JP6984401B2 - Polyarylene sulfide resin composition, molded article, composite structure and manufacturing method - Google Patents

Description

The present invention relates to a polyarylene sulfide resin composition, a molded product, a composite structure, and a method for producing the same.

Polyphenylene sulfide (hereinafter, may be abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter, may be abbreviated as PPS) resin exhibits excellent heat resistance that can maintain a melting point of 270 ° C. or higher. Moreover, it is known to be excellent in mechanical strength, chemical resistance, molding processability, and dimensional stability. Therefore, in general, an additive such as a filler or an elastomer is mixed with the polyarylene sulfide resin and melt-kneaded so as to be dispersed in a matrix made of the polyarylene sulfide resin to obtain a PAS resin composition. Above, it is melt-molded and processed into various molded products such as electrical / electronic equipment parts and automobile parts.

By the way, from the viewpoint of weight reduction of various parts, a highly heat-resistant resin member is used as a substitute for a metal member. However, when it is difficult to replace all metal members with resin due to problems such as mechanical strength, a composite structure obtained by joining and integrating the metal member and the resin member (hereinafter, metal / resin composite structure). ) Is used.
As such a metal / resin composite structure, for example, a method is known in which the surface of a metal member is roughened and then bonded using a polyarylene sulfide resin by an anchor effect. For example, an aluminum alloy or magnesium alloy having a recess with a number average inner diameter of 10 to 80 nm on the surface by a chemical solution treatment such as an erosive aqueous solution or an erosive suspension, or a number average inner diameter of 10 on the surface by treatment with an anodic oxidation method. A composite is known in which a polyphenylene sulfide resin composition is injection-molded into an aluminum alloy having a recess of about 80 nm, and the resin composition is fixed in the recess in a state of being infiltrated (see Patent Document 1).
Further, a method of attaching and joining an adhesive film between a metal and a resin composite structure is also known. For example, a laminated film made of polypropylene and polyphenylene sulfide is heat-fused to stainless steel, and a polyphenylene sulfide resin is injection-molded therein to create a composite structure in the form of a metal / bonding laminated film / resin composite structure (patented patent). See Document 2).

Although the adherence of the molded product composed of the metal parts treated in Patent Document 1 and the resin composition is high, there are problems with the safety of the chemical solution used for the surface treatment and the influence on the environment. Hydrazine is particularly toxic and requires investment in large facilities that are safe and environmentally friendly.

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

Therefore, it is desired to develop a metal / resin composite structure that can be more easily produced and has excellent bonding strength.

JP-A-2007-050630 Japanese Unexamined Patent Publication No. 2013-091269

Therefore, an object to be solved by the present invention is to provide a composite structure having excellent adhesiveness, in which a metal member and a molded product of a polyarylene sulfide resin composition are bonded, and a simple manufacturing method thereof. .. Further, the present invention is to provide a polyarylene sulfide resin composition having excellent adhesiveness to metal parts, a molded product obtained by melt-molding the polyarylene sulfide resin composition having excellent adhesiveness to metal parts, and a method for producing them. ..

As a result of various studies, the inventors of the present application have combined a metal member and a molded product of a polyarylene sulfide resin composition with a polyolefin (a) having a group that reacts with a carbodiimide group and an alicyclic carbodiimide group-containing compound. It has been found that a composite structure having excellent adhesiveness can be easily produced by bonding with an adhesive composition containing a polyolefin which is a reaction product with (b), and the present invention has been solved.

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

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

Further, the present invention is a polyarylene sulfide resin composition used for a composite structure in which a metal member (1) and a molded product (2) of a polyarylene sulfide resin composition are bonded via a polyolefin (3). And
The polyolefin (3)
(I) Containing a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of the alicyclic carbodiimide group-containing compound (b).
The present invention relates to a polyarylene sulfide resin composition for a composite structure.

Further, the present invention is a polyarylene sulfide resin composition used for a composite structure in which a metal member (1) and a molded product (2) of a polyarylene sulfide resin composition are bonded via a polyolefin (3). It is a manufacturing method of
The polyolefin (3)
(I) Containing a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of the alicyclic carbodiimide group-containing compound (b).
The polyarylene sulfide resin composition is melt-kneaded by blending the polyarylene sulfide resin as an essential component.
The present invention relates to a method for producing a polyarylene sulfide resin composition for a composite structure, which comprises the above.

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

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

(Composite structure)
The composite structure of the present invention comprises a metal member (1) and a molded product (2) of a polyarylene sulfide resin composition bonded via an adhesive composition (3).

In the present invention, the bonding between the metal member and the molded product is performed by a 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). After the group contained in the polyolefin is chemically bonded on the surface of the metal member, there is no physical interaction such as van der Waals force with the polyarylene sulfide resin composition, or the polyarylene sulfide resin composition. When a compound having a group having a reactive group with a carbodiimide group is contained on the side, it is considered that excellent adhesiveness is exhibited by a chemical bond.

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

In constructing the composite structure of the present invention, the surface of the metal member (hereinafter, simply referred to as the surface of the metal member) does not require a surface roughening step, but of course, the surface of the metal member has a fine uneven surface (hereinafter, simply referred to as a fine uneven surface). You may have). By performing a surface roughening treatment and providing a fine uneven surface on the surface of the metal member, the action of mechanical bonding is added, and the adhesiveness can be further strengthened.

By subjecting the surface of the metal member of the composite structure of the present invention to a surface roughening treatment and providing a fine uneven surface, the molten adhesive composition (3) penetrates into the concave portion of the fine uneven surface with good fluidity. By solidification, an interface between the metal member and the resin member constituting the molded product (hereinafter, simply referred to as a metal-resin interface) is formed, and the metal member and the molded product of the polyarylene sulfide resin composition are strongly bonded. Can be done.

The distance between the fine uneven portions on the material surface of the metal part is preferably in the range of 5 nm or more, and further in the range of 10 nm or more, from the convex portion to the adjacent convex portion (hereinafter referred to as “between the convex portions”). Is more preferable. The upper limit is not particularly limited because it can flow even if the fluidity is low, but it is preferably in the range of 700 μm or less, and further 500 μm or less because the adhesion tends to improve when the unevenness density is high. It is more preferable that the range is. When the length between the convex portions is within the above range, the adhesive composition (3) used in the present invention can penetrate into the concave portions of the fine concavo-convex surface with good adhesion or wettability, and is excellent at the metal-resin interface. It can exhibit good adhesiveness. Further, it is preferable that the distance between the uneven portions has periodicity because better adhesiveness can be exhibited at the metal-resin interface.

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

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

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

As the surface roughening method, a known method can be used without limitation, and examples thereof include three types of methods.
(1) Immersion method using an erosive aqueous solution or an erosive suspension. It is preferable to have a shape in which fine uneven surfaces are formed on the metal surface, and more preferably, the metal surface has a shape in which a large number of recesses are formed, and the recesses have a number average inner diameter of 3 μm or less. Similarly, it is more preferable that the concave portion has a number average inner diameter in the range of 10 nm to 3 μm.
(2) Anodizing method. By forming a metal oxide layer mainly on the surface, it is preferable to form a large number of openings having a number average inner diameter of 1 μm or less on the surface layer, and similarly, openings having a number average inner diameter of 1 nm to 1 μm. It is more preferable to form a portion, and it is also more preferable to form an opening having a number average inner diameter of 10 to 200 nm.
(3) A method of forming irregularities on a metal surface by pressing a die punch having irregularities created by mechanical cutting, for example, diamond abrasive grain grinding or blasting, or creating an uneven shape on a metal surface by sandblasting or laser processing. how to. Mainly, it is preferable to machine the surface into a large number of recesses, and when forming a continuous shape recess such as the number average inner diameter of the recess or laser machining, the width is preferably in the range of 1 to 1000 μm, and further 10 to 10 It is more preferably in the range of 800 μm.

The metal member is processed into a predetermined shape by cutting, plastic working by pressing, punching, cutting, grinding, electric discharge machining, etc. before forming the fine uneven surface. Is preferable.

A primer layer may be formed on the surface of the metal member that has been surface-treated with the metal. The material constituting the primer layer is not particularly limited, but is usually made of a primer resin material containing a resin component. The primer resin material is not particularly limited, and known materials can be used. Specific examples thereof include known polyolefin-based primers, epoxy-based primers, urethane-based primers and the like other than the polyolefin (3) described later. The method for forming the primer layer is not particularly limited, and for example, a solution of the above-mentioned primer resin material or an emulsion of the above-mentioned primer resin material can be applied to the metal member subjected to the above-mentioned surface treatment to form the primer layer. Examples of the solvent used for making the solution include toluene, methyl ethyl ketone (MEK), dimethylformamide (DMF) and the like. Examples of the medium for the emulsion include an aliphatic hydrocarbon medium and water.

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

(Molded product of polyarylene sulfide resin composition (2))
The polyarylene sulfide resin composition of the present invention comprises a polyarylene sulfide resin as an essential component and, if necessary, blended with other components.

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 having a structure in which an aromatic ring and a sulfur atom are bonded as a repeating unit, and specifically, the following general formula (1).

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

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

Here, in the structural portion represented by the general formula (2), it is particularly preferable that R ¹ and R ² in the formula are hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. In this case, the one that is bound at the para position represented by the following formula (3) and the one that is bound at the meta position represented by the following formula (4) can be mentioned.

Among these, the heat resistance and crystallinity of the polyarylene sulfide resin is that the bond of the sulfur atom to the aromatic ring in the repeating unit has a structure in which the sulfur atom is bonded at the para position represented by the general formula (3). It is preferable in terms of surface.

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

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

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

The physical characteristics of the polyarylene sulfide resin are not particularly limited as long as the effects of the present invention are not impaired, but are as follows.
(Melting point (Tm) and recrystallization temperature (Tc2))
The melting point (Tm) of the polyarylene sulfide resin is preferably in the range of 270 ° C. or higher, more preferably in the range of 270 to 300 ° C., because it is a polyarylene sulfide resin composition having excellent heat resistance and mechanical strength. It is more preferable to have. Further, the recrystallization temperature (Tc2) of the polyarylene sulfide resin is preferably in the range of 200 to 260 ° C. because the polyarylene sulfide resin composition is excellent in heat resistance and mechanical strength.

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

(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 effect of the present invention is not impaired, but 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 a polyarylene sulfide resin is excellent in mechanical properties, fluidity, and abrasion resistance. However, for the non-Newtonian index (N value), the shear rate and shear stress are measured under the conditions of 300 ° C., the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40 using a capillograph. , It is a value calculated by using the following formula.

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

(Production method)
The method for producing the polyarylene sulfide resin is not particularly limited, but for example, 1) a dihalogeno aromatic compound is added in the presence of sulfur and sodium carbonate, and if necessary, a polyhalogeno aromatic compound or other copolymerization component is added. Method of polymerization 2) Method of adding a dihalogeno aromatic compound in the presence of a sulfidizing agent or the like in a polar solvent, and if necessary, a polyhalogeno aromatic compound or other copolymerization component, and polymerizing 3) p-chromo Examples thereof include a method of self-condensing ruthiophenol by adding other copolymerization components if necessary. Among these methods, the method 2) is general-purpose and preferable. At the time of the reaction, an alkali metal salt of a carboxylic acid or a sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above 2) methods, a hydrous sulfide agent is introduced into a mixture containing a heated organic polar solvent and a dihalogeno aromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogeno aromatic compound is introduced in the organic polar solvent. And a sulfidizing agent, if necessary, with a polyhalogeno aromatic compound to react, and the amount of water in the reaction system is in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. A method for producing a polyarylene sulfide resin by control (see JP-A-07-228699), and if necessary with a dihalogeno aromatic compound in the presence of a solid alkali metal sulfide and an aprotonic polar organic solvent. Polyhalogeno aromatic compounds or other copolymerization components are added to add alkali metal hydrosulfides and organic acid alkali metal salts to organic acid alkali metal salts in the range of 0.01 to 0.9 mol per 1 mol of sulfur source. Those obtained by a method of reacting while controlling the amount of water in the reaction system to 1 mol of the aprotonic polar organic solvent in the range of 0.02 mol or less (see WO2010 / 058713 pamphlet) are particularly preferable. Specific examples of the dihalogeno aromatic compound include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4, 4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p '-Dihalodiphenyl ether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and each of the above compounds. Examples of the aromatic ring of the above include compounds having an alkyl group having an alkyl group in the range of 1 to 18 carbon atoms, and examples of the polyhalogeno aromatic compound include 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3. Examples thereof include 5-trihalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene and 1,4,6-trihalonaphthalene. Further, it is desirable that the halogen atom contained in each of the above compounds is a chlorine atom or a bromine atom.

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

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

The polyarylene sulfide resin composition of the present invention may also contain a compound (2a) having reactivity with a carbodiimide group as an optional component. When blended, the ratio thereof 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 with respect to 100 parts by weight of the polyarylene sulfide resin. It is in the range of ~ 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. 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 type epoxy resin, novolak type epoxy resin, and epoxy resin having a polyarylene ether structure (α). Of these, the bisphenol type epoxy resin is preferable because it has excellent adhesiveness.

Examples of the type of epoxy resin for the bisphenol type epoxy resin include glycidyl ethers of bisphenols, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, and the like. Examples thereof include bisphenol S type epoxy resin, bisphenol AD type epoxy resin, and tetrabromobisphenol A type epoxy resin. In the case of the bisphenol type epoxy resin, the epoxy equivalent is 170 to 5000 [g / eq. ] Is preferable, and from the viewpoint of further reducing the amount of gas generated and improving the thermal impact resistance, 200 to 4000 [g / eq. ] Is preferably mentioned.

Examples of the novolak type epoxy resin include a novolak type epoxy resin obtained by reacting a novolak type phenol resin obtained by a condensation reaction between phenols and an aldehyde with epihalohydrin, and specific examples thereof include a novolak type epoxy resin. Examples thereof include type epoxy resin, cresol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-shrink novolak type epoxy resin, naphthol-cresol co-shrink novolak type epoxy resin, and brominated phenol novolak type epoxy resin. When the epoxy resin is a novolak type epoxy resin, the epoxy equivalent is 170 to 300 [g / eq. ] Is preferred, further 190-250 [g / eq. ] Is more preferable.

In addition, these epoxy resins contained in the polyarylene sulfide resin composition used in the present invention are present at the time of melt-kneading when a component acting as a so-called curing agent such as a phenol resin, an amine (active hydrogen compound) and a carboxylic acid anhydride is present. Since the epoxy group disappears by the curing reaction (addition reaction with the active hydrogen compound, co-polycondensation reaction with the acid anhydride), the ratio 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 0.1 equivalent or less, more preferably 0.01 equivalent or less, and most preferably 0 equivalent, that is, in the absence of the total 1 equivalent of the groups.

When the epoxy resin is used as the compound (2a) in the present invention, the mixing ratio thereof is not particularly limited as long as the effect of the present invention is not impaired, but is 0.01 to 100 with respect to 100 parts by weight of the polyarylene sulfide resin. The range 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.

When an epoxy group-containing polyolefin is used as the compound (2a), specific examples of the epoxy group-containing polyolefin include olefin-based elastomers having an epoxy group, but α-olefins are particularly preferable. 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 the vinyl polymerizable compounds having an epoxy group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and their alkyl esters, maleic acid, fumaric acid, and itaconic acid. , Other unsaturated dicarboxylic acids having 4 to 10 carbon atoms and their monos and diesters, α, β-unsaturated dicarboxylic acids such as acid anhydrides and derivatives thereof, glycidyl (meth) acrylates, and the like. Among them, an ethylene-propylene copolymer having an epoxy group in the molecule or an ethylene-butene copolymer is preferable because it improves toughness and impact resistance. Since the olefin wax having an epoxy group also has an epoxy group as a polar group and a polyolefin as a non-polar group, it is included in the above-mentioned olefin having an epoxy group.

When the epoxy group-containing polyolefin is used as the compound (2a) in the present invention, the mixing ratio thereof is not particularly limited as long as the effect of the present invention is not impaired, but is 0.01 with respect to 100 parts by weight of the polyarylene sulfide resin. It is preferably in the range of ~ 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 have various shapes such as fibrous ones and non-fibrous ones such as granular and plate-like ones. Examples include fillers. Specifically, glass fibers, carbon fibers, silane glass fibers, ceramic fibers, aramid fibers, metal fibers, potassium titanate, silicon carbide, calcium silicate, warastonite and other fibers, and natural fibers and other fibrous fillers are used. Can also be used, also glass beads, glass flakes, barium sulfate, clay, pyrophyllite, bentonite, sericite, mica, mica, talc, attapulsite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, zeolite, milled fiber. , Non-fibrous fillers such as calcium sulfate can also be used.

Although the filler is not an essential component in the present invention, when it is blended, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and it varies depending on the respective purposes and is unconditionally defined. However, for example, it 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 contain a thermoplastic elastomer other than the above as an optional component, if necessary. Examples of the thermoplastic elastomer include polyolefin-based elastomers other than the above, fluorine-based elastomers, and silicone-based elastomers. When these elastomers are blended, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and it varies depending on the respective purposes and cannot be unconditionally defined, but is a polyarylene sulfide resin. The range is preferably in the range of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight. In such a range, the impact resistance of the obtained polyarylene sulfide resin composition is improved, which is preferable.

Further, in addition to the above components, the polyarylene sulfide resin composition of the present invention further comprises the polyarylene sulfide resin and other synthetic resins other than the above compound (2a), for example, polyester resin, as appropriate, depending on the intended use. Polyamide resin, polyimide resin, polyetherimide resin, polycarbonate resin, polyphenylene ether resin, polysulphon resin, polyethersulphon resin, polyether ether ketone resin, polyether ketone resin, polyarylene resin, polyethylene resin, polypropylene resin, poly quaternary An optional component may be blended with an ethylene fluoride resin, a polydifluorinated ethylene resin, a polystyrene resin, an ABS resin, a phenol resin, a urethane resin, a liquid crystal polymer, or the like (hereinafter, simply referred to as a synthetic resin). Although the synthetic resin is not an essential component in the present invention, when it is blended, the blending ratio is not particularly limited as long as the effect of the present invention is not impaired, and it varies depending on the respective purposes and is unconditionally. Although it cannot be specified, the polyarylene sulfide resin and the compound (2a) are used as the ratio of the resin component (total of the polyarylene sulfide resin, the polyvinylpyrrolidone and the synthetic resin) to be blended in the polyarylene sulfide resin composition of the present invention. ) Is in the range of 75.0% by weight or more, preferably in the range of 80 to 99.99% by weight, in other words, the above synthetic resin is in the range of 25.0% by weight or less, preferably 0.01. 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 also has a colorant, an antistatic agent, an antioxidant, a heat-resistant stabilizer, an ultraviolet stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a flame retardant aid, and a flame retardant. Known and commonly used additives such as rusting agents and coupling agents may be added as optional components, if necessary. Although these additives are not essential ingredients, when they are blended, the blending ratio is not particularly limited as long as the effects of the present invention are not impaired, and they differ according to their respective purposes and cannot be unconditionally specified. However, for example, the polyarylene sulfide resin is preferably used in the range of 0.01 to 1,000 parts by weight with respect to 100 parts by weight, appropriately adjusted according to the purpose and application so as not to impair the effect of the present invention. Just do it.

In the method for producing a polyarylene sulfide resin composition of the present invention, a polyarylene sulfide resin is used as an essential component, and other arbitrary components are blended as necessary, and melt-kneaded at a temperature equal to or higher than the melting point of the polyarylene sulfide resin.

A preferred method for producing the polyarylene sulfide resin composition of the present invention is to combine the polyarylene sulfide resin and the above optional components in various forms such as powder, pellets, and strips in various forms such as a ribbon blender and a henschel so as to have the above-mentioned compounding ratio. After being charged into a mixer, V-blender, etc. for dry blending, it is charged into a known melt kneader such as a Banbury mixer, a mixing roll, a single-screw or biaxial extruder, and a kneader, and the resin temperature is the melting point of the polyarylene sulfide resin. A step of melt-kneading in the above temperature range, preferably the melting point + 10 ° C. or higher, more preferably the melting point + 10 ° C. to the melting point + 100 ° C., and further preferably the melting point + 20 to the melting point + 50 ° C. Can be manufactured via. Each component may be added to and mixed with the melt kneader at the same time, or may be divided.

As the melt kneader, a twin-screw kneading extruder is preferable from the viewpoint of dispersibility and productivity. For example, a resin component discharge amount in the range of 5 to 500 (kg / hr) and a screw rotation speed of 50 to 500 (rpm) are preferable. It is preferable to perform melt-kneading while appropriately adjusting the range of Is even more preferable. Further, when a filler or an additive is added among the above components, it is preferable to put the filler into the extruder from the side feeder of the twin-screw kneading extruder from the viewpoint of dispersibility. The position of the side feeder is preferably in the range of 0.1 to 0.9 in the ratio of the distance from the extruder resin charging portion to the side feeder with respect to the total screw length of the twin-screw kneading extruder. Above all, the range of 0.3 to 0.7 is particularly preferable.

The polyarylene sulfide resin composition of the present invention obtained by melt-kneading in this manner is a melt mixture containing a polyarylene sulfide resin which is an essential component, an optional component added as necessary, and a component derived from the same. After melt-kneading, it is preferably processed into pellets, chips, granules, powders and the like by a known method, and then pre-dried at a temperature of 100 to 150 ° C. as necessary for various moldings.

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

The molded product of the polyarylene sulfide resin composition of the present invention can be obtained by melt-molding the polyarylene sulfide resin composition. The melt molding may be a known method, and various molding methods such as injection molding, compression molding, composite, sheet, pipe extruding, pultrusion molding, blow molding, transfer molding and the like can be applied, and injection molding in particular. Is suitable. When molding by injection molding, various molding conditions are not particularly limited, and molding can usually be performed by a general method. For example, in an injection molding machine, the resin temperature is in a temperature range equal to or higher than the melting point of the polyarylene sulfide resin, preferably a temperature range of the melting point + 10 ° C. or higher, more preferably a temperature range of + 10 ° C. to a melting point + 100 ° C., still more preferably a melting point. After undergoing the step of melting the polyarylene sulfide resin composition in a temperature range of +20 to a melting point of +50 ° C., the polyarylene sulfide resin composition may be injected into a mold from a resin discharge port for molding. At that time, the mold temperature is also preferably set to a known temperature range, for example, a room temperature (23 ° C.) to 300 ° C., more preferably a range of 40 to 200 ° C., and a temperature range of 120 to 180 ° C. Most preferred.

(Adhesive composition (3))
The adhesive composition (3) used in the present invention contains a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of 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 a compound having a group having an active hydrogen having reactivity with a carbodiimide group. Specific examples thereof include compounds having a group derived from carboxylic acid, amine, alcohol, thiol and the like. Among these, a compound having a group derived from a carboxylic acid is preferably used, and among them, an unsaturated carboxylic acid and / or a derivative thereof is particularly preferable. In addition to the compound having a group having active hydrogen, a compound having a group easily converted into a group having active hydrogen by water or the like can also be preferably used. Specific examples thereof include a compound having an epoxy group and a compound having a glycidyl group. 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 anhydrous carboxylic acid groups and The derivative is mentioned. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group. Specific compounds include (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, and bicyclo [2.2.1] hepto-2. Included are unsaturated carboxylic acids such as −en-5,6-dicarboxylic acids, acid anhydrides thereof, and derivatives thereof (eg, acid halides, amides, imides, esters, etc.). Specific acid anhydrides and derivatives include, for example, maleic anhydride, itaconic acid anhydride, citraconic acid anhydride, phthalic acid tetrahydrochloride, and bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid. Anhydrate; Malenyl Chloride; Malenylimide; dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconic acid, diethyl citraconate, dimethyl tetrahydrophthalate, bicyclo [2.2.1] hept-2-ene Examples thereof include dimethyl-5,6-dicarboxylic acid, 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 acid anhydride, (meth) acrylic acid. , Hydroxyethyl (meth) acrylate, glycidyl methacrylate, aminopropyl methacrylate are preferred. Further, dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid anhydride are particularly preferable. preferable.

As a method for introducing the compound (a2) into the polyolefin (a1), a well-known method can be adopted. For example, a method for graft-copolymerizing the compound (a2) with the polyolefin (a1) or an olefin Examples thereof include a method of radically copolymerizing (a1) and compound (a2). Hereinafter, the case of graft copolymerization and the case of radical copolymerization will be specifically described.

(Graft copolymerization)
The polyolefin (a) having a group that reacts with a carbodiimide group is radically started with a compound (a2) having a group that reacts with a carbodiimide group in the polyolefin (a1), and other ethylenically unsaturated monomers if necessary. It can be obtained 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 containing an aliphatic α-olefin, a cyclic olefin, and a non-conjugated diene as main components in the range of 2 to 20 carbon atoms, and is preferably carbon. It is a polymer containing 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 the copolymer, the content of the olefin as a comonomer is not particularly limited as long as the effect of the present invention is exhibited, but is usually 50 mol% or less, preferably 40 mol% or less, and more preferably 30 mol% or less. be. Among the polyolefins in this range are polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and α-olefins of ethylene, propylene, butene-1 or 4-methylpentene-1 and a copolymer. Crystalline polyolefins such as copolymers are preferred, and polyethylene, polypropylene or propylene-ethylene copolymers are more preferred. Further, both of these can be used in both the isotactic structure and the syndiotactic structure, and there are no particular restrictions on the stereoregularity.

Density of the polyolefin (a1) used in the graft modification (measured in accordance with JIS K7112) is not particularly limited as long as the effect of the present invention, for example, the range of 0.8~1.1g / cm ³ is preferably , 0.8 to 1.05 g / cm ³ is more preferred, and 0.8 to 1.0 g / cm ³ is even more preferred. The melt flow rate (MFR) according to ASTM D1238 at 230 ° C. and a load of 2.16 kg is not particularly limited as long as the effect of the present invention is obtained, but is preferably in the range of 0.01 to 500 g / 10 minutes, preferably 0.05 to 200 g /. The range of 10 minutes is more preferable, and the range of 0.1 to 100 g / 10 minutes is even more preferable. When the density and MFR are within this range, the density and MFR of the graft copolymer after modification are also about the same, which is preferable because it is easy to handle.

The crystallinity of the polyolefin (a1) used for graft modification is not particularly limited as long as the effect of the present invention is obtained, but for example, a range of 2% or more is preferable, a range of 5% or more is more preferable, and a range of 10% is more preferable. The above range is more preferable. When the 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) of the polyolefin (a1) used for graft modification measured by gel permeation chromatography (GPC) is preferably in the range of 5,000 to 500,000, more preferably in the range of 10,000 to 100,000. .. If the number average molecular weight (Mn) is in this range, handling is excellent. In the case of ethylene-based polyolefin, the number average molecular weight can be determined in terms of polyethylene if the amount of comonomer is 10 mol% or less, or in terms of ethylene-propylene if the amount is 10 mol% or more (based on ethylene content of 70 mol%). It is preferable because it is possible.

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

(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 graft amount of the compound (a2) is preferably in the range of 0.05 to 20% by weight, more preferably in the range of 0.05 to 10% by weight, and 0. 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 amount of the graft of the compound (a2) is the net amount of the graft measured after removing the free compound (a2) from the polyolefin (a). The amount of graft can be measured by a known means such as ¹³ C-NMR and ^{1 H-NMR measurement.} When a monomer having an acidic functional group such as an unsaturated carboxylic acid and an acid anhydride thereof is used as the compound (m), the amount of the functional group introduced into the polyolefin (a) can be used as a guide. For example, it is also possible to use an acid value. When maleic anhydride is used as the compound (m), the amount of graft is 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.} Can also be asked.

(Radical copolymerization)
The polyolefin (a) having a group that reacts with a carbodiimide group can also be obtained by radical copolymerizing an olefin (a1') with a compound (a2) having a group that reacts with a carbodiimide group. As the olefin (a1'), the same olefin as the olefin used for forming the polyolefin (a1) used as the above-mentioned polyolefin main chain can be adopted. The method for copolymerizing the olefin (a1') and the compound (a2) is not particularly limited, and a conventionally known radical copolymerization method can be adopted.

(Structure of Polyolefin (a))
The amount (eg, structural unit amount, graft amount) derived from the compound (a2) having a group that reacts with the carbodiimide group in the polyolefin (a) having the group that reacts with the carbodiimide group is particularly limited as long as it is within a known range. Although not, the range of 0.05 to 20% by weight is preferable, the range of 0.05 to 5% by weight is more preferable, and the range of 0.05 to 3% by weight is further preferable. When the amount derived from the compound (m) having a group that reacts with the carbodiimide group is in 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 enables this. If it exceeds the lower limit of the above range, more excellent adhesive strength can be obtained, which is preferable.

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

(Carbodiimide group-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.

In formula (9), R ³ represents a divalent organic group having 2 to 40 carbon atoms.

Polycarbodiimide can be produced by a known method in which a diisocyanate such as an aliphatic diisocyanate, an aromatic diisocyanate, or an alicyclic diisocyanate is subjected to a decarboxylation condensation reaction in the presence of a condensation catalyst in a solvent-free or inert solvent. can.

(Manufacturing method of 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 for producing an isocyanate-terminated polycarbodiimide by a decarboxylation condensation reaction involving decarboxylation of a diisocyanate compound (US Patent No. 2941956, Japanese Patent Application Laid-Open No. 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 diisocyanate compound proceeds in the presence of a carbodiimidization catalyst. Examples of the carbodiimidization catalyst include 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 these 3-phosphoren isomers can be mentioned, and among these, 3-methyl-1-phenyl-2-xyl-2-phenyl-2-xyl is possible from the viewpoint of reactivity. Phenyl-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 carbodiimidization.

The decarboxylation condensation reaction of the diisocyanate compound can be carried out without a solvent or in an inert solvent. Examples of the inert solvent that can be used include alicyclic ethers such as tetrahydroxyfuran (THF), 1,3-dioxane and dioxolane: benzene, toluene, xylene, ethylbenzene and other aromatic hydrocarbons: chlorobenzene, dichlorobenzene and trichlorobenzene. , Parklen, trichloroethane, dichloroethane and the like halogenated hydrocarbons: ethyl acetate, butyl acetate and the like ester solvents: and organic solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone and the like ketone solvents. These may be used alone or in combination of two or more. Among these, toluene, tetrahydroxyfuran and methyl ethyl ketone are preferable.

The temperature in the 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.

Examples of the diisocyanate include aliphatic diisocyanates such as hexamethylene diisocyanate, 2,2-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, and xylyl. Aromatic diisocyanates such as range isocyanates, hydrogenated xylylene diisocyanates, dicyclohexamethylene-2,2'-diisocyanates, dicyclohexylmethane-2,4'-diisocyanates, dicyclohexylmethane-4,4'-diisocyanates, hydrophobic MDI hydrogenated products , 1,4-Cyclohexane diisocyanate, trans 1,4-bis (isocyanatomethyl) cyclohexane, cyclohexane-1,2-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate and other fats. Cyclic diisocyanates and the like are used alone or in admixture.

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

In the present invention, the "aliphatic diisocyanate" is a diisocyanate compound having a cyclic aliphatic hydrocarbon having no aromaticity in the molecule, and the "aliphatic diisocyanate" is a diisocyanate compound excluding an isocyanate group in the molecule. A diisocyanate compound having a chain aliphatic hydrocarbon and having neither a cyclic aliphatic hydrocarbon nor an aromatic hydrocarbon, "aromatic diisocyanate" is a diisocyanate having an aromatic hydrocarbon in its molecule. It shall refer to a compound.

In the decarboxylation condensation reaction, the degree of polymerization of polycarbodiimide can be adjusted by adjusting the amount of catalyst, the reaction temperature, and selecting and adding an end-capping agent, a denaturing agent, and the like. The degree of polymerization is preferably in the range of 2 to 40, more preferably in the range of 4 to 20. As the terminal encapsulant, for example, monoisocyanate such as phenyl isocyanate, trill isocyanate and naphthyl isocyanate, and active hydrogen-containing compounds such as methanol, ethanol, diethylamine, cyclohexylamine, succinic acid, benzoate and ethyl mercaptan can be used. As the condensation catalyst, for example, an alcoholate such as titanium, hafnium, zirconium, sodium and calcium, and an organic phosphorus compound such as phosphorene oxide can be used.

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

Further, in the present invention, as the carbodiimide group-containing compound (b), a compound modified with a compound capable of reacting with isocyanate can also be used. Compounds that can react with isocyanate include methanol having a hydroxyl group, isopropyl alcohol, phenol, polyethylene glycol monomethyl ether and the like: butylamine having an amino group, amines such as diethylamine: propionic acid having a carboxy group, benzoic acid and the like, and acid anhydride. It is possible to use a compound having a above-mentioned property, and it is preferable to use an amine, particularly an aliphatic amine.

(Denaturation of polycarbodiimide with aliphatic amines)
As the carbodiimide group-containing compound (b) used in the present invention, it is preferable to use an aliphatic amine as the compound capable of reacting with the above isocyanate and to use a modified polycarbodiimide. Modification of polycarbodiimide with an aliphatic amine can be performed without a solvent, but the above polycarbodiimide is mixed with an organic solvent, and the aliphatic amine is added thereto in a predetermined equivalent amount with respect to the carbodiimide group, and the mixture is stirred. It is also possible to synthesize by reacting with the above. When an organic solvent is used, the amount of the aliphatic amine added is preferably in the range of 1 to 2 equivalents with respect to 1 equivalent of the carbodiimide group, the excess amount of the aliphatic amine is small, and the amine dissipates during the heat treatment. It is more preferably in the range of 1 to 1.2 equivalents in terms of ease of use. The reaction temperature for the modification of polycarbodiimide with an 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 the modification. Is more preferred. The modification of 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.

(Alphatic amine)
Examples of the aliphatic amine capable of modifying polycarbodiimide include diethylamine, methylisopropylamine, tert-butylethylamine, di-sec-butylamine, dicyclohexylamine, 2-methylpiperidine and the like because of their high dissociability from polycarbodiimide. 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. Included is at least one aliphatic amine selected from the group consisting of -dimethylpiperidine, more preferably selected from the group consisting of diethylamine, tert-butylethylamine, di-sec-butylamine, dicyclohexylamine and 2-methylpiperidine. At least one aliphatic amine is mentioned, and more preferably, di-sec-butylamine is mentioned.

A group formed by modifying a carbodiimide group with an aliphatic amine (hereinafter referred to as a carbodiimide-modified group) has low reactivity and is therefore excellent in storage stability. However, the aliphatic amine is dissociated from the polycarbodiimide. Then, the carbodiimide-modifying group returns to the carbodiimide group before being modified by the aliphatic amine. As described above, since the reactivity of the carbodiimide group is high, when the aliphatic amine dissociates from the polycarbodiimide, the formed carbodiimide group adheres to the polyarylene sulfide resin composition with good adhesion. Further, the higher the dissociability of the aliphatic amine from the polycarbodiimide, the larger the number of carbodiimide groups changed from the carbodiimide-modified group, so that the aliphatic amine adheres to the polyarylene sulfide resin composition with good adhesiveness.

For example, when the aliphatic amine is ^{expressed as NHR 4} R ⁵ (R ⁴ , R ⁵ is a hydrogen atom or an aliphatic group of C1-6, or R ⁴ and R ^{5 form} a C6 alicyclic structure), the formula (9) is used. ), The polycarbodiimide derived from the diisocyanate compound having the carbodiimide group of) is modified with an aliphatic amine to form the carbodiimide modifying group of the formula (10). The carbodiimide-modifying group of the formula (10) has low reactivity due to the steric hindrance of the part of the formula (11) in the formula (10). Then, when the portion of the formula (11) is dissociated, a highly reactive carbodiimide group of the formula (9) is formed, and the modified polycarbodiimide compound cures the resin composition. Therefore, R ⁴ and R ⁵ are preferably C1-6 aliphatic groups, or R ⁴ and R ⁵ having a C6 alicyclic structure, that is, secondary aliphatic amines are preferable.

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 effect of the present invention is obtained, but ranges from 400 to 500,000. The range of 700 to 10,000 is more preferable, the range of 1,000 to 8,000 is even more preferable, and the range of 1,000 to 4,000 is most preferable. When the number average molecular weight (Mn) is in this range, the adhesive strength of the adhesive composition is excellent, which is preferable.

The carbodiimide group-containing compound (b) may contain monocarbodiimide in polycarbodiimide, or may be used alone or in combination of a plurality of compounds.

In the present invention, a commercially available carbodiimide group-containing compound can be used 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, so that the adhesiveness is more excellent. From this, it is preferable to use the carbodiimide group-containing compound (b) in which the number of carbodiimide groups in one molecule is in the range of 5 or more, and it is more preferable to use the carbodiimide group-containing compound (b) in the 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 effect of the present invention is achieved, but as the number of carbodiimide groups in one molecule increases, a crosslinked structure via the carbodiimide group-containing compound (b) is likely to be formed. As a result, the formability may deteriorate, so the range is preferably 30 or less.

The content of the carbodiimide group in the carbodiimide group-containing compound (b) ^{can be measured by 13} C-NMR, IR, a 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 in 13} C-NMR and 2130 to 2140 cm ^{-1 in IR.}

¹³ C-NMR measurement is performed, for example, as follows. That is, 0.35 g of the sample is heated and dissolved in 2.0 ml of hexachlorobutadiene. After filtering this solution with a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is charged into an NMR tube having an inner diameter of 10 mm. ^{Then, 13} C-NMR measurement is performed at 120 ° C. using a GX-500 type NMR measuring device manufactured by JEOL Ltd. The total number of times is 10,000 or more.

(Preparation Method of 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). The adhesive composition (3) can be specifically obtained by melt-kneading such as melt modification, but is not limited to this method.

An example of melt-kneading is shown below. The reaction method is not particularly limited, but the polyolefin (a) and the carbodiimide group-containing compound (b) are charged into, for example, a Henschel mixer, a V-type blender, a tumbler blender, a ribbon blender, or the like and kneaded, and then uniaxial. Examples thereof include a method of melt-kneading with an extruder, a multi-screw extruder, a kneader, a Banbury mixer and the like. Among these, it is preferable to use an apparatus having excellent kneading performance such as a multi-screw extruder, a kneader, and a Banbury mixer because it is possible to obtain an adhesive composition in which each component is more uniformly dispersed and reacted.

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

The temperature at which each of the above components is melt-kneaded 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. It is more preferably in the range of ~ 300 ° C, and even more preferably in the range of 235 to 280 ° C.

The content of the 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, and further preferably in the range of 0. It is in the range of 5 to 30 mmol. Within this range, the adhesiveness is excellent and the cross-linking of the polyolefin (a) via 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 amount of the carbodiimide group-containing compound (b) charged ^{, and can also be measured by 13} C-NMR, IR, a titration method or the like, and the carbodiimide. It is possible to grasp it as a base equivalent. It is possible to observe peaks ^{at 130 to 142 ppm in 13} C-NMR and 2130 to 2140 cm ^{-1 in IR.} The ¹³ C-NMR measurement is performed by, for example, the measurement method described in the above-mentioned method for measuring the carbodiimide group content in the carbodiimide group-containing compound (b).

Further, 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 group is consumed in the process, and the residue of the carbodiimide group linked as the same molecular chain as the polyolefin group contributes to the adhesiveness. When the content of the carbodiimide group is within the above range, the free carbodiimide group is present in the adhesive composition within a range that does not become excessive with respect to the polyolefin (a) having a group that reacts with the carbodiimide group. It is preferable because it has excellent adhesive performance and moldability.

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

After preparing each thermal press sheet for the polyolefin (a) (reference) having a group that reacts with the above carbodiimide group and the adhesive composition (3), infrared absorption is absorbed using an infrared absorption analyzer. To 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 with the absorbance derived from the reacting group. When a group derived from maleic anhydride is used as the group that reacts with the carbodiimide group, the absorbance at around ^{1790 cm-1 can be used.}

Reaction rate (%) = {X / Y} × 100 ... Equation (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 derived from reactive groups The reaction rate determined by the above method for the adhesive composition is usually in the range of 40 to 100%, preferably 60 to 100%, and more preferably 80 to 100%.

The density of the adhesive composition (measured according to JIS K7112) is not particularly limited as long as the effect of the present invention is not impaired, but is in the range of ^{0.870 to 0.940 g / cm 3.} It is preferably in the range of 0.875 to 0.940 g / cm ³ , more preferably in the range of 0.880 to 0.940 g / cm ^{3, and even more preferably in the range of 0.880 to 0.940 g / cm 3.} Within the above range, stable productivity, molding processability and adhesiveness are good, which is preferable.

The melt flow rate (according to MFR, ASTM D1238, 230 ° C., 2.16 kg load) of the adhesive composition is not particularly limited as long as the effect of the present invention is obtained, but is in the range of 0.01 to 500 g / 10 minutes. It is preferably in the range of 0.01 to 200 g / 10 minutes, more preferably in the range of 0.05 to 200 g / 10 minutes, and even more preferably in the range of 0.05 to 150 g / 10 minutes. It is particularly preferable, and most preferably it is in the range of 0.1 to 150 g / 10 minutes.

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

(Additives, etc.)
The adhesive composition (3) contains a polyolefin obtained by reacting the polyolefin (a) with the carbodiimide group-containing compound (b), but the polyolefin (a) and the carbodiimide group-containing compound (as long as the object of the present invention is not impaired). It may contain a resin different from b). Examples of such a resin include an unmodified polyolefin (that is, a polyolefin having no functional group such as an epoxy group, an amino group, a carboxy group, and a carboxylic acid anhydride group) and a group that reacts with a carbodiimide group. Examples thereof include a maleic acid-modified resin and an imine-modified resin. Further, the adhesive composition (3) may 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 product (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3). It is a manufacturing method of
The bonding composition (3) contains a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of the carbodiimide group-containing compound (b), the bonding method (A) or the bonding method. It is characterized by having (B).

(Joining method (A))
The joining method (A) includes a step of joining a metal member having an adhesive composition (3) on the surface of the metal member to be joined to the molded product (2) by melt-molding the polyarylene sulfide resin composition. ..

For example, first, a step of bringing the adhesive composition (3) into contact with the surface of the molded product to be joined to the metal member (1) is performed, and then the metal member having the adhesive composition (3) on the surface is provided. A so-called metal insert that is inserted into a mold of an injection molding machine and then injection-molded using the polyarylene sulfide resin composition on a metal member having an adhesive composition (3) on its surface. A method of performing a molding method can be mentioned. Further, as another form of metal insert molding, a resin film-like material in which a metal member layer having an adhesive composition (3) on the surface is laminated in a film form, or a film-like adhesive composition on a metal member layer. The so-called film insert molding may be performed in which a resin film-like material obtained by laminating the material (3) is inserted into a mold, and the polyarylene sulfide resin composition is melt-molded on the adhesive composition (3) side. The apparatus and manufacturing method in the metal insert molding method or the film insert molding method are not particularly limited, and a commercially available apparatus can be used, or can be carried out according to a conventional method. For a resin film-like material having such a metal member layer, a method (so-called thermal laminating method) in which the adhesive composition (3) is formed into a sheet or a film, the metal member layers are brought into contact with each other, and thermocompression bonding is performed at the same time, or the like. It can also be manufactured by a known laminating method. The heat laminating method includes a method of laminating using a hot press and a method of continuously laminating using a hot roll, and either of them may be used. On the other hand, the polyarylene sulfide resin composition is, for example, in an injection molding machine, in a temperature range in which the resin temperature is equal to or higher than the melting point of the polyarylene sulfide resin composition, preferably above the melting point and within the temperature range of the melting point plus 100 ° C., more preferably. After undergoing the step of melting the polyarylene sulfide resin composition within a temperature range of a melting point of plus 20 ° C. and a melting point of plus 50 ° C., the polyarylene sulfide resin composition may be molded by injecting it into a mold from a resin discharge port. At that time, the mold temperature may be set in a known temperature range, but can be set from a lower temperature, for example, set in the range of room temperature (23 ° C) to 300 ° C, preferably in the range of 40 to 180 ° C. And preferably set in the temperature range of 120 to 180 ° C.

(Joining method (B))
On the other hand, in the joining method (B), the adhesive composition (3) is brought into contact with the surface of the molded product to be joined to the metal member (1) or the surface of the metal member to be joined to the molded product (2). The step of joining the metal member (1) and the molded product (2) via the adhesive composition (3) at a temperature at which the polyarylene sulfide resin composition is melted is included.

In the joining method (B), a molded product of the polyarylene sulfide resin composition of the present invention is produced in advance. The adhesive composition (3) is applied to at least one surface selected from the group consisting of a surface to be bonded to the metal member (1) of the obtained molded product and a surface to be bonded to the molded product (2) of the metal member. ), And then, with the adhesive composition (3) on at least one of the surfaces, the metal member and the molded product are brought into contact with each other and then heated to be joined or heated. After joining, join and then cool. As such a method, for example, a hot plate welding method, a vibration welding method, an ultrasonic welding method, a high frequency welding method, an induction heating welding method, a rotary welding method, a laser welding method, a hot press method, a hot embossing method and the like can be used. As for the apparatus and the manufacturing method used for these joining methods, a commercially available apparatus can be used, or the apparatus can be carried out according to a conventional method. For example, in the hot plate welding method, in order to melt the surface of the molded product to be welded to the metal member, it is melted using a heat source such as a hot plate so that the following temperature conditions are met, and after joining with the metal member, it is added until it cools and hardens. It may be joined by holding it in a pressure state. Further, in vibration welding, ultrasonic welding, and high frequency welding, after the molded product is joined to the metal member, the surface of the molded product to be welded to the metal member is melted. It may be joined by transmitting ultrasonic waves and high frequencies to a molded product or a metal member to generate heat, melting the molded product by the heat generation, and holding the molded product in a pressurized state until it cools and hardens. The method of transmitting vibration, high frequency, and ultrasonic waves may be to bring a resonator or a vibration device into contact with an irradiation or a molded product to vibrate the molded product, whereby the molded product or the metal member itself is vibrated or vibrated. , The heat may be generated by the frictional heat between the molded product and the metal member. On the other hand, in induction heating welding, after the molded product is joined to the metal member, the surface of the molded product to be welded to the metal member is melted, so that the metal member is heated by an induction heating device so as to have the following temperature conditions. The molded product may be joined by generating heat to melt it and holding it in a pressurized state until it cools and hardens. Further, in rotary welding, after holding the molded product and the metal member separately, one of them is gradually brought closer to each other while rotating at a high speed in the range of 100 to 4,000 rotations, and the two come into contact with each other. By the way, the resin may be joined by generating frictional heat so as to have the following temperature conditions, melting the resin, and then holding the resin in a pressurized state until it cools and hardens.

Further, the molded product of the polyarylene sulfide resin composition may be in the form of a film. When the molded product of the polyarylene sulfide resin composition is a film-like material, from the viewpoint of maintaining the smoothness and surface appearance of the film-like material, the following hot press (thermocompression bonding) method and melt extrusion method are particularly applied. A bonding method called a bonding method can also be used, and if the film-like material is a transparent material capable of transmitting a laser beam, a bonding method called a laser welding method can also be used.

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

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

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

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

In the joining method (B) described above, it is basically necessary to melt the molded product and press it against the metal member. Therefore, the heating condition is that the resin temperature is the recrystallization temperature (Tc2) of the polyarylene sulfide resin. It may be appropriately adjusted in the above temperature range, more preferably 240 ° C. or higher, and more preferably 250 ° C. or higher. On the other hand, the upper limit value is not particularly limited as long as it does not decompose the resin, but is preferably in the temperature range of 370 ° C. or lower. Further, when a film-like material or the like maintains excellent smoothness and appearance and exhibits sufficient adhesion, it is appropriately adjusted within a temperature range of the recrystallization temperature (Tc2) or higher and lower than the melting point. On the other hand, if it is required to suppress gas generation due to resin decomposition, prevent resin deterioration, and exhibit better adhesiveness, adjust appropriately within the temperature range above the melting point. It is more preferable to adjust the temperature appropriately within the temperature range of the melting point or higher and the melting point plus 100 ° C., and it is particularly preferable to adjust the temperature appropriately within the temperature range of the melting point plus 20 ° C. and the melting point plus 50 ° C. Further, the pressure conditions for crimping (pressing each other) the metal member and the molded product are not particularly limited as long as the bonded state can be maintained, and for example, the metal member is between the start of heating and the end of cooling. In the direction in which the resin members are pressed against each other, a range of 0.01 [MPa] or more, preferably 0.01 to 100 [MPa], and more preferably 0.05 to 10 [MPa] is sufficient. It may be appropriately adjusted within a range in which the amount of burrs is small while exhibiting the adhesiveness. In the case of the laser welding method, it is not always necessary to press the metal member and the molded product against each other by an external force before welding, and the metal member and the molded product are joined by utilizing the pressure increase generated at the joining interface due to the volume expansion during melting. be able to.

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

(Use of composite structure)
Examples of main applications of the composite structure of the present invention include housings of various home appliances, mobile phones, and electronic devices such as PCs (Personal Computers), and protection / support members for box-shaped electric / electronic component integrated modules. Multiple individual semiconductors or modules, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, tuners. , Speakers, microphones, headphones, small motors, magnetic head bases, power modules, terminal blocks, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other electrical and electronic parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio / video equipment parts such as audio / laser discs / compact discs / DVD discs / Blu-ray discs, lighting parts, refrigerator parts, air conditioners Household and office electrical product parts represented by parts, typewriter parts, word processor parts, water supply parts such as water heaters and baths, temperature sensors, etc .; office computer-related parts, telephone equipment-related parts, facsimile-related parts Machine-related parts such as copying machine-related parts, cleaning jigs, motor parts, writers, typewriters, etc .: Optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternator terminal, Alternator connector, brush holder, slip ring, IC regulator, potential meter base for light die, relay block, inhibitor switch, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake Manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor , Thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust review Data, starter switch, ignition coil and its bobbin, motor insulator, motor rotor, motor core, starter reel, wire harness for transmission, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn Terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, power module, inverter, power device, intelligent power module, isolated gate bipolar transistor , Power control unit, reactor, converter, condenser, insulator, motor terminal block, battery, electric compressor, battery current sensor, junction block, ignition coil for DLI system, etc. It is also applicable to.

The present invention will be described in more detail below with specific examples. In addition, unless otherwise specified, parts and% are based on weight.

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

(Measurement Example 2) Evaluation of composition of adhesive composition Infrared spectroscopy (JASCO Corporation, FT / IR-6100) was performed as a composition analysis of the adhesive composition. The wave number is 600 to 4000 cm ^-1 , and the number of integrations is 64 times. The composition was evaluated from the signals corresponding to each functional group in the obtained spectrum.

(Measurement Example 3) Evaluation of Softening Temperature of Adhesive Composition The DMA measurement of the adhesive composition (TA Instruments Japan, RSA-G2) was carried out in the temperature range of -40 ° C to 200 ° C, and the temperature rise rate was 4 ° C / Min. , Tensile strain 0.1%, frequency 1 Hz. The temperature at which the temperature-dependent spectrum of the storage Young's modulus E'was 0.1 GPa or less when viewed from a low temperature was defined as the softening temperature.

(Measurement Example 4) Measurement of Bonding Strength of Composite Structure of Metal Test Piece / Adhesive Composition / PPS Resin Molded Composite Structure (ISO19095) in which molded bodies of metal test piece / adhesive composition / PPS resin composition are laminated. (Type-B type conforming to the above) was subjected to shear tensile measurement at a tensile speed of 5 mm / min using a material tester (Shimadzu Seisakusho, AG-IS). The measurement temperature was room temperature, and the average value (n = 5) of the maximum values of stress until the composite structure was broken was taken as the joint strength.
(Measurement Example 5) Observation of fracture surface of composite structure Visually observe the peeled surface of the composite structure in which the molded bodies of the metal test piece / adhesive composition / PPS resin composition obtained by shear tensile measurement are laminated. gone. In addition, "PPS" means that the film of the adhesive composition adhered only to the surface of the PPS molded product at the time of peeling, and "aggregate peeling" means that the film of the adhesive composition adhered only to the surface of the PPS molded product and the metal test. Indicates that it was attached to one surface.

(Manufacturing Example 1-1) Manufacture of metal member (A-1) No treatment: A metal piece is cut out from an aluminum plate (material: A5052) to a size of length x width x thickness = 45 mm x 10 mm x 1.5 mm. , The test piece (A-1).
(Manufacturing Example 1-2) Manufacture of metal member (A-2) Metal surface treatment: After further polishing the joint surface (abrasive paper roughness: No. 1000) on the test piece (A-1), the entire surface is YAG. Laser groove processing was performed using a laser marker device (Shibaura Eletech, LAY-791DE). On the surface of the aluminum piece, 25 continuous grooves having a length of 10 mm, a depth of 150 μm, and a width of 100 μm were formed at 100 μm intervals in the form of 25 slits to form a test piece (A-2).

(Production Example 2-1) Production of polyphenylene sulfide resin (B-1) [Step 1]
P-dichlorobenzene (hereinafter abbreviated as "p-DCB") 33.222 kg (226 mol), NMP3. A nitrogen atmosphere was charged with 420 kg (34.5 mol), 27.300 kg of 47.23 wt% NaSH aqueous solution (230 mol as NaSH), and 18.533 g of 49.21 wt% NaOH aqueous solution (228 mol as NaOH). 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 distilled by azeotrope during dehydration was separated by a decanter and returned to the autoclave at any time. In the autoclave after the completion of dehydration, the anhydrous sodium sulfide composition in the form of fine particles was dispersed in p-DCB. Since the NMP content in this composition was 0.079 kg (0.8 mol), 98 mol% (33.7 mol) of the charged NMP was an open ring of NMP (4- (methylamino)). It was shown to be hydrolyzed to a sodium salt (hereinafter abbreviated as "SMAB") of butyric acid). The amount of SMAB in the autoclave was 0.147 mol per mol of sulfur atoms present in the autoclave. The charged NaSH and NaOH is the total amount, since the theoretical amount of dehydration may change anhydrous Na ₂ S is 27.921G, among residual water content in the autoclave 878 g (48.8 mol), 609g (33.8 mol) Is consumed in the hydrolysis reaction between 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. Was showing. The amount of water in the autoclave was 0.065 mol per mol of sulfur atoms present in the autoclave.

[Step 2]
After the completion of the dehydration step, the internal temperature was cooled to 160 ° C., NMP 46.343 kg (467.5 mol) was charged, and the temperature was raised to 185 ° C. The amount of water in the autoclave was 0.025 mol per 1 mol of NMP charged in step 2. When the gauge pressure reached 0.00 MPa, the valve connected to the rectification column was opened, and the temperature was raised to an internal temperature of 200 ° C. over 1 hour. At this time, cooling and valve opening were controlled so that the rectification tower outlet temperature was 110 ° C. or lower. The distilled steam of p-DCB and water was condensed in a condenser, separated by a decanter, and the p-DCB was returned to the autoclave. The amount of distillate 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, and 0.010 mol per mol of sulfur atoms present in the autoclave. .. The amount of SMAB in the autoclave was 0.147 mol per mol of sulfur atoms present in the autoclave, as in step 1. Then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, and the mixture was stirred at 230 ° C. for 1 hour, then raised to 250 ° C. and stirred for 1 hour. The gauge pressure at an internal temperature of 200 ° C. was 0.03 MPa, and the final gauge pressure was 0.40 MPa. After cooling, 650 g of the obtained slurry was poured into 3 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was stirred again with 3 liters of warm water for 1 hour, washed and then filtered. This operation was repeated 4 times. The cake was adjusted to pH 4.0 by adding 3 liters of warm water and acetic acid again, stirred for 1 hour, washed, and then filtered. The cake was stirred again with 3 liters of warm water for 1 hour, washed and then filtered. This operation was repeated twice. It was dried overnight at 120 ° C. using a hot air dryer to obtain a white powdery PPS resin (B-1). The melt viscosity of this polymer at 300 ° C. was 41 Pa · s. The non-Newtonian index was 1.07.

(Production Example 2-2) Production of polyphenylene sulfide resin (B-2) "Then, the temperature is raised from 200 ° C. to 230 ° C. over 3 hours, the temperature is raised to 230 ° C. for 1 hour, and then the temperature is raised to 250 ° C. Then, the portion to be "stirred for 1 hour" was heated to "then, the temperature was raised from 200 ° C. to 230 ° C. over 3 hours, and the temperature was raised to 250 ° C. after stirring at 230 ° C. for 1.5 hours." 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 mixture was stirred for a time. 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) Flake-shaped sodium sulfide (60.3 wt% Na 2)} was added to a 150-liter autoclave with a stirring blade and a bottom valve connected to a pressure gauge, thermometer, and capacitor. S) 19.413 kg and 45.0 kg of NMP were charged. The temperature was raised to 209 ° C. with stirring under a nitrogen stream to distill off 4.644 kg of water (the amount of residual water was 1.13 mol per mol of sodium sulfide). Then, the autoclave was sealed and cooled to 180 ° C., and charged with 22.185 kg of paradichlorobenzene, 0.027 kg of 1,2,4-trichlorobenzene and 18.0 kg of NMP. The temperature was raised to 0.1 MPa with a gauge pressure using nitrogen gas at a liquid temperature of 150 ° C. to start the temperature rise. After holding at a liquid temperature of 240 ° C. for 2 hours, the reaction proceeded while stirring at a liquid temperature of 260 ° C. for 3 hours, and the upper part of the autoclave was cooled by sprinkling water. Next, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. While cooling the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. The maximum pressure during the reaction was 0.85 MPa. After the reaction, the mixture 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 injected under pressure. After stirring for 30 minutes, the mixture was cooled, the bottom valve was opened at 100 ° C., the reaction slurry was transferred to a 150 liter plate filter, pressure filtered at 120 ° C., 16 kg of NMP was added, and pressure filtration was performed. After filtration, NMP was removed by stirring at 150 ° C. for 2 hours under reduced pressure using a 150 liter vacuum dryer with a stirring blade to obtain a white powdery PPS resin (B-3). The melt viscosity of this polymer at 300 ° C. 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 Anhydrous Maleic Acid-Modified Polypropylene (PP-MA) Polypropylene (Density = 0.912 g / cm ³ , Co., Ltd. ) Prime Polymer Co., Ltd.) in 100 parts by weight, maleic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) in 1 part by weight, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexin-3 ( 0.30 part by weight (manufactured by Nichiyu Co., Ltd.) was 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 . The amount of maleic anhydride grafted was measured by infrared spectroscopy (FT-IR) and found to be 0.9% by weight.

(Production Example 3-1b) Production of polycarbodiimide (b1) having an alicyclic structure 100 parts by weight of dicyclohexylmethane 4,4'-diisocyanate (VESTANAT H12MDI manufactured by Degusa Japan Co., Ltd.), polyalkylene carbonate diol ( Asahi Kasei Chemicals Co., Ltd., DURANOL T-5651, molecular weight 1000) 71.8 parts by weight, phenylisocyanate 17.1 parts by weight, 245 parts by weight of toluene and carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-) 1-Oxide) 1.0 part by weight is put into a reaction vessel equipped with a reflux tube and a stirrer, stirred at 100 ° C. for 3 hours under a nitrogen stream, and absorbed by an isocyanate group near a ^{wavelength of 2270 cm-1 by FT-IR measurement.} It was confirmed that the peak had almost disappeared, and an ^{absorption peak due to a carbodiimide group having a wavelength of around 2150 cm-1} was confirmed 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 the mixture was stirred for 5 hours. Next, it was confirmed by FT-IR measurement that the absorption peak due to the group represented by the formula (11) was generated near the ^{wavelength of 1660 cm -1} , and the absorption peak due to the carbodiimide group near the ^{wavelength of 2150 cm -1 was almost extinguished.} The modified polycarbodiimide compound (b1) was obtained.

(Production Example 3-1c) Production of Adhesive Composition (C-1) 100 parts by weight of maleic anhydride-modified polypropylene (PP-MA) prepared above and 1.9 parts by weight of modified polycarbodiimide compound (b1). 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 an aromatic structure Tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., "Cosmonate T-80" 2,4-tolylene diisocyanate / 2,6- 100 parts by weight of tolylene diisocyanate (75-85 / 15-25), 71.0 parts by weight of polyalkylene carbonate diol (Asahi Kasei Chemicals Co., Ltd., DURANOL T-5651, molecular weight 1000), 16.8 parts by weight of phenylisocyanate. 245 parts by weight of toluene (boiling point 110.6 ° C.) and 1.0 part by weight of carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide) in a reaction vessel equipped with a reflux tube and a stirrer. After charging, the mixture was stirred at 100 ° C. for 3 hours under a nitrogen stream, and it was confirmed by infrared absorption (IR) spectrum measurement that the absorption peak due to the isocyanate group near the ^{wavelength 2270 cm -1} had almost disappeared, and the wavelength was around ^{2150 cm -1.} The absorption peak of the carbodiimide group was confirmed 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 the mixture was stirred for 5 hours. Next, by infrared absorption (IR) spectrum measurement, an absorption peak due to the group represented by the formula (11) was generated near the ^{wavelength of 1660 cm -1} , and the absorption peak due to the carbodiimide group near the ^{wavelength 2150 cm -1 almost disappeared.} After confirming that, a modified polycarbodiimide compound (b2) was obtained.

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

(Production Example 3-3b) Production of polycarbodiimide (b3) having an aliphatic structure 100 parts by weight of hexamethylene diisocyanate, polyalkylene carbonate diol (manufactured by Asahi Kasei Chemicals Co., Ltd., DURANOL T-5651, molecular weight 1000) 71.0 weight 16.6 parts by weight of phenylisocyanate, 245 parts by weight of toluene (boiling point 110.6 ° C.) and 1.0 part by weight of carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide). And put it in a reaction vessel equipped with a stirrer, stir at 100 ° C for 4 hours under a nitrogen stream, and confirmed by infrared absorption (IR) spectrum measurement that the absorption peak due to the isocyanate group near the ^{wavelength of 2270 cm-1 was almost eliminated.} At the same time, ^{an absorption peak due to a carbodiimide group having a wavelength of around 2150 cm-1} 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 the mixture was stirred for 5 hours. Next, it was confirmed by FT-IR measurement that the absorption peak due to the group represented by the formula (11) was generated near the ^{wavelength of 1660 cm -1} , and the absorption peak due to the carbodiimide group near the ^{wavelength of 2150 cm -1 was almost extinguished.} The 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 of the modified carbodiimide group-containing compound (b3). The parts by weight were mixed and extruded at a cylinder temperature of 250 ° C. using a twin-screw kneader to produce pellets of the adhesive composition (C-3).

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

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

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

(Examples 1 to 18)
(Manufacturing of Polyarylene Sulfide Resin Composition)
Each material was uniformly mixed with a tumbler according to the composition components and blending amounts (all by weight) shown in Tables 1 to 5. After that, the compounded material was put into a twin-screw extruder with a vent (Nippon Steel Works, TEX30α), and melt-kneaded by setting the resin component discharge amount 30 kg / hr, screw rotation speed 220 rpm, and set resin temperature to 320 ° C. Pellets of polyphenylene sulfide resin composition were obtained.

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

(Evaluation of composite structure of metal test piece / adhesive composition / PPS resin composition)
The composite structure in which the obtained metal test piece / adhesive composition / PPS resin composition molded body was laminated was left at room temperature for 24 hours, and then a shear tensile test was performed as in Measurement Example 4 to obtain a bonding strength. Then, the fracture surface was observed as in 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 as the metal test piece in the same manner as above. A composite structure in which molded bodies of / adhesive composition / PPS resin composition were laminated was prepared and evaluated. The results are shown in Tables 1-5.

The compounding ratios of the compounded resins and materials in Tables 1 to 5 represent parts by weight, and the following are used.
GF: Glass filler (chopped strand length 200 μm, average diameter 10 μm)
BF-7L: Olefin Elastomer "Bond First-7L" manufactured by Sumitomo Chemical Co., Ltd. (ethylene-glycidyldimethacrylate-vinyl acetate)
"Epoxy 7050": Epoxy resin "Epoxy 7050" manufactured by DIC Corporation (epoxy equivalent 1750-2100 g / equivalent)
"Epoxy N-673": Epoxy resin "Epoxy N-673" manufactured by DIC Corporation (epoxy equivalent 205-215 g / equivalent)
"Novatec": High-density polyethylene "Novatec" manufactured by Mitsubishi Chemical Holdings, Inc.

1 ... Metal member 2-1 ... Polyarylene sulfide resin composition 2-2 ... Polyarylene sulfide resin composition molded body 3 ... Adhesive composition

Claims (14)

A method for producing a composite structure in which a metal member (1) and a molded product (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3).
The bonding composition (3) contains a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of the carbodiimide group-containing compound (b), a bonding method (A) or a bonding method. A manufacturing method comprising (B).
Joining method (A)
The present invention comprises a step of joining a metal member having an adhesive composition (3) on the surface of the metal member to be joined to the molded product (2) by melt-molding the polyarylene sulfide resin composition.
Joining method (B)
The polyarylene sulfide resin composition in a state where 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). Includes a step of joining the metal member (1) and the molded product (2) via the adhesive composition (3) at a temperature at which the metal member (1) melts. The production 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-cyclohexanediisocyanate and trans 1,4-bis (isocyanatomethyl) cyclohexane. The manufacturing method according to claim 1. The production method according to claim 1, wherein the carbodiimide group-containing compound (b) is obtained by modifying a polycarbodiimide compound with an aliphatic amine. A step of joining a metal member having an adhesive composition (3) on the surface of the metal member to be joined to the molded product (2) by melt-molding the polyarylene sulfide resin composition.
or,
The 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), and then the polyarylene sulfide resin is used. at temperatures which the composition is melted, via adhesive composition (3), that have a a step of joining the metal members (1) and the molded article (2) the method請Motomeko 1, wherein .. The production method according to claim 1, wherein the polyarylene sulfide resin composition contains the compound (2a) having reactivity with a carbodiimide group in the range of 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin. .. 6. The compound according to claim 6, wherein 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 production 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 product (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3).
The adhesive composition (3)
(I) Containing a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of the alicyclic carbodiimide group-containing compound (b).
A composite structure characterized by. A polyarylene sulfide resin composition used for a composite structure in which a metal member (1) and a molded product (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3). ,
The polyarylene sulfide resin composition contains the compound (2a) having reactivity with a carbodiimide group in the range of 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin, and
The adhesive composition (3)
(I) Containing a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of the alicyclic carbodiimide group-containing compound (b).
A polyarylene sulfide resin composition for a composite structure characterized by. A method for producing a polyarylene sulfide resin composition used for a composite structure in which a metal member (1) and a molded product (2) of a polyarylene sulfide resin composition are bonded via an adhesive composition (3). And
The polyarylene sulfide resin composition contains the compound (2a) having reactivity with a carbodiimide group in the range of 0.01 to 100 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin, and
The adhesive composition (3)
(I) Containing a polyolefin (a) having a group that reacts with a carbodiimide group and a polyolefin that is a reaction product of the alicyclic carbodiimide group-containing compound (b).
The polyarylene sulfide resin composition is melt-kneaded by blending the polyarylene sulfide resin as an essential component.
A method for producing a polyarylene sulfide resin composition for a composite structure. A molded product obtained by melt molding the polyarylene sulfide resin composition for a composite structure according to claim 11. Polyarylene sulfide resin composition for a composite structure, comprising a step of producing a 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. A method for manufacturing a molded product.

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