JP6809199B2 - Metal member-polyarylene sulfide resin member composite - Google Patents

Description

The present invention relates to a metal member-polyarylene sulfide resin member composite having excellent bonding strength on the bonding surface and a method for producing the same. More specifically, the present invention is excellent in impact resistance, light weight and mass productivity, and particularly in automobiles and aircraft. Metal members with excellent bonding strength-polyarylene sulfide resin member composites and metal members with excellent bonding strength-polyarylene sulfide resin member composites, which are useful for parts of transportation equipment such as It relates to a method for stable manufacturing while maintaining joining reliability.

In order to reduce the weight of parts of transportation equipment such as automobiles and aircraft, a method of replacing a part of metal with resin is being studied. In addition, as a method of compositely integrating resin and metal, a method of inserting a metal member having a surface that has been physically and / or chemically treated into a mold, and injection molding the resin to directly integrate the resin (hereinafter referred to as). , Sometimes referred to as injection insert molding method) is attracting attention from the viewpoints of good mass productivity, small number of parts, low cost, high design flexibility, and low environmental load, and the manufacturing process of portable electronic devices such as smartphones. Etc. (see, for example, Patent Documents 1 to 3).

Polyarylene sulfide (hereinafter, sometimes abbreviated as PAS) represented by poly (p-phenylene sulfide) (hereinafter, may be abbreviated as PPS) has excellent mechanical properties, thermal properties, and It has electrical characteristics and chemical resistance, and is widely used in many electrical and electronic equipment parts, automobile equipment parts, and other OA equipment parts.

Further, since PAS is excellent in melt fluidity, it exhibits excellent bonding strength in an injection insert molding method with a metal member having a surface subjected to physical treatment and / or chemical treatment.

On the other hand, the ultrasonic flaw detection test is generally used as a method for inspecting defects such as voids in a sample. For example, inspection of a friction stir joint, inspection of a joint surface of a metal part, and a joint of a metal ceramic-joint. (For example, see Patent Documents 4 to 6).

Japanese Patent No. 5701414 Japanese Patent No. 5714193 Japanese Patent No. 4020957 Japanese Patent No. 43696999 Japanese Unexamined Patent Publication No. 2008-119711 Japanese Patent No. 3638462

However, in the metal member-resin member composite obtained by the injection insert molding method proposed in Patent Documents 1 to 3, it is possible to obtain a composite having a certain bonding strength, but in injection insert molding, the apparatus Poor bonding between the metal member and the polyarylene sulfide resin member may occur due to malfunction, mistake in setting conditions, length of resin residence time in the injection molding machine cylinder, etc., and defects such as voids may occur on the joint surface. , There was a large variation in individual performance differences, and there was a problem in making a stable product. In addition, in order to obtain information on the joint state of the joint surface of the obtained composite, inspection by a fracture test such as evaluating the joint strength by a tensile test of the composite is common, and such a method is a reliable product. It cannot be used for sexual confirmation. As a countermeasure, a sampling test is also adopted, but there are problems such as a decrease in yield and poor mass productivity. Therefore, in consideration of industrial mass production and quality control, a metal member-resin member composite in which the joint state of the joint surface of the composite, for example, the defect occurrence state is quantitatively quantified by a non-destructive test, is desired. It was.

The inspection by the ultrasonic flaw detection test proposed in Patent Documents 4 to 6 does not target the metal member-resin member composite, and does not describe any metal member-resin member composite.

Therefore, the present invention maintains the reliability of a metal member-polyarylene sulfide resin member composite having excellent bonding strength between a metal member and a polyarylene sulfide resin member and a metal member-polyarylene sulfide resin member composite having excellent bonding strength. It is an object of the present invention to provide a method for stable production as it is.

As a result of diligent studies to solve the above problems, the present inventor has found that the metal member-polyarylene sulfide resin member composite having a reflection intensity of ultrasonic waves reflected on the joint surface at a certain ratio or less is excellent in bonding. The present invention has been completed by finding that it has strength, is excellent in joining reliability, and is a member, part, product, etc. having excellent impact resistance, light weight, and mass productivity.

That is, the present invention is a metal member-polyarylene sulfide resin member composite in which a metal member and a polyarylene sulfide resin member are directly integrated by injection molding, and is formed on a joint surface between the metal member and the polyarylene sulfide resin member. On the other hand, the present invention relates to a metal member-polyarylene sulfide resin member composite and a method for producing the same, wherein the echo height of the ultrasonic waves that emit ultrasonic waves and are reflected at the joint surface is 35% or less.

The present invention will be described in detail below.

The metal member-polyarylene sulfide resin member composite of the present invention is a metal member-polyarylene sulfide resin member composite in which a metal member and a polyarylene sulfide resin member are directly integrated by injection molding, and is formed on a joint surface thereof. On the other hand, the echo height of the ultrasonic waves that emit ultrasonic waves and are reflected at the joint surface is 35% or less, and particularly preferably the echo height of the ultrasonic waves is 30% or less. Here, when the echo height of the ultrasonic wave exceeds 35%, the bonding strength is inferior. Regarding this point, it is assumed that there are voids and defects on the joint surface that easily reflect ultrasonic waves. The echo height in the present invention is expressed as the ratio of the irradiation intensity to the reflection intensity (reflection intensity / irradiation intensity * 100), which is the intensity of the ultrasonic waves reflected on the joint surface.

Then, as a method for measuring the echo height of ultrasonic waves, for example, an ultrasonic flaw detection test can be used. As the ultrasonic flaw detection test, there are a one-probe method using one ultrasonic probe and a two-probe method using a plurality of ultrasonic probes, both of which can be used. Further, as the one probe method, there are a direct contact method in which the joint is in direct contact with the joint, a water immersion flaw detection method in which the joint is submerged, and the like, and any of them can be used, and in particular, minute defects on the joint surface can be accurately detected. The water immersion flaw detection method is preferable because it can be detected. Further, as the ultrasonic flaw detection test, a reflection method or a transmission method is known, and among them, it is possible to identify the position of a defect inside the composite, inside a metal member or inside a polyarylene sulfide resin member. The reflection method is preferable because it is possible to discriminate defects in the joint surface and defects in the joint surface. The reflection method in the ultrasonic flaw detection test is that ultrasonic waves are transmitted from the ultrasonic probe of the ultrasonic flaw detection test device toward the joint surface, and if there are voids, defects, etc. on the joint surface, the ultrasonic waves are reflected. This is a test method that returns to the ultrasonic probe.

The echo height of the ultrasonic wave is the ratio of the reflection intensity to the irradiation intensity of the ultrasonic wave, and when there are no voids or defects in the joint surface, the ultrasonic wave is not reflected by the joint surface and the joint surface is not reflected. The echo height in is close to 0%. On the other hand, when there is a defect on the joint surface, ultrasonic waves are reflected by the joint surface and the echo height becomes large, and when there is a defect larger than the ultrasonic beam diameter spreading in the joint surface direction, the echo height is 100. Approaching%. The location of defects in the reflection method can be calculated by multiplying the propagation time of ultrasonic waves by the speed of sound, and from the time when the echo height is detected, defects on the joint surface, inside metal members, or polyarylene sulfide. Any of the defects inside the resin member can be discriminated, and the echo height at the position corresponding to the defect on the joint surface is defined as the echo height of the joint surface. The echo height of the ultrasonic wave is defined as the echo height at which the transmitted ultrasonic wave passes through the metal member of the metal member-polyarylene sulfide resin member composite and is reflected from the joint surface. It is preferable because it can eliminate defects such as voids inside the member and detect it with high accuracy.

The incident wave of ultrasonic waves transmitted from the ultrasonic probe is a vertical flaw detection method in which the incident wave is transmitted perpendicularly to the joint surface, or the incident wave is transmitted from an arbitrary angle other than perpendicular to the joint surface. Among them, the vertical flaw detection method is preferable because the distance passing through the inside of the metal member-polyarylene sulfide resin member composite is short and the reflected wave can be efficiently received. Further, the frequency transmitted from the ultrasonic probe of the ultrasonic flaw detection test may be an ultrasonic probe that transmits any frequency as long as it is in the frequency range of 20 KHz or higher, which is called ultrasonic wave. Among them, it is preferable to use a probe that emits high-frequency ultrasonic waves of 10 MHz or more, preferably 20 MHz or more, particularly 25 MHz or more, because it can detect minute defects. Commercially available ultrasonic probes can be used, and specific examples thereof include (trade name) water-immersed probes V324-SU, V316-SU (manufactured by Olympus Corporation), (trade name). Water immersion probe 10C5I (manufactured by Japan Probe Co., Ltd.), (trade name) Water immersion probe MI (manufactured by Inspection Technology Laboratory Co., Ltd.), (trade name) High-frequency probe V358-SU, V356 -SU (manufactured by Olympus Corporation), high frequency probe 25E6I (manufactured by Japan Probe Co., Ltd.) and the like can be mentioned.

The polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention may be any one belonging to the category generally referred to as polyarylene sulfide resin, and the polyarylene sulfide resin may be used. Examples thereof include homopolymers or copolymers consisting of p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Specific examples of the polyarylene sulfide resin include poly (p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide ether, and the like, among which heat resistance and strength characteristics are particularly excellent. Poly (p-phenylene sulfide) is preferable because it provides an excellent polyarylene sulfide resin composition.

Further, the polyarylene sulfide resin (A) is mechanically measured at a melt viscosity measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg by a high-grade flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. A polyarylene sulfide resin having 50 to 2000 poise is preferable because a polyarylene sulfide resin composition having excellent strength and thin-wall fluidity can be obtained.

As a method for producing the polyarylene sulfide resin (A), it can be produced by a method known as a method for producing a polyarylene sulfide resin, for example, an alkali metal sulfide salt and a polyhaloaromatic compound in a polar solvent. Can be obtained by polymerizing. Examples of the polar organic solvent at that time include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, dimethylacetamide and the like, and examples of the alkali metal sulfide salt include sulfide. Anhydrous or hydrates of sodium, rubidium sulfide, lithium sulfide can be mentioned. Further, the alkali metal sulfide salt may be a reaction of an alkali metal hydroxide salt and an alkali metal hydroxide. Examples of the polyhaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenylsulfone, and 4 , 4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorodibiphenyl and the like.

The polyarylene sulfide resin (A) is a linear one, a polyhalogen compound having a trihalogen or higher added in a small amount at the time of polymerization to introduce a slight crosslinked or branched structure, and a molecular chain of the polyarylene sulfide resin. A part and / or end of the above is modified with a functional group such as a carboxyl group, a carboxymetal salt, an alkyl group, an alkoxy group, an amino group or a nitro group, or heat-treated in a non-oxidizing inert gas such as nitrogen. And the like, and a mixture of these polyarylene sulfide resins may be used. Further, the polyarylene sulfide resin (A) is subjected to acid cleaning, hot water cleaning or cleaning treatment with an organic solvent such as acetone or methyl alcohol to carry out sodium atom, polyarylene sulfide resin oligomer, salt, 4- (N). -Methyl-chlorophenylamino) Butanoate may have reduced impurities such as sodium salt.

The polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention is a metal member-polyarylene sulfide resin member composite having particularly few defects on the joint surface and having excellent impact resistance. Therefore, it is preferable that the modified ethylene-based copolymer (B) is further blended. The modified ethylene-based copolymer includes ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α, β. -Unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer and ethylene anhydride graft-modified ethylene-α- It is preferably at least one modified ethylene-based copolymer selected from the group consisting of olefin copolymers. The blending amount of the modified ethylene-based copolymer (B) is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin (A).

Since the polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention is a metal member-polyarylene sulfide resin member composite having particularly excellent strength and impact resistance, it is a glass fiber. A mixture of (C) is preferable. As the glass fiber (C), any glass fiber (C) may be used as long as it is generally referred to as glass fiber. Specific examples of the glass fibers include chopped strands having an average fiber diameter of 6 to 14 μm, chopped strands composed of flat glass fibers having a fiber cross-sectional aspect ratio of 2 to 4, milled fibers, roving and other glass fibers; silane fibers. Aluminosilicate glass fiber; Hollow glass fiber; Non-hollow glass fiber, etc. Among them, metal member-polyarylene sulfide resin member composite with few defects on the joint surface and excellent impact resistance. It is preferably a chopped strand having an average fiber diameter of 6 to 14 μm, or a chopped strand made of flat glass fiber having an aspect ratio of 2 to 4 in the fiber cross section. Two or more of these glass fibers (C) can be used in combination, and if necessary, they are surface-treated in advance with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound. You may use the thing. The amount of the glass fiber (C) blended is 100 parts by weight of the polyarylene sulfide resin (A) because it is a metal member-polyarylene sulfide resin member composite having few defects on the joint surface and excellent impact resistance. It is preferably 5 to 120 parts by weight.

The polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention contains calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, and silica as long as the effects of the present invention are not impaired. , Tarku, clay, calcium sulfate, kaolin, wallastenite, zeolite, silicon oxide, magnesium oxide, zirconium oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, hydrotalcite, glass powder, glass balloon, glass It may be the one to which flakes are added.

Further, the polyarylene sulfide resin (A) is a conventionally known crystal nucleating agent such as talc, kaolin, silica, etc.; a polyalkylene oxide oligomer-based compound, a thioether-based compound, and an ester-based compound, as long as the effects of the present invention are not impaired. , Plasticizers such as organic phosphorus compounds; antioxidants; heat stabilizers; lubricants; UV inhibitors; one or more ordinary additives such as foaming agents may be added.

Further, the polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention can be obtained from various thermocurable resins, thermoplastic resins such as epoxy, as long as the object of the present invention is not deviated. Resin, cyanate ester resin, phenol resin, polyimide, silicone resin, polyester, polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamideimide, polyamide-based elastomer, It may be a mixture of one or more of polyester-based elastomer, polyalkylene oxide and the like.

The metal member-polyarylene sulfide resin member composite of the present invention is a composite in which a polyarylene sulfide resin member and a metal member are directly integrated by injection molding, and the metal member has a particularly low reflected ultrasonic intensity. Therefore, it is preferable that the metal member has a surface that has been physically and / or chemically treated.

The metal member may be a member made of any material as long as it belongs to the category of the metal member, and among them, when it is made into a polyarylene sulfide resin member composite, it can be applied to various uses. , Aluminum member, aluminum alloy member, copper member, copper alloy member, magnesium member, magnesium alloy member, iron member, titanium member, titanium alloy member, metal member which is a stainless steel member, in particular. Aluminum members, aluminum alloy members, magnesium members, magnesium alloy members, titanium members, and metal members which are titanium alloy members, which are excellent in weight reduction, are preferable, and aluminum members and aluminum alloy members are more preferable. is there. Further, the metal member may be a wrought material represented by a plate, a cast material represented by die casting, or a metal member made of a forged material.

The metal member is preferably a metal member whose surface is physically and / or chemically treated, and when it is directly integrated with the polyarylene sulfide resin member by performing the physical treatment and / or chemical treatment. , A metal member-polyarylene sulfide resin member composite having a lower reflected ultrasonic intensity can be obtained. The surface of the metal member can be physically and / or chemically treated by any method, and the physical treatment includes, for example, minute particles on the surface. Examples thereof include a method of contacting or colliding solid particles, a method of irradiating high-energy electromagnetic rays, and more specifically, sandblasting treatment, liquid honing treatment, laser processing, and the like. Further, examples of the abrasive during the sandblasting treatment and the liquid honing treatment include sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, plastic beads and the like. Further, as the laser processing, the methods proposed in WO2007 / 072603 and Japanese Patent Application Laid-Open No. 2015-142960 can also be mentioned.

In addition, examples of the chemical treatment include anodizing treatment methods, chemical treatment methods with an aqueous solution of an acid or an alkali, and the like. The anodizing treatment may be, for example, a method of performing an electrification reaction in an electrolytic solution using a metal member as an anode to form an oxide film on the surface thereof, and is generally known as an anodizing method in the field of plating and the like. The method described above can be used. More specifically, for example, 1) a DC electrolysis method in which electrolysis is performed by applying a constant DC voltage, 2) a bipolar electrolysis method in which electrolysis is performed by applying a voltage in which an AC component is superimposed on a DC component, and the like can be mentioned. .. As a specific example of the anodizing method, the method proposed in WO2004 / 055248 can be mentioned. Further, as a method of chemically treating with an aqueous solution of acid or alkali, for example, a method of immersing a metal member in an aqueous solution of acid or alkali to chemically treat the surface of the metal member may be used, and as an aqueous solution of acid or alkali at that time. For example, a phosphoric acid compound such as phosphoric acid; a chromium acid compound such as chromium acid; a hydrofluoric acid compound such as hydrofluoric acid; a nitrate compound such as nitric acid; a hydrochloric acid compound such as hydrochloric acid; Sulfuric acid-based compounds of the above; alkaline aqueous solutions such as sodium hydroxide and ammonia aqueous solutions; methods of chemical treatment with triazine thiol aqueous solutions, triazine thiol derivative aqueous solutions and the like can be mentioned, and more specific examples thereof include JP-A-10-096088. , JP-A-10-056263, JP-A-04-032585, JP-A-04-032583, JP-A-02-298284, WO2009 / 151099, WO2011 / 104944, etc. And so on.

The physical treatment and / or chemical treatment may be performed alone or in combination. For example, a metal member which has been physically treated and then chemically treated is used as a metal. The member-polyarylene sulfide resin member composite may be used.

As a method for producing the metal member-polyarylene sulfide resin member composite, any method can be used as long as the metal member and the polyarylene sulfide resin member can be directly integrated by injection molding. Above all, it is preferable to integrate by the injection insert molding method because the composite can be produced particularly efficiently. Then, as the injection insert molding method, for example, a metal member is mounted in a mold, the metal member is filled with a molten polyarylene sulfide resin to form a polyarylene sulfide resin member, and the metal member and the polyarylene sulfide resin member are formed. A method of forming a complex in which and is directly integrated can be mentioned. The melting temperature of the polyarylene sulfide resin at this time can be 280 to 340 ° C., and since the molding machine for insert molding is particularly excellent in productivity, injection insert molding is performed using an injection molding machine. It is preferable to do so. In particular, since it is a metal member-polyarylene sulfide resin member composite having low reflected ultrasonic intensity, the mold temperature at the time of insert molding is preferably 130 ° C. or higher, and the holding pressure is 1 MPa or higher. preferable.

Then, as a method for producing the metal member-polyarylene sulfide resin member composite of the present invention, the molten polyarylene sulfide resin is directly integrated with the metal member in the above-mentioned (1) injection molding mold by injection molding. In the step of forming the metal member-polyarylene sulfide resin member composite, at least the step of measuring the ultrasonic intensity (2) Ultrasonic flaw detection test on the joint surface of the metal member-polyarylene sulfide resin member composite. A step of transmitting ultrasonic waves from the device and measuring the intensity of the ultrasonic waves reflected at the joint surface (echo height of the ultrasonic waves), and a step of eliminating a complex having a high reflected ultrasonic intensity (3) Joining by passing through a step of selecting and removing a metal member-polyarylene sulfide resin member composite in which the echo height (= reflection intensity / irradiation intensity * 100) exceeds a standard value, for example, 35%, from the manufacturing process. It is possible to stably provide only a metal member-polyarylene sulfide resin member composite having excellent strength without undergoing inspection by fracture while maintaining reliability.

The metal member-polyarylene sulfide resin member composite of the present invention has high bonding strength, excellent bonding reliability, and excellent impact resistance, light weight, and mass productivity. In particular, these characteristics are exhibited. , Suitable for parts of transportation equipment such as automobiles and aircraft that require reliability.

The metal member-polyarylene sulfide resin member composite of the present invention is excellent in joint strength of the joint surface, impact resistance, light weight and mass productivity, and is particularly useful for parts of transportation equipment such as automobiles and aircraft. It stably produces a highly reliable metal member-polyarylene sulfide resin member composite, and its industrial value is extremely high.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

The polyarylene sulfide resin (A), the modified ethylene-based copolymer (B), and the glass fiber (C) used in Examples and Comparative Examples are shown below.

<Polyarylene sulfide resin (A)>
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-1)): melt viscosity 190 poisons.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-2)): melt viscosity 400 poisons.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-3)): melt viscosity 80 poisons.

<Modified ethylene copolymer (B)>
Ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (B-1) (hereinafter referred to as modified ethylene copolymer (B-1)): manufactured by Alchema Co., Ltd., ( Product name) Bondine AX8390.
Ethylene-α, β-unsaturated carboxylic acid glycidyl ester-α, β-unsaturated carboxylic acid alkyl ester copolymer (B-2) (hereinafter referred to as modified ethylene-based copolymer (B-2)): Made by Sumitomo Chemical Co., Ltd. (trade name) Bond First 7M.
Ethylene-α, β-unsaturated carboxylic acid-glycidyl ester copolymer (B-3) (hereinafter referred to as modified ethylene copolymer (B-3)): manufactured by Sumitomo Chemical Co., Ltd. (trade name) ) Bond First E.

<Glass fiber (C)>
Glass fiber (C-1); manufactured by Owens Corning Japan Co., Ltd. (trade name) RES03-TP91; fiber diameter 10 μm, fiber length 3 mm
Glass fiber (C-2); chopped strand manufactured by Nitto Boseki Co., Ltd., (trade name) CSG-3PA 830, aspect ratio of fiber cross section 4.

<Synthesis Example 1 (Synthesis of PPS (A-1))>
To 15 liters autoclave equipped with a stirrer was charged with flaky sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1814g, 30% sodium hydroxide solution (30% NaOHaq) 48g and N- methyl-2-pyrrolidone 3679G, nitrogen flow The temperature was gradually raised to 200 ° C. with stirring, and 380 g of water was distilled off. After cooling to 190 ° C., 2107 g of p-dichlorobenzene and 985 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. over 25 minutes, and further polymerized at 250 ° C. for 3 hours. After the polymerization, N-methyl-2-pyrrolidone was recovered from the polymerized slurry under reduced pressure by a distillation operation. The final temperature reached was 170 ° C. and the pressure was 4.7 kPa. Warm water at 80 ° C. was added to the obtained cake and washed to a slurry concentration of 20%, and warm water was added again in the same manner to raise the temperature to 175 ° C. and the poly (p-phenylene sulfide) was washed twice in total. The obtained polyphenylene sulfide was dried at 105 ° C. for 24 hours. Next, the dried polyphenylene sulfide was filled in a batch type rotary kiln type firing device, heated to 240 ° C. in a nitrogen atmosphere, and cured by holding for 1 hour, whereby PPS (A-) having a melt viscosity of 190 poise was performed. 1) was obtained.

<Synthesis Example 2 (Synthesis of PPS (A-2))>
To 15 liters autoclave equipped with a stirrer, flaky sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1814g, granular caustic soda (100% NaOH: Wako Pure Chemical special grade) 8.7 g and N- methyl-2-pyrrolidone 3232 g was charged, the temperature was gradually raised to 200 ° C. while stirring under a nitrogen stream, and 340 g of water was distilled off. After cooling to 190 ° C., 2107 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. over 25 minutes and polymerized at 250 ° C. for 2 hours. Next, 509 g of distilled water was press-fitted into this system at 250 ° C., the temperature was raised to 255 ° C., and a polymerization reaction was further carried out for 1 hour. After the polymerization, N-methyl-2-pyrrolidone was recovered from the polymerized slurry under reduced pressure by a distillation operation. The final temperature reached was 170 ° C. and the pressure was 4.7 kPa. Warm water at 80 ° C. was added to the obtained cake and washed to a slurry concentration of 20%, and warm water was added again in the same manner to raise the temperature to 175 ° C. and the poly (p-phenylene sulfide) was washed twice in total. The obtained poly (p-phenylene sulfide) was dried at 105 ° C. for 24 hours to obtain PPS (A-2) having a melt viscosity of 400 poise.

<Synthesis Example 3 (Synthesis of PPS (A-3))>
To 15 liters autoclave equipped with a stirrer, flaky sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1814g, granular caustic soda (100% NaOH: Wako Pure Chemical special grade) 8.7 g and N- methyl-2-pyrrolidone 3232 g was charged, the temperature was gradually raised to 200 ° C. while stirring under a nitrogen stream, and 339 g of water was distilled off. After cooling to 190 ° C., 2085 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. over 25 minutes and polymerized at 250 ° C. for 2 hours. After the polymerization, N-methyl-2-pyrrolidone was recovered from the polymerized slurry under reduced pressure by a distillation operation. The final temperature reached was 170 ° C. and the pressure was 4.7 kPa. Warm water at 80 ° C. was added to the obtained cake and washed to a slurry concentration of 20%, and then warm water was added again in the same manner and the temperature was raised to 175 ° C. to wash the poly (p-phenylene sulfide). The obtained poly (p-phenylene sulfide) was dried at 105 ° C. for 24 hours to obtain PPS (A-3) having a melt viscosity of 80 poise.

The evaluation / measurement method of the obtained polyarylene sulfide resin and metal member-polyarylene sulfide resin member composite is shown below.

~ Measurement of melt viscosity of polyarylene sulfide resin ~
The melt viscosity was measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg with a high-grade flow tester (manufactured by Shimadzu Corporation, trade name CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm. It was.

~ Evaluation of metal joint strength ~
The bonding strength of the composite of the metal member and the PPS resin member was evaluated by the tensile shear bonding strength having a bonding area of 50 mm ² according to ISO19095.

~ Ultrasonic flaw detection test ~
The composite of the metal member and the PPS resin member was subjected to an ultrasonic flaw detection test by a water immersion type ultrasonic flaw detection test using a composite which is a tensile shear test piece having a joint area of 50 mm ² prepared in accordance with ISO19095. For the water-immersed ultrasonic flaw detection test, the bonded composite and the ultrasonic probe (Olympus (trade name) water-immersed probe V324-SU) were installed at a distance of 25 mm in the water tank. Then, the ultrasonic waves transmitted from the ultrasonic probe at a frequency of 25 MHz at intervals of 0.1 mm are arranged perpendicular to the joint surface so as to pass through the inside of the metal member and be focused at the joint portion, and the reflected ultrasonic waves are transmitted. The echo heights of a total of 500 points were obtained by receiving with an ultrasonic probe, and the average value of the echo heights was taken as the echo height of the test piece.

Example 1
After cleaning the surface by immersing a test piece made of an aluminum alloy (A5052) (length 40 mm, width 18 mm, thickness 1.5 mm) in acetone, the test piece is subjected to a 10% by mass aqueous solution of sodium hydroxide. Then, the test piece made of an aluminum alloy (A5052) was chemically treated on the surface of the aluminum alloy by immersing it in a 10 wt% aqueous nitrate solution and further anodizing it in a 30 wt% aqueous phosphoric acid solution at a current density of 2 A / dm ² for 20 minutes. Got

A twin-screw extruder in which 15 parts by weight of an ethylene-based copolymer (B-1) was uniformly mixed with 100 parts by weight of PPS (A-1) obtained in Synthesis Example 1 and heated to a cylinder temperature of 300 ° C. It was put into a hopper (manufactured by Toshiba Machine Co., Ltd., (trade name) TEM-35-102B). On the other hand, the glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder so as to be 30 parts by weight with respect to 100 parts by weight of the PPS (A-1), and melt-kneaded to pelletize. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained test piece made of aluminum alloy (A5052) was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which the cylinder temperature was 310 ° C., the mold temperature was 150 ° C., and the holding pressure was 70 MPa. A poly (p-phenylene sulfide) resin composition is injection-molded using (trade name) SE75S), and an aluminum alloy member-PPS resin composition member, which is a test piece for evaluating shear bonding strength having a bonding area of 50 mm ² according to ISO19095. A complex was prepared. Then, an ultrasonic flaw detection test was performed on the joint surface. In addition, the joint strength of the test piece subjected to the ultrasonic flaw detection test was evaluated according to ISO19095.

The echo height of the obtained aluminum alloy member-PPS resin composition member composite was 26%, and the bonding strength was 43 MPa.

Example 2
After cleaning the surface by immersing a test piece made of aluminum die-cast alloy (ADC12) (length 40 mm, width 18 mm, thickness 1.5 mm) in acetone, the test piece is subjected to a laser having a wavelength of 1.064 μm. A test piece made of an aluminum die-cast alloy (ADC12) in which the surface of the aluminum die-cast alloy was physically treated was obtained by performing laser treatment for scanning 1000 times in the orthogonal direction at a hatching width of 0.06 mm, a frequency of 9 KHz, and a speed of 80 mm / sec. ..

A twin-screw extruder in which 10 parts by weight of an ethylene-based copolymer (B-1) was uniformly mixed with 100 parts by weight of PPS (A-3) obtained in Synthesis Example 3 and heated to a cylinder temperature of 300 ° C. It was put into a hopper (manufactured by Toshiba Machine Co., Ltd., (trade name) TEM-35-102B). On the other hand, the glass fiber (C-2) was charged from the hopper of the side feeder of the twin-screw extruder so as to be 110 parts by weight with respect to 100 parts by weight of the PPS (A-3), and melt-kneaded to pelletize. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained test piece made of aluminum die-cast alloy (ADC12) was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which a cylinder temperature of 310 ° C., a mold temperature of 150 ° C., and a holding pressure of 30 MPa was set. An aluminum die-cast alloy member-PPS resin composition member composite was prepared by injection molding using (trade name) SE75S) and a test piece for evaluating shear bonding strength having a bonding area of 50 mm ² according to ISO19095. Then, an ultrasonic flaw detection test was performed on the joint surface. In addition, the joint strength of the test piece subjected to the ultrasonic flaw detection test was evaluated according to ISO19095.

The echo height of the obtained aluminum die-cast alloy member-PPS resin composition member composite was 27%, and the bonding strength was 40 MPa.

Example 3
After cleaning the surface by immersing a test piece made of aluminum (A1050) (length 40 mm, width 18 mm, thickness 1.5 mm) in ethanol, the test piece is sandblasted with 0.1 mm alumina powder. After roughening by treatment, the test piece is then immersed in a 1% by weight aqueous solution of sodium hydroxide and then a 1% by weight aqueous sulfuric acid solution, and finally the test piece is distilled water containing 1% by weight of ethanolamine at 95 ° C. By immersing the mixture in a mixed solution for 10 minutes and subjecting the surface to boehmite treatment, a test piece made of aluminum (A1050) was obtained by physically treating the aluminum surface and then chemically treating the surface.

A twin-screw extruder in which 25 parts by weight of an ethylene-based copolymer (B-2) was uniformly mixed with 100 parts by weight of PPS (A-2) obtained in Synthesis Example 2 and heated to a cylinder temperature of 300 ° C. It was put into a hopper (manufactured by Toshiba Machine Co., Ltd., (trade name) TEM-35-102B). On the other hand, the glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder so as to be 15 parts by weight with respect to 100 parts by weight of PPS (A-2), and melt-kneaded to pelletize. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained aluminum (A1050) test piece was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which the cylinder temperature was 310 ° C., the mold temperature was 160 ° C., and the holding pressure was set to 50 MPa. Name) SE75S) was used for injection molding to prepare an aluminum member-PPS resin composition member composite which is a test piece for evaluating shear joint strength having a joint area of 50 mm ² according to ISO19095. Then, an ultrasonic flaw detection test was performed on the joint surface. In addition, the joint strength of the test piece subjected to the ultrasonic flaw detection test was evaluated according to ISO19095.

The echo height of the obtained aluminum member-PPS resin composition member composite was 30%, and the bonding strength was 35 MPa.

Example 4
After cleaning the surface by immersing a test piece made of an aluminum alloy (A6063) (length 40 mm, width 18 mm, thickness 1.5 mm) in acetone, the test piece is made of # 120 alumina and then # 800. A test piece made of an aluminum alloy (A60603) in which the surface of the aluminum alloy was physically treated was obtained by performing a liquid honing treatment with alumina and finally # 2000 alumina.

A twin-screw extruder in which 6 parts by weight of an ethylene-based copolymer (B-3) was uniformly mixed with 100 parts by weight of PPS (A-1) obtained in Synthesis Example 1 and heated to a cylinder temperature of 300 ° C. It was put into a hopper (manufactured by Toshiba Machine Co., Ltd., (trade name) TEM-35-102B). On the other hand, the glass fiber (C-1) was charged from the hopper of the side feeder of the twin-screw extruder so as to be 45 parts by weight with respect to 100 parts by weight of PPS (A-1), and melt-kneaded to pelletize. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained test piece made of aluminum alloy (A6063) was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which the cylinder temperature was 310 ° C., the mold temperature was 140 ° C., and the holding pressure was set to 10 MPa. An aluminum alloy member-PPS resin composition member composite, which is a test piece for evaluating shear bonding strength having a bonding area of 50 mm ² , was produced by injection molding using (trade name) SE75S) and according to ISO19095. Then, an ultrasonic flaw detection test was performed on the joint surface. In addition, the joint strength of the test piece subjected to the ultrasonic flaw detection test was evaluated according to ISO19095.

The echo height of the obtained aluminum alloy member-PPS resin composition member composite was 34%, and the bonding strength was 30 MPa.

Example 5
The same method as in Example 1 using the PPS resin composition obtained by the same method as in Example 1 and the test piece made of aluminum alloy (A5052) except that the mold temperature was 130 ° C. and the holding pressure was 5 MPa. To prepare an aluminum alloy member-PPS resin composition member composite. And evaluated.

The obtained aluminum alloy member-PPS resin composition member composite showed an echo height of 34% and a bonding strength of 30 MPa.

Example 6
Using the PPS resin composition obtained by the same method as in Example 1 and the test piece made of aluminum alloy (A5052), the test piece made of aluminum alloy (A5052) was set in a mold, and the cylinder temperature was 310 ° C. and gold. Injection molding using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd. (trade name) SE75S) in which the mold temperature is 140 ° C. and the holding pressure is set to 40 MPa, and a shear joint strength evaluation test with a joint area of 50 mm ² according to ISO19095. A piece of aluminum alloy member-PPS resin composition member composite was prepared. Then, the test piece obtained in the injection molding step was taken out by a servo robot (manufactured by Yushin Seiki Co., Ltd. (trade name) YC) and conveyed to the measurement step by the ultrasonic flaw detection test device in the next step by a belt conveyor.

The composite is subjected to the aluminum alloy member-PPS resin composition member composite and an ultrasonic probe (manufactured by Olympus (trade name) water-immersed probe V324-SU) in a water tank by a multi-axis robot (manufactured by Fanac). ) Is 25 mm away, and the ultrasonic waves are installed perpendicular to the joint surface so that they pass through the inside of the aluminum alloy member and are focused at the joint. Next, ultrasonic waves are transmitted from the ultrasonic probe at a frequency of 25 MHz at intervals of 0.1 mm, and the reflected ultrasonic waves are received by the ultrasonic probe to obtain echo heights of a total of 500 points, and the echo heights are obtained. When the average value of was calculated, the echo height of the test piece was 28%.

Further, the aluminum alloy member-PPS resin composition member composite is set to be conveyed in advance to a parts storage box (echo height 35% or less) or an exclusion box (echo height exceeding 35%) according to the echo height. The composite was taken out by a multi-axis robot (manufactured by Fanac), and then the composite was transferred to a parts storage box for storing a composite having an echo height of 35% or less. When the bonding strength of all the aluminum alloy member-PPS resin composition member composites in the parts storage box was evaluated according to ISO19095, the bonding strength was 39 MPa or more.

比較例１〜３
金型温度、保圧を表２に示す条件とした以外は、実施例１と同様の方法により得たＰＰＳ樹脂組成物、アルミニウム合金（Ａ５０５２）製試験片を用いて、実施例１と同様の方法により複合体を製造し、評価を行った。

Comparative Examples 1-3
The same as in Example 1 using the PPS resin composition obtained by the same method as in Example 1 and the test piece made of aluminum alloy (A5052) except that the mold temperature and holding pressure were set to the conditions shown in Table 2. The composite was produced by the method and evaluated.

The obtained composite had a large echo height and was inferior in bonding strength to the metal.

Comparative Example 4
Using the aluminum alloy (A5052) test piece and PPS resin composition obtained by the same method as in Example 1, the aluminum alloy (A5052) test piece was set in a mold, and the cylinder temperature was 310 ° C. and gold. Injection molding was performed using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd. (trade name) SE75S) with a mold temperature of 110 ° C. and a holding pressure of 10 MPa, and a shear bonding strength evaluation test with a bonding area of 50 mm ² according to ISO19095. A piece of aluminum alloy member-PPS resin composition member composite was prepared. Then, the aluminum alloy member-PPS resin composition member composite obtained in the injection molding process is taken out by a servo robot (manufactured by Yushin Seiki Co., Ltd. (trade name) YC), and an ultrasonic flaw detection test in the next process is performed on a belt conveyor. It was transported to the measurement process by the device.

The aluminum alloy member-PPS resin composition member composite and the aluminum alloy member-PPS resin composition member composite and an ultrasonic probe (manufactured by Olympus (trade name)) are used in a water tank by a multi-axis robot (manufactured by Fanac). The water-immersed probe V324-SU) was installed at a distance of 25 mm and perpendicular to the joint surface so that ultrasonic waves passed through the inside of the aluminum alloy member and focused at the joint. Next, ultrasonic waves are transmitted from the ultrasonic probe at a frequency of 25 MHz at intervals of 0.1 mm, and the reflected ultrasonic waves are received by the ultrasonic probe to obtain echo heights of a total of 500 points, and the echo heights are obtained. When the average value of was calculated, the echo height of the test piece was 40%.

The composite is taken out by a multi-axis robot (manufactured by Fanac) which is previously set to be transported to a parts storage box (echo height 35% or less) or an exclusion box (echo height exceeding 35%) according to the echo height. The aluminum alloy member-PPS resin composition member composite was transferred to an exclusion box for storing the composite having an echo height of more than 35%, and the aluminum alloy member-PPS resin composition member composite was eliminated. When the bonding strength of all of the aluminum alloy member-PPS resin composition member composites was evaluated according to ISO19095, all the bonding strengths were 23 MPa or less.

Comparative Example 5
Using the PPS resin composition obtained by the same method as in Example 1 and the test piece made of aluminum alloy (A5052), the test piece made of aluminum alloy (A5052) was set in a mold, and the cylinder temperature was 340 ° C. Injection molding using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd. (trade name) SE75S) with a mold temperature of 140 ° C. and a holding pressure of 20 MPa, and a shear bonding strength evaluation test with a bonding area of 50 mm ² according to ISO19095. A piece of aluminum alloy member-PPS resin composition member composite was prepared.

The ultrasonic probe (Olympus (trade name) water-immersed probe V324-SU) for transmission and reception in the water tank and the aluminum alloy member-PPS resin composition member composite are each at a distance of 25 mm. The ultrasonic waves transmitted from the ultrasonic probe at a frequency of 25 MHz at 0.1 mm intervals pass through the inside of the metal member, are focused at the joint, and are transmitted to the PPS resin composition member on the joint surface. It was placed vertically. Next, ultrasonic waves were transmitted from the ultrasonic probe at a frequency of 25 MHz, and the reflection intensity was measured with the ultrasonic probe for reception, but sufficient reflection intensity could not be obtained, and the echo height was measured. It was interrupted. A large number of voids were observed inside the PPS resin composition member of the composite, and the bonding strength was too low to be said to be bonding.

The composite of the present invention provides a metal member-polyarylene sulfide resin member composite having no defects such as voids on the joint surface, excellent joint reliability, and excellent impact resistance, light weight, and mass productivity. It is particularly useful for complexes of transportation equipment such as automobiles and aircraft.

Claims (3)

A method for producing a metal member-polyarylene sulfide resin member composite, which comprises undergoing at least the following steps (1) to (3).
(1) A step of directly integrating a molten polyarylene sulfide resin with a metal member in an injection molding die by injection molding to form a metal member-polyarylene sulfide resin member composite. (2) A step of transmitting ultrasonic waves from an ultrasonic flaw detection tester to a joint surface of a metal member-polyarylene sulfide resin member composite and measuring the intensity of the ultrasonic waves reflected by the joint surface as an echo height.
(3) A step of selecting a metal member-polyarylene sulfide resin member composite using the echo height of ultrasonic waves as a reference value, and excluding the metal member-polyarylene sulfide resin member composite exceeding the reference value from the manufacturing process. (2) The method for producing a metal member-polyarylene sulfide resin member composite according to claim 1, wherein the step is a step by a water immersion flaw detection method. (3) The method for producing a metal member-polyarylene sulfide resin member composite according to claim 1 or 2, wherein the reference value of the echo height in the step is 35%.