JP2018164988A - Metal member-polyarylene sulfide resin member complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal member-polyarylene sulfide resin member complex which is excellent in bonding strength between the metal member and the polyarylene sulfide resin member, and to provide a method for stably producing the metal member-polyarylene sulfide resin member complex having excellent bonding strength.SOLUTION: A metal member-polyarylene sulfide resin member complex is formed by directly integrating a metal member and a polyarylene sulfide resin member by injection molding, in which decay time of sound pressure at a frequency where the sound pressure becomes maximum is 2 millisecond or more in frequency distribution wave form of the sound pressure obtained in striking the bonding face of the metal member and the polyarylene sulfide resin member.SELECTED DRAWING: None

Description

  The present invention relates to a metal member-polyarylene sulfide resin member composite excellent in bonding strength of a bonding surface and a method for producing the same, and more specifically, excellent in impact resistance, light weight, and mass productivity, and particularly in automobiles and aircraft. Metal member-polyarylene sulfide resin member composite with excellent bonding strength between metal member and polyarylene sulfide resin member useful for transportation equipment parts such as metal member-polyarylene sulfide resin member composite with excellent bonding strength The present invention relates to a method for stably manufacturing while maintaining reliability.

  In order to reduce the weight of parts of transportation equipment such as automobiles and airplanes, a method of replacing a part of metal with resin has been studied. In addition, as a method for composite integration of resin and metal, a metal member having a surface that has been subjected to physical treatment and / or chemical treatment is inserted into a mold, and resin is injection-molded and directly integrated (hereinafter referred to as “integrated resin”). , Which is sometimes referred to as an injection insert molding method), is attracting attention from the viewpoints of good mass productivity, small number of parts, low cost, high design freedom, and low environmental load. (For example, refer to Patent Documents 1 to 3).

  Polyarylene sulfides (hereinafter sometimes abbreviated as PAS) represented by poly (p-phenylene sulfide) (hereinafter also abbreviated as PPS) have excellent mechanical properties, thermal properties, It has electrical properties and chemical resistance, and is widely used for many electrical / electronic equipment members, automotive equipment members, and other OA equipment members.

  Moreover, 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 hammering test is generally used as a method for inspecting defects such as voids in a specimen, and has been proposed as an inspection method for concrete, refractory, thin plate, FRP structures, for example (for example, patents). References 4-7).

Japanese Patent No. 5701414 Japanese Patent No. 5714193 Japanese Patent No. 4020957 Japanese Patent No. 4768927 JP 2002-340869 A Japanese Patent Laid-Open 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 member having a certain bonding strength. Due to malfunctions, mistakes in setting conditions, and the length of the resin residence time in the cylinder of the injection molding machine, defective bonding between the metal member and the polyarylene sulfide resin member may occur, resulting in defects such as voids on the bonding surface. However, there was a large variation in individual performance differences, and there were problems in making stable products. In addition, in order to obtain information on the bonding state of the joint surface of the obtained composite, inspection by a destructive test such as evaluating the joint strength by a tensile test of the composite is generally performed, and such a method is reliable for the product. It cannot be used for sex confirmation. As a countermeasure, a test by sampling is also employed, but there arises a problem that the yield is lowered and the mass productivity is poor. Therefore, in consideration of industrial mass production and quality control, there is a demand for a metal member-resin member composite in which the joining state of the joint surface of the composite, for example, the defect occurrence state is quantitatively quantified by a nondestructive test. It was.

  The inspection by the hammering test proposed in Patent Documents 4 to 7 is not intended for the metal member-resin member composite, and does not describe any metal member-resin member composite.

  Therefore, the present invention stably manufactures a metal member-polyarylene sulfide resin member composite excellent in joint strength between a metal member and a polyarylene sulfide resin member and a metal member-polyarylene sulfide resin member composite excellent in joint strength. It is an object to provide a method for doing this.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the sound pressure decay time at the frequency at which the sound pressure is maximum in the sound pressure frequency distribution waveform obtained when the joint surface is struck. A 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. As a result, the present invention has been completed.

  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, wherein the joint surface between the metal member and the polyarylene sulfide resin member is formed. A metal member-polyarylene sulfide resin member composite characterized in that, in a frequency distribution waveform of sound pressure obtained when hit, a decay time of the sound pressure at a frequency at which the sound pressure is maximum is 2 milliseconds or more. The present invention relates to a body and a manufacturing method thereof.

  The present invention is 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 obtained by directly integrating a metal member and a polyarylene sulfide resin member by injection molding, and the joint surface thereof is In the frequency distribution waveform of sound pressure obtained at the time of striking, the sound pressure decay time at a frequency where the sound pressure is maximum is 2 milliseconds or more, and particularly preferably, the decay time is 4 milliseconds or more. . Here, when the decay time is less than 2 milliseconds, the bonding strength is inferior. In this regard, it is assumed that there are voids and defects on the joint surface where the sound pressure tends to attenuate. 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.

  As a method for measuring the sound pressure decay time, for example, a hammering test can be used. The sound hit test is a test using a device composed of a hitting device, a sound collecting device, and a sound pressure analyzing device. In the frequency distribution waveform obtained by Fourier transforming the sound pressure obtained by hitting the composite. 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 maximum.

  The decay time is attenuated to 1/10 of the maximum sound pressure at the frequency at which the sound pressure is maximum in the frequency distribution waveform obtained by Fourier transforming the sound pressure obtained by striking the composite. In the case where there is no defect on the joint surface, the sound pressure sound time at the joint surface becomes longer and the decay time becomes longer. On the other hand, when there is a defect in the joint surface, the sound pressure is quickly attenuated at the joint surface and the decay time is shortened. The decay time is the decay time of the frequency at which the sound pressure is maximum in the frequency distribution waveform obtained by Fourier transforming the sound pressure obtained by striking the composite, and the frequency at which the sound pressure is maximum 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.

  A commercially available striking device such as a hammer or an impactor can be used as a striking device for striking the composite in the sound test. A commercially available sound level meter or microphone can be used as a sound collecting device for collecting the sound pressure generated by striking the composite. As a specific example of the sound level meter, (trade name) sound level meter NL- 42, NL-52 (manufactured by Lion Co., Ltd.), (trade name) sound level meter LA-3560, LA-3260 (manufactured by Ono Sokki Co., Ltd.), specific examples of the microphone include microphone MI-1211, And MI-1235 (manufactured by Ono Sokki Co., Ltd.). The sound pressure level at the time of sound collection when hitting can easily determine the decay time, so the full scale that is the difference between the maximum sound pressure and the minimum sound pressure is 100 ± 30 dB. It is preferably 100 ± 15 dB. The sound pressure level can be adjusted by the distance between the striking device and the composite and the distance between the composite 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. Specific examples include (trade name) Movelet MV-6000, MVA-600 (manufactured by Cosmo Keiki Co., Ltd.), (trade name) ESFIEL DS-3000, DS-3204 (manufactured by Ono Sokki Co., Ltd.), etc. Is mentioned.

  As the polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention, any polyarylene sulfide resin may be used as long as it belongs to a category generally referred to as a polyarylene sulfide resin. Is, for example, a homopolymer or copolymer comprising a p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, or biphenylene sulfide unit. Specific examples of the polyarylene sulfide resin include poly (p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and polyphenylene. Mentioned sulfide ether, among which, in particular heat resistance, since the polyarylene sulfide resin composition excellent in strength properties, preferably a poly (p- phenylene sulfide).

  Furthermore, the polyarylene sulfide resin (A) is mechanically measured at a melt viscosity measured at a temperature of 315 ° C. and a load of 10 kg using a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. A polyarylene sulfide resin composition having a strength of 50 to 2000 poise 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 polyarylene sulfide resin production method. For example, an alkali metal sulfide or polyhaloaromatic compound in a polar solvent. Can be obtained by polymerizing. Examples of the polar organic solvent in this case include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexyl pyrrolidone, dimethylformamide, dimethylacetamide and the like. Examples include sodium, rubidium sulfide, and lithium sulfide anhydrides or hydrates. Moreover, as an alkali metal sulfide metal salt, you may react the alkali metal hydrosulfide salt and the alkali metal hydroxide. Examples of the polyhaloaromatic compound include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4′-dichlorodiphenylsulfone, 4 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, 4,4'-dichlorodibiphenyl, and the like.

  In addition, the polyarylene sulfide resin (A) may be a linear one, a polyhalogen compound of trihalogen or higher added during polymerization to introduce a slight cross-linked or branched structure, and the molecular chain of the polyarylene sulfide resin. A part and / or terminal of the product is modified with a functional group such as a carboxyl group, a carboxy metal salt, an alkyl group, an alkoxy group, an amino group, or a nitro group, or a heat treatment in a non-oxidizing inert gas such as nitrogen. And a mixture of these polyarylene sulfide resins may be used. The polyarylene sulfide resin (A) is washed with an acid, hot water or an organic solvent such as acetone or methyl alcohol, so that sodium atoms, oligomers of polyarylene sulfide resin, salt, 4- (N Impurities such as sodium salt of -methyl-chlorophenylamino) butanoate may be 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 few impact surface defects and excellent impact resistance. In view of this, it is preferable to blend the modified ethylene copolymer (B). The modified ethylene 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 maleic anhydride graft-modified ethylene-α- It is preferably at least one modified ethylene copolymer selected from the group consisting of olefin copolymers. The 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 particularly excellent in strength and impact resistance, glass fiber What mix | blends (C) is preferable. 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 an aspect ratio of 2 to 4 in the fiber cross section, glass fibers such as milled fibers and rovings; silane fibers An aluminosilicate glass fiber; a hollow glass fiber; a non-hollow glass fiber, etc. Among them, a metal member-polyarylene sulfide resin member composite having few joint surface defects and excellent impact resistance is obtained. 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 is preferable. Two or more kinds of these glass fibers (C) can be used in combination, and if necessary, surface treatment is performed in advance with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound. A thing may be used. The compounding amount of the glass fiber (C) is a metal member-polyarylene sulfide resin member composite having particularly few impact surface defects and excellent impact resistance. Therefore, the polyarylene sulfide resin (A) is 100 parts by weight. The amount is preferably 5 to 120 parts by weight.

  The polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member complex of the present invention is within the range not impairing the effects of the present invention, and calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica , Talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, silicon oxide, magnesium oxide, zirconium oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, hydrotalcite, glass powder, glass balloon, glass A flake may be added.

  The polyarylene sulfide resin (A) is a conventionally known crystal nucleating agent such as talc, kaolin, and silica; a polyalkylene oxide oligomer compound, a thioether compound, and an ester compound within a range not impairing the effects of the present invention. Plasticizers such as organic phosphorus compounds; antioxidants; heat stabilizers; lubricants; ultraviolet light inhibitors; and one or more usual additives such as foaming agents may be added.

  Furthermore, the polyarylene sulfide resin (A) constituting the metal member-polyarylene sulfide resin member composite of the present invention is a range of various thermosetting resins, thermoplastic resins, such as epoxy, without departing from the object of the present invention. 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 of polyester-based elastomers, polyalkylene oxides and the like may be mixed and used.

  The metal member-polyarylene sulfide resin member composite of the present invention is obtained by directly integrating a polyarylene sulfide resin composition member and a metal member by injection molding. Therefore, a metal member having a surface subjected to physical treatment and / or chemical treatment is preferable.

  The metal member may be a member made of any material as long as it belongs to the category of a metal member, and among them, it is possible to adapt to various uses when a polyarylene sulfide resin member composite is used. A metal member that is an aluminum member, an aluminum alloy member, a copper member, a copper alloy member, a magnesium member, a magnesium alloy member, an iron member, a titanium member, a titanium alloy member, or a stainless steel member is preferable. An aluminum member, an aluminum alloy member, a magnesium member, a magnesium alloy member, a titanium member, and a metal member made of a titanium alloy are preferable, and more preferably an aluminum member and an aluminum alloy member. is there. 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 the metal member is directly integrated with the polyarylene sulfide resin member by performing the physical treatment and / or chemical treatment. Thus, a metal member-polyarylene sulfide resin member composite having a longer sound pressure decay time can be obtained. And, as a method for physical treatment and / or chemical treatment of the surface of the metal member, any method can be used for physical treatment and / or chemical treatment. Examples thereof include a method of bringing solid particles into contact with or colliding with each other, a method of irradiating high-energy electromagnetic radiation, and the like, and more specifically, a sand blasting process, a liquid honing process, a laser processing process, and the like. Further, examples of the abrasive used in the sand blasting process and the liquid honing process include sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, and plastic beads. Moreover, as a laser processing, the method etc. which are proposed by WO2007 / 072603 and Unexamined-Japanese-Patent No. 2015-142960 can also be mentioned.

  Examples of the chemical treatment include an anodizing treatment method, a chemical treatment method using an acid or alkali aqueous solution, and the like. The anodizing treatment may be, for example, a method in which a metal member is used as an anode to perform an electrification reaction in an electrolytic solution to form an oxide film on the surface, and is generally known as an anodic oxidation method in the field of plating and the like. Can be used. More specifically, for example, 1) a DC electrolysis method in which electrolysis is performed by applying a constant DC voltage, and 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. . Specific examples of the anodic oxidation method include a method proposed in WO 2004/055248 and the like. Moreover, as a method of chemically treating with an acid or alkali aqueous solution, for example, a method of immersing a metal member in an acid or alkali aqueous solution and chemically treating the surface of the metal member may be used. For example, phosphoric acid compounds such as phosphoric acid; chromic acid compounds such as chromic acid; hydrofluoric acid compounds such as hydrofluoric acid; nitric acid compounds such as nitric acid; hydrochloric acid compounds such as hydrochloric acid; And sulfuric acid compounds; alkaline aqueous solutions such as sodium hydroxide and aqueous ammonia; methods of chemical treatment with triazine thiol aqueous solution and triazine thiol derivative aqueous solution, and the like. More specific examples include JP-A-10-096088. Japanese Patent Laid-Open No. 10-056263, Japanese Patent Laid-Open No. 04-032585, Japanese Patent Laid-Open No. 04-032583, Flat 02-298284, JP-WO2009 / 151,099 discloses a method proposed such as Japanese Patent WO2011 / one hundred and four thousand nine hundred and forty-four, and the like.

  The physical treatment and / or chemical treatment may be carried out alone or in combination, for example, using a metal member that has been subjected to chemical treatment after physical treatment of the surface. A member-polyarylene sulfide resin member composite may be used.

  As the 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. Among them, it is preferable to integrate by an injection insert molding method because a composite can be produced particularly efficiently. The injection insert molding method includes, for example, mounting a metal member in a mold, filling the metal member with a molten polyarylene sulfide resin to obtain a polyarylene sulfide resin member, and the metal member and the polyarylene sulfide resin member. Can be mentioned as a composite in which and are directly integrated. The melting temperature of the polyarylene sulfide resin at this time can be 280 to 340 ° C. As a molding machine for performing insert molding, injection molding can be performed using an injection molding machine because it is particularly excellent in productivity. Preferably it is done. In particular, since the metal member-polyarylene sulfide resin member composite having a long sound pressure decay time is used, the mold temperature during insert molding is preferably 130 ° C. or higher, and the holding pressure is 1 MPa or higher. Is preferred.

  And as a manufacturing method of the metal member-polyarylene sulfide resin member composite of the present invention, the above-mentioned (1) the molten polyarylene sulfide resin is directly integrated with the metal member in the injection mold by injection molding, In the step of making the metal member-polyarylene sulfide resin member composite, at least the decay time of the sound pressure is measured. (2) The sound hitting the joint surface of the metal member-polyarylene sulfide resin member composite In the step of measuring the sound pressure decay time at the frequency at which the sound pressure is maximum in the frequency distribution waveform of the sound pressure obtained by hitting from the test device and hitting, the step of eliminating the complex with a short decay time (3) a step of selecting and removing a metal member-polyarylene sulfide resin member composite having a sound pressure decay time of less than 2 milliseconds from the production process; Through the metal member excellent in bonding strength - it is possible to provide stably without undergoing inspection by destroying only the polyarylene sulfide resin member complex.

  The metal member-polyarylene sulfide resin member composite of the present invention has high bonding strength, excellent reliability of bonding, and also has excellent characteristics such as impact resistance, light weight and mass productivity. It is suitably used for parts of transportation equipment such as automobiles and airplanes that require reliability.

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

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  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 poise.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-2)): Melt viscosity 400 poise.
Poly (p-phenylene sulfide) (hereinafter referred to as PPS (A-3)): Melt viscosity 80 poise.

<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 Arkema 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 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); 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 Nittobo Co., Ltd. (trade name) CSG-3PA 830, aspect ratio 4 of fiber cross section.

<Synthesis Example 1 (Synthesis of PPS (A-1))>
A 15 liter autoclave equipped with a stirrer was charged with 1814 g of flaky sodium sulfide (Na ₂ S.2.9H ₂ O), 48 g of 30% sodium hydroxide solution (30% NaOHaq) and 3679 g of N-methyl-2-pyrrolidone, and a nitrogen stream 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. The 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 polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry under reduced pressure by distillation. The final temperature reached 170 ° C. and the pressure was 4.7 kPa. The obtained cake was washed with 80 ° C. warm water to give a slurry concentration of 20%, and again warm water was added in the same manner to raise the temperature to 175 ° C., and the poly (p-phenylene sulfide) was washed twice. The obtained polyphenylene sulfide was dried at 105 ° C. overnight. Subsequently, the dried polyphenylene sulfide is filled in a batch-type rotary kiln-type baking apparatus, heated to 240 ° C. in a nitrogen atmosphere, and subjected to curing treatment by holding for 1 hour, whereby a PPS (A- 1) was obtained.

<Synthesis Example 2 (Synthesis of PPS (A-2))>
In a 15 liter autoclave equipped with a stirrer, 1814 g of flaky sodium sulfide (Na ₂ S · 2.9H ₂ O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical), and N-methyl-2-pyrrolidone 3232 g was charged and gradually heated 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. The 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 injected into this system at 250 ° C., and the temperature was raised to 255 ° C. to conduct a polymerization reaction for another hour. After polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry under reduced pressure by distillation. The final temperature reached 170 ° C. and the pressure was 4.7 kPa. The obtained cake was washed with 80 ° C. warm water to give a slurry concentration of 20%, and again warm water was added in the same manner to raise the temperature to 175 ° C., and the poly (p-phenylene sulfide) was washed twice. The obtained poly (p-phenylene sulfide) was dried overnight at 105 ° C. to obtain PPS (A-2) having a melt viscosity of 400 poise.

<Synthesis Example 3 (Synthesis of PPS (A-3))>
In a 15 liter autoclave equipped with a stirrer, 1814 g of flaky sodium sulfide (Na ₂ S · 2.9H ₂ O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical), and N-methyl-2-pyrrolidone 3232 g was charged and gradually heated 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. The 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 polymerization, N-methyl-2-pyrrolidone was recovered from the polymerization slurry under reduced pressure by distillation. The final temperature reached 170 ° C. and the pressure was 4.7 kPa. The obtained cake was washed with 80 ° C. warm water to a slurry concentration of 20%, and again warm water was added in the same manner to raise the temperature to 175 ° C. to wash poly (p-phenylene sulfide). The obtained poly (p-phenylene sulfide) was dried overnight at 105 ° C. to obtain PPS (A-3) having a melt viscosity of 80 poise.

  Evaluation and measurement methods of the obtained polyarylene sulfide resin and metal member-polyarylene sulfide resin member composite are 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 using a Koka type flow tester (trade name: CFT-500, manufactured by Shimadzu Corporation) equipped with a die having a diameter of 1 mm and a length of 2 mm. It was.

~ Evaluation of metal bonding strength ~
The joint strength of the composite of the metal member and the PPS resin composition member was evaluated by a tensile shear joint strength with a joint area of 50 mm ² according to ISO 19095.

~ Percussion test ~
A composite of a metal member and a PPS resin composition member is composed of a striking device, a sound collecting device, and a sound pressure analyzing device using a tensile shear test piece having a joining area of 50 mm ² manufactured in accordance with ISO 19095. A hammering test was performed using a hammering test apparatus. The bonded composite is placed on the sponge so that the bonded composite and the hammer are at a distance of 10 mm, and the striking direction is perpendicular to the joint surface on the metal member side. The sound pressure obtained when the full scale of the sound level meter was set to 110 decibels when struck and installed (Rion (trade name) NL-52) at a distance of 100 mm was analyzed. A frequency distribution was obtained by Fourier transform using an apparatus (trade name MV-6000 manufactured by Cosmo Keiki Co., Ltd.), and the decay time of the sound pressure at a frequency at which the sound pressure was maximum was measured. The test was repeated three times for each joined body, and the average value of the decay time was defined 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 was hatched with a laser having a wavelength of 1.064 μm. A test piece made of aluminum die-casting alloy (ADC12) was obtained by physically processing the surface of the aluminum die-casting alloy by performing laser processing of scanning 1000 times in the orthogonal direction at a frequency 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 copolymer (B-1) is 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. (Toshiba Machine, (trade name) TEM-35-102B) was put into a hopper. On the other hand, 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 be pelletized. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained aluminum die cast alloy (ADC12) test piece was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) with a cylinder temperature of 300 ° C., a mold temperature of 150 ° C., and a holding pressure of 60 MPa was set. (Trade name) SE75S) is used to injection-mold a poly (p-phenylene sulfide) resin composition, and in accordance with ISO 19095, an aluminum die-cast alloy member-PPS resin composition, which is a test piece for shear joint strength evaluation having a joint area of 50 mm ² An object member composite was produced. Then, a sound test for the joint surface was performed. Further, the bonding strength of the test piece subjected to the hammering test was evaluated according to ISO19095.

  The resulting aluminum die-cast alloy member-PPS resin composition member composite had a decay time of 6 milliseconds at a frequency of 10 kHz at which the sound pressure was maximum, 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 aluminum alloy (A6063) in ethanol, the test piece was treated with 0.5 mm alumina powder and then with 0.1 mm After roughening by sandblasting using alumina powder, the test piece was immersed in a 1 wt% aqueous sodium hydroxide solution and further a 1 wt% sulfuric acid aqueous solution, and finally the test piece was added with 1 wt% ethanolamine at 95 ° C. A test piece made of aluminum alloy (A6063) was obtained by dipping in a distilled water mixed solution containing 2% for 5 minutes and subjecting the surface to a boehmite treatment, and then chemically treating the aluminum alloy surface after physical treatment.

  A twin screw extruder in which 10 parts by weight of an ethylene copolymer (B-1) is uniformly mixed in advance with 100 parts by weight of PPS (A-3) obtained in Synthesis Example 3 and heated to a cylinder temperature of 300 ° C. (Toshiba Machine, (trade name) TEM-35-102B) was put into a hopper. On the other hand, 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 be pelletized. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained aluminum alloy (A6063) test piece was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., with a cylinder temperature of 300 ° C., a mold temperature of 150 ° C., and a holding pressure of 25 MPa, injection molded using a trade name) SE75S), in accordance with ISO19095, bonding area to produce an aluminum alloy member -PPS resin composition member complex shear bonding strength evaluation test piece 50 mm ^2. Then, a sound test for the joint surface was performed. Further, the bonding strength of the test piece subjected to the hammering test was evaluated according to ISO19095.

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

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

  A twin screw extruder in which 20 parts by weight of an ethylene copolymer (B-2) is uniformly mixed in advance with 100 parts by weight of PPS (A-2) obtained in Synthesis Example 2 and heated to a cylinder temperature of 300 ° C. (Toshiba Machine, (trade name) TEM-35-102B) was put into a hopper. On the other hand, 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 PPS (A-2), and melt-kneaded to be pelletized. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained aluminum alloy (A5052) test piece was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., with a cylinder temperature of 300 ° C., a mold temperature of 160 ° C., and a holding pressure of 40 MPa, Product name) SE75S) was injection molded, and an aluminum alloy member-PPS resin composition member composite, which was a test piece for evaluating shear joint strength having a joint area of 50 mm ² , was prepared according to ISO 19095. Then, a sound test for the joint surface was performed. Further, the bonding strength of the test piece subjected to the hammering test was evaluated according to ISO19095.

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

Example 4
After the surface was cleaned by immersing a test piece (40 mm × 18 mm × 1.5 mm thickness) made of aluminum (A1100) in acetone, the test piece was washed with a 5 wt% sodium hydroxide aqueous solution and then 20 wt. A test piece made of aluminum (A1100) in which the aluminum surface was chemically treated was obtained by immersing in an aqueous solution of 30% nitric acid and anodizing in an aqueous solution of 30% by weight phosphoric acid 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 copolymer (B-3) is 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. (Toshiba Machine, (trade name) TEM-35-102B) was put into a hopper. On the other hand, 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 be pelletized. A poly (p-phenylene sulfide) resin composition was prepared.

The obtained test piece made of aluminum (A1100) was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (commodity) set to a cylinder temperature of 300 ° C., a mold temperature of 140 ° C., and a holding pressure of 10 MPa. Name) SE75S) was injection molded, and in accordance with ISO 19095, an aluminum member-PPS resin composition member composite, which was a test piece for evaluating shear joint strength with a joint area of 50 mm ² , was produced. Then, a sound test for the joint surface was performed. Further, the bonding strength of the test piece subjected to the hammering test was evaluated according to ISO19095.

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

Example 5
Except that the mold temperature was 135 ° C. and the holding pressure was 5 MPa, a PPS resin composition obtained by the same method as in Example 1 and an aluminum die cast alloy (ADC12) test piece were used. An aluminum die cast alloy member-PPS resin composition member composite was produced by the method. And evaluated.

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

Example 6
Using the PPS resin composition obtained by the same method as in Example 1 and an aluminum die-cast alloy (ADC12) test piece, the aluminum die-cast alloy (ADC12) test piece was set in a mold and the cylinder temperature was 300 ° 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 50 MPa, and in accordance with ISO 19095, a shearing joint strength evaluation of a joint area of 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 process was taken out by a servo robot (manufactured by Yushin Seiki Co., Ltd., (trade name) YC), and conveyed to a measurement process using a hammering test apparatus in the next process by a belt conveyor.

  The composite was placed on a sponge by a multi-axis robot (manufactured by FANUC) so that the joint composite and the hammer were at a distance of 10 mm and the striking direction was 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 set to have a distance of 100 mm. Next, the sound pressure obtained with the sound level meter when the full scale of the sound level meter was set to 110 decibels when struck is applied to a sound pressure analyzer (trade name MV-6000 manufactured by Cosmo Keiki Co., Ltd.). The Fourier transform is performed to obtain a frequency distribution. Further, the decay time of the sound pressure at the frequency at which the sound pressure is maximum is measured three times in total, and the average value of the decay times is calculated. More than milliseconds.

  Further, the aluminum die-cast alloy member-PPS resin composition member composite was set in advance so as to be conveyed to a parts storage box (attenuation time of 2 milliseconds or more) or an exclusion box (attenuation time of less than 2 milliseconds) by an attenuation time. The composite was taken out by a multi-axis robot (manufactured by FANUC) and then transferred to a parts storage box for storing the composite having an attenuation time of 2 milliseconds 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 ISO 19095, the bonding strength was all 39 MPa or more.

Comparative Examples 1-3
Except that the mold temperature and holding pressure were set as shown in Table 2, using a PPS resin composition obtained by the same method as in Example 1 and a test piece made of an aluminum die cast alloy (ADC12), the same as in Example 1. A composite was produced by the method described above and evaluated.

  The obtained composite had a short decay time and was inferior in bonding strength with metal.

Comparative Example 4
Using an aluminum die-cast alloy (ADC12) test piece and a 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. , Injection molding using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., (trade name) SE75S) set at a mold temperature of 110 ° C. and a holding pressure of 10 MPa, and in accordance with ISO 19095, evaluation of shear joint strength with a joint area of 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). It was conveyed to the measurement process.

  The aluminum die-casting alloy member-PPS resin composition member composite is moved by a multi-axis robot (manufactured by FANUC) with a distance of 10 mm between the joining composite and the hammer and the striking direction perpendicular to the joining surface on the aluminum die-casting alloy member side. It was installed on the sponge so that the striking position and the sound level meter (manufactured by Lion (trade name) NL-52) were at a distance of 100 mm. Next, when the full scale of the sound level meter is set to 110 decibels when hit, the sound pressure obtained with the sound level meter is sent to a sound pressure analyzer (trade name MV-6000 manufactured by Cosmo Keiki Co., Ltd.). The Fourier transform is performed to obtain a frequency distribution. Further, the decay time of the sound pressure at a frequency at which the sound pressure is maximum is measured three times in total, and the average value of the decay times is calculated. Showed less than milliseconds.

  The composite is taken out by a multi-axis robot (manufactured by FANUC) that is set in advance so as to be conveyed to a parts storage box (attenuation time of 2 milliseconds or more) or an exclusion box (attenuation time of less than 2 milliseconds) by an attenuation time, The aluminum die-cast 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 milliseconds, and the aluminum die-cast alloy member-PPS resin composition member composite was excluded. When the bonding strength of all the aluminum die cast alloy member-PPS resin composition member composites was evaluated according to ISO 19095, all the bonding strengths were 22 MPa or less.

  The composite of the present invention provides a metal member-polyarylene sulfide resin member composite that is free of defects such as voids on the joint surface, has excellent joint reliability, and is excellent in impact resistance, light weight, and mass productivity. It is particularly useful for composites of transportation equipment such as automobiles and airplanes.

Claims (5)

It is a metal member-polyarylene sulfide resin member composite obtained by directly integrating a metal member and a polyarylene sulfide resin member by injection molding, and is obtained when the joining surface of the metal member and the polyarylene sulfide resin member is hit. A metal member-polyarylene sulfide resin member composite characterized in that, in the frequency distribution waveform of the sound pressure, the sound pressure decay time at a frequency at which the sound pressure is maximum is 2 milliseconds or more. The metal member-polyarylene sulfide resin member composite according to claim 1, wherein the metal member is a metal member having a surface subjected to physical treatment and / or chemical treatment. For 100 parts by weight of the polyarylene sulfide resin (A), an ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, an 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 maleic anhydride 1 to 40 parts by weight of at least one modified ethylene copolymer (B) selected from the group consisting of graft-modified ethylene-α-olefin copolymers and 5 to 120 parts by weight of glass fiber (C). The metal member-polyarylene sulfide resin member composite according to claim 1 or 2, wherein A method for producing a metal member-polyarylene sulfide resin member composite comprising at least the following steps (1) to (3):
(1) A step in which a molten polyarylene sulfide resin is directly integrated with a metal member in an injection mold by injection molding to form a metal member-polyarylene sulfide resin member composite. (2) The frequency at which the sound pressure is maximized in the frequency distribution waveform of the sound pressure obtained when the metal member-polyarylene sulfide resin member composite is struck against the joint surface and struck. Measuring the decay time of the sound pressure at.
(3) A step of selecting a metal member-polyarylene sulfide resin member complex with a sound pressure decay time as a reference value, and removing a metal member-polyarylene sulfide resin member complex less than the reference value from the manufacturing process. (3) The method for producing a metal member-polyarylene sulfide resin member composite according to claim 4, wherein the reference value of the decay time in the step is 2 milliseconds.