JP6911447B2 - Metal member-polyarylene sulfide resin member complex - Google Patents

Description

The present invention relates to a metal member-polyarylene sulfide resin member composite having excellent bonding strength of a 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 production while maintaining 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. Further, as a method of compositely integrating resin and metal, a method of inserting a metal member having a surface subjected to physical treatment and / or chemical treatment into a mold, injection molding the resin, and directly integrating the resin (hereinafter 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 so on. 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 tapping sound test is generally used as a method for inspecting defects such as voids in a sample, and has been proposed as, for example, an inspection method for concrete, refractories, thin plates, and FRP structures (for example, patents). Refer to References 4 to 7).

Japanese Patent No. 5701414 Japanese Patent No. 5714193 Japanese Patent No. 4020957 Japanese Patent No. 4768927 JP-A-2002-340869 Japanese Unexamined Patent Publication No. 7-20097 Japanese Patent No. 4736501

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 the 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 complex, inspection by a fracture test such as evaluating the joint strength by a tensile test of the complex 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 state of defect occurrence is quantitatively quantified by a non-destructive test is desired. rice field.

The inspection by the tapping sound test proposed in Patent Documents 4 to 7 does not target the metal member-resin member complex, and does not describe any metal member-resin member complex.

Therefore, the present invention stably produces a metal member-polyarylene sulfide resin member composite having excellent bonding strength between the metal member and the polyarylene sulfide resin member and a metal member-polyarylene sulfide resin member composite having excellent bonding strength. It is intended to provide a way to do this.

As a result of diligent studies to solve the above problems, the present inventor has found that the sound pressure decay time at the frequency at which the sound pressure is maximized in the frequency distribution waveform of the sound pressure obtained when the joint surface is hit. The metal member-polyarylene sulfide resin member composite having a certain ratio or more has excellent bonding strength, excellent bonding reliability, and excellent impact resistance, light weight, and mass productivity. We have found that it is a member, a part, a product, etc., and have completed the present invention.

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 a joint surface between the metal member and the polyarylene sulfide resin member is formed. In the frequency distribution waveform of the sound pressure obtained at the time of striking, the metal member-polyarylene sulfide resin member composite is characterized in that the decay time of the sound pressure at the frequency where the sound pressure is maximum is 2 milliseconds or more. It relates to the body and its manufacturing method.

Hereinafter, the present invention will be described in detail.

The metal member-polyarylene sulfide resin member composite of the present invention is a metal member-polyarylene sulfide resin member composite in which the metal member and the polyarylene sulfide resin member are directly integrated by injection molding, and the joint surface thereof is formed. In the frequency distribution waveform of the sound pressure obtained at the time of striking, the decay time of the sound pressure at the frequency at which the sound pressure is maximized is 2 milliseconds or more, particularly preferably 4 milliseconds or more. .. Here, if the damping time is less than 2 milliseconds, the bonding strength is inferior. Regarding this point, it is assumed that there are voids and defects on the joint surface where the sound pressure is easily attenuated. The attenuation time in the present invention is expressed as the time until the maximum sound pressure is attenuated to 1/10 of the sound pressure at the frequency at which the sound pressure is maximum.

Then, as a method for measuring the sound pressure attenuation time, for example, a tapping sound test can be used. The tapping sound test is a test using a device composed of a striking device, a sound collecting device, and a sound pressure analyzer, and is a frequency distribution waveform obtained by Fourier transforming the sound pressure obtained by striking the complex. This is a test method for discriminating defects on the joint surface from the decay time of the sound pressure at the frequency at which the sound pressure is maximized.

Then, the decay time is a frequency distribution waveform obtained by Fourier transforming the sound pressure obtained by striking the complex, and the sound pressure is attenuated to 1/10 of the maximum sound pressure at the frequency at which the sound pressure is maximum. If there is no defect in the joint surface, the sound pressure at the joint surface becomes longer and the decay time becomes longer. On the other hand, if there is a defect in the joint surface, the sound pressure is rapidly attenuated at the joint surface and the decay time is shortened. Further, the decay time is the decay time of the frequency at which the sound pressure becomes maximum in the frequency distribution waveform obtained by Fourier-converting the sound pressure obtained by striking the complex, and the frequency having the maximum sound pressure is used. In this case, it is possible to easily determine the decay time depending on the presence or absence of defects on the joint surface.

As a striking device for striking the complex in the striking sound test, a commercially available striking device such as a hammer or an impactor can be used. A commercially available sound level meter or microphone can be used as a sound collecting device that collects the sound pressure generated by hitting the complex, and a specific example of the sound level meter is the sound level meter NL-. 42, NL-52 (manufactured by Rion Co., Ltd.), sound level meter LA-3560, LA-3260 (manufactured by Ono Sokki Co., Ltd.), specific examples of the microphone are microphone MI-1211, MI-1235 (manufactured by Ono Sokki Co., Ltd.) and the like can be mentioned. As for the sound pressure level when collecting sound when hit, the full scale, which is the difference between the maximum sound pressure and the minimum sound pressure, is 100 ± 30 decibels because the attenuation time can be easily determined. It is preferably 100 ± 15 decibels, and more preferably 100 ± 15 decibels. The sound pressure level can be adjusted by the distance between the striking device and the complex and the distance between the complex and the sound collecting device.

A commercially available analyzer can be used as an analyzer for measuring the decay time of the frequency at which the sound pressure is maximized from the frequency distribution obtained by Fourier transforming the sound pressure obtained by the sound collector. Examples include (trade name) Movelet MV-6000, MVA-600 (manufactured by Cosmo Keiki Co., Ltd.), (trade name) Esfeel DS-3000, DS-3204 (manufactured by Ono Sokki Co., Ltd.), etc. Can be mentioned.

The polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention may be any material that belongs to the category generally called 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. It is preferably poly (p-phenylene sulfide) 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 points is preferable because a polyarylene sulfide resin composition having excellent strength and thin-wall fluidity can be obtained.

The polyarylene sulfide resin (A) can be produced by a method known as a method for producing a polyarylene sulfide resin, for example, an alkali metal sulfide salt or 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 sulfide metal 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 slightly 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 washing, hot water washing or washing 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) It may be one in which impurities such as a sodium salt of butanoate are reduced.

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 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 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 fiber 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, a metal member-polyarylene sulfide resin member composite having few defects on the joint surface and excellent impact resistance is formed. It is preferably a chopped strand having an average fiber diameter of 6 to 14 μm, or a chopped strand made of flat glass fibers 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. On the other hand, 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 compound, a thioether compound, and an ester compound, as long as the effects of the present invention are not impaired. , Plasticizers such as organic phosphorus compounds; antioxidants; thermal 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 thermosetting 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, One or more kinds such as a polyester-based elastomer and a polyalkylene oxide may be mixed and used.

The metal member-polyarylene sulfide resin member composite of the present invention is a material in which a polyarylene sulfide resin composition member and a metal member are directly integrated by injection molding, and the metal member has a particularly sound pressure decay time. 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 polyaluminum 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. be. Further, the metal member may be a wrought material typified by a plate, a cast material typified 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 the metal member is directly integrated with the polyarylene sulfide resin member by the physical treatment and / or chemical treatment. , A metal member-polyarylene sulfide resin member composite having a longer sound pressure decay time 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 amounts 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, a sandblasting treatment, a liquid honing treatment, a laser processing treatment, 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 an anodization treatment method, a method of chemical treatment 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 electrolysis 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 and the like 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. Is, 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; chemical treatment methods with triazine thiol aqueous solutions, triazine thiol derivative aqueous solutions and the like can be mentioned. , 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 complex 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 it is possible to manufacture the composite 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 a long sound pressure decay time, the mold temperature at the time of insert molding is preferably 130 ° C. or higher, and the holding pressure is 1 MPa or higher. Is 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 decay time of the sound pressure is (2) tapping sound on the joint surface of the metal member-polyarylene sulfide resin member composite. In the process of measuring the decay time of the sound pressure at the frequency where the sound pressure is maximum in the frequency distribution waveform of the sound pressure obtained by striking from the test device and striking, and the step of eliminating the complex having a short decay time. A certain (3) metal member-polyarylene sulfide resin member composite having a sound pressure decay time of less than 2 milliseconds is selected from the manufacturing process and eliminated, so that the metal member having excellent bonding strength-polyarylene It is possible to stably provide only the sulfide resin member composite without undergoing inspection by fracture.

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, and in particular, these characteristics. , 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 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 4 of fiber cross section.

<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. The obtained cake was washed with warm water at 80 ° C. to a slurry concentration of 20%, and again warm water was added in the same manner to raise the temperature to 175 ° C., and 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 poisons 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 the 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. The obtained cake was washed with warm water at 80 ° C. to a slurry concentration of 20%, and again warm water was added in the same manner to raise the temperature to 175 ° C., and 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 complex 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. rice field.

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

~ Hitting sound test ~
The composite of the metal member and the PPS resin composition member is composed of a striking device, a sound collecting device, and a sound pressure analyzer using a tensile shear test piece having ^{a joint area of 50 mm 2 prepared in accordance with ISO19095.} A tapping sound test was performed using a tapping sound test device. The joint composite is arranged on the sponge so that the distance between the joint composite and the hammer is 10 mm and the striking direction is perpendicular to the joint surface on the metal member side, and further, the striking position and the sound level meter. Sound pressure analysis was performed by installing the sound level meter (trade name) NL-52 manufactured by Rion at a distance of 100 mm and setting the full scale of the sound level meter to 110 decibels when hit. A frequency distribution was obtained by Fourier conversion with an apparatus (Movelet MV-6000 manufactured by Cosmo Instruments (trade name)), and the decay time of the sound pressure at the frequency at which the sound pressure was maximized was measured. The test was repeated three times for each bonded body, and the average value of the decay times was taken as the decay time of the test piece.

Example 1
After cleaning the surface by immersing a test piece (40 mm × 18 mm × 1.5 mm thickness) made of an aluminum die-cast alloy (ADC12) in acetone, the test piece is hatched using 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 of scanning 1000 times in the orthogonal direction at a wavelength of 0.08 mm, a frequency of 5 KHz, and a speed of 80 mm / sec.

A twin-screw extruder in which 12 parts by weight of an ethylene-based copolymer (B-1) was uniformly mixed in advance 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 PPS (A-1), 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 the cylinder temperature was set to 300 ° C, the mold temperature was set to 150 ° C, and the holding pressure was set to 60 MPa. A poly (p-phenylene sulfide) resin composition is injection-molded using (trade name) SE75S), and an aluminum die-cast alloy member-PPS resin composition, which is a test piece for evaluating shear bonding strength ^{having a bonding area of 50 mm 2 according to ISO19095.} A material member composite was produced. Then, a tapping sound test of the joint surface was performed. Further, the test piece subjected to the tapping sound test was evaluated for the joint strength according to ISO19095.

The decay time of the obtained aluminum die-cast alloy member-PPS resin composition member composite at a frequency of 10 kHz at which the sound pressure was maximum was 6 milliseconds, and the bonding strength was 42 MPa.

Example 2
After cleaning the surface by immersing a test piece (40 mm × 18 mm × 1.5 mm thickness) made of an aluminum alloy (A6063) in ethanol, the test piece is made of 0.5 mm alumina powder and then 0.1 mm. It is roughened by sandblasting with alumina powder, then the test piece is immersed in a 1% by weight sodium hydroxide aqueous solution and then a 1% by weight sulfuric acid aqueous solution, and finally the test piece is immersed in 1% by weight of ethanolamine at 95 ° C. By immersing the aluminum alloy in a mixed solution of distilled water containing% for 5 minutes and subjecting the surface to a boehmite treatment, a test piece made of an aluminum alloy (A6063) was obtained by chemically treating the surface of the aluminum alloy after the physical treatment.

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 100 parts by weight with respect to 100 parts by weight of PPS (A-3), 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 set to 300 ° C., the mold temperature was set to 150 ° C., and the holding pressure was set to 25 MPa. An aluminum 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, a tapping sound test of the joint surface was performed. Further, the test piece subjected to the tapping sound test was evaluated for the joint strength according to ISO19095.

The decay time of the obtained aluminum alloy member-PPS resin composition member composite at a frequency of 10 kHz at which the sound pressure became maximum was 5 milliseconds, and the bonding strength was 39 MPa.

Example 3
After cleaning the surface by immersing a test piece (40 mm × 18 mm × 1.5 mm thickness) made of an aluminum alloy (A5052) in acetone, the test piece is made of # 100 alumina, then # 500 alumina, and then. A test piece made of an aluminum alloy (A5052) in which the surface of the aluminum alloy was physically treated was obtained by performing a liquid honing treatment with # 1000 alumina and finally # 2000 alumina.

A twin-screw extruder in which 20 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-2) was charged from the hopper of the side feeder of the twin-screw extruder so as to be 20 parts by weight with respect to 100 parts by weight of the PPS (A-2), 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 set to 300 ° C., the mold temperature was set to 160 ° C., and the holding pressure was set to 40 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, a tapping sound test of the joint surface was performed. Further, the test piece subjected to the tapping sound test was evaluated for the joint strength according to ISO19095.

The decay time of the obtained aluminum alloy member-PPS resin composition member composite at a frequency of 10 kHz at which the sound pressure became maximum was 4 milliseconds, and the bonding strength was 34 MPa.

Example 4
After cleaning the surface by immersing a test piece made of aluminum (A1100) (40 mm × 18 mm × 1.5 mm thickness) in acetone, the test piece is subjected to a 5% by weight aqueous solution of sodium hydroxide and then 20 weights. A test piece made of aluminum (A1100) whose aluminum surface was chemically treated was obtained by immersing it in a% nitric acid aqueous solution and further anodizing it in a 30 wt% phosphoric acid aqueous solution at a current density of 1 A / dm ^{2 for 20 minutes.}

A twin-screw extruder in which 7 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 70 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 aluminum (A1100) test piece was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which a cylinder temperature of 300 ° C., a mold temperature of 140 ° C., and a holding pressure was set to 10 MPa was set. 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 bonding strength ^{having a bonding area of 50 mm 2 according to ISO19095.} Then, a tapping sound test of the joint surface was performed. Further, the test piece subjected to the tapping sound test was evaluated for the joint strength according to ISO19095.

The decay time of the obtained aluminum member-PPS resin composition member composite at a frequency of 10 kHz at which the sound pressure was maximized was 4.2 ms, and the bonding strength was 32 MPa.

Example 5
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 die-cast alloy (ADC12) except that the mold temperature was 135 ° C. and the holding pressure was 5 MPa. An aluminum die-cast alloy member-PPS resin composition member composite was prepared by the method. And evaluated.

The obtained aluminum die-cast alloy member-PPS resin composition member composite had an attenuation time of 4 milliseconds at a frequency of 10 kHz at which the sound pressure was maximized, and a bonding strength of 31 MPa.

Example 6
Using the PPS resin composition obtained by the same method as in Example 1 and the test piece made of aluminum die-cast alloy (ADC12), the test piece made of aluminum die-cast alloy (ADC12) was set in a mold, and the cylinder temperature was 300 ° C. a mold temperature of 140 ° C., an injection molding machine set to a holding pressure to 50 MPa (manufactured by Sumitomo Heavy Industries, (trade name) SE75S) was injection-molded using, in accordance with ISO19095, shear bond strength evaluation of the bonding area 50 mm ² An aluminum die-cast alloy member-PPS resin composition member composite, which is a test piece for use, 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 tapping sound test device in the next step by a belt conveyor.

The composite is installed on a sponge by a multi-axis robot (manufactured by FANUC) so that the joint composite and the hammer are at a distance of 10 mm and the striking direction is perpendicular to the joint surface on the aluminum die-cast alloy member side. , The striking position and the sound level meter (manufactured by Rion (trade name) NL-52) were installed so as to have a distance of 100 mm. Next, when the full scale of the sound level meter was set to 110 decibels when hit, the sound pressure obtained by the sound level meter was applied to a sound pressure analyzer (Cosmo Instrument (trade name) Movelet MV-6000). The sound pressure decay time at the frequency at which the sound pressure is maximized was measured three times in total, and the average value of the decay time was calculated. As a result, the decay time of the test piece was 4. Showed more than a millisecond.

Further, the aluminum die cast alloy member-PPS resin composition member composite is set to be conveyed in advance to a parts storage box (decay time of 2 ms or more) or an exclusion box (damping time of less than 2 ms) according to the decay time. It was taken out by a multi-axis robot (manufactured by Fanac) and then transferred to a parts storage box for storing the complex with a decay time of 2 ms or more. When the bonding strength of all the aluminum die-cast 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.

Comparative Examples 1 to 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 die-cast alloy (ADC12) except that the mold temperature and holding pressure were set to the conditions shown in Table 2. The complex was produced by the method of the above and evaluated.

The obtained complex had a short decay time and was inferior in bonding strength to a metal.

Comparative Example 4
Using the aluminum die-cast alloy (ADC12) test piece and PPS resin composition obtained by the same method as in Example 1, the aluminum die-cast alloy (ADC12) test piece was set in a mold, and the cylinder temperature was 300 ° C. a mold temperature of 110 ° C., an injection molding machine set to a holding pressure to 10 MPa (manufactured by Sumitomo Heavy Industries, (trade name) SE75S) was injection-molded using, in accordance with ISO19095, shear bond strength evaluation of the bonding area 50 mm ² An aluminum die-cast alloy member-PPS resin composition member composite, which is a test piece for use, was prepared. Then, the aluminum die-cast 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 a tapping sound test device in the next process is used on a belt conveyor. It was transported to the measurement process by.

The aluminum die-cast alloy member-PPS resin composition member composite was subjected to a multi-axis robot (manufactured by FANUC) so that the distance between the joint composite and the hammer was 10 mm and the striking direction was perpendicular to the joint surface on the aluminum die-cast alloy member side. It was installed on the sponge so that the striking position and the sound level meter (manufactured by Rion (trade name) NL-52) were at a distance of 100 mm. Next, when the full scale of the sound level meter was set to 110 decibels when hit, the sound pressure obtained by the sound level meter was applied to a sound pressure analyzer (Cosmo Instrument (trade name) Movelet MV-6000). The sound pressure decay time at the frequency at which the sound pressure is maximized was measured three times in total, and the average value of the decay time was calculated. As a result, the decay time of the test piece was 2. It showed less than a millisecond.

The composite is taken out by a multi-axis robot (manufactured by Fanac) that is previously set to be transported to a parts storage box (damping time of 2 ms or more) or an exclusion box (damping time of less than 2 ms) according to the decay time, and then is taken out. The aluminum diecast alloy member-PPS resin composition member composite was transferred to an exclusion box for storing the composite having a decay time of less than 2 ms, and the aluminum diecast alloy member-PPS resin composition member composite was eliminated. When the bonding strength of all of the aluminum die-cast alloy member-PPS resin composition member composites was evaluated according to ISO19095, all the bonding strengths were 22 MPa or less.

The composite of the present invention provides a metal member-polyarylene sulfide resin member complex 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 metal member that undergoes at least the following steps (1) to (3) -a method for manufacturing a polyarylene sulfide resin member composite, wherein the metal member is an aluminum member or an aluminum alloy member- A method for producing a polyarylene sulfide resin member composite.
(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 complex. (2) The maximum sound pressure and the minimum sound pressure level when the joint surface of the metal member-polyarylene sulfide resin member composite is struck from the tapping sound test device and the sound is collected by the sound collecting device when struck. A step of measuring the decay time of the sound pressure at the frequency at which the sound pressure is maximized in the frequency distribution waveform obtained by Fourier-converting the obtained sound pressure with an analyzer with a full scale of 100 ± 30 decibels, which is the difference in sound pressure. ..
Were selected polyarylene sulfide resin member complexes, the metal member is less than the reference value - - (3) the reference value of sound decay time metal member as above 2 msec eliminated from the manufacturing process of the polyarylene sulfide resin member complex Process to do. (2) The method for producing a metal member-polyarylene sulfide resin member composite according to claim 1, wherein the tapping sound test device in the step is a hammer or an impactor, and the sound collector is a sound level meter or a microphone. .. (1) The method for producing a metal member-polyarylene sulfide resin member composite according to claim 1 or 2, wherein the joint area of the metal member-polyarylene sulfide resin member composite in the step is 50 mm ^2.