JP2019111790A - Polyarylene sulfide resin composition, molded article, composite structure, and manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal/resin composite structure having excellent adhesion, which is formed by joining a metal member and a molded article of a polyarylene sulfide resin composition, and a method for producing the same. Further, the present invention provides a polyarylene sulfide resin composition having excellent adhesion to metal parts, and a molded article obtained by melt-molding the same, which has excellent adhesion to metal parts. SOLUTION: A metal member and a molded article of a polyarylene sulfide resin composition are bonded via a polyolefin which is a reaction product of a polyolefin (a) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (b). Metal/resin composite structure to be bonded together, manufacturing method. Furthermore, a polyarylene sulfide resin composition having excellent adhesion to metal parts, a molded article excellent in adhesion to metal parts obtained by melt-molding the same, a composite structure thereof, and a method for producing the same. [Selection diagram] Figure 1

Description

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

  Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin typified by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin exhibits excellent heat resistance which can maintain a melting point of 270 ° C. or more And it is known that it is excellent also in mechanical strength, chemical resistance, moldability, and dimensional stability. Therefore, in general, additives such as fillers and elastomers are blended into polyarylene sulfide resin, and melt kneading is performed so as to be dispersed in a matrix composed of polyarylene sulfide resin, to obtain PAS resin composition Above, it melt-molds and is processed into various molded articles as electric / electronic device parts, automobile parts, etc.

By the way, a high heat resistant resin member is used as a metal member substitute from the viewpoint of weight reduction of various parts. However, when it is difficult to replace all the 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, there is known a method of roughening the surface of a metal member and bonding using a polyarylene sulfide resin by an anchor effect. For example, an aluminum alloy or magnesium alloy having concave portions with a number average inner diameter of 10 to 80 nm on the surface by a chemical solution treatment such as an aggressive aqueous solution or erosive suspension, or a number average inner diameter 10 on the surface by treatment with an anodic oxidation method. There is known a composite formed by injection molding a polyphenylene sulfide resin composition into an aluminum alloy having a recess of -80 nm, and fixing the resin composition in a state where the resin composition has entered the recess (see Patent Document 1).
Also known is a method of bonding and bonding an adhesive film between a metal and a resin composite structure. For example, a laminated film consisting of polypropylene and polyphenylene sulfide is heated and fused to stainless steel, and a polyphenylene sulfide resin is injection molded there to form a composite structure in the form of a laminated film / resin composite structure for metal / adhesive (patented) Reference 2).

  Although the adhesion between a metal part treated in Patent Document 1 and a molded article made of a resin composition is high, there are problems with the safety of the chemical solution used for surface treatment and the influence of the environment. In particular, hydrazine is highly toxic, and it is necessary to invest in a large-scale facility that can handle safety and environmental impact.

  The method of Patent Document 2 does not require a roughening process of the metal surface by using a chemical solution, but in order to join a metal and a resin, it is necessary to create an adhesive member for laminating two types of films having different affinities. In addition, the bonding strength of the metal / adhesive laminated film / resin composite structure obtained by the method is as low as about 3 MPa.

  Therefore, development of a metal / resin composite structure that can be more simply created and has excellent bonding strength is desired.

JP 2007-050630 A JP, 2013-091269, A

  Therefore, the problem to be solved by the present invention is to provide a composite structure having excellent adhesion, in which a metal member and a molded article of a polyarylene sulfide resin composition are joined, and a simple manufacturing method thereof. . Another object of the present invention is to provide a polyarylene sulfide resin composition having excellent adhesion to metal parts, and a molded article having excellent adhesion to metal parts, which is obtained by melt-forming the same, and a method for producing them. .

  As a result of conducting various studies, the inventors of the present application have found that a metal member and a molded article of a polyarylene sulfide resin composition, a polyolefin (a) having a group that reacts with a carbodiimide group, and an alicyclic carbodiimide group-containing compound By joining via the adhesive composition containing the polyolefin which is a reaction product with (b), it discovers that the composite structure which is excellent in adhesiveness can be manufactured simply, and came to solve the present invention.

That is, the present invention is a method for producing a composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3). ,
The bonding composition (3) includes a polyolefin which is a reaction product of a polyolefin (a) having a group which reacts with a carbodiimide group and a carbodiimide group-containing compound (b), a bonding method (A) or a bonding method Having (B) (however, bonding methods (A) and (B) are as follows,
Bonding method (A)
And bonding the metal member having the bonding composition (3) on the surface of the metal member to be bonded to the molded article (2) by melt-molding the polyarylene sulfide resin composition.
Bonding method (B)
A polyarylene sulfide resin composition in a state in which an adhesive composition (3) is in contact with the surface of the molded article to be bonded to the metal member (1) or the surface of the metal member to be bonded to the molded article (2) Bonding the metal member (1) and the molded article (2) through the bonding composition (3) at a temperature at which the metal melts. A manufacturing method characterized by the above.

Further, the present invention is a composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are joined via a polyolefin (3),
The polyolefin (3) is
(I) including a polyolefin which is a reaction product of a polyolefin (a) having a group reactive with a carbodiimide group and an alicyclic carbodiimide group-containing compound (b),
The present invention relates to a composite structure characterized by

The present invention also relates to a polyarylene sulfide resin composition used for a composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are joined via a polyolefin (3). And
The polyolefin (3) is
(I) including a polyolefin which is a reaction product of a polyolefin (a) having a group reactive with a carbodiimide group and an alicyclic carbodiimide group-containing compound (b),
The present invention relates to a polyarylene sulfide resin composition for a composite structure characterized by

The present invention also relates to a polyarylene sulfide resin composition used for a composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are joined via a polyolefin (3). Manufacturing method of
The polyolefin (3) is
(I) including a polyolefin which is a reaction product of a polyolefin (a) having a group reactive with a carbodiimide group and an alicyclic carbodiimide group-containing compound (b),
The polyarylene sulfide resin composition contains the polyarylene sulfide resin as an essential component, and is melt-kneaded;
The present invention relates to a method for producing a polyarylene sulfide resin composition for a composite structure, characterized in that

  According to the present invention, it is an object of the present invention to provide a composite structure having excellent adhesion, in which a metal member and a molded article of a polyarylene sulfide resin composition are joined, and a simple method for producing the same. Furthermore, the present invention can provide a polyarylene sulfide resin composition having excellent adhesion to metal parts, a molded article having excellent adhesion to metal parts, and a method for producing them, which is obtained by melt-molding the composition. .

FIG. 1 shows an embodiment of the bonding method (A), wherein the polyarylene sulfide resin is applied to a metal member having a bonding composition (3) on its surface, which is inserted in a mold (not shown). It is a process of injection molding using the composition. FIG. 2 shows an embodiment of the bonding method (B), in which the adhesive composition (3) is provided on the surface to be bonded to the molded product (left view), and then the metal member and the molded product are It is the process of heating and joining after contacting or heating and joining after joining (right figure).

(Complex structure)
The composite structure of the present invention is obtained by bonding a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition via an adhesive composition (3).

  In the present invention, the bonding of the metal member and the molded article is achieved by physical interaction between the surface of the metal member and the adhesive composition (3) such as van der Waals force, or in the adhesive composition (3). The group contained in the polyolefin is chemically bonded to the surface of the metal member, and further, physical interaction such as van der Waals force with the polyarylene sulfide resin composition or the polyarylene sulfide resin composition When the side includes a compound having a group having reactivity with a carbodiimide group, it is considered that the chemical bond exhibits excellent adhesion.

(Metal member (1))
Examples of the metal that constitutes the metal member include aluminum, copper, magnesium, iron, titanium, and alloys containing them. More specifically, iron, for example, stainless steel, steel, etc., iron as a main component, that is, 20% by weight or more, more preferably 50% by weight or more, still more preferably 80% by weight; , Alloys containing manganese, chromium, tungsten, molybdenum, phosphor, titanium, vanadium, nickel, zirconium, boron etc. (hereinafter referred to as iron alloys), aluminum or aluminum as a main component, copper, manganese, silicon, magnesium , Alloys containing zinc and nickel (hereinafter referred to as aluminum alloys), magnesium, and alloys containing magnesium, as well as zinc, aluminum, zirconium etc. (hereinafter referred to as magnesium alloys), copper and copper as main components As well as other alloys containing zinc, tin, phosphorus, nickel, magnesium, silicon, chromium Hereinafter, a copper alloy) and, or titanium, as a main component titanium, other copper, manganese, silicon, magnesium, zinc, alloys containing nickel (hereinafter, titanium alloy) and the like. Among these, iron, iron alloy, aluminum alloy, magnesium alloy, copper alloy, titanium alloy are more preferable, and iron alloy, aluminum alloy, magnesium alloy is more preferable.

  In the construction of the composite structure of the present invention, the surface roughening step is not necessary for the surface of the metal member (hereinafter simply referred to as the metal member surface), but of course the fine uneven surface (hereinafter simply referred to as fine uneven surface) on the metal member surface ) May be included. By applying the surface roughening treatment and providing a fine uneven surface on the surface of the metal member, the function of mechanical bonding is also added, and the adhesion can be further enhanced.

  By subjecting the surface of the metal member of the composite structure of the present invention to a surface roughening treatment to provide a fine asperity surface, the molten bonding composition (3) penetrates with good fluidity into the recesses of the fine asperity surface. By solidification, an interface with the metal member and the resin member constituting the molded article (hereinafter simply referred to as a metal-resin interface) is formed, and the metal member and the molded article of the polyarylene sulfide resin composition are strongly joined. It can be done.

  The distance between the minute projections and depressions on the metal part material surface is preferably in the range of 5 nm or more, and more preferably 10 nm or more, from the projection to the adjacent projection (hereinafter referred to as "between projections"). Is more preferred. The upper limit value is not particularly limited because it can flow in even if the fluidity is low, but is preferably 700 μm or less, and more preferably 500 μm or less, since the adhesiveness tends to be improved when the unevenness density is high. More preferably, it is in the range of When the length between the convex portions is in the above range, the adhesive composition (3) used in the present invention can enter the concave portions of the fine uneven surface with good adhesion or wettability, and is excellent at the metal-resin interface. Good adhesion. Furthermore, it is preferable that the interval between the concavo-convex portions have periodicity, because a more excellent adhesion can be exhibited at the metal-resin interface.

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

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

  Further, the uneven shape in the fine uneven surface is not particularly limited, and may be formed as a recess having a hole diameter smaller than the distance between the convex portions by surface roughening described later, and the surface roughening is further advanced The shape may be observed in a forested state as a rounded convex portion, that is, a protrusion having a three-dimensional surface such as a spherical shape, a cylindrical shape having a smooth end, or a shape like a wart or a saccharide sugar.

Although the method of surface roughening can use especially a well-known method without limitation, For example, three types of methods are mention | raise | lifted.
(1) Immersion method with aggressive aqueous solution or aggressive suspension. It is preferable that the metal surface has a shape in which a fine uneven surface is formed, 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 to set the concave portion in the range of 10 nm to 3 μm in number average inner diameter.
(2) Anodizing method. By forming a metal oxide layer mainly on the surface, it is preferable to form an opening having a range of a large number average inner diameter of 1 μm or less in the surface layer, and similarly an opening having a range of a number average inner diameter of 1 nm to 1 μm. It is more preferable to form a part, and it is more preferable to form an opening having a number average inner diameter of 10 to 200 nm as well.
(3) A method of forming irregularities on the metal surface by pressing a mold punch having irregularities formed by mechanical cutting, for example, diamond abrasive grinding or blasting, or forming an irregular shape on the metal surface by sand blasting or laser processing how to. It is preferable to mainly process the surface into a large number of recesses, and in the case of forming a number average inner diameter of the recesses or a recess having a continuous shape such as laser processing, the width is preferably in the range of 1 to 1000 μm. More preferably, it is in the range of 800 μm.

  The metal member is processed into a predetermined shape by cutting, metal working with a press or the like, punching, cutting, grinding, electric discharge machining or the like before forming the fine uneven surface described above. Is preferred.

  A primer layer may be formed on the surface of the metal member subjected to the surface treatment of the metal. Although the material which comprises a primer layer is not specifically limited, Usually, it consists of a primer resin material containing a resin component. The primer resin material is not particularly limited, and known materials can be used. Specifically, known polyolefin-based primers, epoxy-based primers, urethane-based primers and the like other than the polyolefin (3) described later can be mentioned. Although the formation method of a primer layer is not specifically limited, For example, the solution of said primer resin material and the emulsion of said primer resin material can be coated and formed in the metal member which performed the said surface treatment. Examples of the solvent used for forming a solution include toluene, methyl ethyl ketone (MEK), dimethylphosphoramide (DMF) and the like. Media for emulsions include aliphatic hydrocarbon media, water, and the like.

  Further, in the case of the film insert molding method, a structure in which a molded article of a polyarylene sulfide resin composition is joined to a resin film-like product in which a metal member layer is laminated in a film shape via a metal member layer. Get the body. The metal member layer may be formed on the resinous film by transferring or printing a film such as a metal foil, or by plating. At that time, as the resinous film material, it is possible to use polyethylene terephthalate (PET), polybutylene terephthalate (PBT) resin, polyethylene naphthalate (PEN) resin, polyamide 6, polyamide resin such as polyamide 66 (PA6, PA66), polyimide resin A resin film having heat resistance, such as a cured product of an active energy ray-polymerizable resin composition containing, as a main component, a polyiimide resin, a polyvinyl alcohol resin, and a (meth) acrylic resin containing a radically polymerizable unsaturated group Is preferably used. Among them, a PET resin film is most preferably used because it is excellent in cost, aesthetics and transparency. In addition, there is no restriction | limiting in particular, manufacture of the resin-made film-like substance which laminated | stacked the metal member layer in film form can also use a commercially available apparatus, and can also be performed according to a conventional method.

(Molded article of polyarylene sulfide resin composition (2))
The polyarylene sulfide resin composition of the present invention is formed by blending the polyarylene sulfide resin as an essential component with other components as necessary.

  The polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin as an essential component. The polyarylene sulfide resin used in the present invention has a resin structure in which a repeating unit has a structure in which an aromatic ring and a sulfur atom are bonded, and more specifically, the following general formula (1)

(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, an ethoxy group). Structural site and, if necessary, the following general formula (2)

It is resin which makes a trifunctional structural site represented by these, and a repeating unit. The range of 0.001 to 3 mol% is preferable, and the range of 0.01 to 1 mol% is particularly preferable with respect to the total number of moles with other structural parts. Is preferred.

Here, the structural moiety represented by the general formula (2) is preferably a hydrogen atom from the viewpoint of mechanical strength of the polyarylene sulfide resin, in particular, R ¹ and R ² in the formula In the case, those bonded at the para position represented by the following formula (3) and those bonded at the meta position represented by the following formula (4) can be mentioned.

  Among these, it is particularly preferred that 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 (3), in the heat resistance and crystallinity of the polyarylene sulfide resin. Preferred in terms of

  Moreover, the said polyarylene sulfide resin is not only the structural part represented by the said General formula (1) or (2), but following Structural formula (5)-(8)

The structural moiety represented by may be contained in an amount of 30 mol% or less of the total of the structural moiety represented by the general formula (1) and the general formula (2). In particular, in the present invention, it is preferable that the structural parts represented by the above general formulas (5) to (8) be 10 mol% or less from the viewpoints of heat resistance and mechanical strength of the polyarylene sulfide resin. When the polyarylene sulfide resin contains structural sites represented by the above general formulas (5) to (8), the bonding manner thereof may be either a random copolymer or a block copolymer. Good.

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

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 polyarylene sulfide resin is preferably in the range of 270 ° C. or higher, 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. It is more preferable that In addition, the recrystallization temperature (Tc2) of the polyarylene sulfide resin is preferably in the range of 200 to 260 ° C. because it becomes a polyarylene sulfide resin composition excellent in heat resistance and mechanical strength.

(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 furthermore, the balance of fluidity and mechanical strength is good Thus, 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 a polyarylene sulfide resin using Shimadzu flow tester CFT-500D, 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10 (mm The melt viscosity is a value measured after holding for 6 minutes at 1) (1 mm).

(Non-Newtonian index)
The non-Newtonian index of the polyarylene sulfide resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably in the range of 0.90 to 2.00. When a linear polyarylene sulfide resin is used, the non-Newtonian index is preferably in the range of 0.90 to 1.50, and more preferably in the range of 0.95 to 1.20. Such polyarylene sulfide resin is excellent in mechanical physical properties, fluidity, and abrasion resistance. However, for non-Newtonian index (N value), shear rate and shear stress were measured under the condition of 300 ° C, ratio of orifice length (L) to orifice diameter (D), L / D = 40 using Capirograph. , It is the value calculated using the following formula.

[However, SR shows a shear rate (sec- ¹ ), SS shows a shear stress (dyne / cm < ² >), and K shows 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, the more branched the structure is.

(Production method)
The method for producing the polyarylene sulfide resin is not particularly limited. For example, 1) a dihalogeno aromatic compound in the presence of sulfur and sodium carbonate, if necessary a polyhalogeno aromatic compound or other copolymerization component is added, Method of polymerizing, 2) Method of polymerizing a dihalogeno aromatic compound in a polar solvent in the presence of a sulfidizing agent and the like, if necessary a polyhalogeno aromatic compound or other copolymerization components, 3) p-chloro There is a method of self-condensing ruthiophenol, if necessary, adding other copolymerizable components, and the like. Among these methods, the method 2) is versatile and preferred. During the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or alkali hydroxide may be added to adjust the degree of polymerization. Among the above methods 2), the hydrous sulfidizing agent is introduced into the mixture containing the heated organic polar solvent and the dihalogeno aromatic compound at a rate such that water can be removed from the reaction mixture, and the dihalogeno aromatic compound is dissolved in the organic polar solvent And sulfidizing agent, if necessary, added with polyhalogeno aromatic compound to make them react, and the amount of water in the reaction system in the range of 0.02 to 0.5 mol per mol of the organic polar solvent A method of producing a polyarylene sulfide resin by control (see JP-A-H07-228699) or a dihalogeno aromatic compound in the presence of solid alkali metal sulfide and aprotic polar organic solvent, if necessary A polyhalogeno aromatic compound or other copolymerization component is added, an alkali metal hydrosulfide and an organic acid alkali metal salt, a sulfur source 1 The amount of the organic acid alkali metal salt in the range of 0.01 to 0.9 mol per mol and the water content in the reaction system are controlled to the range of 0.02 mol or less per mol of the aprotic polar organic solvent Those obtained by the reaction method (see WO 2010/058713 pamphlet) are particularly preferred. 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 Compounds having an alkyl group in the range of 1 to 18 carbon atoms in the aromatic ring thereof, and examples of polyhalogenoaromatic compounds include Benzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6- Trihalo naphthalene etc. are mentioned. Moreover, as for the halogen atom contained in said each compound, it is desirable that they are a chlorine atom and 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 completion of the polymerization reaction, the reaction mixture may be used as it is, or as acid or base Then, the solvent is distilled off under reduced pressure or normal pressure, and then the solid product after evaporation of the solvent is water, a reaction solvent (or an organic solvent having an equivalent solubility to a low molecular weight polymer), acetone, methyl ethyl ketone , Washing with a solvent such as alcohols one or more times, and further neutralizing, washing with water, filtering and drying, or (2) water, acetone, methyl ethyl ketone, alcohols, etc. in the reaction mixture after completion of the polymerization reaction Solvents such as ethers, halogenated hydrocarbons, aromatic hydrocarbons and aliphatic hydrocarbons (soluble in the polymerization solvent used, and at least Method to add solid solvent such as polyarylene sulfide and inorganic salt by adding a solvent which is a poor solvent to rearylene sulfide as a precipitating agent, and filtering these, filtering, washing and drying, or (3) After completion of the polymerization reaction, a reaction solvent (or an organic solvent having equivalent solubility to a low molecular weight polymer) is added to the reaction mixture and stirred, followed by filtration to remove a low molecular weight polymer, water, Washing with a solvent such as acetone, methyl ethyl ketone or alcohols one or more times, followed by neutralization, washing with water, filtration and drying, (4) After completion of the polymerization reaction, add water to the reaction mixture and wash with water, A method of acid treatment at the time of filtration, if necessary water washing, 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 the reaction solvent Wash Further washing with water, a method of filtering and drying, and the like.

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

  The polyarylene sulfide resin composition of the present invention can also contain a compound (2a) having reactivity with a carbodiimide group as an optional component. When it is blended, the ratio is preferably in the range of 0.01 to 100 parts by weight, more preferably in the range of 0.01 to 100 parts by weight, still more preferably 0.01 to 100 parts by weight of the polyarylene sulfide resin. And 100 parts by weight.

  As such a compound (2a), any compound having a functional group represented by an epoxy group, an alcoholic hydroxyl group, a carboxy group, or a carboxylic acid anhydride group (-(CO) O (CO)-) is known. The following compounds can be used. For example, epoxy resin, epoxy group-containing polyolefin and the like can be mentioned.

  The epoxy resin used in the present invention is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include bisphenol epoxy resins, novolac epoxy resins, and epoxy resins having a polyarylene ether structure (α). Among these, bisphenol-type epoxy resin is mentioned as a preferable thing from the thing which is excellent in adhesiveness.

  Examples of the epoxy resin of the bisphenol type epoxy resin include glycidyl ethers of bisphenols, and specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, Examples thereof include bisphenol S epoxy resin, bisphenol AD epoxy resin, and tetrabromobisphenol A epoxy resin. In the case of a bisphenol epoxy resin, the epoxy equivalent is 170 to 5000 [g / eq. It is preferable that it is in the range of 200 to 4000 g / eq. From the viewpoint that the amount of gas generation can be further reduced and the viewpoint that the thermal shock resistance is improved. The thing of the range of is preferably mentioned.

  Further, as the type of novolac type epoxy resin, novolac type epoxy resin obtained by reacting a novolac type phenol resin obtained by condensation reaction of a phenol and an aldehyde with an epihalohydrin can be mentioned. Specific examples thereof include phenol novolac. Epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin, naphthol-phenol co-convoluted novolac epoxy resin, naphthol-cresol co-convoluted novolac epoxy resin, brominated phenol novolac epoxy resin. When the epoxy resin is a novolak type epoxy resin, the epoxy equivalent is 170 to 300 g / eq. From the viewpoint of improving the thermal shock resistance and the fluidity and the adhesiveness with the metal member. The range of 190 to 250 [g / eq. The thing of the range of is more preferable.

  These epoxy resins contained in the polyarylene sulfide resin composition used in the present invention may be melted and kneaded in the presence of a component acting as a so-called curing agent, such as a phenol resin, an amine (active hydrogen compound) or a carboxylic acid anhydride. Since the epoxy group disappears by the curing reaction (addition reaction with an active hydrogen compound, copolycondensation reaction with an acid anhydride), the proportion of the curing agent component in the polyarylene sulfide resin composition is the epoxy in the epoxy resin component The active group in the curing agent is at most 0.1 equivalent, more preferably at most 0.01 equivalent, most preferably at most 0 equivalent, ie in the absence, relative to a total of 1 equivalent of groups.

  When an epoxy resin is used as the compound (2a) in the present invention, the proportion thereof is not particularly limited as long as the effects of the present invention are not impaired, but 0.01 to 100 with respect to 100 parts by weight of the polyarylene sulfide resin. It is preferably in the range of parts by weight, more preferably in the range of 0.5 to 20 parts by weight, and most preferably in the range of 1 to 15 parts by weight.

  Moreover, when using an epoxy-group-containing polyolefin as said compound (2a), although the olefin-type elastomer which has an epoxy group can be mentioned specifically as this epoxy-group-containing polyolefin, Especially preferably, with alpha-olefins, It can be obtained by copolymerization with the vinyl polymerizable compounds having an epoxy group. Examples of the α-olefins include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene and butene-1. Examples of vinyl polymerizable compounds having an epoxy 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 and itaconic acid And other unsaturated dicarboxylic acids having 4 to 10 carbon atoms and mono and diesters thereof, α, β-unsaturated dicarboxylic acids and their derivatives such as acid anhydrides thereof, and glycidyl (meth) acrylate, etc. Among them, ethylene-propylene copolymers having an epoxy group in the molecule, or ethylene-butene copolymers are preferred for the improvement of toughness and impact resistance. In addition, since the olefin wax which has an epoxy group also has an epoxy group as a polar group and has polyolefin as a nonpolar group, it shall be contained in the olefin which has said epoxy group.

  When an epoxy group-containing polyolefin is used as the compound (2a) in the present invention, the proportion thereof is not particularly limited as long as the effects of the present invention are not impaired, but 0.01 relative to 100 parts by weight of the polyarylene sulfide resin The amount is preferably in the range of 100 to 100 parts by weight, more preferably in the range of 0.1 to 50 parts by weight, and particularly preferably in the range of 1 to 20 parts by weight.

  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 for example, various shapes such as fibrous, non-fibrous such as granular or plate, etc. Fillers and the like can be mentioned. Specifically, fibrous fillers such as glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, fibers such as potassium titanate, silicon carbide, calcium silicate and wollastonite, natural fibers, 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 it is blended, the proportion of the blend is not particularly limited as long as the effects of the present invention are not impaired, and it differs depending on the respective purposes. Although it can not be carried out, for example, the amount is preferably in the range of 1 to 600 parts by weight, and more preferably in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin. 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 optionally contain other thermoplastic elastomer as an optional component. As a thermoplastic elastomer, polyolefin-type elastomers other than the above, a fluorine-type elastomer, or a silicone type elastomer is mentioned. When these elastomers are compounded, the proportion of the compounding is not particularly limited as long as the effects of the present invention are not impaired, and it differs depending on the respective purposes, and can not be generally specified, but polyarylene sulfide resin The amount is preferably in the range of 0.01 to 10 parts by weight, and more preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight. Such a range is preferable because the impact resistance of the resulting polyarylene sulfide resin composition is improved.

  Furthermore, in addition to the above components, the polyarylene sulfide resin composition of the present invention may be any synthetic resin other than the above polyarylene sulfide resin and the above compound (2a), for example, a polyester resin. Polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polyetheretherketone resin, polyetherketone resin, polyarylene resin, polyethylene resin, polypropylene resin, polytetramer A fluorinated ethylene resin, a polydifluorinated ethylene resin, a polystyrene resin, an ABS resin, a phenol resin, a urethane resin, a liquid crystal polymer, etc. (hereinafter simply referred to as a synthetic resin) can be blended as an optional component. In the present invention, the synthetic resin is not an essential component, but when compounded, the proportion of the compound is not particularly limited as long as the effects of the present invention are not impaired, and it differs according to each purpose. Although it can not be specified, the polyarylene sulfide resin and the compound (2a) as a ratio of the resin component (the total of the polyarylene sulfide resin, the polyvinyl pyrrolidone and the synthetic resin) blended in the polyarylene sulfide resin composition of the present invention In the range of not more than 25.0% by weight, preferably 0.01% by weight of the above synthetic resin so that the total of the above becomes 75.0% by weight or more, preferably 80 to 99.99% by weight. In the range of -20.0% by weight, it may be appropriately adjusted and used 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 may further contain a coloring agent, an antistatic agent, an antioxidant, a heat resistant stabilizer, an ultraviolet light stabilizer, an ultraviolet light absorber, a foaming agent, a flame retardant, a flame retardant auxiliary, Known and conventional additives such as a rust agent and a coupling agent may be blended as an optional component as required. These additives are not essential components, but when compounded, the proportions of the additives are not particularly limited as long as the effects of the present invention are not impaired, and they differ depending on the respective purposes, and it is generally defined Although it can not be used, for example, it is suitably adjusted and used in a range of preferably 0.01 to 1,000 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin according to the purpose and application so as not to impair the effects of the present invention. Just do it.

  In the method for producing the polyarylene sulfide resin composition of the present invention, the polyarylene sulfide resin is used as an essential component, and other optional components are blended as necessary, and melt kneading is performed at or above the melting point of the polyarylene sulfide resin.

  In a preferred method for producing the polyarylene sulfide resin composition of the present invention, the polyarylene sulfide resin and the above-mentioned optional components are in various forms such as powder, pellets, strips, etc., so as to obtain the blending ratio described above. The mixture is charged in a mixer or V blender and dry-blended, and then charged in a known melt kneader such as a Banbury mixer, mixing roll, single or twin screw extruder and kneader, and the resin temperature is the melting point of polyarylene sulfide resin Process for melting and kneading in the temperature range above, preferably the melting point + 10 ° C. or more, more preferably the melting point + 10 ° C. to the melting point + 100 ° C., still more preferably the melting point +20 to the melting point + 50 ° C. Can be manufactured. The addition and mixing of the respective components to the melt-kneader may be carried out simultaneously or separately.

  The melt kneader is preferably a twin-screw kneader from the viewpoint of dispersibility and productivity, and for example, the discharge amount of the resin component is in the range of 5 to 500 (kg / hr) and the screw rotation speed is 50 to 500 (rpm). It is preferable to perform melt-kneading while appropriately adjusting the range of (1) and (2) melt-kneading under the condition that their ratio (discharge amount / screw rotation speed) is in the range of 0.02 to 5 (kg / hr / rpm). Is more preferred. Moreover, when adding a filler and an additive among the said components, it is preferable to inject | throw-in in this extruder from the side feeder of the said twin-screw kneading extruder from a dispersible viewpoint. It is preferable that the ratio of the distance from the said extruder resin injection | throwing-in part to this side feeder to the position of this side feeder is 0.1-0.9 with respect to the screw whole length of the said twin-screw kneading extruder. Among them, 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 way is a melt mixture containing the polyarylene sulfide resin as an essential component, optional components to be added as necessary, and components derived from them. After melt-kneading, it is preferably processed into the form of pellets, chips, granules, powder and the like by a known method, and if necessary, subjected to preliminary drying at a temperature of 100 to 150 ° C. to be subjected to various moldings.

  The polyarylene sulfide resin composition of the present invention produced by the above production method has a polyarylene sulfide resin as a matrix, and forms a morphology in which the optional component is dispersed, if an optional component is added as needed. As a result, when the compound (2a) having reactivity with a carbodiimide group is further contained in the polyarylene sulfide resin composition between the polyolefin (3) and the polyarylene sulfide resin (A), the compound (2) It is considered that it forms a chemical bond with 2a) and exhibits excellent adhesion.

  The molded object of the polyarylene sulfide resin composition of this invention is obtained by melt-molding the said polyarylene sulfide resin composition. Melt molding may be a known method, for example, various molding methods such as injection molding, compression molding, extrusion molding of composites, sheets, pipes, etc., pultrusion molding, blow molding, transfer molding, etc. can be applied, but in particular injection molding Is suitable. In the case of molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a generally common method. For example, in the injection molding machine, the resin temperature is a temperature range equal to or higher than the melting point of the polyarylene sulfide resin, preferably a temperature range equal to the melting point + 10 ° C. or more, more preferably a melting point + 10 ° C. to a melting point + 100 ° C., still more preferably a melting point After passing through the step of melting the polyarylene sulfide resin composition in the temperature range of +20 to the melting point + 50 ° C., the composition may be injected from the resin discharge port into the mold and molded. At that time, the mold temperature is also preferably in a known temperature range, for example, a range of room temperature (23 ° C.) to 300 ° C., more preferably 40 to 200 ° C., and set in a temperature range of 120 to 180 ° C. Most preferred.

(Composition for bonding (3))
The adhesive composition (3) used in the present invention contains a polyolefin that is a reaction product of a polyolefin (a) having a group that reacts with a carbodiimide group and a carbodiimide group-containing compound (b).

  The polyolefin (a) having a group that reacts with a carbodiimide group can be obtained by introducing a compound (a2) having a group that reacts with a carbodiimide group into the polyolefin (a1). The polyolefin (a) may be used alone or in combination of two or more.

  Examples of the compound (a2) include compounds having a group having an active hydrogen having reactivity with a carbodiimide group. Specifically, compounds having a group derived from a carboxylic acid, an amine, an alcohol, a thiol and the like can be mentioned. Among these, compounds having a group derived from a carboxylic acid are suitably used, and among them, unsaturated carboxylic acids and / or their derivatives are particularly preferable. In addition to compounds having a group having active hydrogen, compounds having a group that is easily converted to a group having active hydrogen by water or the like can also be preferably used. Specifically, compounds having an epoxy group and compounds having a glycidyl group can be mentioned. The compound (a2) may be used alone or in combination of two or more.

  When an unsaturated carboxylic acid and / or a derivative thereof is used as the compound (a2), an unsaturated compound having one or more carboxylic acid groups and a derivative thereof, preferably an unsaturated compound having one or more carboxylic anhydride groups and The derivative is mentioned. As unsaturated group, a vinyl group, vinylene group, unsaturated cyclic hydrocarbon group is mentioned, for example. Specific compounds include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2.2.1] hept-2 And unsaturated carboxylic acids such as -ene-5, 6-dicarboxylic acid, acid anhydrides thereof, and derivatives thereof (for example, acid halides, amides, imides, esters, etc.). As specific acid anhydrides and derivatives, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid Anhydride: Malenyl chloride; Malenyl imide; Dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, dimethyl citraconate, dimethyl tetrahydrophthalate, bicyclo [2.2.1] hept-2-ene Dimethyl-5,6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl (meth) acrylate and aminopropyl (meth) acrylate.

  When an unsaturated carboxylic acid and / or a derivative thereof is used as the compound (a2), one type may be used alone, or two or more types may be used. Among these, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, (meth) acrylic acid Preferred are hydroxyethyl (meth) acrylate, glycidyl methacrylate and aminopropyl methacrylate. Furthermore, dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic anhydride, etc. are particularly preferred. preferable.

  As a method of introducing the compound (a2) into the polyolefin (a1), a known method can be adopted. For example, a method of graft copolymerizing the compound (a2) to the polyolefin (a1), an olefin The method of radically copolymerizing (a1) and a compound (a2) is mentioned. The case of graft copolymerization and the case of radical copolymerization will be separately described below.

(Graft copolymerization)
The polyolefin (a) having a group that reacts with a carbodiimide group is a compound (a2) that has a group that reacts with a carbodiimide group in the polyolefin (a1), and optionally other ethylenically unsaturated monomers, etc. It is possible to obtain by graft copolymerization in the presence of an agent.

(Polyolefin (a1))
The polyolefin (a1) used as the main chain of the polyolefin (a) is a polymer mainly composed of an aliphatic α-olefin having a carbon number of 2 to 20, a cyclic olefin and a nonconjugated diene, preferably carbon It is a polymer having an aliphatic α-olefin in the range of 2 to 10 atoms, more preferably an aliphatic α-olefin in the range of 2 to 8 carbon atoms as a main component. These olefins may be used alone or in combination of two or more. In the case of a copolymer, the content of an olefin as a comonomer is not particularly limited as long as the effects of the present invention can be obtained, but is usually 50 mol% or less, preferably 40 mol% or less, more preferably 30 mol% or less is there. Among polyolefins in such a range, polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and α-olefins of ethylene, propylene, butene-1 or 4-methylpentene-1 and a comonomer Crystalline polyolefins such as copolymers are preferred, and polyethylene, polypropylene or propylene-ethylene copolymers are more preferred. Moreover, these can be used in both an isotactic structure and a syndiotactic structure, and there is no particular limitation on the stereoregularity.

The density (measured according to JIS K7112) of the polyolefin (a1) used for graft modification is not particularly limited as long as the effects of the present invention are exhibited, but for example, a range of 0.8 to 1.1 g / cm ³ is preferable The range of 0.8 to 1.05 g / cm ³ is more preferable, and the range of 0.8 to 1.0 g / cm ³ is more preferable. The melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg according to ASTM D1238 is not particularly limited as long as the effects of the present invention are exhibited, but a range of 0.01 to 500 g / 10 min is preferable, 0.05 to 200 g / min. The range of 10 minutes is more preferable, and the range of 0.1 to 100 g / 10 minutes is more preferable. If the density and the MFR are in this range, the density of the graft copolymer after modification and the MFR will be comparable, and it is easy to handle and preferable.

  The degree of crystallization of the polyolefin (a1) used for graft modification is not particularly limited as long as the effects of the present invention are exhibited, but for example, a range of 2% or more is preferable, a range of 5% or more is more preferable, 10% The above range is more preferable. If the degree of crystallinity is in this range, it is preferable because the handling of the graft copolymer after modification is excellent.

  The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the polyolefin (a1) used for graft modification is preferably in the range of 5,000 to 500,000, and more preferably in the range of 10,000 to 100,000. . When the number average molecular weight (Mn) is in this range, the handling is excellent. The number average molecular weight may be determined in terms of polyethylene when the amount of comonomer is 10 mol% or less and in ethylene-propylene conversion (based on 70 mol% of ethylene content) when the amount of comonomer is 10 mol% or less. It is preferable because it is possible.

  The production of the polyolefin (a1) used for graft modification can be carried out by any conventionally known method, and for example, an olefin can be polymerized using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, etc. . Further, the polyolefin used for graft modification may be any form of resin and elastomer, and both of isotactic structure and syndiotactic structure can be used, and there is no particular limitation on stereoregularity. It is also possible to use commercially available resins as they are.

(Graft polymerization method)
The method for grafting the compound (a2) to the polyolefin (a1) is not particularly limited, and conventionally known graft polymerization methods such as a solution method and a melt-kneading method can be adopted.

The amount of the compound (a2) to be grafted is preferably 0.05 to 20% by weight, more preferably 0.05 to 10% by weight, based on 100% by weight of the polyolefin (a). The range of 05 to 5% by weight is more preferable, and the range of 0.05 to 3% by weight is most preferable. The grafting amount of the compound (a2) is a net grafting amount measured after removing the free compound (a2) from the polyolefin (a). The grafting amount can be determined by a known means such as ¹³ C-NMR or ¹ H-NMR measurement. When a monomer having an acidic functional group such as unsaturated carboxylic acid and its acid anhydride is used as the compound (m), the amount serving as a measure of the amount of the functional group introduced into the polyolefin (a) is For example, it is also possible to use an acid value. When maleic anhydride is used as the compound (m), the grafting amount is measured based on the absorption spectrum of the carbonyl group of maleic anhydride which is usually detected in the vicinity of 1780 to 1790 cm ⁻¹ using an infrared spectrophotometer. You can also ask for

(Radical copolymerization)
The polyolefin (a) having a group that reacts with a carbodiimide group can also be obtained by radical copolymerization of an olefin (a1 ′) and a compound (a2) that has a group that reacts with a carbodiimide group. As olefin (a1 '), it is possible to employ the same olefin as in the case of forming polyolefin (a1) used as the above-mentioned polyolefin main chain. It does not specifically limit about the method to copolymerize an olefin (a1 ') and a compound (a2), The conventionally well-known radical copolymerization method is employable.

(Composition of polyolefin (a))
The amount (example: structural unit amount, grafting amount) derived from the compound (a2) having a group that reacts with a carbodiimide group in the polyolefin (a) that has a group that reacts with a carbodiimide group is particularly limited within a known range. Although it is not a thing, the range of 0.05 to 20 weight% is preferable, the range of 0.05 to 5 weight% is more preferable, and the range of 0.05 to 3 weight% is more preferable. If the amount derived from the compound (m) having a group that reacts with a carbodiimide group is within the above range, the polyolefin (a) and the carbodiimide group-containing compound (a2) are suitably crosslinked to produce an adhesive composition It is preferable because it becomes possible. Above the lower limit value of the above range, a more excellent adhesion is obtained, which is preferable.

Moreover, the density (measured according to JIS K7112) of the polyolefin (a) having a group that reacts with a carbodiimide group is not particularly limited as long as it is a known range, but 0.870 to 0.940 g / The range of cm ³ is preferable, the range of 0.875 to 0.940 g / cm ³ is more preferable, and the range of 0.880 to 0.940 g / cm ³ is more preferable.

(Carbodiimide-containing compound (b))
The carbodiimide group-containing compound (b) is, for example, a polycarbodiimide having a repeating unit represented by the general formula (9). The carbodiimide group-containing compound (b) may be used alone or in combination of two or more.

Wherein (9), ^{R 3} represents a divalent organic group of 2 to 40 carbon atoms.

  Polycarbodiimides can be produced by a known method in which diisocyanates such as aliphatic diisocyanates, aromatic diisocyanates and alicyclic diisocyanates are subjected to a decarboxylation condensation reaction in the presence of a condensation catalyst in the absence or in an inert solvent. it can.

(Method for producing polycarbodiimide)
The polycarbodiimide used in the present invention can be produced by various methods using a diisocyanate compound as a raw material. For example, a method of producing an isocyanate-terminated polycarbodiimide by a decarboxylation condensation reaction involving decarbon dioxide of a diisocyanate compound (US Pat. No. 2,941,956 or JP-B-47-33279, J. Org. Chem, 28, 2069) -2075 (1963), Chemical Review 1981, Vol. 81, No. 4, p619-621 etc.).

  The decarboxylation condensation reaction of the above diisocyanate compound proceeds in the presence of a carbodiimidization catalyst. The carbodiimidization catalyst includes, for example, 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3 -Methyl-2-phospholene-1-oxide and phosphorene oxides such as 3-phospholene isomers thereof, and the like, and among them, among these, from the viewpoint of reactivity, 3-methyl-1-phenyl-2- can be mentioned. Phosphorene-1-oxide is preferred. The amount of the carbodiimidization catalyst is preferably in the range of 0.1 to 1.0% by weight with respect to the alicyclic diisocyanate compound used for the carbodiimidization.

  The decarboxylation condensation reaction of the diisocyanate compound can be carried out without a solvent or can be carried out in an inert solvent. As an inert solvent which can be used, alicyclic ethers such as tetrahydroxyfuran (THF), 1,3-dioxane, dioxolane and the like: aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene: chlorobenzene, dichlorobenzene, trichlorobenzene Halogenated hydrocarbons such as perchlorene, trichloroethane and dichloroethane: Ester solvents such as ethyl acetate and butyl acetate: and organic solvents such as ketone solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone and cyclohexanone. One of these may be used alone, or two or more may be combined. Among these, toluene, tetrahydroxy furan and methyl ethyl ketone are preferable.

  The temperature in the above decarboxylation condensation reaction is not particularly limited, but is preferably in the range of 40 to 200 ° C., more preferably in the range of 50 to 130 ° C. When the reaction is carried out in an inert solvent, it is preferably in the range of 40 ° C. to the boiling point of the solvent.

  As diisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, 2,2-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, xylylene Hydrogenated diisocyanates such as aromatic diisocyanates, hydrogenated xylylene diisocyanate, dicyclohexylmethane-2,2'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, polymeric MDI , 1,4-cyclohexane diisocyanate, trans 1,4-bis (isocyanatomethyl) cyclohexane, cyclohexane-1,2 Diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, alicyclic diisocyanates such as isophorone diisocyanate is used singly or mixed.

  In the present invention, among the alicyclic, aliphatic and aromatic diisocyanates, a polycarbodiimide compound obtained by a decarboxylation condensation reaction using an alicyclic diisocyanate as a main component is preferable from the viewpoint of exhibiting more excellent adhesion. In that case, the alicyclic diisocyanate may be used in combination with an aliphatic diisocyanate or an aromatic diisocyanate from the viewpoint of heat resistance, fluidity, gelation suppression, and the like, as long as the effects of the present invention are not impaired. When aliphatic and / or aromatic diisocyanates are used in combination, alicyclic diisocyanate is preferably in the range of 50% by weight or more, more preferably 80% by weight or more, based on the total of alicyclic, aliphatic and aromatic diisocyanates. , More preferably 90 wt% or more, and most preferably 100 wt%.

  In the present invention, “alicyclic diisocyanate” means a diisocyanate compound having a cyclic aliphatic hydrocarbon having no aromaticity in the molecule, and “aliphatic diisocyanate” means that an isocyanate group is removed in the molecule, A diisocyanate compound having a linear aliphatic hydrocarbon and having neither a cyclic aliphatic hydrocarbon nor an aromatic hydrocarbon, "aromatic diisocyanate" refers to a diisocyanate having an aromatic hydrocarbon in the molecule Refers to a compound.

  In the decarboxylation condensation reaction, the degree of polymerization of polycarbodiimide can be controlled by adjusting the amount of catalyst, the reaction temperature, and selecting and adding an end capping agent, a modifier and the like. The polymerization degree is preferably in the range of 2 to 40, and more preferably in the range of 4 to 20. As the end capping agent, for example, monoisocyanate such as phenyl isocyanate, tolyl isocyanate and naphthyl isocyanate, and active hydrogen-containing compounds such as methanol, ethanol, diethylamine, cyclohexylamine, succinic acid, benzoic acid and ethyl mercaptan can be used. As the condensation catalyst, for example, organophosphorus compounds such as alcoholates such as titanium, hafnium, zirconium, sodium, calcium and the like and phosphalene oxide can be used.

  In the present invention, as the carbodiimide group-containing compound (b), a compound having a molecular weight controlled to an appropriate degree of polymerization can also be used by using a compound that reacts with the terminal isocyanate group of polycarbodiimide such as monoisocyanate. As monoisocyanate for sealing the end of polycarbodiimide and controlling the polymerization degree in this way, for example, phenyl isocyanate, p- and m-tolyl isocyanate, p-isopropylphenyl isocyanate and the like can be used. In particular, phenyl isocyanate is suitably used.

  In the present invention, as the carbodiimide group-containing compound (b), one modified with a compound capable of reacting with isocyanate can also be used. Compounds capable of reacting with isocyanate include methanol having hydroxyl group, isopropyl alcohol, phenol, polyethylene glycol monomethyl ether etc .: amine such as butylamine having amino group, diethylamine etc .: propionic acid having carboxy group, benzoic acid etc. and acid anhydride Among them, it is preferable to use an amine, particularly an aliphatic amine.

(Modification of polycarbodiimide with aliphatic amine)
As the carbodiimide group-containing compound (b) used in the present invention, it is preferable to use a compound modified with polycarbodiimide using an aliphatic amine as a compound capable of reacting with the above-mentioned isocyanate. The modification of polycarbodiimide with aliphatic amine can be carried out without solvent, but the above polycarbodiimide is mixed with an organic solvent, to which an aliphatic amine is added so as to be a predetermined equivalent to a carbodiimide group, and stirred It can also be synthesized by reacting it. The amount of aliphatic amine added in the case of using an organic solvent is preferably in the range of 1 to 2 equivalents relative to 1 equivalent of carbodiimide group, and the amount of excess aliphatic amine is small, and the amine dissipates during heat treatment. More preferably, it is in the range of 1 to 1.2 equivalents in terms of easiness. The reaction temperature of the modification of polycarbodiimide with aliphatic amine is preferably in the range of normal temperature (about 25 ° C.) to 80 ° C., preferably 40 to 80 ° C., from the viewpoint of suppressing the reaction rate and side reactions during modification. Is more preferable. The modification of the polycarbodiimide with an aliphatic amine is preferably carried out with stirring, and the reaction time varies depending on the temperature, but is preferably about 0.1 to 10 hours.

(Aliphatic amine)
As aliphatic amines capable of modifying polycarbodiimides, diethylamine, methylisopropylamine, tert-butylethylamine, di-sec-butylamine, dicyclohexylamine, 2-methylpiperidine and the like because of high dissociativeness from polycarbodiimides At least one aliphatic amine selected from the group consisting of 2,6-dimethylpiperidine, preferably diethylamine, tert-butylethylamine, di-sec-butylamine, dicyclohexylamine, 2-methylpiperidine and 2,6 -At least one aliphatic amine selected from the group consisting of -dimethylpiperidine, more preferably diethylamine, tert-butylethylamine, di-sec-butylamine, dicyclohexyl At least one aliphatic amine can be mentioned is selected from the Min and the group consisting of 2-methyl-piperidine, further preferably di -sec- butylamine.

  The group formed by modifying the carbodiimide group with an aliphatic amine (hereinafter referred to as carbodiimide modifying group) is excellent in storage stability due to low reactivity, but the aliphatic amine is dissociated from polycarbodiimide. The carbodiimide modification then reverts to the carbodiimide group prior to modification with the aliphatic amine. As described above, since the reactivity of the carbodiimide group is high, when the aliphatic amine is dissociated from the polycarbodiimide, it adheres to the polyarylene sulfide resin composition with good adhesiveness by the formed carbodiimide group. Moreover, since the number of carbodiimide groups changed from a carbodiimide modification group will increase, so that the dissociative property from the polycarbodiimide in aliphatic amine is high, it adhere | attaches with a polyarylene sulfide resin composition with sufficient adhesiveness.

For example, when the aliphatic amine is NHR ⁴ R ⁵ and (R ⁴ , R ⁵ is a hydrogen atom or a C 1-6 aliphatic group, or R ⁴ and R ^{5 form} a C6 alicyclic structure), the formula (9 When a polycarbodiimide derived from a diisocyanate compound having a carbodiimide group of the above is modified with an aliphatic amine, a carbodiimide modifying group of the formula (10) is formed. The carbodiimide-modified group of formula (10) is less reactive due to steric hindrance of the moiety of formula (11) in formula (10). And when the part of Formula (11) dissociates, the carbodiimide group of Formula (9) with high reactivity will be formed, and a modified polycarbodiimide compound will harden a resin composition. Therefore, R ⁴ and R ⁵ are preferably a C1-6 aliphatic group, or one having a C6 alicyclic structure with R ⁴ and R ⁵ , that is, a secondary aliphatic amine.

  The polystyrene-equivalent number average molecular weight (Mn) determined by gel permeation chromatography (GPC) of the carbodiimide group-containing compound (b) is not particularly limited as long as the effects of the present invention are exhibited, but the range of 400 to 500,000 is Preferably, the range of 700 to 10,000 is more preferable, the range of 1,000 to 8,000 is more preferable, and the range of 1,000 to 4,000 is most preferable. It is preferable for the number average molecular weight (Mn) to be in this range because the adhesion of the adhesive composition is excellent.

  The carbodiimide group-containing compound (b) may contain monocarbodiimide in polycarbodiimide, and it is also possible to use one or more compounds in mixture.

  In the present invention, it is also possible to use a commercially available carbodiimide group-containing compound as it is.

  Further, in the present invention, as the number of carbodiimide groups in one molecule of the carbodiimide group-containing compound (b) increases, the number of reaction points increases, and hence the adhesion is more excellent. From this, it is preferable to use a carbodiimide group-containing compound (b) in which the number of carbodiimide groups in one molecule is 5 or more, and it is more preferable to use a carbodiimide group-containing compound (b) in a range of 10 or more. The upper limit of the number of carbodiimide groups in one molecule is not particularly limited as long as the effects of the present invention are exhibited, but when the number of carbodiimide groups in one molecule increases, a crosslinked structure via the carbodiimide group-containing compound (b) is easily formed Since the moldability may be deteriorated, the range of 30 or less is preferable.

The content of the carbodiimide group in the carbodiimide group-containing compound (b) can be measured by ¹³ C-NMR, IR, titration method or the like, and can be grasped as a carbodiimide group equivalent. It is possible to observe peaks at 130 to 142 ppm for ¹³ C-NMR and at 2130 to 2140 cm ⁻¹ for IR.

^{The 13} C-NMR measurement is performed, for example, as follows. That is, 0.35 g of a sample is heated and dissolved in 2.0 ml of hexachlorobutadiene. The solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the mixture is charged into an NMR tube with an inner diameter of 10 mm. Then, ¹³ C-NMR measurement is performed at 120 ° C. using a GX-500 type NMR measurement apparatus manufactured by Nippon Denshi Co., Ltd. The number of integrations is 10,000 or more.

(Method of preparing adhesive composition (3))
The adhesive composition (3) is obtained by reacting a polyolefin (a) having a group that reacts with a carbodiimide group with a carbodiimide group-containing compound (b). Specifically, the adhesive composition (3) can be obtained by melt-kneading like melt modification, but it is not limited to this method.

  Below, the example in the case of melt-kneading is shown. The reaction method is not particularly limited, but after charging the polyolefin (a) and the carbodiimide group-containing compound (b) into, for example, a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, etc. The method of melt-kneading with an extruder, a multi-screw extruder, a kneader, a Banbury mixer etc. is mentioned. Among these, using an apparatus having excellent kneading performance such as a multi-screw extruder, a kneader, or a Banbury mixer is preferable because an adhesive composition in which each component is more uniformly dispersed and reacted can be obtained.

  The polyolefin (a) and the carbodiimide group-containing compound (b) are mixed in advance and then supplied from the hopper, and some components are supplied from the hopper and installed in any part between the hopper and the extruder tip. It is possible to take any method of supplying other components from the supply port.

  The temperature at the time of melt-kneading each of the above components can be reacted at the highest melting point or higher of the melting points of the components to be mixed, but specifically it is preferably in the range of 180 to 320 ° C. 230 The range of 300 to 300 ° C. is more preferable, and the range of 235 to 280 ° C. is more preferable.

  The content of carbodiimide group in the adhesive composition is preferably in the range of 0.1 to 50 mmol, more preferably in the range of 0.2 to 40 mmol, still more preferably 0. It is in the range of 5 to 30 mmol. When it is in this range, the adhesiveness is excellent, and crosslinking of the polyolefin (a) through the carbodiimide group-containing compound (b) can be suppressed, which is preferable.

The content of the carbodiimide group in the adhesive composition can be calculated from the preparation amount of the carbodiimide group-containing compound (b), and can also be measured by ¹³ C-NMR, IR, titration method, etc. It is possible to grasp as a group equivalent. It is possible to observe peaks at 130 to 142 ppm for ¹³ C-NMR and at 2130 to 2140 cm ⁻¹ for IR. In addition, a < ¹³ > C-NMR measurement is performed by the measuring method as described in the measuring method of the carbodiimide group content in the above-mentioned carbodiimide group containing compound (b), for example.

  The adhesive composition is produced by reacting the carbodiimide group (NCN) of the carbodiimide group-containing compound (b) with the group that reacts with the carbodiimide group of the polyolefin (a) as described above. A certain amount of carbodiimide groups in the process is consumed, and residues of carbodiimide groups linked as polyolefins and the same molecular chain contribute to adhesion. If the content of the carbodiimide group is within the above-mentioned range, free carbodiimide groups will be present within the range not exceeding an excess in the adhesive composition with respect to the polyolefin (a) having a group that reacts with the carbodiimide group. It is preferable because it is excellent in adhesion performance and molding processability.

  Moreover, the reaction rate of polyolefin (a) and a carbodiimide group containing compound (b) can be evaluated by the following method.

After preparing each heat press sheet to polyolefin (a) (reference) which has a group which reacts with the above-mentioned carbodiimide group, and composition for adhesion (3), infrared absorption is carried out using an infrared absorption analysis device. Measure From the obtained chart, the absorbance derived from the group that reacts with the carbodiimide group in the polyolefin (a), the absorbance derived from the group that reacts with the carbodiimide group in the polyolefin (a), and the carbodiimide group in the adhesive composition The reaction rate can be calculated using the following formula (α1) by comparing the difference between the absorbances derived from the groups to be reacted. In addition, when the group originating in maleic anhydride is used as group which reacts with a carbodiimide group, the light absorbency of 1790 cm < ^-1 > vicinity can be used.

Reaction rate (%) = {X / Y} × 100 .. Formula (α1)
X = difference between the absorbance derived from the group that reacts with the carbodiimide group in the polyolefin (a) and the absorbance derived from the group that reacts with the carbodiimide group in the adhesive composition Y = the carbodiimide group in the polyolefin (a) Absorbance from Reactive Group The reaction rate of the adhesive composition determined by the above method is usually in the range of 40 to 100%, preferably 60 to 100%, and more preferably 80 to 100%.

Further, the density of the adhesive composition (measured in accordance with JIS K7112) is not particularly limited as long as the effects of the present invention are not impaired, but is in the range of 0.870 to 0.940 g / cm ^3. it is preferable, more preferably in the range of 0.875~0.940g / cm ^3, more preferably in the range of 0.880~0.940g / cm ^3. It is preferable that the content is in the above-mentioned range because the stable productivity, the molding processability and the adhesiveness are good.

  The melt flow rate (MFR, according to ASTM D1238, 230 ° C., 2.16 kg load) of the adhesive composition is not particularly limited as long as the effects of the present invention are exhibited, but is in the range of 0.01 to 500 g / 10 min Is preferably in the range of 0.01 to 200 g / 10 min, more preferably in the range of 0.05 to 200 g / 10 min, and in the range of 0.05 to 150 g / 10 min. Are particularly preferred, and most preferably in the range of 0.1 to 150 g / 10 min.

  The carbodiimide group is changed to a urea group by water absorption, but the urea group also exhibits high reactivity with the polyarylene sulfide resin and the like. Therefore, the adhesive composition may contain a polyolefin in which the carbodiimide group is converted to a urea group by, for example, water in the air, which is one of the preferred embodiments of the present invention.

(Such as additives)
The adhesive composition (3) contains a polyolefin in which the polyolefin (a) and the carbodiimide group-containing compound (b) are reacted, but the polyolefin (a) and the carbodiimide group-containing compound The resin may be different from b). As such a resin, for example, a group which reacts with a carbodiimide group in addition to a non-modified polyolefin (ie, a polyolefin having no functional group such as an epoxy group, an amino group, a carboxy group, a carboxylic acid anhydride group) A modified resin having the following formulae may be mentioned, for example, a maleic acid modified resin, an imine modified resin. The adhesive composition (3) may also contain an unreacted polyolefin (a). These resins may be used alone or in combination of two or more.

(Joining method)
The method for producing a composite structure of the present invention is a composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3). Manufacturing method of
The bonding composition (3) includes a polyolefin which is a reaction product of a polyolefin (a) having a group which reacts with a carbodiimide group and a carbodiimide group-containing compound (b), a bonding method (A) or a bonding method It is characterized by having (B).

(Joining method (A))
The bonding method (A) includes a step of melt-molding a polyarylene sulfide resin composition to a metal member having a bonding composition (3) on the surface of a metal member to be bonded to the molded article (2). .

  For example, first, the step of bringing the bonding composition (3) into contact with the surface of the molded article to be bonded to the metal member (1) is performed, and then the metal member having the bonding composition (3) on the surface is A so-called metal insert which is inserted into a mold of an injection molding machine and subsequently injection molded using a polyarylene sulfide resin composition on a metal member having a bonding composition (3) on its surface There is a method of performing a molding method. In addition, as another form of metal insert molding, a resinous film-like product in which a metal member layer having an adhesive composition (3) on the surface is laminated in the form of a film, or a composition for adhesion in the form of a film It may be so-called film insert molding in which a resinous film-like product obtained by laminating the product (3) is inserted into a mold and the polyarylene sulfide resin composition is melt-formed on the adhesive composition (3) side. The apparatus and manufacturing method in the metal insert molding method or film insert molding method are not particularly limited, and commercially available devices can be used, or can be performed according to a conventional method. The resinous film-like product having such a metal member layer is formed into a sheet or film shape with the adhesive composition (3), brought into contact with the metal member layer, and simultaneously subjected to thermocompression bonding (so-called thermal lamination method) It can also be produced by a known laminating method. The heat laminating method includes a method of bonding using a heat press and a method of bonding continuously using a heat roll, and either method may be used. On the other hand, in the polyarylene sulfide resin composition, for example, in an injection molding machine, the resin temperature is within the temperature range above the melting point of the polyarylene sulfide resin composition, preferably within the temperature range above the melting point and 100 ° C. After passing through the step of melting the polyarylene sulfide resin composition within the temperature range of the melting point plus 20 ° C. and the melting point plus 50 ° C., the resin may be injected from the resin discharge port into the mold. At that time, the mold temperature may be in a known temperature range, but setting from a lower temperature is possible, for example, in a range of room temperature (23 ° C.) to 300 ° C., preferably 40 to 180 ° C. It can be set preferably in a temperature range of 120 to 180.degree.

(Bonding method (B))
On the other hand, in the bonding method (B), the adhesive composition (3) is in contact with the surface of the molded product to be bonded to the metal member (1) or the surface of the metal member to be bonded to the molded product (2). And a step of bonding the metal member (1) and the molded article (2) via the bonding composition (3) at a temperature at which the polyarylene sulfide resin composition melts.

  In the bonding method (B), molded articles of the polyarylene sulfide resin composition of the present invention are produced in advance. An adhesive composition (3) on at least one surface selected from the group consisting of the surface of the obtained molded product to be bonded to the metal member (1) and the surface of the metal member to be bonded to the molded product (2). And contacting the metal member with the molded article in a state of having the adhesive composition (3) on at least one of the surfaces, or heating or joining, or heating After joining, it joins and it cools. Such methods include, for example, methods such as hot plate welding, vibration welding, ultrasonic welding, high frequency welding, induction heating welding, rotational welding, laser welding, hot pressing, and hot embossing. The apparatus and manufacturing method which can be mentioned and used for these bonding methods can use a commercially available apparatus, and can also be performed according to a conventional method. For example, in the hot plate welding method, in order to melt the molding surface to be welded to the metal member, it is melted using a heat source such as a hot plate so as to satisfy the following temperature conditions. It may be joined by holding in a pressure state. Also, in vibration welding, ultrasonic welding, and high frequency welding, after the molded product is joined to a metal member, the surface of the molded product to be welded to the metal member is melted, so that vibration or A sound wave or a high frequency may be transmitted to a molded product or a metal member to generate heat, and the molded product may be melted by the heat generation and held under pressure until it cools and solidifies. The way of transmitting vibration, high frequency and ultrasonic waves is to contact the resonator or vibration device with the irradiation or molded product and vibrate the molded product, whereby the molded product or the metal member itself is vibrated or The heat may be generated by the frictional heat between the molded product and the metal member. On the other hand, in the 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 the metal member is heated by the induction heating device so as to meet the following temperature conditions. The molded articles may be heated and melted to be joined by holding in a pressurized state until they cool and solidify. Further, in rotational welding, after the molded product and the metal member were separately held, one of them was gradually brought close while rotating at high speed in the range of 100 to 4,000 rotation, and both were in contact By the way, friction heat may be generated to melt the resin so as to satisfy the following temperature conditions, and then the resin may be joined by holding in a pressurized state until it cools and solidifies.

  The molded article of the polyarylene sulfide resin composition may be a film-like article. In the case where the molded article of the polyarylene sulfide resin composition is a film-like product, particularly 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 A bonding method called can also be used, and furthermore, if the film-like material is a transparent material capable of transmitting a laser beam, a bonding method called laser welding can be used.

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

  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, and then pressed against a forming roll and cooled and solidified while being pressed against a metal member. . The laser welding method is applicable when the molded product can transmit a laser beam, and after the molded product is joined to the metal member, the laser beam is applied to the metal member surface from the molded product side so as to satisfy the following temperature conditions. Irradiation may be performed to generate heat, and the molded product may be melted and bonded by holding under pressure 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, it is possible to use a so-called hot embossing method in which the metal member is simultaneously embossed and pressed while heating a molded article of the polyarylene sulfide resin composition. By using the hot embossing method, it is possible to manufacture a molded article having a three-dimensional shape and a fine pattern, and when the fine pattern by the metal member is an electric circuit, it may be a molded circuit part. it can.

  In the present invention, the term "film-like material" generally refers to so-called foils, films, sheets, and plates in this manner, and refers to those having a thickness of 0.001 to 9 mm.

  The bonding method (B) described above basically needs to melt the molded product and press-bond it to a metal member, so the heating conditions are such that the resin temperature is the recrystallization temperature (Tc2) of the polyarylene sulfide resin The temperature may be appropriately adjusted in the above temperature range, and is preferably 240 ° C. or more, more preferably 250 ° C. or more. On the other hand, the upper limit value is not particularly limited as long as the resin is not decomposed, but a temperature range of 370 ° C. or less is preferable. Furthermore, while maintaining excellent smoothness and appearance, such as a film-like material, when exhibiting sufficient adhesion, it is suitably adjusted within the temperature range of the recrystallization temperature (Tc2) or more and less than the melting point. On the other hand, if it is desired to suppress the gas generation due to resin decomposition and to prevent resin deterioration and to exhibit more excellent adhesion, adjust appropriately in the temperature range above the melting point. It is more preferable to adjust appropriately within the temperature range of the melting point or more and the melting point plus 100 ° C., and it is particularly preferable to adjust appropriately within the temperature range of the melting point plus 20 ° C. and the melting point plus 50 ° C. Further, the pressure conditions for pressure bonding (pressing each other) the metal member and the molded product are not particularly limited as long as the bonding state can be maintained. For example, the metal member may be between the heating start and the cooling end. In the direction in which the resin member and the resin member push each other, the range of 0.01 [MPa] or more, preferably 0.01 to 100 [MPa], more preferably 0.05 to 10 [MPa], is sufficient. It may be appropriately adjusted within a range where a small amount of burr can be obtained while exhibiting adhesion. In the case of the laser welding method, it is not always necessary to press the metal member and the molded product together by an external force before welding, and bonding is performed using a pressure increase generated at the bonding interface due to volume expansion during melting. be able to.

  The thickness of the layer composed of the adhesive composition in the composite structure is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of excellent adhesion, a range of 10 μm or more is preferable, and 50 μm or more Is more preferable, the range of 100 μm or more is more preferable, and the range of 1200 μm or less is preferable, the range of 600 μm or less is more preferable, and the range of 300 μm or less is more preferable.

(Use of composite structure)
Examples of main applications of the composite structure of the present invention include casings of electronic devices such as various home appliances, mobile phones, and PCs (Personal Computers), protection / supporting members for box-type electric / electronic component integrated modules, Several individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, varicon cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners Speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabola antennas, computer related parts, etc .; VTR parts, TV department Articles, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio / video equipment parts such as audio / laser disc / compact disc / DVD disc / blu-ray disc, lighting parts, refrigerator parts, air conditioner parts, type writer Parts, word processor parts, or household appliances such as water heaters, bath water level, water-supply equipment parts such as temperature sensors, etc. Office electronic products parts; office computer related parts, telephone related parts, facsimile related parts, copier related Parts related to machinery, such as cleaning jigs, motor parts, lighters, typewriters, etc. Optical devices such as microscopes, binoculars, cameras, clocks, etc., precision machine related parts; alternator terminals, alternator connectors, brushes Holder, slip ring, IC legi Controllers, Potentiometer Bases for Light Doors, Relay Blocks, Inhibitor Switches, Various Valves such as Exhaust Gas Valves, Various Fuel-Related, Exhaust, and Intake Systems, Air Intake Nozzle Snorkels, Intake Manifolds, Fuel Pumps, Engine Cooling Water Joints, Carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating warm air flow Control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, dust rive , 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, coil for fuel related electromagnetic valve, connector for fuse, horn terminal , Electrical parts insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, igniter case, power module, inverter, power device, intelligent power module, insulated gate bipolar transistor, Power control unit, reactor, converter, capacitor, insulator, motor terminal The invention can also be applied to various other applications such as automobiles, vehicle-related parts such as cases for housing a table, a battery, an electric compressor, a battery current sensor, a junction block, an ignition coil for a DLI system and the like.

  The present invention will be described in more detail by way of specific examples below. Moreover, parts and% are based on weight unless otherwise noted.

(Measurement Example 1) Measurement of Melt Viscosity of Polyphenylene Sulfide Resin The polyphenylene sulfide resin produced in the reference example was subjected to 300 ° C., load: 1.96 × 10 ⁶ Pa, L / L using a flow tester (Shimadzu Corporation, CFT-500 D). It measured after holding for 6 minutes by D = 10 (mm) / 1 (mm).

(Measurement Example 2) Compositional Evaluation of Adhesive Composition As a compositional analysis of the adhesive composition, infrared spectroscopy (JASCOFT, FT / IR-6100) was performed. The wave number is 600 to 4000 cm ^-1 and the number of integrations is 64 times. Composition evaluation was performed from the signal corresponding to each functional group of the acquired spectrum.

(Measurement example 3) Softening temperature evaluation of the composition for adhesion The DMA measurement (TA Instruments Japan, RSA-G2) of the composition for adhesion is performed at a temperature range of -40 ° C to 200 ° C, with a temperature rising rate of 4 ° C / Min. , Tensile strain 0.1%, frequency 1 Hz. The temperature dependence spectrum of the storage Young's modulus E ′ started at a low temperature and was regarded as a softening temperature at which the temperature became 0.1 GPa or less.

(Measurement Example 4) Bonding Strength Measurement of Composite Structure of Metal Specimen / Composition for Bonding / PPS Resin Molding A Composite Structure in which a Molding of Metal Specimen / Composition for Bonding / PPS Resin Composition is Laminated (ISO 19095) The Type-B type according to the above was subjected to shear tension measurement at a tensile speed of 5 mm / min using a material tester (Shimadzu Corporation, AG-IS). The measurement temperature was room temperature, and the average value (n = 5) of the maximum values of the stress up to the fracture of the composite structure was taken as the bonding strength.
(Measurement Example 5) Observation of the fractured surface of the composite structure Visual observation of the peeled surface in the composite structure in which the molded articles of the metal test piece / adhesive composition / PPS resin composition subjected to shear tension measurement are laminated. went. In addition, "PPS" means that the film of the composition for adhesion was adhering only to the PPS molded article surface at the time of peeling, and the "cohesive peeling" means that the film of the adhesive composition is the PPS molded article surface and metal test Indicates that it was attached to one surface.

(Production Example 1-1) Production of Metal Member (A-1) No treatment: A metal piece is cut out from an aluminum plate (material: A5052) into a size of length × width × thickness = 45 mm × 10 mm × 1.5 mm , And test pieces (A-1).
(Production Example 1-2) Production of metal member (A-2) Metal surface treatment: The test surface (A-1) was further polished on the bonding surface (abrasive paper roughness: No. 1000), and then the entire surface was subjected to YAG Laser groove processing was performed using a laser marker device (Shibaura Eletech, LAY-791 DE). A continuous groove with a length of 10 mm, a depth of 150 μm, and a width of 100 μm was formed in a slit shape at intervals of 100 μm on the surface of the aluminum piece to make a test piece (A-2).

Production Example 2-1 Production of Polyphenylene Sulfide Resin (B-1) [Step 1]
Pressure gauge, thermometer, condenser, decanter, p-dichlorobenzene (abbreviated below as "p-DCB") 33.222 kg (226 moles), NMP3. 420 kg (34.5 mol), 27.300 kg of 47.23 wt% aqueous NaSH solution (230 moles as NaSH), and 18.533 g of 49.21 wt% aqueous solution of NaOH (228 moles as NaOH) are charged, and a nitrogen atmosphere is stirred. The temperature was raised to 173 ° C. over 5 hours to distill 27.300 kg of water, and then the autoclave was sealed. The p-DCB which was distilled off azeotropically at the time of dehydration was separated by a decanter and returned to the autoclave as needed. After completion of the dehydration, the inside of the autoclave was in a state where the particulate anhydrous sodium sulfide composition was dispersed in p-DCB. Since the content of NMP in this composition was 0.079 kg (0.8 mol), 98 mol% (33.7 mol) of NMP charged 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 0.147 moles per mole of sulfur atoms present in the autoclave. The total amount of charged NaSH and NaOH is 27.921 g when the total amount of NaSH and NaOH is changed to anhydrous Na ₂ S is 609 g (33.8 mol) out of 878 g (48.8 mol) of residual water 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 269 g (14.9 mol) remains in the autoclave in the form of water or water of crystallization. It was shown. The water content in the autoclave was 0.065 moles per mole of sulfur atoms present in the autoclave.

[Step 2]
After completion of the above dehydration step, the internal temperature was cooled to 160 ° C., 46.343 kg (467.5 mol) of NMP was charged, and the temperature was raised to 185 ° C. The water content 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. for 1 hour. Under the present circumstances, it controlled by cooling and valve-opening so that the rectification tower outlet temperature might be 110 degrees C or less. The distilled mixed vapor of p-DCB and water was condensed by a condenser, separated by a decanter, and p-DCB was returned to the autoclave. The amount of distilled water was 228 g (12.7 mol).

[Step 3]
The water content in the autoclave at the start of step 3 was 41 g (2.3 mol), 0.005 mol per mol of NMP charged in step 2, 0.010 mol per mol of sulfur atom present in the autoclave . The amount of SMAB in the autoclave was 0.147 moles per mole of sulfur atoms present in the autoclave, as in step 1. Next, the inner temperature was raised from 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 0.40 MPa. After cooling, 650 g of the obtained slurry was poured into 3 liters of water, stirred at 80 ° C. for 1 hour, and filtered. The cake was again stirred with 3 liters of hot water for 1 hour, washed and filtered. This operation was repeated four times. The cake was again adjusted to pH 4.0 with the addition of 3 liters of warm water and acetic acid, stirred for 1 hour, washed and filtered. The cake was again stirred with 3 liters of hot water for 1 hour, washed and filtered. This operation was repeated twice. It dried at 120 degreeC overnight using a hot-air dryer, and obtained white powdery PPS resin (B-1). The melt viscosity at 300 ° C. of this polymer was 41 Pa · s. The non-Newtonian index was 1.07.

(Production Example 2-2) Production of Polyphenylene Sulfide Resin (B-2) "Next, the internal temperature is raised from 200 ° C to 230 ° C over 3 hours, and after stirring for 1 hour at 230 ° C, the temperature is raised to 250 ° C "Then, the portion to be stirred for 1 hour.""Next, raise the internal temperature from 200 ° C to 230 ° C over 3 hours, stir at 230 ° C for 1.5 hours, and then raise the temperature to 250 ° C, 1 A white powdery PPS resin (hereinafter referred to as B-2) was obtained in the same manner as in Production Example 1 except that the stirring was performed for a while. The melt viscosity of the obtained polymer was 73 Pa · s, and the non-Newtonian index was 1.07.

(Production Example 2-3) Production of polyphenylene sulfide resin (B-3) Flaky sodium sulfide (60.3 wt% Na _{2) in} a 150 liter autoclave equipped with a pressure gauge, a thermometer, a stirring blade connected with a condenser and a bottom valve S) 19.413 kg of NMP and 45.0 kg of NMP were charged. The temperature was raised to 209 ° C. while stirring under a nitrogen stream, and 4.644 kg of water was distilled off (the amount of remaining water is 1.13 moles per mole of sodium sulfide). Then, the autoclave was closed and cooled to 180 ° C., and 22.185 kg of paradichlorobenzene, 0.027 kg of 1,2,4-trichlorobenzene and 18.0 kg of NMP were charged. The temperature was raised by pressurizing to 0.1 MPa with gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. After holding at a liquid temperature of 240 ° C. for 2 hours, the reaction was allowed to proceed while stirring at a liquid temperature of 260 ° C. for 3 hours, and the upper part of the autoclave was cooled by sprinkling water. Then, the temperature was lowered and cooling of the upper part of the autoclave was stopped. During cooling of the upper part of the autoclave, the solution temperature was kept constant so as not to decrease. The maximum pressure during the reaction was 0.85 MPa. After the reaction, the reaction solution was cooled, and at a temperature of 170 ° C., a solution containing 0.284 kg (2.25 mol) of oxalic acid dihydrate in 0.663 kg of NMP was pressure-injected. After stirring for 30 minutes, it was cooled, the bottom valve was opened at 100 ° C., the reaction slurry was transferred to a 150 liter flat plate filter, pressure filtered at 120 ° C., 16 kg of NMP was added and pressure filtered. After filtration, NMP was removed by stirring under reduced pressure at 150 ° C. for 2 hours using a 150-liter vacuum dryer equipped with a stirring blade to obtain a white powdery PPS resin (B-3). The melt viscosity at 300 ° C. of this polymer was 77 Pa · s. The non-Newtonian index was 1.25.

(Production Example 3-1) Production of adhesive composition (C-1) (Production example 3-1a) Production of maleic anhydride-modified polypropylene (PP-MA) Polypropylene (density = 0.912 g / cm ³ , (strain ) 1 part by weight of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) to 100 parts by weight of Prime Polymer Co., Ltd., 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3 0.30 parts by weight of NOF Corporation (manufactured by Nippon Oil Co., Ltd.) were mixed and extruded at a cylinder temperature of 210 ° C. using a twin-screw kneader to obtain maleic anhydride-modified polypropylene (PP-MA).

The obtained maleic anhydride modified polypropylene (PP-MA) was dissolved in xylene, poured into acetone, and reprecipitated to purify the maleic anhydride modified polypropylene (PP-MA). The density of the obtained PP-MA was 0.916 g / cm ³ . Moreover, it was 0.9 weight% when the amount of graft | grafting of maleic anhydride was measured by infrared spectroscopy (FT-IR).

(Production Example 3-1b) Production of Polycarbodiimide (b1) Having an Alicyclic Structure Dicyclohexylmethane 4,4′-diisocyanate (manufactured by Degussa Japan Ltd., VESTANAT H12 MDI) 100 parts by weight, polyalkylene carbonate diol ( Asahi Kasei Chemicals Co., Ltd. product, DURANOL T-5651, molecular weight 1000) 71.8 parts by weight, phenyl isocyanate 17.1 parts by weight, toluene 245 parts by weight and carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene- 1.0 part by weight of 1-oxide) is charged into a reaction vessel equipped with a reflux condenser and a stirrer, stirred at 100 ° C. for 3 hours under a nitrogen stream, and absorbed by an isocyanate group having a wavelength of about 2270 cm ⁻¹ by FT-IR measurement While confirming that the peak has almost disappeared, cm ^-1 was confirmed absorption peak due to the front and rear of the carbodiimide group to obtain a polycarbodiimide having an alicyclic structure.

Subsequently, the polycarbodiimide in the reaction vessel was cooled to 50 ° C. Then, 59.3 parts by weight of diisopropylamine was added and stirred for 5 hours. Subsequently, it was confirmed by FT-IR measurement that an absorption peak by the group represented by the formula (11) was generated in the vicinity of a wavelength 1660 cm ^-1 and an absorption peak by a carbodiimide group in the vicinity of a wavelength 2150 cm ^-1 almost disappeared. Thus, a modified polycarbodiimide compound (b1) was obtained.

Production Example 3-1c Production of Adhesive Composition (C-1) 100 parts by weight of the maleic anhydride-modified polypropylene (PP-MA) prepared above and 1.9 parts of the modified polycarbodiimide compound (b1) The resulting mixture and each of the parts were mixed and extruded at a cylinder temperature of 250 ° C. using a twin-screw kneader to obtain pellets of the adhesive composition (C-1).

Production Example 3-2b Production of Polycarbodiimide (b2) Having Aromatic Structure Tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., “Cosmonate T-80” 2,4-tolylene diisocyanate / 2, 6— 100 parts by weight of a mixture of tolylene diisocyanate (75-85 / 15-25), 71.0 parts by weight of a polyalkylene carbonate diol (Asahi Kasei Chemicals Corporation, DURANOL T-5651, molecular weight 1000), 16.8 parts by weight of phenyl isocyanate Parts, 245 parts by weight of toluene (boiling point 110.6 ° C.) and 1.0 parts by weight of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a reaction vessel equipped with a reflux condenser and a stirrer Charge, and stir for 3 hours at 100 ° C under nitrogen stream, measure the infrared absorption (IR) spectrum It reaffirmed more of the absorption peak due to the isocyanate group in the vicinity of a wavelength of 2270 cm ^-1 is almost disappeared, check the absorption peak by wavelength 2150 cm ^-1 before and after the carbodiimide groups to obtain a polycarbodiimide having an aromatic structure.

Subsequently, the polycarbodiimide in the reaction vessel was cooled to 50 ° C. Then, 42.8 parts by weight of diethylamine was added and stirred for 5 hours. Then, an absorption peak by the group represented by the formula (11) is generated in the vicinity of the wavelength 1660 cm ⁻¹ by infrared absorption (IR) spectrum measurement, and an absorption peak by the carbodiimide group in the vicinity of the wavelength 2150 cm ⁻¹ almost disappears It confirmed that the modified polycarbodiimide compound (b2) was obtained.

Production Example 3-2c Production of Adhesive Composition (C-2) 100 parts by weight of the maleic anhydride-modified polypropylene (PP-MA) prepared above and 1.9 parts by weight of a modified polycarbodiimide compound (b2) And extruded using a twin-screw kneader at a cylinder temperature of 250.degree. C. to produce pellets of the adhesive composition (C-2).

Production Example 3-3b Production of Polycarbodiimide (b3) Having Aliphatic Structure 100 parts by weight of hexamethylene diisocyanate, polyalkylene carbonate diol (manufactured by Asahi Kasei Chemicals Corporation, DURANOL T-5651, molecular weight 1000) 71.0 weight Parts, 16.6 parts by weight of phenyl isocyanate, 245 parts by weight of toluene (boiling point 110.6 ° C.) and 1.0 parts by weight of a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a reflux tube And charged in a reaction vessel equipped with a stirrer, stirred at 100 ° C. for 4 hours under a nitrogen stream, and infrared absorption (IR) spectrum measurement confirmed that the absorption peak due to the isocyanate group near a wavelength of 2270 cm ⁻¹ almost disappeared And a carbodiimide group around 2150 cm ⁻¹ The absorption peak was confirmed to obtain a polycarbodiimide having an aliphatic structure.

Subsequently, the polycarbodiimide in the reaction vessel was cooled to 50 ° C. Then, 59.3 parts by weight of diisopropylamine was added and stirred for 5 hours. Subsequently, it was confirmed by FT-IR measurement that an absorption peak by the group represented by the formula (11) was generated in the vicinity of a wavelength 1660 cm ^-1 and an absorption peak by a carbodiimide group in the vicinity of a wavelength 2150 cm ^-1 almost disappeared. Thus, a modified polycarbodiimide compound (b3) was obtained.

Production Example 3-3c Production of Adhesive Composition (C-3) 100 parts by weight of the maleic anhydride-modified polypropylene (PP-MA) prepared above and 1.9 parts of the modified carbodiimide group-containing compound (b3) Parts by weight were mixed, respectively, and extruded using a twin-screw kneader at a cylinder temperature of 250 ° C. to produce pellets of the bonding composition (C-3).

  The pellets of the obtained adhesive composition (C-1, C-2, C-3) are pressed with a hot press heated to 200 ° C., and the adhesive composition (C-1, C-2, C-) The film of 3) was obtained.

When the FT-IR measurement of the film of the obtained composition for bonding (C-1, C-2, C-3) was performed, the signal (1790 cm ^-1 ) derived from maleic anhydride was not observed, so the reaction rate Was judged to be 100%.

  The films of the obtained adhesive compositions (C-1) to (C-3) were cut into 10 mm × 50 mm with scissors and subjected to DMA measurement, and the softening temperature was 100 for the adhesive composition (C-1). ° C, composition for adhesion (C-2) was 108 ° C, composition for adhesion (C-3) was 96 ° C.

(Examples 1 to 18)
(Production of Polyarylene Sulfide Resin Composition)
Each material was uniformly mixed with a tumbler according to the composition component and compounding quantity (all weight part) described in Tables 1-5. Then, the compounding material is charged into a vented twin screw extruder (Japan Steel Works, TEX30α), and melt kneading is performed by setting the resin component discharge amount 30 kg / hr, screw rotation speed 220 rpm, and setting resin temperature to 320 ° C. Pellets of the polyphenylene sulfide resin composition were obtained.

(Preparation of composite structure of metal test piece / adhesion composition / PPS resin composition)
A metal test piece is preheated to 200 ° C. on a hot plate, a film of the above adhesive composition is cut into 10 mm × 5 mm size with scissors and melted on the surface (10 mm × 5 mm) to be bonded to the polyarylene sulfide resin composition. I wore it. Subsequently, a metal test piece in which the bonding composition is fused is set in a mold (mold temperature is 140 ° C.) of an injection molding machine (Sumitomo Heavy Industries, Ltd., SV-50M), and the treated surface of the metal test piece The pellets of the polyphenylene sulfide resin composition prepared above are insert-molded at a screw temperature of 320 ° C. so that the resin composition is bonded to (10 mm × 5 mm), and the metal test piece / adhesion composition / PPS resin composition The composite structure (Type-B type based on ISO19095) which the molded object laminated | stacked was obtained.

(Evaluation of composite structure of metal test piece / adhesion composition / PPS resin composition)
The composite structure in which the obtained molded product of the metal test piece / the composition for bonding / the PPS resin composition was laminated was allowed to stand at room temperature for 24 hours, and then a shear tensile test was performed as in Measurement Example 4 to obtain a bonding strength. Subsequently, the fractured surface was observed as in the measurement example 5. The results are shown in Tables 1-5.

(Comparative Examples 1 to 3)
Instead of the adhesive compositions (C-1) to (C-3), a commercially available high-density polyethylene (Mitsubishi Chemical Holdings Novatec) is used as the adhesive composition, and the film is used for the metal test piece in the same manner as described above. A composite structure in which molded articles of / adhesive composition / PPS resin composition were laminated was prepared and evaluated. The results are shown in Tables 1-5.

In addition, the compounding ratio of the compound resin in Table 1-5, and the compounding ratio of material represent a weight part, and used the following.
GF: Glass filler (chopped strands 200 μm, average diameter 10 μm)
BF-7L: Olefin Elastomer "bond first-7L" (Ethylene-glycidyl dimethacrylate-vinyl acetate) manufactured by Sumitomo Chemical Co., Ltd.
“Epiclon 7050”: Epoxy resin “Epiclon 7050” manufactured by DIC Corporation (epoxy equivalent 1750-2100 g / equivalent)
“Epiclon N-673”: Epoxy resin “Epiclon N-673” manufactured by DIC Corporation (epoxy equivalent 205-215 g / equivalent)
"Novatec": High density polyethylene "Novatec" manufactured by Mitsubishi Chemical Holdings Corporation

DESCRIPTION OF SYMBOLS 1 ..... Metal member 2-1 ... Polyarylene sulfide resin composition 2-2 ... Molded body of polyarylene sulfide resin composition 3 ... Composition for adhesion

Claims (14)

A method for producing a composite structure comprising a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition joined via an adhesive composition (3),
The bonding composition (3) includes a polyolefin which is a reaction product of a polyolefin (a) having a group which reacts with a carbodiimide group and a carbodiimide group-containing compound (b), a bonding method (A) or a bonding method (B) having, The manufacturing method characterized by the above-mentioned.
Bonding method (A)
And bonding the metal member having the bonding composition (3) on the surface of the metal member to be bonded to the molded article (2) by melt-molding the polyarylene sulfide resin composition.
Bonding method (B)
A polyarylene sulfide resin composition in a state in which an adhesive composition (3) is in contact with the surface of the molded article to be bonded to the metal member (1) or the surface of the metal member to be bonded to the molded article (2) Bonding the metal member (1) and the molded article (2) through the bonding composition (3) at a temperature at which the metal melts.   The method according to claim 1, wherein the carbodiimide group-containing compound (b) is a polycarbodiimide produced by a decarboxylation condensation reaction using a raw material containing an alicyclic diisocyanate compound.   The alicyclic diisocyanate compound is at least one selected from the group consisting of isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-cyclohexane diisocyanate and trans 1,4-bis (isocyanatomethyl) cyclohexane. The method according to claim 1, wherein   The method according to claim 1, wherein the carbodiimide group-containing compound (b) is obtained by modifying a polycarbodiimide compound with an aliphatic amine. Bonding a metal member having a bonding composition (3) on the surface of a metal member to be bonded to the molded product (2) by melt-molding a polyarylene sulfide resin composition;
Or
An adhesive composition (3) is brought into contact with at least one of the surface of the molded product to be bonded to the metal member (1) or the surface of the metal member to be bonded to the molded product (2). Bonding the metal member (1) and the molded article (2) via the bonding composition (3) at a temperature at which the composition melts, and
The manufacturing method of Claim 1 which has the process of joining a metal member and the molded article of a polyarylene sulfide resin composition.   The production method according to claim 1, wherein the polyarylene sulfide resin composition contains the compound (2a) having reactivity with a carbodiimide group in an amount of 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin. .   The compound (2a) is a compound having a functional group represented by an epoxy group, an alcoholic hydroxyl group, a carboxy group, or a carboxylic acid anhydride group (-(CO) O (CO)-). Production method.   The method according to claim 6 or 7, wherein the compound (2a) is an epoxy resin or an epoxy group-containing polyolefin resin.   The production method according to any one of claims 1 to 8, wherein the polyarylene sulfide resin composition is a melt-kneaded product. A composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3),
The adhesive composition (3) is
(I) including a polyolefin which is a reaction product of a polyolefin (a) having a group reactive with a carbodiimide group and an alicyclic carbodiimide group-containing compound (b),
Composite structure characterized by A polyarylene sulfide resin composition used in a composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are joined via an adhesive composition (3), ,
The adhesive composition (3) is
(I) including a polyolefin which is a reaction product of a polyolefin (a) having a group reactive with a carbodiimide group and an alicyclic carbodiimide group-containing compound (b),
The polyarylene sulfide resin composition for composite structures characterized by the above-mentioned. A method of producing a polyarylene sulfide resin composition used for a composite structure in which a metal member (1) and a molded article (2) of a polyarylene sulfide resin composition are joined via an adhesive composition (3) And
The adhesive composition (3) is
(I) including a polyolefin which is a reaction product of a polyolefin (a) having a group reactive with a carbodiimide group and an alicyclic carbodiimide group-containing compound (b),
The polyarylene sulfide resin composition contains the polyarylene sulfide resin as an essential component, and is melt-kneaded;
The manufacturing method of the polyarylene sulfide resin composition for composite structures characterized by the above.   A molded article obtained by melt-molding the polyarylene sulfide resin composition for a composite structure according to claim 11.   A polyarylene sulfide resin composition for a composite structure, comprising a step of producing the polyarylene sulfide resin composition for a composite structure by the production method according to claim 12 and a step of melt-molding the obtained polyarylene sulfide resin composition. Method of producing a molded article of an object.