JP6950281B2 - Polyarylene sulfide resin composition, molded article, metal / resin composite structure and manufacturing method - Google Patents

Description

The present invention relates to polyarylene sulfide resin compositions, molded articles, metal / resin composite structures, and methods for producing them.

Polyphenylene sulfide (hereinafter sometimes abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin can maintain a melting point of 270 ° C. or higher while exhibiting excellent heat resistance. It is known to be excellent in mechanical strength, chemical resistance, molding processability, and dimensional stability. Therefore, in general, an additive such as a filler or an elastomer is mixed with a 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, a highly heat-resistant resin member is used as a substitute for a metal member. 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, metal / resin composite structure). ) Is used. As such a metal / resin composite structure, for example, a method is known in which the surface of a metal member is roughened and then bonded using a polyarylene sulfide resin by an anchor effect. For example, an aluminum alloy or magnesium alloy having a recess with a number average inner diameter of 10 to 80 nm on the surface by a chemical solution treatment such as an erosive aqueous solution or an erosive suspension, or a number average inner diameter of 10 on the surface by treatment with an anodic oxidation method. An aluminum alloy having a recess of ~ 80 nm, polyphenylene sulfide and a specific ratio of maleic anhydride-modified ethylene-based copolymer, glycidyl methacrylate-modified ethylene-based copolymer, glycidyl ether-modified ethylene-based copolymer and ethylene alkyl acrylate-based copolymer. A composite is known in which a resin composition containing one or more polyolefin-based resins selected from the group consisting of coalesses is injection-molded, and the resin composition is fixed in a recess in a state of being infiltrated (Patent Documents). 1). Since the inner diameter of the fine recesses on the metal surface formed by the treatment method is also very fine, it is difficult for the resin composition to penetrate, and therefore the metal parts and the molded product composed of the resin composition adhere to each other. The power was not enough.

However, the problem is that the polyarylene sulfide resin composition has a high temperature at which it solidifies (crystallizes) from the molten state (recrystallization temperature: Tc2), so that the molten polyarylene sulfide resin composition is brought into contact with the metal member. The cause was that the resin composition solidified (crystallized) before flowing into the fine irregularities on the surface of the metal member. Therefore, it has been desired to develop a resin composition containing a polyarylene sulfide resin having a lower recrystallization temperature (Tc2).

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 of inserting a meta-body into a part of the skeleton, the recrystallization temperature of the polyarylene sulfide resin itself to be used decreases, and the melting point also reaches a temperature far below 270 ° C. It had the property of decreasing. As a result, the metal / resin composite structure produced by using the metal / resin composite structure has an excellent adhesion between the metal member and the molded product of the polyarylene sulfide resin composition, but has a property that the heat resistance is remarkably lowered.

JP-A-2007-050630 JP-A-2009-050630

Therefore, the problem to be solved by the present invention is to provide a metal / resin composite structure in which a metal member and a molded product of a polyarylene sulfide resin composition are bonded to each other and have excellent heat resistance and adhesion, and a method for producing the same. To do. Further, the present invention has a polyarylene sulfide resin composition having excellent adhesion to metal parts and excellent heat resistance, and a melt-molded polyarylene sulfide resin composition having excellent adhesion to metal parts and also having heat resistance. The purpose is to provide excellent molded products.

As a result of various studies conducted by the inventors of the present application, the polyarylene sulfide resin composition obtained by blending a polyvinylpyrrolidone resin with a polyarylene sulfide resin exhibits excellent adhesion to a metal member and is poly. We have found that the arylene sulfide resin maintains the original excellent heat resistance, and have solved the present invention.

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 a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added to 100 parts by mass of the polyarylene sulfide resin (A). (B) relates to a metal / resin composite structure, 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 formed by joining a metal member and a molded product of a polyarylene sulfide resin composition.
The polyarylene sulfide resin composition comprises a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added to 100 parts by mass of the polyarylene sulfide resin (A). The present invention relates to a polyarylene sulfide resin composition, wherein (B) is in the range of 0.01 to 100 parts by mass.

Further, the present invention relates to a molded product obtained by molding the 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 product of a polyarylene sulfide resin composition are joined.
It has (1) a step of joining the polyarylene sulfide resin composition by melt molding on the surface of the metal member, or (2) a step of joining the metal member and the molded product of the polyarylene sulfide resin composition. matter,
The polyarylene sulfide resin composition comprises a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added 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 formed by joining a metal member and a molded product of the polyarylene sulfide resin composition.
Having a step of melt-kneading the polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, the polyvinylpyrrolidone (B) is 0.01 with respect to 100 parts by mass of the polyarylene sulfide resin (A). The present invention relates to a method for producing a polyarylene sulfide resin composition, which comprises a range of about 100 parts by mass.

Further, the present invention is a method for producing the molded product used for 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 a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added 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, it is an object of the present invention to provide a metal / resin composite structure in which a metal member and a molded product of a polyarylene sulfide resin composition are bonded to each other and have excellent heat resistance and adhesion, and a method for producing the same. Further, the present invention has a polyarylene sulfide resin composition having excellent adhesion to metal parts and excellent heat resistance, and a melt-molded polyarylene sulfide resin composition having excellent adhesion to metal parts and also having 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 product and the metal member is considered to be mainly based on a physical bond or a chemical bond, although the mechanical bond also contributes. Therefore, a known joining method capable of joining the polyarylene sulfide resin composition or a molded product thereof with the surface of the metal member with fluidity can be used. Hereinafter, (1) a step of joining the polyarylene sulfide resin composition by melt molding on the surface of the metal member (referred to as joining method 1), and (2) a molded product of the metal member and the polyarylene sulfide resin composition. The process of joining with (referred to as joining method 2) will be described separately.

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 material obtained by laminating metal member layers in a film form is inserted into a mold, and a polyarylene sulfide resin composition is melt-molded on the metal member layer side, so-called. It may be film insert molding. 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 carried out 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 above the melting point and within the temperature range of plus 100 ° C., more preferably plus 20 ° C. and plus 50 ° C. After undergoing the step of melting the polyarylene sulfide resin composition within a temperature range, the polyarylene sulfide resin composition may be molded by injecting it into a mold from a resin discharge port. At that time, the mold temperature may be set 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 be done. As described above, the polyarylene sulfide resin composition of the present invention can be set in a temperature range of 120 to 180 ° C., which is preferable as a normal molding temperature, has a low recrystallization temperature (Tc2), and is excellent in low-temperature moldability. Since it also has characteristics, it has moldability such as appearance and filling property and mechanical properties even at a mold temperature under relatively low temperature conditions such as room temperature (23 ° C.) or higher, preferably 40 ° C. or higher and lower than 120 ° C. , It is preferable to obtain a molded product having excellent chemical resistance.

As the joining method 2, the molded product of the polyarylene sulfide resin composition of the present invention is joined by being in contact with a metal member and then heated, or by being heated and then being brought into contact with a metal member and then joined. Cooling. Examples thereof include a hot plate welding method, a vibration welding method, an ultrasonic welding method, a high frequency welding method, an induction heating welding method, a rotary welding method, a laser welding method, a hot press method, and a hot embossing method. As the apparatus used for the method and the manufacturing method, a commercially available apparatus can be used, or the apparatus can be carried out according to a conventional method. For example, in the hot plate welding method, in order to melt the surface of a molded product that is welded to a metal member, it is melted using a heat source such as a hot plate so that the following temperature conditions are met, and after joining with the metal member, it is added until it cools and hardens. It may be joined by holding it in a pressure state. Further, in vibration welding, ultrasonic welding, and high frequency 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. It may be joined by transmitting ultrasonic waves and high frequencies to a molded product or a metal member to generate heat, melting the molded product by the heat generation, and holding the molded product in a pressurized state until it cools and hardens. Vibration, high frequency, and ultrasonic waves may be transmitted by bringing a resonator or a vibrating device into contact with the irradiated or molded product to vibrate the molded product, thereby causing the molded product or the metal member itself to vibrate or vibrate. , The heat may be generated by the 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. Therefore, the metal member is heated by an induction heating device so as to have the following temperature conditions. The molded product may be joined by generating heat to melt it and holding it in a pressurized state until it cools and hardens. Further, in rotary welding, after holding the molded product and the metal member separately, one of them is gradually brought closer to each other while rotating at a high speed in the range of 100 to 4,000 rotations, and the two come into contact with each other. By the way, the resin may be joined by generating frictional heat so as to have the following temperature conditions, melting the resin, and then holding the resin in a pressurized state until it cools and hardens.

Further, 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 material, from the viewpoint of maintaining the smoothness and surface appearance of the film-like material, the following hot press (thermocompression bonding) method and melt extrusion method are particularly applied. A bonding method called a bonding method can also be used, and if the film-like material is a transparent material capable of transmitting a laser beam, a bonding 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 in which a film of a film-like polyarylene sulfide resin composition is thermocompression bonded to a metal member under high temperature and high pressure, and the thermocompression bonding is performed by a heating roll. Although it is carried out by a method or a hot plate press, the method using a heating roll is preferable from the viewpoint of the production process.

Further, in the case of the melt extrusion transfer method, the polyarylene sulfide resin composition may be melted by a melt extruder and extruded into a film, then pressed against a shaping roll and cooled and solidified while being pressure-bonded to a metal member. .. Further, the laser welding method can be applied when the molded product can transmit a laser beam, and after joining the molded product to the metal member, a laser beam is applied from the molded product side to the metal member surface so as to have the following temperature conditions. It may be joined by irradiating and generating heat, melting the molded product, and holding it in a pressurized state until it cools and hardens.

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 can be used in which the metal member is joined by simultaneously performing embossing and foil stamping while heating the molded product of the polyarylene sulfide resin composition. By using the hot embossing method, it is possible to manufacture a molded product having a three-dimensional shape and a fine pattern, and when the fine pattern made of a metal member is an electric circuit, it can be used as a molded circuit component. can.

In the present invention, the term "film-like material" refers to so-called foils, films, sheets, and plates collectively as described above, and refers to those having a thickness in the range of 0.001 to 9 mm.

In the joining method 2 described above, it is basically necessary to melt the molded product and press it against the metal member. Therefore, the heating condition is that the resin temperature is equal to or higher than the recrystallization temperature (Tc2) of the polyarylene sulfide resin. It may be adjusted appropriately within the temperature range, but from the viewpoint of maintaining excellent smoothness and appearance of film-like materials and exerting sufficient adhesion, the temperature is equal to or higher than the recrystallization temperature (Tc2) and the melting point. It is preferable to make appropriate adjustments within a temperature range of less than, and on the other hand, from the viewpoint of suppressing gas generation due to resin decomposition and preventing resin deterioration and exhibiting better adhesion, the temperature range above the melting point is appropriately adjusted. It is preferable to adjust the temperature, and it is more preferable to adjust the temperature within the temperature range of the melting point plus 100 ° C. Further, the pressure conditions for crimping (pressing each other) the metal member and the molded product are not particularly limited as long as the bonded state can be maintained. For example, the metal member is between the start of heating and the end of cooling. 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], and more preferably 0.05 to 10 [MPa] is sufficient. It may be adjusted as appropriate within a range in which the amount of burrs is small while exhibiting the 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 an external force before welding, and the metal member and the molded product are joined by utilizing the pressure increase generated at the joining interface due to the volume expansion during melting. be able to.

(Metal member)
Examples of the type of metal constituting the metal member include aluminum, copper, magnesium, iron, titanium, and alloys containing them. More specifically, the main component is iron, for example, stainless steel, steel, etc., that is, 20% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass, and other carbons and silicon. , Manganese, chromium, tungsten, molybdenum, phosphor, titanium, vanadium, nickel, zirconium, boron, etc. (hereinafter, iron alloy), aluminum, aluminum as the main component, copper, manganese, silicon, magnesium , Alloys containing zinc and nickel (hereinafter referred to as aluminum alloys), alloys containing magnesium and magnesium as the main components, and alloys containing zinc, aluminum and zirconium (hereinafter referred to as magnesium alloys), copper and copper as the main components. In addition, alloys containing zinc, tin, phosphorus, nickel, magnesium, silicon, and chromium (hereinafter referred to as copper alloys), titanium, and titanium as the main component, as well as copper, manganese, silicon, magnesium, zinc, and nickel. Examples thereof include alloys containing (hereinafter, titanium alloys). Of these, iron, iron alloys, aluminum alloys, magnesium alloys, copper alloys and titanium alloys are more preferable, and iron alloys, aluminum alloys and magnesium alloys 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 surface of the metal member) preferably has a fine uneven surface (hereinafter, simply referred to as a fine uneven surface). In the present invention, the bonding between the metal member and the molded product provides excellent adhesion by intermolecular force or chemical interaction, which is considered to be due to the polyvinylpyrrolidone resin blended as an essential component in the polyarylene sulfide resin composition. However, by further performing a surface roughening treatment and providing a fine uneven surface on the surface of the metal member, the adhesion force can be further strengthened by the action of mechanical bonding.

By subjecting the surface of the metal member of the metal / resin composite structure of the present invention to a surface roughening treatment and providing a fine concavo-convex surface, the molten polyarylene sulfide resin composition penetrates into the recess of the fine concavo-convex surface with good fluidity. By solidifying the metal member, 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 to each other. sell.

In the metal member used in the present invention, it is preferable that a fine concavo-convex surface is formed on the material surface of the metal portion by surface roughening, but the distance between the concavo-convex portions is from a convex portion to an adjacent convex portion (hereinafter, convex portion). The length of the space) is preferably in the range of 5 nm or more, and more preferably in the range of 10 nm or more. The upper limit value 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, and further 500 μm or less because the adhesion tends to improve when the unevenness density is high. More preferably, it is in the range. When the length between the convex portions is within the above range, the polyarylene sulfide resin composition used in the present invention can penetrate into the concave portions of the fine concavo-convex surface with good adhesion, and excellent adhesion is provided at the metal-resin interface. Can be demonstrated. Further, it is preferable that the distance between the uneven portions has periodicity because better adhesion can be exhibited at the metal-resin interface.

Further, the height difference of the uneven portion is preferably in the range of 50 nm or more, and more preferably in the range of 100 nm or more. The upper limit value tends to improve as the height difference increases, so it is not particularly limited, but it is in the range of 500 μm or less in consideration of filling the uneven portion with resin so as not to generate voids. Is preferable.

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

Further, the uneven shape of the fine uneven surface is not particularly limited, and may be formed as a concave portion having a pore diameter smaller than the distance between the convex portions by surface roughening described later, and the surface roughening is further promoted. The shape may be observed in a forested state as a rounded convex portion, that is, a cylinder having a spherical shape or a smooth end, or a protrusion having a three-dimensional aspect such as a wart shape or a karinto shape.

As the surface roughening method, a known method can be used without limitation, and examples thereof include three types of methods.
(1) Immersion method with an erosive aqueous solution or an erosive suspension. It is preferable to have a shape in which fine uneven surfaces are formed on the metal surface, and more preferably, 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) Anodization method. By mainly forming a metal oxide layer on the surface, it is preferable to form a large number of openings having a number average inner diameter of 1 μm or less on the surface layer, and similarly, openings having a number average inner diameter of 1 nm to 1 μm. It is more preferable to form a portion, and it is more preferable to form an opening having a number average inner diameter range of 10 to 200 nm.

(3) A method of forming irregularities on a metal surface by pressing a mold punch having irregularities created by mechanical cutting, for example, diamond abrasive grain grinding or blasting, or creating an uneven shape on a 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 continuous shape recess such as the number average inner diameter of the recess or laser machining, the width is preferably in the range of 1 to 1000 μm, and further 10 to 10 More preferably, it is in the range of 800 μm.

Before forming the above-mentioned fine uneven surface, the metal member is processed into a predetermined shape by plastic working such as cutting, pressing, punching, cutting, grinding, electric discharge machining and the like. Is preferable.

A primer layer may be formed on the surface of the metal member that has been surface-treated with metal. The material constituting the primer layer is not particularly limited, but is usually composed of a primer resin material containing a resin component. The primer resin material is not particularly limited, and known ones can be used. Specific examples thereof include known polyolefin-based primers, epoxy-based primers, and urethane-based primers. The method for forming the primer layer is not particularly limited, and for example, a solution of the above-mentioned primer resin material or an emulsion of the above-mentioned primer resin material can be applied to the metal member subjected to the above-mentioned surface treatment to form the primer layer. Examples of the solvent used for making the solution include toluene, methyl ethyl ketone (MEK), dimethylformamide (DMF) and the like. Examples of the medium for the emulsion include an aliphatic hydrocarbon medium and water.

Further, in the case of the film insert molding method, the molded product of the polyarylene sulfide resin composition is joined to the resin film-like material in which the metal member layers are laminated in a film shape via the metal member layer. The body is obtained. The metal member layer may be formed on the resin film-like material by transferring or printing a film-like material such as a metal foil, or by plating. At that time, the resin film-like material includes polyethylene terephthalate (PET), polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polyamide 6, polyamide 66 (PA6, PA66) and other polyamide resins, and polyimide resin. A resin film having heat resistance such as a cured product of an active energy ray-polymerizable resin composition containing a polyidimide resin, a polyvinyl alcohol resin, or a (meth) acrylic resin containing a radically polymerizable unsaturated group as a main component. Is preferably used. Among them, the PET resin film is most preferably used because it is excellent in cost, beauty, and transparency. The production of a resin film-like product in which metal member layers are laminated in a film-like shape is not particularly limited, and a commercially available device 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 polyvinylpyrrolidone (B) as essential components, and is described above with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is characterized in that polyvinylpyrrolidone (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 structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit. Specifically, 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）

(In the formula, R ¹ and R ² independently represent a hydrogen atom, an alkyl group in the range of 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, and an ethoxy group). The structural part to be formed 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。

It is a resin having a trifunctional structural part represented by (1) and a repeating unit as a repeating unit. 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 the other structural sites. Is preferable.

Here, the structural portion represented by the general formula (2) ^{is preferably a hydrogen atom, particularly preferably R 1} and R ² in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. In this case, those that are combined at the para position represented by the following formula (4) and those that are combined at the meta position represented by the following formula (5) can be 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（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, the heat resistance and crystallinity of the polyarylene sulfide resin is that the bond of the sulfur atom to the aromatic ring in the repeating unit has a structure in which the sulfur atom is bonded at the para position represented by the general formula (4). It is preferable in terms of surface.

Further, the polyarylene sulfide resin has not only the structural parts represented by the general formulas (2) and (3) but also 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 portion represented by the above may be contained in an amount of 30 mol% or less of the total of the structural portion represented by the general formula (2) and the general formula (3). In particular, in the present invention, the structural portion represented by the general formulas (6) to (9) is 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 structural sites represented by the general formulas (6) to (9), 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 is preferably 3 mol% or less, particularly 1 It is preferably mol% or less.

The physical characteristics 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 higher, and further in the range of 270 to 300 ° C., because it is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. More preferably. Further, the recrystallization temperature (Tc2) of the resin (A) is preferably in the range of 200 to 260 ° C. because it is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength.

(Melting 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 further improves the 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 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 (mm) using a polyarylene sulfide resin, a flow tester manufactured by Shimadzu Corporation, CFT-500D. ) / 1 (mm), 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 effects of the present invention are not impaired, but is preferably in the range of 0.99 to 2.00. When a linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.99 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, for the non-Newtonian index (N value), the shear rate and shear stress are measured under the conditions of 300 ° C., the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40 using a capillograph. , It is a value calculated by 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。

[However, SR indicates the shear rate (sec- ¹ ), SS indicates the shear stress (Dyne / cm ² ), and K indicates 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, but for example, 1) a dihalogeno aromatic compound in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymerization component. In addition, a method of polymerizing, 2) a method of adding a dihalogeno aromatic compound in the presence of a sulfidizing agent or the like in a polar solvent, and if necessary, a polyhalogeno aromatic compound or other copolymerizing component, and polymerizing the mixture, 3) Examples thereof include a method of self-condensing p-chlorothiophenol by adding other copolymerization components if necessary. Among these methods, the method 2) is general-purpose and preferable. At the time of the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above 2) methods, a hydrous sulfide agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogeno aromatic compound is introduced in the organic polar solvent. And a sulfide agent, if necessary, and a polyhalogeno aromatic compound to react with each other, and the amount of water in the reaction system should be in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by control (see JP-A-07-228649), or if necessary with a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent. Polyhalogeno aromatic compounds or other copolymerization components are added to add alkali metal hydrosulfides and organic acid alkali metal salts to organic acid alkali metal salts in the range of 0.01 to 0.9 mol per mol of sulfur source. Those obtained by a method of reacting while controlling 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 (see WO2010 / 058713 pamphlet) are particularly preferable. Specific examples of dihalogeno aromatic compounds 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'-dihalodiphenylsulfone, 4,4'-dihalodiphenylsulfoxide, 4,4'-dihalodiphenylsulfide, and the above compounds. Examples of the aromatic ring of the above are compounds having an alkyl group having an alkyl group in the range of 1 to 18 carbon atoms, and examples of the polyhalogeno aromatic compound are 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3. Examples thereof include 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene and 1,4,6-trihalonaphthalene. Further, it is desirable that the halogen atom contained in each of the above compounds is a chlorine atom or a bromine atom.

The method for post-treating the reaction mixture containing the polyarylene sulfide resin obtained in the polymerization step is not particularly limited. For example, (1) after completion of the polymerization reaction, the reaction mixture is first used as it is, or an acid or a base. After adding the solvent, the solvent was distilled off under reduced pressure or normal pressure, and then the solid substance after the solvent was distilled off was water, a reaction solvent (or an organic solvent having equivalent solubility in a low molecular weight polymer), acetone, and methyl ethyl ketone. , Wash once or twice or more with a solvent such as alcohols, and further neutralize, wash with water, filter and dry, or (2) after completion of the polymerization reaction, add water, acetone, methyl ethyl ketone, alcohols, etc. to the reaction mixture. Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (solvents that are soluble in the polymerization solvent used and poor at least for polyarylene sulfide) are used as precipitants. Addition to precipitate solid products such as polyarylene sulfide and inorganic salts, which are separated by filtration, washed and dried, or (3) after completion of the polymerization reaction, a reaction solvent (or a small molecule) is added to the reaction mixture. An organic solvent having the same solubility as the polymer) is added and stirred, and then filtered to remove the low molecular weight polymer, and then washed once or twice or more with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc. Then, neutralization, washing with water, filtration and drying are performed. (4) After completion of the polymerization reaction, water is added to the reaction mixture for washing with water, filtration, and if necessary, acid treatment with water at the time of washing with water. , (5) After completion of the polymerization reaction, the reaction mixture is filtered, washed once or twice or more with a reaction solvent, if necessary, and further washed with water, filtered and dried. ..

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

(Polyvinylpyrrolidone)
The polyarylene sulfide resin composition of the present invention contains polyvinylpyrrolidone (B) as an essential component. The average molecular weight of the polyvinylpyrrolidone is not particularly limited, but the mass average molecular weight is preferably in the range of 3,000 to 2,000,000, more preferably in the range of 500,000 to 1,500,000, and further. It is preferably in the range of 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 and is in the range of 4,500 to 13,500. Is preferable, and the range is particularly preferably in the range of 9,000 to 108,000. For the mass average molecular weight, a GPC device (manufactured by Tosoh Corporation) prepared by preparing a tetrahydrofuran solution (0.1 wt%) of polyvinylpyrrolidone and equipped with a TSKGelGHxl series 5000, 3000, 2000, 1000 columns and a differential refractometer (RI) detector. Using HLC-8220 GPC), the sample solution injection volume was 50 μl, tetrahydrofuran was used as the mobile phase (1 ml / min), and the measurement was performed at 40 ° C. The mass average molecular weight was calculated from a calibration curve made of standard styrene. However, it is possible to appropriately change the measurement conditions within a range that does not substantially affect the measured value of the mass average molecular weight.

Polyvinylpyrrolidone may be linear or crosslinked. Examples of polyvinylpyrrolidone (B) include 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 are preferably mentioned. However, in the formula (1), n represents a repeating unit, preferably in the range of 30 to 18,000. Further, R ¹ is a hydrogen atom, an alkyl group or an alkoxy group in the range of 1 to 6 carbon atoms, preferably a methyl group, an i- or n-propyl group, or a butyl group, of which a hydrogen atom is preferable.

The method for producing polyvinylpyrrolidone can be a known method and is not particularly limited as long as the effect of the present invention is not impaired. For example, a method of reacting 2-pyrrolidone with acetylene as a raw material (Leppe method). ) And the method based on the dehydration reaction of N-hydroxyethylpyrrolidone, preferably N-hydroxyethylpyrrolidone obtained by subjecting N-hydroxyethylpyrrolidone to a vapor phase dehydration reaction and having a γ-butyrolactone content reduced to, for example, 500 ppm or less. -Examples include a method of radical polymerization of vinylpyrrolidone by appropriately adding a known polymerization initiator or basic pH adjuster.

Here, the N-vinylpyrrolidone is described by 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 above equation (1).

The polyvinylpyrrolidone used in the present invention is preferably a copolymer using the N-vinylpyrrolidone as a raw material, but N-vinyl represented by the general formula (10) is used as long as the effects of the present invention are not impaired. A copolymer using pyrrolidone or another monomer as a raw material may be used. In that case, the amount of the other monomer used is preferably 10% by mass or less, more preferably 1% by mass or less, and 0. It is more preferably 1% by mass or less.

Examples of other monomers include 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）

Examples thereof include polymerizable unsaturated monomers containing a pyrrolidinyl group represented by. Here, X is a substituent having a radically polymerizable double bond, and has 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 formulas (12) to (17), R ¹ is a hydrogen atom, an alkyl group or an alkoxy group in the range of 1 to 6 carbon atoms, preferably a methyl group, an i- or n-propyl group, or a butyl group. .) Can be mentioned.

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 polyvinylpyrrolidone (B) blended is not particularly limited as long as the effects of the present invention are not impaired, but is in the range of 0.01 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). It is 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. .. In 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 product 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), phosphite, hypophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, metaphosphoric acid, acidic metaphosphoric acid, hexametaphosphoric acid, pyrophosphoric acid, and acidic pyrophosphoric acid. The metal element of the metal salt contains 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, hypophosphorus Barium Acid, Aluminum Hypophosphate, Zinc Hypophosphate, 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, Magnesium Metaphosphate, Calcium Acid Metaphosphate, Barium Acidic Metaphosphate, Zinc Acid Metaphosphate, Magnesium Hexamethaphosphate, Calcium Hexamethaphosphate, Barium Hexamethaphosphate, Zinc Hexametaphosphate, Magnesium Pyrophosphate, Pyro Calcium phosphate, barium pyrophosphate, zinc pyrophosphate, magnesium acid pyrophosphate, calcium pyrophosphate, barium pyrophosphate, zinc pyrophosphate, etc. include calcium polyphosphate, zinc polyphosphate, calcium tripolyphosphate, zinc tripolyphosphate. Is preferred.

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, and for example, 100 parts by mass of the polyarylene sulfide resin (A). On the other hand, it is preferably in the range of 0.001 to 50 parts by mass, more preferably in the range of 0.05 to 30 parts by mass, and further preferably in the range of 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 to a metal member, and the obtained molded product exhibits good heat resistance, which is preferable. ..

The polyarylene sulfide resin composition of the present invention may contain a silane coupling agent (D) as an optional component, if necessary. The silane coupling agent is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include silane coupling agents having an epoxy group, an isocyanato group, an amino group or a hydroxyl group. Examples of such a silane coupling agent 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-Isocyanatopropyl ethyl diethoxysilane, 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 (D) 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, 100 parts by mass of the polyarylene sulfide resin (A). On the other hand, it 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 preferably 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 to a metal member, and the obtained molded product exhibits good heat resistance, which is preferable. ..

The polyarylene sulfide resin composition of the present invention or a molded product thereof is blended with at least one selected from the group consisting of the phosphate and the silane coupling agent to have the melting point (Tm) of the resin (A). ), While maintaining the melting point (Tm) of the resin (A) as the recrystallization temperature (Tc2) of the polyarylene sulfide resin composition or its molded product, further from the recrystallization temperature (Tc2) of the resin (A). Can be lowered. Regarding the specific range of decrease in recrystallization temperature (Tc2), the composition of essential components and optional components is determined in consideration of the relationship with other properties such as mechanical properties according to the use and purpose of the molded product. Since it is necessary, it cannot be unconditionally specified, but preferably, the polyarylene sulfide resin composition of the present invention or a molded product thereof is recrystallized when the phosphate or the silane coupling agent is blended. 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. can. That is, the polyarylene sulfide resin composition and the molded product of the present invention when the phosphate or the silane coupling agent is blended have a difference ΔT between the melting point (Tm) and the recrystallization temperature (Tc2). It can also be preferably in the range of 90 ° C. or higher, more preferably in the range of 90 to 130 ° C., and even more preferably in the range of 100 to 120 ° C. Therefore, the present invention keeps the melting point (Tm) of the polyarylene sulfide resin composition and the molded product of the present invention in the case where the phosphate or the silane coupling agent is blended, 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 in the range of 200 ° C. or lower, more preferably in the range of 120 to 200 ° C., and further preferably in the range of 160 to 200 ° C. be able to. The melting point (Tm) of the polyarylene sulfide resin composition of the present invention or a molded product thereof maintains the melting point (Tm) of the resin (A), which means that the melting points are substantially the same. The temperature difference between the Tm (° C.) of the polyarylene sulfide resin composition or its molded product and the Tm (° C.) of the polyarylene sulfide resin (A) blended as an essential component is preferably 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, and have various shapes such as fibrous ones and non-fibrous ones such as granular and plate-like ones. Examples include fillers. Specifically, glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, warastonite and other fibers, and natural fibers and other fibrous fillers are used. Can also be used, glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulsite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber , Non-fibrous fillers such as calcium sulfate can also be used.

Although the filler is not an essential component in the present invention, when it is blended, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and it varies according to each purpose and is generally defined. However, for example, it is preferably in the range of 1 to 600 parts by mass, and more preferably in the range of 10 to 200 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). 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, fluoroelastomers, and silicone-based elastomers, and among them, polyolefin-based elastomers are preferable. When these elastomers are blended, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and the polyallylen sulfide resin is different depending on the respective purposes and cannot be unconditionally specified. (A) The range is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass. In such a range, the impact resistance of the obtained polyarylene sulfide resin composition is improved, which is preferable.

The polyolefin-based elastomer is, for example, an α-olefin and a vinyl polymerizable compound having a functional group when a functional group is further imparted by homopolymerization of α-olefin or copolymerization of different α-olefins. It can be obtained by copolymerization. Examples of the α-olefin include those in the range of 2 to 8 carbon atoms such as ethylene, propylene and butene-1. The functional group includes 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 α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester and their alkyl esters, maleic acid and fumar. Examples thereof include acids, itaconic acids and other α, β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters and their acid anhydrides, etc.), and glycidyl (meth) acrylates. Among these, ethylene-propylene copolymers and ethylene-butene copolymers having at least one functional group selected from the group consisting of the above-mentioned epoxy group, carboxy group, and acid anhydride group are mechanically used. It is preferable from the viewpoint of improving strength, particularly toughness and impact resistance.

Further, in addition to the above components, the polyarylene sulfide resin composition of the present invention further comprises, depending on the intended use, the polyarylene sulfide resin and other synthetic resins other than the polyvinylpyrrolidone, such as polyester resin and polyamide resin. Polyethylene 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, polytetrafluorinated ethylene A resin, a polydifluorinated ethylene resin, a polystyrene resin, an ABS resin, a phenol resin, a urethane resin, a liquid crystal polymer, or the like (hereinafter, simply referred to as a synthetic resin) can be blended as an optional component. Although the synthetic resin is not an essential component in the present invention, when it is blended, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and it varies depending on the respective purposes and is unconditionally different. Although it cannot be specified, the proportion of the resin component (total of the polyarylene sulfide resin, the polyvinylpyrrolidone 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 polyvinylpyrrolidone. In other words, the total is in the range of 75.0% by mass or more, preferably in the range of 80 to 99.99% by mass, in other words, the above synthetic resin is in the range of 25.0% by mass or less, preferably 0.01 to 20%. It may be appropriately adjusted and used in the range of 0.0% by mass according to the purpose and application so as not to impair the effect of the present invention.

In addition, the polyarylene sulfide resin composition of the present invention also has a colorant, an antistatic agent, an antioxidant, a heat-resistant stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a flame retardant aid, and an anti-flammable agent. Known and commonly used additives such as a rust agent and a coupling agent may be blended as optional components, if necessary. These additives are not essential ingredients, but when they are blended, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and they differ according to their respective purposes and can be unconditionally specified. However, for example, with respect to 100 parts by mass of the polyarylene sulfide resin (A), it is appropriately adjusted in the range of 0.01 to 1,000 parts by mass according to the purpose and application so as not to impair the effects of the present invention. And use it.

In the method for producing a polyarylene sulfide resin composition of the present invention, the polyarylene sulfide resin (A) and the polyvinylpyrrolidone (B) are blended as essential components and melted at a temperature equal to or higher than the melting point of the polyarylene sulfide resin (A). Knead.

A preferable method for producing the polyarylene sulfide resin composition of the present invention is to obtain the above-mentioned compounding ratio, the polyarylene sulfide resin (A), each of the essential components of the polyvinylpyrrolidone (B), and if necessary, the above. Arbitrary ingredients are put into a ribbon blender, Henschel mixer, V blender, etc. in various forms such as powder, pellets, and strips for dry blending, and then a Banbury mixer, mixing roll, single-screw or twin-screw extruder, and kneader. A temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin, preferably a temperature range in which the melting point is + 10 ° C. or higher, and more preferably a temperature in which the melting point is + 10 ° C. to + 100 ° C. It can be produced through a step of melt-kneading in a range, more preferably in a temperature range of melting point +20 to melting point +50 ° C. Each component may be added to and mixed with the melt kneader at the same time, or may be divided.

As the melt kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. 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 range of, and melt-knead under the condition that the ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). Is even more preferable. Further, when a filler or an additive is added among the components, it is preferable to put the filler into the extruder from the side feeder of the twin-screw kneading extruder from the viewpoint of dispersibility. The position of the side feeder is preferably in the range of 0.1 to 0.9 in the ratio of the distance from the extruder resin input portion to the side feeder with respect to the total screw length of the twin-screw kneading extruder. 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 comprises a polyarylene sulfide resin (A) which is an essential component, the polyvinylpyrrolidone (B), an optional component added as necessary, and the like. It is a melt mixture containing the components derived from the above, and after the melt kneading, it is processed into pellets, chips, granules, powders and the like by a known method, and then pre-dried at a temperature of 100 to 150 ° C. as necessary. Therefore, it is preferable to use it for various moldings.

The polyarylene sulfide resin composition of the present invention produced by the above-mentioned production method uses a polyarylene sulfide resin as a matrix, and in the matrix, the polyvinylpyrrolidone (B) which is an essential component and a component derived from them are required. It forms a morphology in which arbitrary components added according to the above are dispersed. The pyrrolidone skeleton contained in polyvinylpyrrolidone has excellent compatibility with the polyarylene sulfide resin skeleton, and due to the presence of electron orbitals (2Pz orbitals) formed at the bonding site between carbon atoms and oxygen atoms, the surface of the metal member. It is thought that it exhibits excellent adhesion to the metal member by forming a physical interaction between the van der Waals force and 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. Be done.

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 polyvinylpyrrolidone (the polyvinylpyrrolidone) is contained in the matrix. B) and the phosphate (C) or the silane coupling agent (D), components derived from them, and components to be added as needed form a dispersed morphology. As a result, while maintaining the excellent heat resistance, chemical resistance, etc. inherent in the polyarylene sulfide resin composition, in addition to the above-mentioned physical interactions and chemical bonds, a lower recrystallization temperature is further achieved. Due to the properties of the resin composition, it is easy to penetrate into the fine irregularities on the surface of the metal member, and as a result, the wettability is further improved. Therefore, it is preferable. The polyarylene sulfide resin composition of the present invention maintains the inherent melting point of 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 (Tc2). The recrystallization temperature (Tc2) of A) can be further lowered by the action of polyvinylpyrrolidone, which has excellent compatibility with the polyarylene sulfide resin due to the pyrrolidone skeleton, and is poly during melt-kneading. It is considered that the polyarylene sulfide resin composition exhibits a low crystallization temperature (Tc2) as a result of delaying the crystallization of the arylene sulfide resin. Further, when the phosphate or the coupling agent is blended, although it is an optional component, the molecular chains of the polyarylene sulfide resin are mercaptide with the metal element derived from the phosphate of the sulfur atom at the molecular end. The polyarylene sulfide resin composition is lower as a result of the molecular chain being extended by forming a bond or binding to the coupling agent, and the effect of extending the molecular chain can further delay the above-mentioned crystallization. It is believed that the crystallization temperature (Tc2) can be exhibited.

The polyarylene sulfide resin composition of the present invention can be used for various moldings such as injection molding, compression molding, composite, extrusion molding of sheets, pipes, etc., drawing molding, blow molding, transfer molding, etc. It is also suitable for injection molding because of its excellent properties. When molding by injection molding, various molding conditions are not particularly limited, and molding can usually be performed by a general method. For example, in an injection molding machine, the resin temperature is in a temperature range equal to or higher than the melting point of the polyarylene sulfide resin, preferably in a temperature range of the melting point + 10 ° C. or higher, more preferably in a temperature range of + 10 ° C. to + 100 ° C. After undergoing the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to a melting point of +50 ° C., the polyarylene sulfide resin composition may be formed by injecting it into a mold from a resin discharge port. At that time, the mold temperature can also be set in a known temperature range, for example, in the range of room temperature (23 ° C.) to 300 ° C., preferably in the range of 40 to 180 ° C. The polyarylene sulfide resin composition of the present invention can be set in a temperature range of 120 to 180 ° C., which is preferable as a normal molding temperature, and as described above, the recrystallization temperature (Tc2) is low and the low temperature moldability is excellent. Since it also has characteristics, it is possible to obtain a molded product having excellent moldability such as appearance and filling property, mechanical properties, and chemical resistance even at a mold temperature under relatively low temperature conditions such as 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 housings for various home appliances, mobile phones, electronic devices such as PCs (Personal Computers), and protection for box-shaped electric / electronic component integrated modules. Support members ・ Multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, prints Electricity represented by boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc. Electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio / video equipment parts such as audio / laser discs / compact discs / DVD discs / Blu-ray discs, lighting parts, refrigerators Household and office electrical parts such as parts, air conditioner parts, typewriter parts, word processor parts, water supply parts for water heaters and baths, temperature sensors, etc .; office computer related parts, telephone equipment related parts, Facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, writers, typewriters, and other machine-related parts: microscopes, binoculars, cameras, watches, and other optical equipment, precision machine-related parts; Alternator terminal, alternator connector, brush holder, slip ring, IC regulator, potential meter base for light dial, relay block, inhibitor switch, various valves such as exhaust gas valve, fuel-related / exhaust system / intake system 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, crank shaft 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, Dus Tributor, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter reel, wire harness for transmission, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn terminal It can also be applied to automobile / vehicle-related parts such as insulating plates for electrical components, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, and ignition device cases, and various other applications.

(Measurement of melt viscosity of polyphenylene sulfide resin)
The polyphenylene sulfide resin produced in the reference example was used in a flow tester manufactured by Shimadzu Corporation, CFT-500D, at 300 ° C., a load of 1.96 × 10 ⁶ Pa, and L / D = 10 (mm) / 1 (mm). It was measured 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 recrystallization temperature (Tc2) of the polyarylene sulfide resin obtained in the reference example and the comparative reference example and the polyarylene sulfide resin composition obtained in the comparative example are the resin or the resin. The composition was melted at 350 ° C. and then rapidly cooled to prepare an amorphous film, and about 4 mg of the composition was weighed and measured using a differential scanning calorimeter (“DSC8500” manufactured by PerkinElmer).

(Reference Example 1) Production of polyphenylene sulfide resin (PPS-1) p-dichlorobenzene (hereinafter, "p-DCB") in a 150-liter autoclave with a stirring blade in which a pressure gauge, a thermometer, a condenser, a decanter, and a rectification tower are connected. 33.222 kg (226 mol), NMP 2.280 kg (23 mol), 47.23 mass% NaSH aqueous solution 27.300 kg (230 mol as NaSH), and 49.21 mass% NaOH aqueous solution 18.533 g (abbreviated as). 228 mol) of NaOH was charged, and the temperature was raised to 173 ° C. over 5 hours in a nitrogen atmosphere with stirring to distill 27.300 kg of water, and then the autoclave was sealed. The p-DCB distilled by azeotrope during dehydration was separated by a decanter and returned to the autoclave at any time. In the autoclave after the completion of dehydration, the anhydrous sodium sulfide composition in the form of fine particles 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 an open ring of NMP (4- (methylamino)). It was shown that it was hydrolyzed to a sodium salt of (butyric acid) (hereinafter abbreviated as "SMAB"). The amount of SMAB in the autoclave was 0.097 mol per mole of sulfur atoms present in the autoclave. The charged NaSH and NaOH is the total amount, since the theoretical amount of dehydration may change anhydrous Na ₂ S is 27.921G, among residual water content in the autoclave 621 g (34.5 moles), 401 g (22.3 mol) 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 water of crystallization. Was showing. The amount of water in the autoclave was 0.053 mol per mol of sulfur atoms present in the autoclave.

After the completion of the dehydration step, the internal temperature was cooled to 160 ° C., a solution contained in 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 rectification column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled steam of mixed p-DCB and water was condensed by a condenser, separated by a decanter, and the p-DCB was returned to the autoclave. The amount of distilled water was 179 g (9.9 mol), the amount of water 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 the case of dehydration.

Then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, and the mixture was stirred at 230 ° C. for 1 hour, then raised 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 warm water at 80 ° C., stirred for 1 hour, and then filtered. The cake was stirred again with 30 liters of warm water for 1 hour, washed and then 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 after stirring for 1 hour, the operation of filtering was repeated twice, and the cake was dried overnight at 120 ° C. using a hot air circulation dryer to obtain a PPS resin (hereinafter referred to as PPS resin) on a white powder. , PPS-1) was obtained. The melt viscosity of the obtained polymer was 98 Pa · s. The melting point (Tm) was 282 ° C. and the recrystallization temperature (Tc2) was 203 ° C.

(Reference Example 2) Production of polyphenylene sulfide resin (PPS-2) 45% sodium sulfide (47.55% by mass NASH) 14 in a 150-liter autoclave with a stirring blade and bottom valve connected to a pressure gauge, thermometer, and capacitor. .148 kg, 48% caustic soda (48.7 mass% NaOH) 9.474 kg, and N-methyl-2-pyrrolidone 38.0 kg were charged. The temperature was raised to 209 ° C. with stirring under a nitrogen stream, and 12.150 kg of water was distilled off (the amount of residual water was 1.13 mol per 1 mol of NaSH). Then, 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 started by pressurizing the liquid temperature 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, the reaction was carried out at 260 ° C. for 3 hours while cooling by sprinkling water on the upper part of the autoclave when the temperature was raised to 260 ° C. While cooling the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. Next, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. The maximum pressure during the reaction was 0.87 MPa. After the reaction, the 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 filtration was performed at 120 ° C. To the obtained cake, 50 kg of warm water at 70 ° C. was added and stirred, and then the cake was filtered. 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. Further, 25 kg of warm water was added, the mixture was stirred for 1 hour, filtered, and then 25 kg of warm water was added and filtered, and the operation was repeated twice. The obtained cake was dried at 120 ° C. for 15 hours using a hot air circulation 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 (Tc2) 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, and after stirring at 230 ° C. for 1 hour, the temperature was raised to 250 ° C. "The mixture was stirred for 1 hour.""Then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, the temperature was raised at 230 ° C. for 3 hours, the temperature was raised to 250 ° C., and the mixture was 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, the mixture was stirred at room temperature for 1 hour, and then filtered." 30 liters of water was added to the cake, the pH was adjusted to 6.0 with carbonated water, the mixture was stirred at room temperature for 1 hour, and then filtered. ”Except for the two points, the procedure was the same as in Reference Example 1. , PPS-3 was obtained. The melt viscosity of the obtained polymer was 171 Pa · s. The melting point (Tm) was 280 ° C., and the recrystallization temperature (Tc2) was 211 ° C.

(Reference example 4)
The same procedure as in Reference Example 2 was carried out except that 65.3 g of 1,3,5-trichlorobenzene (0.3 mol% with respect to 1 mol of NaSH) was added at the same time as paradichlorobenzene to obtain a polyphenylene sulfide resin (PPS-4). .. The obtained polymer had a melt viscosity of 2840 Pa · s. The melting point (Tm) was 284 ° C. and the recrystallization temperature (Tc2) 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 (Tc2) was 146 ° C.

(Examples 1 to 9 and Comparative Examples 1 to 5) Production of PPS resin compositions According to the composition components and blending amounts (all by mass) shown in Tables 1 to 3, each material was uniformly mixed with a tumbler. After that, the compounded material was put into a twin-screw extruder "TEX30α" with a vent from Japan Steel Works, Ltd., and melt-kneaded by setting the resin component discharge rate to 25 kg / hr, the screw rotation speed to 250 rpm, and the set resin temperature to 330 ° C. , Resin composition pellets were obtained. The melting point (Tm) and recrystallization temperature (Tc2) of the pellets were determined and shown in Tables 1 to 3.

Next, the obtained pellets were melt-kneaded at 320 ° C., 40 rpm for 5 minutes, and the kneaded product was made into a press film at 320 ° C., 15 MPa for 6 minutes. Obtained. As a metal foil on the film, copper foil (Fukuda Metal Foil Powder Industry Co., Ltd. "CF-T9LK-UN-35", vertical 100 mm x horizontal 100 mm x thickness 35 μm, Rz of the joint surface = 10.5 μm, hereinafter, copper (Foil 1), copper foil (Fukuda Metal Foil Powder Industry Co., Ltd. "CF-T9LK-SV-35", vertical 100 mm x horizontal 100 mm x thickness 35 μm, Rz of the joint surface = 1.0 μm, hereinafter referred to as copper foil 2. ) Or aluminum foil (“Mitsubishi foil” manufactured by Mitsubishi Aluminum Co., Ltd., vertical 100 mm × horizontal 100 mm × thickness 12 μm, Rz of the joint surface = 1.3 μm, hereinafter referred to as aluminum foil) is placed on a hot press machine at 290 ° C. It was set and heat-bonded with 5 [MPa] for 3 minutes. The following various evaluation tests were carried out using the obtained conjugate. The results of the tests and evaluations are shown in Tables 1 to 3. However, the surface roughness Rz of the metal foil was measured by a surface roughness measuring instrument (“SE-3500K type” manufactured by Kosaka Research Institute) by a method based on JIS-B0601.

(Measurement Example 2) Adhesion test between PPS molded product and metal foil The obtained test piece was tested by a method conforming to the cross-cut method (JIS K5400: 1990). That is, after making a total of 100 regions on the metal foil surface of the test pieces obtained in Examples and Comparative Examples by making cuts that divide the test pieces into 10 equal parts at 1 mm intervals in each of the vertical and horizontal directions, they are adhered to the surface on which these regions are formed. Adhesion test was performed using tape (“Cyril 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 (RTA100, manufactured by Orientec) after applying pressure on the adhesive tape once back and forth with a 2 kg roller and leaving it for 1 hour so that the adhesive tape could be peeled off constantly. , Pulled in the 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.

The numerical values of the compositions in Tables 1 to 3 indicate parts by mass. The same applies to the table below.
* 1 ΔTc2 is a value obtained by subtracting Tc2 (° C.) of the PPS resin used as the raw material in each example 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: 105,000 to 1200000)
PVP-2 Polyvinylpyrrolidone Resin "K-85" manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 900,000 to 1050,000)
PVP-3 Polyvinylpyrrolidone Resin "K-30" manufactured by Nippon Shokubai Co., Ltd. (mass average molecular weight: 80,000 to 120,000)
PVP-4 Polyvinylpyrrolidone Resin "Pittscol K-17L" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (mass average molecular weight: 9000 to 120,000)

Zinc Polyphosphate Kikuchi Color Co., Ltd. "ZP-SB"

Epoxysilane 3-glycidoxypropyltrimethoxysilane Dow Corning Co., Ltd. "SH-6040"

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 a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added to 100 parts by mass of the polyarylene sulfide resin (A). A metal / resin composite structure in which (B) is in the range of 0.1 to 50 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). It's a combination
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 based on 100 parts by mass of the polyarylene sulfide resin. The metal / resin composite structure according to claim 1, which is in the 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 higher. The polyvinylpyrrolidone (B) has the following general formula (1).

(In the formula, n represents a repeating unit and is in the range of 30 to 18,000. R1 is a hydrogen atom and an alkyl group or an alkoxy group in the range of 1 to 6 carbon atoms.) 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 the form of a film. The metal / resin composite structure according to any one of claims 1 to 6, wherein the metal member is in the form of a film. The metal / resin composite structure according to any one of claims 1 to 7, wherein the metal / resin composite structure is a molding 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 a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added to 100 parts by mass of the polyarylene sulfide resin (A). A polyarylene sulfide resin composition, wherein (B) is in the range of 0.1 to 50 parts by mass. A molded product obtained 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.
It has (1) a step of joining the polyarylene sulfide resin composition by melt molding on the surface of the metal member, or (2) a step of joining the metal member and the molded product of the polyarylene sulfide resin composition. matter,
The polyarylene sulfide resin composition comprises a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added to 100 parts by mass of the polyarylene sulfide resin (A). A method for producing a metal / resin composite structure, wherein (B) is in the range of 0.1 to 50 parts by mass. A method for producing 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.
Having a step of melt-kneading the polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, the polyvinylpyrrolidone (B) is 0.1 based on 100 parts by mass of the polyarylene sulfide resin (A). A method for producing a polyarylene sulfide resin composition, which comprises a range of about 50 parts by mass. A method for producing the molded product used for 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 a polyarylene sulfide resin (A) and polyvinylpyrrolidone (B) as essential components, and the polyvinylpyrrolidone is added to 100 parts by mass of the polyarylene sulfide resin (A). A method for producing a molded product, wherein (B) is in the range of 0.1 to 50 parts by mass. The method for producing a molded product according to claim 14, wherein the mold temperature is in the range of 40 to 180 ° C.