. be able to. The melting point (Tm) of the polyarylene sulfide resin composition of the present invention or its molded product maintains the melting point (Tm) of the resin (A), and the melting point is substantially the same. Preferably, the temperature difference between the Tm (° C.) of the polyarylene sulfide resin composition or molded product thereof and the Tm (° C.) of the polyarylene sulfide resin (A) blended as an essential component is within 10 ° C., more preferably It means that it is within 5 ° C.

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

  In the present invention, the filler is not an essential component, but when blended, the proportion of the blend is not particularly limited as long as it does not impair the effects of the present invention, and differs depending on the purpose and is generally specified. Although it cannot do, it is preferable that it is the range of 1-600 mass parts with respect to 100 mass parts of polyarylene sulfide resin (A), for example, and it is more preferable that it is the range of 10-200 mass parts. In such a range, the resin composition is preferable because it exhibits good mechanical strength and moldability.

  The polyarylene sulfide resin composition of the present invention may contain a thermoplastic elastomer as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. Among these, polyolefin-based elastomers are preferable. When blending these elastomers, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and it varies depending on each purpose and cannot be specified in general. (A) It is preferable that it is the range of 0.01-10 mass parts with respect to 100 mass parts, and it is more preferable that it is the range of 0.1-5 mass parts. Within such a range, the resulting polyarylene sulfide resin composition is preferred because the impact resistance is improved.

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

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

  Furthermore, in addition to the above components, the polyarylene sulfide resin composition of the present invention may further include other synthetic resins excluding the polyarylene sulfide resin and the polyvinyl pyrrolidone, depending on the application, for example, a polyester resin, a polyamide resin, Polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetrafluoroethylene Resin, polydifluoroethylene resin, polystyrene resin, ABS resin, phenol resin, urethane resin, liquid crystal polymer and the like (hereinafter simply referred to as synthetic resin) can be blended as optional components. In the present invention, the synthetic resin is not an essential component, but when blended, the proportion of the blend is not particularly limited as long as it does not impair the effects of the present invention, and differs depending on the respective purpose. Although it cannot be defined, the ratio of the resin component (the total of the polyarylene sulfide resin, the polyvinyl pyrrolidone, and the synthetic resin) to be blended in the polyarylene sulfide resin composition of the present invention is the ratio of the polyarylene sulfide resin and the polyvinyl pyrrolidone. In other words, the total synthetic resin is in the range of 25.0% by mass or less, preferably 0.01-20, so that the total is in the range of 75.0% by mass or more, preferably in the range of 80-99.99% by mass. In the range of 0.0 mass%, it may be appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention.

  In addition, the polyarylene sulfide resin composition of the present invention includes other colorants, antistatic agents, antioxidants, heat stabilizers, UV stabilizers, UV absorbers, foaming agents, flame retardants, flame retardant aids, You may mix | blend well-known and usual additives, such as a rust agent and a coupling agent, as an arbitrary component as needed. These additives are not essential components, but when blended, the proportion of the blend is not particularly limited as long as the effect of the present invention is not impaired, and differs depending on each purpose, and is generally defined. However, for example, with respect to 100 parts by mass of the polyarylene sulfide resin (A), preferably in the range of 0.01 to 1,000 parts by mass, appropriately adjusted according to the purpose and application so as not to impair the effects of the present invention. Can be used.

  The method for producing a polyarylene sulfide resin composition according to the present invention comprises blending a polyarylene sulfide resin (A) and the polyvinyl pyrrolidone (B) as essential components, and melting above the melting point of the polyarylene sulfide resin (A). Knead.

  A preferred method for producing the polyarylene sulfide resin composition of the present invention is that the polyarylene sulfide resin (A) and the essential components of the polyvinyl pyrrolidone (B) are mixed as described above, and, if necessary, the above Arbitrary components are put into ribbon blenders, Henschel mixers, V blenders, etc. in various forms such as powders, pellets, strips, etc., dry blended, then Banbury mixers, mixing rolls, single or twin screw extruders and kneaders The temperature is such that the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably the melting point + 10 ° C or higher, more preferably the melting point + 10 ° C to the melting point + 100 ° C. Melting and kneading in the range, more preferably in the temperature range of melting point +20 to melting point + 50 ° C. It can be produced through a degree. Addition and mixing of each component to the melt kneader may be performed simultaneously or may be performed separately.

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

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

  The polyarylene sulfide resin composition of the present invention produced by the above production method uses a polyarylene sulfide resin as a matrix, and the polyvinyl pyrrolidone (B) as an essential component in the matrix, components derived therefrom, and necessary Depending on the case, an optional component to be added forms a dispersed morphology. The pyrrolidone skeleton contained in the polyvinyl pyrrolidone has excellent compatibility with the polyarylene sulfide resin skeleton, and the surface of the metal member due to the presence of electron orbits (2Pz orbitals) formed at the bonding sites of carbon atoms and oxygen atoms. It is considered that it exhibits excellent adhesion to the metal member by forming a physical interaction due to the van der Waals force and a chemical bond by the intermolecular force between the functional group formed on the surface of the metal member. It is done.

  Further, when the polyarylene sulfide resin composition of the present invention contains the phosphate or the silane coupling agent as an optional component, the polyarylene sulfide resin is used as a matrix, and the polyvinyl pyrrolidone ( B) and the phosphate (C) to the silane coupling agent (D), components derived therefrom, and components added as necessary are formed. As a result, while maintaining the excellent heat resistance and chemical resistance inherent in the polyarylene sulfide resin composition, in addition to the above-described physical interaction and chemical bonding, a lower recrystallization temperature is also achieved. Due to the nature of the resin composition it has, it becomes easier to penetrate into the fine irregularities on the surface of the metal member, and the wettability is further improved. As a result, mechanical bonding due to the anchor effect is also exhibited, and the adhesion to the metal member is further improved. Therefore, it is preferable. The polyarylene sulfide resin composition of the present invention maintains the melting point inherent in the polyarylene sulfide resin, and the recrystallization temperature (Tc2) of the polyarylene sulfide resin composition or a molded product thereof is set to the resin ( A) can be further reduced from the recrystallization temperature (Tc2) because of the action of polyvinylpyrrolidone having a property excellent in compatibility with the polyarylene sulfide resin due to the pyrrolidone skeleton. As a result of delaying the crystallization of the arylene sulfide resin, it is considered that the polyarylene sulfide resin composition exhibits a low crystallization temperature (Tc2). Further, when the phosphate or the coupling agent is added as an optional component, the molecular chain of the polyarylene sulfide resin is a mercaptide with the metal element derived from the phosphate of the sulfur atom at the molecular end. As a result of the formation of a bond or a bond with a coupling agent, the molecular chain is extended, and the effect of extending the molecular chain can further delay the above crystallization, resulting in a lower polyarylene sulfide resin composition. It is thought that the crystallization temperature (Tc2) can be exhibited.

  The polyarylene sulfide resin composition of the present invention can be subjected to various moldings such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, pultrusion molding, blow molding, transfer molding, etc. It is suitable for injection molding because of its excellent properties. In the case of molding by injection molding, various molding conditions are not particularly limited, and can be usually molded by a general method. For example, in an injection molding machine, the resin temperature is a temperature range above the melting point of the polyarylene sulfide resin, preferably the temperature range above the melting point + 10 ° C., more preferably the temperature range from the melting point + 10 ° C. to the melting point + 100 ° C., more preferably the melting point. After passing through the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to melting point + 50 ° C., the resin discharge port may be injected into the mold and molded. At that time, the mold temperature can also be set to a known temperature range, for example, a room temperature (23 ° C.) to 300 ° C., preferably a range of 40 to 180 ° C. The polyarylene sulfide resin composition of the present invention can be set to a preferable temperature range of 120 to 180 ° C. as a normal molding temperature, and has a low recrystallization temperature (Tc2) as described above and excellent low temperature moldability. Since it also has characteristics, a molded product excellent in moldability such as appearance and filling properties, mechanical properties, and chemical resistance can be obtained even at a relatively low mold temperature range of 40 ° C or higher and lower than 120 ° C. be able to.

(Use of metal / resin composite structure)
Examples of main applications of the metal / resin composite structure of the present invention include various home appliances, mobile phones, and casings of electronic devices such as PCs (Personal Computers), box-type electrical / electronic component integrated module protection / Support members-Multiple 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, prints Electricity and power represented by substrates, 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, etc. Electronic parts: VTR parts, TV parts, irons Hair dryer, rice cooker parts, microwave oven parts, sound parts, audio / video equipment parts such as audio / laser disc / compact disc / DVD disc / Blu-ray disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts Or home appliances such as water heaters, bath water volume, temperature sensor, etc., office electrical appliance parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts, washing Machine-related parts represented by jigs, motor parts, writers, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternator terminals, alternator connectors, brush holders, slip rings , IC regulator, line Todiya potentiometer base, relay block, inhibitor switch, various valves such as exhaust gas valves, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant 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, thermostat base for air conditioner, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter Switches, ignition coils and their bobbins, motor insulators, motor rotors, motor cores, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, connectors for fuses, horn terminals, electrical components It can also be applied to automotive and vehicle related parts such as insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, and other various uses.

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

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

Reference Example 1 Production of Polyphenylene Sulfide Resin (PPS-1) A 150-liter autoclave with stirring blades connected to a pressure gauge, thermometer, condenser, decanter, and rectifying tower was added to p-dichlorobenzene (hereinafter “p-DCB”). Abbreviated to 33.222 kg (226 mol), NMP 2.280 kg (23 mol), 47.23 wt% NaSH aqueous solution 27.300 kg (230 mol as NaSH), and 49.21 wt% NaOH aqueous solution 18.533 g ( 228 mol) was added as NaOH, and the temperature was raised to 173 ° C. over 5 hours under stirring in a nitrogen atmosphere. After distilling 27.300 kg of water, the autoclave was sealed. The p-DCB distilled azeotropically during dehydration was separated with a decanter and returned to the autoclave as needed. In the autoclave after the completion of the dehydration, the finely divided anhydrous sodium sulfide composition was dispersed in p-DCB. Since the NMP content in this composition was 0.069 kg (0.7 mol), 97 mol% (22.3 mol) of the charged NMP was a ring-opened product of NMP (4- (methylamino) It was shown to be hydrolyzed to the sodium salt of butyric acid (hereinafter abbreviated as “SMAB”). The amount of SMAB in the autoclave was 0.097 mol per mol of sulfur atoms present in the autoclave. When the total amount of NaSH and NaOH charged is changed to anhydrous Na ₂ S, the theoretical dehydration amount is 27.921 g. Therefore, 401 g (22.3 mol) out of the remaining water amount 621 g (34.5 mol) in the autoclave. Is consumed in the hydrolysis reaction of NMP and NaOH and does not exist in the autoclave as water, and the remaining 220 g (12.2 mol) remains in the autoclave in the form of water or crystal water. Was showing. The amount of water in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.

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

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

(Reference Example 2) Production of polyphenylene sulfide resin (PPS-2) 45% sodium hydrosulfide (47.55 mass% NaSH) 14 was added to a 150 liter autoclave with a pressure gauge, a thermometer, a stirring blade connected with a condenser and a bottom valve. .148 kg, 48% sodium hydroxide (48.7 mass% NaOH) 9.474 kg and N-methyl-2-pyrrolidone 38.0 kg were charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. to distill 12.150 kg of water (the amount of water remaining was 1.13 mol per 1 mol of NaSH). Thereafter, the autoclave was sealed and cooled to 180 ° C., and 17.129 kg of paradichlorobenzene and 16.0 kg of N-methyl-2-pyrrolidone were charged. The temperature was raised by pressurizing to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. After stirring at a liquid temperature of 220 ° C. for 4 hours, when the temperature was raised to 260 ° C., the reaction was carried out at 260 ° C. for 3 hours while cooling by sprinkling the upper part of the autoclave. The upper part of the autoclave was kept constant during cooling to prevent the liquid temperature from dropping. Next, the temperature was lowered and cooling of the upper part of the autoclave was stopped. The maximum pressure during the reaction was 0.87 MPa. After the reaction, the reaction mixture was cooled, the bottom valve was opened at 100 ° C., the reaction slurry was transferred to a 150 liter flat plate filter and pressure filtered at 120 ° C. To the obtained cake, 50 kg of 70 ° C. warm water was added and stirred, followed by filtration. Further, 25 kg of warm water was added and filtered. Next, 25 kg of warm water was added, the pH was adjusted to 4.5 with acetic acid, the mixture was stirred for 1 hour, filtered, and then 25 kg of warm water was added and filtered. Furthermore, after adding 25 kg of warm water and stirring for 1 hour and filtering, the operation of adding 25 kg of warm water and filtering was repeated twice. The obtained cake was dried at 120 ° C. for 15 hours using a hot air circulating dryer to obtain PPS-2. The melt viscosity of the obtained polymer was 108 Pa · s. The melting point (Tm) was 278 ° C., and the recrystallization temperature (Tc 2) was 240 ° C.

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

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

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

(Examples 1-9 and Comparative Examples 1-5) Manufacture of PPS resin composition Each material was uniformly mixed with the tumbler according to the composition component and the compounding quantity (all mass part) which are described in Tables 1-3. After that, the compounded material is put into a twin-screw extruder “TEX30α” with a ventilator at Nippon Steel Co., Ltd., and melt kneaded by setting a resin component discharge rate of 25 kg / hr, a screw rotation speed of 250 rpm, and a set resin temperature of 330 ° C. A pellet of the resin composition was obtained. The melting point (Tm) and recrystallization temperature (Tc2) of the pellet were determined and shown in Tables 1-3.

  Next, the obtained pellets were melt-kneaded at 320 ° C., 40 rpm for 5 minutes, and the kneaded product was formed into a press film at 320 ° C., 15 MPa for 6 minutes, and a film of 200 mm × width 200 mm × thickness 0.1 mm was prepared. Obtained. Copper foil (Fukuda Metal Foil Powder Co., Ltd. “CF-T9LK-UN-35”, vertical 100 mm × width 100 mm × thickness 35 μm, joint surface Rz = 10.5 μm, hereinafter copper, as metal foil on the film Foil 1), copper foil (Fukuda Metal Foil Industry Co., Ltd. “CF-T9LK-SV-35”, vertical 100 mm × width 100 mm × thickness 35 μm, joint surface Rz = 1.0 μm, hereinafter referred to as copper foil 2 ) Or aluminum foil (Mitsubishi Aluminum Co., Ltd. “Mitsubishi foil”, length 100 mm × width 100 mm × thickness 12 μm, joint surface Rz = 1.3 μm, hereinafter referred to as aluminum foil) and placed on a 290 ° C. hot press machine It was set and thermocompression bonded at 5 [MPa] for 3 minutes. The following various evaluation tests were performed using the obtained joined body. The results of the test and evaluation are shown in Tables 1-3. However, the surface roughness Rz of the metal foil was measured by a surface roughness measuring device (“SE-3500K type” manufactured by Kosaka Laboratory) in accordance with JIS-B0601.

(Measurement Example 2) Adhesion Test between PPS Molded Product and Metal Foil The obtained test piece was tested by a method based on the cross-cut method (JIS K5400: 1990). That is, a total of 100 regions were formed on the surface of the metal foil of the test pieces obtained in Examples and Comparative Examples by dividing them into 10 equal parts at 1 mm intervals in the vertical and horizontal directions, and then adhered to the surface on which these regions were formed. An adhesion test was performed using a tape (“Cello Tape” (registered trademark) manufactured by Nichiban Co., Ltd.). The measurement was performed under the same temperature and humidity conditions using a Tensilon Universal Tensile Tester (Orientec, RTA100) after 1 reciprocating pressure application with a 2 kg roller and leaving for 1 hour so that the peeling of the adhesive tape is constant. And pulled in a 180 ° direction at a speed of 300 mm / min. The number of peeled cells and the number of remaining cells after the adhesion test were counted, and the remaining cells are shown in Tables 1 to 3.

In addition, the numerical value of the composition in Tables 1-3 shows a mass part. The following table is the same.
* 1 ΔTc2 is a value obtained by subtracting Tc2 (° C.) of the PPS resin used as the raw material from Tc2 (° C.) of the test piece (PPS resin molded product) obtained in each example.
In addition, each raw material in the table is as follows.

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

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

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

Claims (15)

A metal / resin composite structure formed by joining a metal member and a molded product of a polyarylene sulfide resin composition,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). The metal / resin composite structure, wherein (B) is in the range of 0.01 to 100 parts by mass.   The metal / resin composite structure according to claim 1, wherein the polyarylene sulfide resin composition has a melting point (Tm) of 270 ° C or higher and a recrystallization temperature (Tc2) of 250 ° C or lower. The polyarylene sulfide resin composition further comprises at least one selected from the group consisting of a phosphate (C) containing a metal belonging to Group 2 or Group 12 of the periodic table, and a silane coupling agent (D). Blended,
The phosphate (C) is in the range of 0.001 to 50 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin, and the silane coupling agent (D) is with respect to 100 parts by mass of the polyarylene sulfide resin. The metal / resin composite structure according to claim 1, which is in a range of 0.01 to 30 parts by mass.   The metal / resin composite structure according to claim 3, wherein the polyarylene sulfide resin composition has a difference ΔT between a melting point (Tm) and a recrystallization temperature (Tc2) of 90 ° C or more. The polyvinylpyrrolidone (B) is represented by the following general formula (1)

(Wherein n represents a repeating unit and is in the range of 30 to 18,000. R ¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group.) The metal / resin composite structure according to any one of claims 1 to 3. The metal / resin composite structure according to any one of claims 1 to 5, wherein the resin member is in a film form. The metal / resin composite structure according to any one of claims 1 to 6, wherein the metal member is in a film form. The metal / resin composite structure according to any one of claims 1 to 7, wherein the metal / resin composite structure is a molded circuit component.   The metal / resin composite structure according to any one of claims 1 to 8, wherein the polyarylene sulfide resin composition is a melt-kneaded product. A polyarylene sulfide resin composition used for a metal / resin composite structure formed by joining a metal member and a molded product of a polyarylene sulfide resin composition,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). (B) is 0.01-100 mass parts, The polyarylene sulfide resin composition characterized by the above-mentioned.   A molded article formed by molding the polyarylene sulfide resin composition according to claim 10. A method for producing a metal / resin composite structure in which a metal member and a molded product of a polyarylene sulfide resin composition are joined,
(1) a step of joining the surface of the metal member by melt-molding the polyarylene sulfide resin composition, or (2) a step of joining the metal member and the molded product of the polyarylene sulfide resin composition. about,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). (B) is the range of 0.01-100 mass parts, The manufacturing method of the metal / resin composite structure characterized by the above-mentioned. A method for producing a polyarylene sulfide resin composition used for a metal / resin composite structure in which a metal member and a molded article of a polyarylene sulfide resin composition are joined,
Having a step of melt-kneading polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and for 100 parts by mass of polyarylene sulfide resin (A), the polyvinylpyrrolidone (B) is 0.01 A method for producing a polyarylene sulfide resin composition, which is in the range of ˜100 parts by mass. A method for producing the molded product used in a metal / resin composite structure in which a metal member and a molded product of a polyarylene sulfide resin composition are joined,
Having a step of molding the polyarylene sulfide resin composition in a mold,
The polyarylene sulfide resin composition comprises polyarylene sulfide resin (A) and polyvinyl pyrrolidone (B) as essential components, and the polyvinyl pyrrolidone with respect to 100 parts by mass of the polyarylene sulfide resin (A). (B) is the range of 0.01-100 mass parts, The manufacturing method of the molded article characterized by the above-mentioned.   The method for producing a molded product according to claim 14, wherein the mold temperature is in the range of 40 to 180 ° C.