JP2021020447A - Metal member-polyarylene sulfide resin member composite and manufacturing method of the same - Google Patents

Abstract

To provide a metal member-polyarylene sulfide resin member composite having excellent mechanical properties and airtightness useful as a composite of transportation equipment such as an automobile and an aircraft, and a manufacturing method of the same.SOLUTION: A metal member-polyarylene sulfide resin member composite is formed by directly integrating a metal member 1, 2 and a polyarylene sulfide resin member 3 by injection molding, and a joint surface between a metal member of the metal member-polyarylene sulfide resin member composite and a polyarylene sulfide resin member contains a penetrant for a penetrant inspection test. A weight increase rate of the metal member-polyarylene sulfide resin member composite by the penetrant for the penetrant inspection test is 2 mg or less per square centimeter of joint area.SELECTED DRAWING: Figure 1

Description

The present invention relates to a metal member-polyarylene sulfide resin member composite having excellent joint surface characteristics and a method for producing the same. More specifically, the present invention is excellent in impact resistance, light weight, mechanical properties and mass productivity, and in particular, an automobile. Manufacture of metal members-polyarylene sulfide resin member composites and metal members-polyarylene sulfide resin member composites, which are useful for parts of transportation equipment such as aircraft and aircraft, and have excellent airtightness between polyarylene sulfide resin members. It's about the method.

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 that has been physically and / or chemically treated into a mold, and injection molding the resin to directly integrate the resin (hereinafter referred to as). , Sometimes referred to as injection insert molding method) is attracting attention from the viewpoints of good mass productivity, small number of parts, low cost, high design freedom, and low environmental load, and the manufacturing process of portable electronic devices such as smartphones. Etc. (see, for example, Patent Documents 1 to 3).

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

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

On the other hand, the penetrant inspection is a method of detecting the position and size of a defect by infiltrating a defect opened on the surface of a material with a liquid by using a capillary phenomenon and developing the liquid that has penetrated the defect. It is generally applied and has been proposed as, for example, a method for inspecting a metal composite plate, a method for inspecting a metal welded portion, and a method for inspecting a bonding interface between metals (see, for example, Patent Documents 4 to 6).

Japanese Patent No. 5701414 Japanese Patent No. 5714193 Japanese Patent No. 4020957 Japanese Patent No. 3200296 Japanese Unexamined Patent Publication No. 2001-141667 Japanese Patent No. 6346888

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

Further, the inspection by the penetrant inspection proposed in Patent Documents 4 to 6 relates to a composite of metals, and no study has been made on the joining of dissimilar members such as a composite of a metal member and a resin member. It wasn't.

Therefore, the present invention stabilizes a metal member-polyarylene sulfide resin member composite having excellent mechanical properties and airtightness 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 an object of the present invention to provide a method for producing a plastic.

As a result of diligent studies to solve the above problems, the present inventor has a metal member-polyarylene sulfide resin in which the weight increase rate when the penetrant for penetrant inspection is permeated into the joint surface is a certain rate or less. We have found that the member composite has excellent airtightness, has excellent airtightness reliability, and has excellent impact resistance, light weight, and mass productivity, and has been found to be a member, part, product, or the like. Has been completed.

That is, in the present invention, a penetration flaw detection test is performed on the joint surface between the metal member and the polyarylene sulfide resin member of the metal member-polyarylene sulfide resin member composite in which the metal member and the polyarylene sulfide resin member are directly integrated by injection molding. A metal member-polyarylene sulfide resin member composite containing a penetrant for permeation, and the weight increase rate of the metal member-polyarylene sulfide resin member composite by the penetrant for permeation detection test is 2 per square centimeter of joint area. The present invention relates to a method for producing a metal member-polyarylene sulfide resin member composite and a metal member-polyarylene sulfide resin member composite, which are characterized by having a weight of milligram or less.

The present invention will be described in detail below.

The metal member-polyarylene sulfide resin member composite of the present invention is a metal member-polyarylene sulfide resin member composite in which a metal member and a polyarylene sulfide resin member are directly integrated by injection molding, and is formed on a joint surface thereof. By contacting the penetrant for penetrant inspection, the penetrant for penetrant inspection is contained, and the weight increase rate due to the penetrant for penetrant inspection is 2 mg or less per square centimeter of joint area, which is particularly preferable. Has a weight increase rate of 1 milligram or less per square centimeter of joint area. Here, if the rate of weight increase due to the penetrant for penetrant inspection exceeds 2 mg per square centimeter of joint area, there is a high possibility that voids or defects are present on the joint surface, and the metal member-polyarylene sulfide resin member composite The body will have problems such as inferior airtightness and joint strength.

The metal member constituting the metal member-polyaluminum sulfide resin member composite of the present invention may be a member made of any material as long as it belongs to the category of the metal member, and among them, the composite with the polyaluminum sulfide resin member. Since it can be applied to various applications, aluminum member, aluminum alloy member, copper member, copper alloy member, magnesium member, magnesium alloy member, iron member, titanium member, titanium. Alloy members and metal members such as stainless steel members are preferable, and aluminum members, aluminum alloy members, magnesium members, magnesium alloy members, titanium members, titanium alloy members, copper members, which are particularly excellent in weight reduction, A metal member which is a copper alloy member is preferable, and an aluminum member and an aluminum alloy member are more preferable. Further, the metal member may be a wrought material represented by a plate, a cast material represented by die casting, or a metal member made of a forged material.

The metal member is preferably a metal member whose surface is physically and / or chemically treated, and when 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 excellent airtightness, bonding strength, etc., in which the penetration of the penetrant for the penetration flaw detection test is suppressed can be obtained. The surface of the metal member can be physically and / or chemically treated by any method, and the physical treatment includes, for example, minute particles on the surface. Examples thereof include a method of contacting or colliding solid particles, a method of irradiating high-energy electromagnetic rays, and more specifically, sandblasting treatment, liquid honing treatment, laser processing, and the like. Further, examples of the abrasive during the sandblasting treatment and the liquid honing treatment include sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, plastic beads and the like. Further, as the laser processing, the methods proposed in WO2007 / 072603 and Japanese Patent Application Laid-Open No. 2015-142960 can also be mentioned.

In addition, examples of the chemical treatment include 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 electrification reaction in an electrolytic solution using a metal member as an anode to form an oxide film on the surface thereof, and is generally known as an anodizing method in the field of plating and the like. The method described above can be used. More specifically, for example, 1) a DC electrolysis method in which electrolysis is performed by applying a constant DC voltage, 2) a bipolar electrolysis method in which electrolysis is performed by applying a voltage in which an AC component is superimposed on a DC component, and the like can be mentioned. .. As a specific example of the anodizing method, the method proposed in WO2004 / 055248 can be mentioned. Further, as a method of chemically treating with an aqueous solution of acid or alkali, for example, a method of immersing a metal member in an aqueous solution of acid or alkali to chemically treat the surface of the metal member may be used, and as an aqueous solution of acid or alkali at that time. For example, a phosphoric acid compound such as phosphoric acid; a chromium acid compound such as chromium acid; a hydrofluoric acid compound such as hydrofluoric acid; a nitrate compound such as nitric acid; a hydrochloric acid compound such as hydrochloric acid; Sulfuric acid-based compounds of the above; alkaline aqueous solutions such as sodium hydroxide and ammonia aqueous solutions; methods of chemical treatment with triazine thiol aqueous solutions, triazine thiol derivative aqueous solutions and the like can be mentioned, and more specific examples thereof include JP-A No. 10-096088. , JP-A-10-056263, JP-A-04-032585, JP-A-04-032583, JP-A-02-298284, WO2009 / 151099, WO2011 / 104944, etc. And so on.

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

The polyarylene sulfide resin constituting the metal member-polyarylene sulfide resin member composite of the present invention may be any one that belongs to the category generally called polyarylene sulfide resin, and the polyarylene sulfide resin is, for example, Examples thereof include homopolymers or copolymers consisting of p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Specific examples of the polyarylene sulfide resin include poly (p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, polyphenylene sulfide ether, and the like, among which polyarylene, which is particularly excellent in heat resistance and strength characteristics. Since it is a sulfide resin member, it is preferably poly (p-phenylene sulfide).

Further, since the polyarylene sulfide resin can efficiently obtain a metal member-polyarylene sulfide resin member composite having excellent bonding strength and airtightness, a height of 1 mm in diameter and 2 mm in length is attached. It is preferable that the polyarylene sulfide resin has a melt viscosity of 50 to 2000 poisons measured by a chemical flow tester under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg.

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

The polyarylene sulfide resin includes a linear one, a polyhalogen compound having a trihalo or higher added in a small amount at the time of polymerization to introduce a slight crosslinked or branched structure, a part of the molecular chain of the polyarylene sulfide resin, and the like. / Or the terminal 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 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-). It may be one in which impurities such as a sodium salt of chlorophenylamino) butanoate are reduced.

Further, since it is possible to form a metal member-polyarylene sulfide resin member composite having few defects on the joint surface and excellent impact resistance, the polyarylene sulfide resin member is blended with a modified ethylene-based copolymer. It is preferable that the product is made of Examples of the modified ethylene-based copolymer include ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α, β-unsaturated carboxylic acid glycidyl ester copolymer, and 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, ethylene anhydride graft-modified ethylene- Examples thereof include α-olefin copolymers. The blending amount of the modified ethylene-based copolymer is preferably 1 to 40 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin.

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

Polyarylene sulfide resin members further include, for example, calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wallastenite, zeolite, silicon oxide, magnesium oxide, zirconium oxide, oxidation. It may be added with tin, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, hydrotalcite, glass powder, glass balloon, and glass flakes. Also, conventionally known crystal nucleating agents such as talc, kaolin and silica; plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds and organophosphorus compounds; antioxidants; heat stabilizers; lubricants; ultraviolet rays. Inhibitor; One or more ordinary additives such as a foaming agent may be added. Further, various thermosetting resins and thermoplastic resins such as epoxy resin, cyanate ester resin, phenol resin, polyimide, silicone resin, polyester, polyamide, polyphenylene oxide, polycarbonate, polysulfone, polyetherimide, polyethersulfone, poly One or more of ether ketone, polyether ether ketone, polyamideimide, polyamide-based elastomer, polyester-based elastomer, polyalkylene oxide and the like may be mixed and used.

The penetrant test penetrant contained in the joint surface of the metal member-polyarylene sulfide resin member composite of the present invention is not limited as long as it is known as the penetrant test penetrant, and is commercially available, for example. The penetrant, ink, organic solvent, etc. of the above can be mentioned, and among them, the penetrant adhering to other than the joint surface can be easily removed visually, so that the penetrant is colored red or the like containing a dye or pigment. Of these, those using a dye are particularly preferable because they are soluble in an organic solvent and easily penetrate into voids or defects on the joint surface. Further, the penetrant for the penetrant inspection test preferably has a large specific gravity of being capable of accurately measuring the weight increase rate of the complex before and after the penetrant inspection test, and is 0.8 or more. Those having a specific gravity are more preferable, and those having a specific gravity of 0.9 or more are particularly preferable. In addition, since it easily penetrates into voids or defects on the joint surface and the weight increase rate can be measured accurately because it easily stays on the joint surface, it has a kinematic viscosity of 1 to 500 mm ² / sec at room temperature. It is preferable that As specific examples of the penetrant for penetrant inspection, (trade name) Microcheck penetrant (manufactured by Ichinen Chemicals Co., Ltd.), (trade name) Color Check FP-S (manufactured by Taseto Co., Ltd.), (trade name) ) X stamper dye-based ink X-200 (manufactured by Shachihata Co., Ltd.) and the like.

As a method for measuring the weight of each composite before and after contact with the penetrant for penetrant inspection, for example, a method of weighing the weight of each composite before and after contact with an electronic balance, a high-precision weighing sensor, or the like can be mentioned. Can be done. Then, the weight increase rate is obtained by dividing the difference between the weight of the composite after contact with the penetrant for penetrant inspection test and the weight of the composite before contact by the joint area, and as the weight increase rate per square centimeter of joint area. You can get it.

As a method of contacting the penetrant for the penetrant inspection test with the joint surface of the metal member-polyarylene sulfide resin member composite and allowing the penetrant for the penetrant inspection test to permeate the joint surface, for example, the joint surface of the composite. Examples thereof include a method of applying the penetrant for penetrant inspection and a method of immersing the joint surface of the composite in a container in which the penetrant for penetrant inspection is immersed. Then, after the penetrant for the penetrant inspection test is brought into contact with the joint surface of the composite, the pressure is preferably reduced or pressurized in order to remove the influence of air or the like existing in the voids or defects of the joint surface. .. When the pressure is reduced, for example, it is preferable to put the complex to which the penetrant for the penetration flaw detection test is attached in a container such as a desiccator or a vacuum can and reduce the pressure to a pressure of 1 mmHg or less, and particularly to increase the weight increase rate. Since it can be detected with high accuracy, it is preferable to reduce the pressure to 0.5 mmHg or less. The time for holding the complex under reduced pressure is preferably 3 minutes or more, and particularly preferably 5 minutes or more because the weight increase rate can be detected accurately. Further, when the pressure is applied, for example, it is preferable to put the composite to which the penetrant for the penetrant inspection test is attached into a pressure vessel or the like and pressurize the pressure under pressure, for example, 0.1 MPa or more, and particularly the weight increase rate. It is preferable to apply a pressure of 0.5 MPa or more because the pressure can be detected accurately. The time for holding the composite under pressure is preferably 3 minutes or more, and particularly preferably 5 minutes or more because the weight increase rate can be detected accurately.

Any method may be used as a method for producing the metal member-polyarylene sulfide resin member composite of the present invention, and among them, the metal member-polyarylene sulfide resin member composite of the present invention can be efficiently produced. Therefore, it is preferable that the manufacturing method goes through at least the following steps (1) to (3).
(1) Step: A molten polyarylene sulfide resin is directly integrated with a metal member in an injection molding die by injection molding to form a metal member-polyarylene sulfide resin member composite, and a metal member-polyarylene sulfide resin member composite. The process of measuring the weight of a body.
(2) Step; The penetrant for penetrant inspection test is brought into contact with the joint surface of the metal member-polyarylene sulfide resin member composite whose weight has been measured by the step (1), and the penetrant for penetrant inspection test is applied to the joint surface. The process of penetrating and measuring its weight.
(3) Step; A step of calculating a weight increase rate from the weight measured in the (2) step, and selecting and recovering a metal member-polyarylene sulfide resin member composite in which the weight increase rate is within a reference value.

The above step (1) is a step of forming a metal member-polyarylene sulfide resin member composite in which a metal member and a polyarylene sulfide resin member are directly integrated and measuring the weight thereof, and is a step of measuring the weight of the metal member and the polyarylene sulfide resin member. Any method can be used as long as it can be directly integrated by injection molding, and among them, since it is possible to produce a composite particularly efficiently, it should be integrated by injection insert molding method. Is preferable. 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, insert molding is performed because it is possible to efficiently manufacture a metal member-polyarylene sulfide resin member composite having a small weight increase rate when the penetrant for penetrant inspection is permeated into the joint surface. The mold temperature is preferably 130 ° C. or higher, and the holding pressure is preferably 1 MPa or higher.

In addition, injection molding such as polyarylene sulfide resin drying temperature during injection molding, polyarylene sulfide resin drying time, injection molding time, injection molding mold holding time, metal member-polyarylene sulfide resin member composite cooling time, etc. The conditions can be appropriately selected, and the injection molding mold holding time is preferably 1 second or longer, the injection molding time is preferably between 0.3 and 5 seconds, and the cooling time is preferably 4 seconds or longer. preferable.

Then, as a method for measuring the weight of the obtained metal member-polyarylene sulfide resin member composite, the above-mentioned method can be mentioned.

In the above step (2), the penetrant inspection penetrant is brought into contact with the joint surface of the metal member-polyarylene sulfide resin member composite whose weight has been measured by the step (1), and the penetrant inspection penetrant is brought into contact with the joint surface. Is a process of penetrating and measuring its weight. Examples of the permeation method and the weight measurement method at that time include the above-mentioned methods.

In the above step (3), the weight increase rate due to the penetrant inspection immersion liquid is calculated from the respective weights measured in the above steps (1) and (2), and the weight increase rate is within the reference value of the metal member. -A step of obtaining a metal member-polyarylene sulfide resin member composite having the desired performance by selecting and recovering the polyarylene sulfide resin member composite. As a method of calculating the weight increase rate at that time, the above-mentioned method can be mentioned. Further, the reference value can be appropriately selected depending on the performance of the target metal member-polyarylene sulfide resin member composite, and a metal member-polyarylene sulfide resin member composite particularly excellent in airtightness, bonding strength, etc. can be selected. For the purpose of obtaining, it is preferable that the reference value of the increase rate is 2 mg or less per 1 square centimeter of the joint area, and in particular, the weight increase rate is 1 mg or less per 1 square centimeter of the joint area. Is preferable. Then, by selecting and recovering the metal member-polyarylene sulfide resin member composite having a weight increase rate within the reference value, only the excellent metal member-polyarylene sulfide resin member composite is inspected by destruction. It is possible to manufacture stably without any problem.

Then, when a metal member-polyarylene sulfide resin member composite having a weight increase rate outside the reference value is generated in the step (3), the polyarylene sulfide resin drying, which is an injection molding condition in the step (1), is generated. Temperature, polyarylene sulfide resin drying time, injection molding temperature, injection molding mold temperature, injection molding time, injection molding mold holding pressure, injection molding mold holding time, metal member-polyarylene sulfide resin member composite cooling time It is preferable to use a manufacturing method for optimizing the molding conditions by controlling one or more of the molding conditions. Controls at this time include imparting melt fluidity of the molten polyarylene sulfide resin, suppressing entrainment of gas generated from the molten resin on the joint surface, and when trying to take out a molded product before the molten resin solidifies and shrinks. It is preferable to take measures such as suppressing the occurrence of mold release defects, and specific examples of imparting melt fluidity of the molten polyarylene sulfide resin include an increase in the injection molding temperature, an increase in the injection molding mold temperature, and an injection molding metal. Measures can be taken by increasing the mold holding pressure, extending the injection molding mold holding time, etc., and specific examples of suppressing entrainment of gas generated from the molten resin on the joint surface include extension of the injection time and poly. Measures can be taken by increasing the drying temperature of the arylene sulfide resin and extending the drying time of the polyarylene sulfide resin, and the mold release defect that occurs when the molded product is taken out before the molten polyarylene sulfide resin solidifies and shrinks. As a specific example of the suppression of the above, a response by extending the cooling time of the metal member-polyarylene sulfide resin member composite can be mentioned.

The metal member-polyarylene sulfide resin member composite of the present invention has excellent airtightness, excellent airtightness reliability, and also has 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 airtightness 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.

; Schematic view of the lid material for airtightness evaluation. ; Schematic view of the container for airtightness evaluation used in the examples.

1; Metal member.
2; Metal member.
3; Polyarylene sulfide resin member.
4; Metal lid plate.

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

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

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

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

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

<Synthesis Example 1 (Synthesis of PPS (A-1))>
To 15 liters autoclave equipped with a stirrer was charged with flaky sodium sulfide _{(Na 2 S · 2.9H 2 O} ) 1814g, 30% sodium hydroxide solution (30% NaOHaq) 48g and N- methyl-2-pyrrolidone 3679G, nitrogen flow The temperature was gradually raised to 200 ° C. with stirring, and 380 g of water was distilled off. After cooling to 190 ° C., 2107 g of p-dichlorobenzene and 985 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 1 hour, then heated to 250 ° C. over 25 minutes, and further polymerized at 250 ° C. for 3 hours. After the polymerization, N-methyl-2-pyrrolidone was recovered from the polymerized slurry under reduced pressure by a distillation operation. The final temperature reached was 170 ° C. and the pressure was 4.7 kPa. Warm water at 80 ° C. was added to the obtained cake and washed to a slurry concentration of 20%, and warm water was added again in the same manner to raise the temperature to 175 ° C. and the poly (p-phenylene sulfide) was washed twice in total. The obtained polyphenylene sulfide was dried at 105 ° C. for 24 hours. Next, the dried polyphenylene sulfide was filled in a batch type rotary kiln type firing device, heated to 240 ° C. in a nitrogen atmosphere, and cured by holding for 1 hour, whereby PPS (A-) having a melt viscosity of 190 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. Warm water at 80 ° C. was added to the obtained cake and washed to a slurry concentration of 20%, and warm water was added again in the same manner to raise the temperature to 175 ° C. and the poly (p-phenylene sulfide) was washed twice in total. The obtained poly (p-phenylene sulfide) was dried at 105 ° C. for 24 hours to obtain PPS (A-2) having a melt viscosity of 400 poise.

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

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

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

~ Measurement of increase rate and mechanical properties by penetrant for penetrant inspection test ~
For the composite of the metal member and the polyarylene sulfide resin member, a tensile shear test piece having a bonding area of 50 mm ² prepared according to ISO19095 was prepared. First, the weight of the tensile shear test piece is weighed using an electronic balance (Metal Toledo Co., Ltd., (trade name) XS205DUV), and the red dye-based ink (Shachihata Co., Ltd., (trade name) XR- 2N, specific gravity 1.0, viscosity 400 Pa · sec) is placed in a beaker, then immersed in ink so that the joint end face of the tensile shear test piece is immersed, and then the beaker is placed in a glass desiccator and an oil rotary vacuum pump (Albac). The pressure was reduced at 0.2 mmHg for 10 minutes using (trade name) GLD-201B manufactured by Co., Ltd. Next, the desiccator was opened to the atmosphere, excess ink adhering to the tensile shear test piece was removed with acetone, and then the weight of the tensile shear test piece was weighed using an electronic balance (Metal Toledo Co., Ltd. (trade name) XS205DUV). Weighed and determined the rate of weight increase per square centimeter of joint area.

Further, the tensile shear test piece was broken according to the joint strength measuring method of ISO19095, the breaking strength was measured, the broken joint surface was visually observed, and the intrusion of ink into the joint surface was visually observed.
◯: No ink intrusion or very small amount.
×: Ink intrusion is clearly seen.

~ Airtightness test and evaluation of airtightness ~
Distilled water was placed in an aluminum container with an open top, and the container and the lid material shown in FIG. 1 were welded and sealed to prepare a container for airtightness evaluation shown in FIG. After holding the airtightness evaluation container at 90 ° C. for 200 hours, the temperature was brought to room temperature, and the interface between the metal member, the lid material and the polyarylene sulfide resin member was immersed in a liquid for inspection. The inside of the container was pressurized to 0.5 MPa and held for 1 minute to evaluate the airtightness. The evaluation of the lid material with the penetrant for the penetrant inspection test was carried out in the same manner as described above.
◯: When no bubbles were generated from the interface immersed in the inspection liquid, it was judged that the airtightness was excellent.
X: When bubbles were generated from the interface immersed in the inspection liquid, it was judged that the airtightness was inferior.

Example 1
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 subjected to a 10% by mass aqueous solution of sodium hydroxide and then 10 A test piece made of an aluminum alloy (A5052) was obtained by chemically treating the surface of the aluminum alloy by immersing it in a weight% aqueous nitric acid solution and further anoxidizing it in a 30% by weight aqueous phosphoric acid solution at a current density of 2 A / dm ² for 20 minutes. ..

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

The obtained test piece made of aluminum alloy (A5052) was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which the cylinder temperature was 310 ° C., the mold temperature was 150 ° C., and the holding pressure was 70 MPa. A poly (p-phenylene sulfide) resin composition is injection-molded using (trade name) SE75S), and an aluminum alloy member-PPS resin composition member, which is a test piece for evaluating shear bonding strength having a bonding area of 50 mm ² according to ISO19095. Along with producing the composite, insert molding was performed into the shape shown in FIG. 1 to prepare a lid material, and the penetration evaluation of the aluminum alloy member-PPS resin composition member composite with a penetrating liquid for a penetration flaw detection test was performed. The weight increase rate per square centimeter of the joint area of the single-shaped aluminum alloy member-PPS resin composition member composite is 0.5 mg, and the joint area of the aluminum alloy member-PPS resin composition member composite of the lid material 1 The rate of weight gain per square centimeter was 0.6 milligrams.

When the obtained test piece-shaped aluminum alloy member-PPS resin composition member composite was broken according to ISO19095, it showed a breaking strength of 43 MPa, and the penetration of ink into the fracture surface was extremely small. Further, as a result of the airtightness evaluation of the aluminum alloy member-PPS resin composition member composite of the lid material, no bubbles were generated and it was good.

Example 2
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 0.06 mm, a frequency of 9 KHz, and a speed of 80 mm / sec.

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

The obtained test piece made of aluminum die-cast alloy (ADC12) was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which a cylinder temperature of 310 ° C., a mold temperature of 150 ° C., and a holding pressure of 30 MPa was set. Injection molding was performed using (trade name) SE75S), and an aluminum die-cast alloy member-PPS resin composition member composite was prepared from a test piece for evaluating shear joint strength having a joint area of 50 mm ² according to ISO19095, and FIG. An insert molding was performed in the shape shown to prepare a lid material, and a permeation evaluation of the aluminum die-cast alloy member-PPS resin composition member composite with a permeation liquid for a permeation flaw detection test was performed. As a result, a test piece-shaped aluminum die-cast alloy member-PPS The weight increase rate per square centimeter of the joint area of the resin composition member composite is 0.8 mg, and the weight increase rate of the aluminum alloy member-PPS resin composition member composite of the lid material is 0 per square centimeter of the joint area. It was 9.9 milligrams.

When the obtained test piece-shaped aluminum die-cast alloy member-PPS resin composition member composite was broken according to ISO19095, it showed a breaking strength of 44 MPa, and the penetration of ink into the fracture surface was extremely small. Further, as a result of the airtightness evaluation of the aluminum alloy member-PPS resin composition member composite of the lid material, no bubbles were generated and it was good.

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

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

The obtained aluminum (A1050) test piece was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which the cylinder temperature was 310 ° C., the mold temperature was 160 ° C., and the holding pressure was 70 MPa. Name) SE75S) is used for injection molding, and according to ISO19095, 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 , is produced and has the shape shown in FIG. A lid material was produced by insert molding, and the penetration evaluation of the aluminum member-PPS resin composition member composite with the penetrating liquid for the penetration flaw detection test was performed. As a result, the aluminum alloy member in the shape of a test piece-PPS resin composition member composite was evaluated. The weight increase rate per square centimeter of the joint area of the body is 0.7 mg, and the weight increase rate of the aluminum alloy member-PPS resin composition member composite of the lid material is 0.5 mg per square centimeter of the joint area of the lid material. It was.

When the obtained test piece-shaped aluminum alloy member-PPS resin composition member composite was broken according to ISO19095, it showed a breaking strength of 45 MPa, and the penetration of ink into the fracture surface was extremely small. Further, as a result of the airtightness evaluation of the aluminum alloy member-PPS resin composition member composite of the lid material, no bubbles were generated and it was good.

Example 4
The same method as in Example 1 using the PPS resin composition obtained by the same method as in Example 2 and the test piece made of aluminum alloy (A5052) except that the mold temperature was 130 ° C. and the holding pressure was 25 MPa. The aluminum alloy member-PPS resin composition member composite was prepared in accordance with the above method, and the permeation evaluation of the aluminum member-PPS resin composition member composite with the permeation liquid for the permeation detection test was performed. As a result, the aluminum alloy member-PPS in the shape of a test piece was evaluated. The weight increase rate per square centimeter of the joint area of the resin composition member composite is 1.0 mg, and the weight increase rate of the aluminum alloy member-PPS resin composition member composite of the lid material is 0 per square centimeter of the joint area. It was 9.9 milligrams.

When the obtained test piece-shaped aluminum alloy member-PPS resin composition member composite was broken according to ISO19095, it showed a breaking strength of 41 MPa, and the penetration of ink into the fracture surface was extremely small. Further, as a result of the airtightness evaluation of the aluminum alloy member-PPS resin composition member composite of the lid material, no bubbles were generated and it was good.

Example 5
Using the PPS resin composition obtained by the same method as in Example 1 and the test piece made of aluminum alloy (A5052), the test piece made of aluminum alloy (A5052) was set in a mold, and the cylinder temperature was 310 ° C. and gold. 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 40 MPa, and a shear bonding strength evaluation test with a bonding area of 50 mm ² according to ISO19095. 100 pieces of aluminum alloy member-PPS resin composition member composites were 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 by a belt conveyor. Each of the complexes was weighed by a multi-axis robot (manufactured by FANUC) and an electronic balance (manufactured by A & D Co., Ltd. (trade name) AD-4212D).

Next, each of the composites was immersed in a vacuum container containing a red dye-based ink (manufactured by Shachihata x Stamp, Inc. (trade name) XR-2N, specific gravity 1.0, viscosity 400 Pa · sec), and the decompression device was used. The pressure was reduced at 0.1 mmHg for 5 minutes. Next, the vacuum vessel is set to normal pressure, excess ink adhering to other than the joint surface of the composite is removed with acetone, and each of the composites is subjected to an electronic balance (manufactured by A & D Co., Ltd. (trade name)). Weighed by AD-4212D).

Then, the weight increase rate per 1 square centimeter of the joint area of the aluminum alloy member-PPS resin composition member composite of 100 points in total was determined. Further, a multi-axis robot (Fanac) in which the aluminum alloy member-PPS resin composition member composite is previously set to be transported to a parts storage box (below the reference value) or an exclusion box (exceeds the reference value) according to the weight increase rate. Then, it was transferred to a parts storage box for storing an aluminum alloy member-PPS resin composition member composite below a standard value. The reference value at that time was set to a weight increase rate of 2 milligrams per square centimeter of joint area.

All of the aluminum alloy member-PPS resin composition member composites transferred to the parts storage box showed a breaking strength of 40 MPa or more, and the intrusion of ink into the fracture surface was extremely small. Incidentally, the composite of the exclusion box had a low breaking strength of 30 MPa or less, and clear ink penetration was confirmed in the fracture surface.

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

The obtained composite had a large rate of weight increase per square centimeter of joint area, and was inferior in mechanical properties and airtightness.

Example 6
When the aluminum alloy member-PPS resin composition member composite was manufactured under the same conditions as in Example 5, the molding was transported to the exclusion box. Therefore, the mold temperature was changed from 140 ° C to 160 ° C and the holding pressure was maintained. The molding conditions were controlled from 40 MPa to 50 MPa, the poly (p-phenylene sulfide) resin composition dried at 120 ° C. for 5 hours was injection-molded, and the molding of the aluminum alloy member-PPS resin composition member composite was repeated again. ..

All of the aluminum alloy member-PPS resin composition member composites transferred to the parts storage box showed a breaking strength of 40 MPa or more, and the intrusion of ink into the fracture surface was extremely small. By the way, there was only one exclusion box complex.

Example 7
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 aluminum die-cast alloy (ADC12) and a lid material obtained by physically treating the surface of the aluminum die-cast alloy surface were obtained by performing laser treatment of scanning 1000 times in the orthogonal direction at 0.08 mm, a frequency of 9 KHz, and a speed of 80 mm / sec. ..

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

The pelletized poly (p-phenylene sulfide) resin composition was dried at 120 ° C. for 5 hours using a pellet dryer (manufactured by Matsui Seisakusho, (trade name) Speed Dryer PO-80).

The obtained test piece made of aluminum die-cast alloy (ADC12) was set in a mold, and an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd.) in which a cylinder temperature of 310 ° C., a mold temperature of 150 ° C., and a holding pressure of 1 MPa was set. Injection molding was performed using (trade name) SE75S), and 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 in a cooling time of 30 seconds according to ISO19095. .. Injection molding was repeated for 20 cycles to prepare 20 test piece-shaped aluminum die-cast alloy member-PPS resin composition member composites. Further, insert molding is performed in the shape shown in FIG. 1 under the same molding conditions as the test piece to prepare a lid material, and injection molding is repeated for 20 cycles to prepare 20 aluminum die-cast alloy members-PPS resin composition member composites of the lid material. did. Then, the permeation evaluation of the aluminum die-cast alloy member-PPS resin composition member composite with the penetrant for the penetrant inspection test was performed. At that time, the reference value of the weight increase rate per 1 square centimeter of the joint area was set to 2.0 mg. The weight increase rate per square centimeter of the joint area of the test piece-shaped aluminum die-cast alloy member-PPS resin composition member composite shows a variation in the range of 1.9 to 3.2 mg, and exceeds the standard value of 2.0 mg. Eighteen were detected and eliminated. The weight increase rate per square centimeter of the joint area of the aluminum die-cast alloy member-PPS resin composition member composite of the lid material shows a variation in the range of 1.9 to 3.9 mg, and exceeds the standard value of 2.0 mg. 19 were detected / excluded.

Next, the test piece subjected to the penetrant inspection test was evaluated for joint strength according to ISO 19095. The bonding strength was 30 MPa to 40 MPa. On the other hand, the bonding strength of the excluded composite was 11 to 28 MPa, which was inferior to the bonding strength with the metal, and ink penetrated into the fracture surface. Moreover, the airtightness evaluation of the aluminum die-cast alloy member-PPS resin composition member composite of the lid material was good. On the other hand, the excluded complex was a complex having poor airtightness due to the generation of bubbles.

Then, the holding pressure is then increased from 1 MPa to 50 MPa, and the test piece made of the aluminum die-cast alloy (ADC12) is set in a mold having a mold temperature of 150 ° C. and molded at a cylinder temperature of 310 ° C. and a holding pressure time of 5 seconds. Controlling the conditions, the poly (p-phenylene sulfide) resin composition dried at 120 ° C. for 5 hours was injection-molded with an injection time of 1 second, and the aluminum die-cast alloy member-PPS resin composition member composite was cooled for 30 seconds. The injection molding was repeated at the above to prepare 20 more aluminum die-cast alloy member-PPS resin composition member composites. Further, insert molding was performed in the shape shown in FIG. 1 under the same molding conditions as the test piece, and injection molding of the lid material was repeated for 20 cycles to prepare 20 more aluminum die-cast alloy member-PPS resin composition member composites of the lid material. ..

The weight increase rate per square centimeter of the joint area of the obtained aluminum die-cast alloy member-PPS resin composition member composite is stable in the range of 0.4 to 1.2 mg, and some of them exceed the standard value. There wasn't. The bonding strength was stable in the range of 37 MPa to 40 MPa, and the penetration of ink into the fracture surface was extremely small. Further, the weight increase rate per 1 square centimeter of the joint area of the aluminum die-cast alloy member-PPS resin composition member composite of the lid material is stable in the range of 0.5 to 1.3 mg, and the airtightness of the lid material is stable. As a result of the evaluation, no bubbles were generated and it was good.

Example 8
After cleaning the surface by immersing the aluminum (A1050) test piece (40 mm × 18 mm × 1.5 mm thickness) and the aluminum (A1050) member and lid plate having the shape shown in FIG. 1 in ethanol, the said The test piece was roughened by sandblasting with 0.1 mm and then 0.01 mm of alumina powder, and then the test piece was immersed in a 1 wt% aqueous sodium hydroxide solution and then a 1 wt% aqueous sulfuric acid solution, and finally. The test piece was immersed in a mixed solution of distilled water containing 1% by weight of ethanolamine at 95 ° C. for 10 minutes, and the surface was subjected to boehmite treatment to physically treat the aluminum surface and then chemically treat the aluminum (A1050) test. Pieces and lids were obtained.

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

The pelletized poly (p-phenylene sulfide) resin composition was dried at 120 ° C. for 5 hours using a pellet dryer (manufactured by Matsui Seisakusho, (trade name) Speed Dryer PO-80).

The obtained test piece made of aluminum (A1050) was set in a mold and set to a cylinder temperature of 310 ° C., a mold temperature of 150 ° C., a holding pressure of 50 MPa, and a holding time of 5 seconds (Sumitomo Heavy Industries). A poly (p-phenylene sulfide) resin composition was injection-molded with an injection time of 0.1 seconds using (trade name) SE75S manufactured by Kogyo Co., Ltd., and a test piece for evaluating shear bonding strength having a bonding area of 50 mm ² according to ISO19095. An aluminum member-PPS resin composition member composite was produced with a cooling time of 30 seconds. Injection molding was repeated for 20 cycles to prepare 20 test piece-shaped aluminum member-PPS resin composition member composites. Further, insert molding was performed in the shape shown in FIG. 1 under the same molding conditions as the test piece to prepare a lid material, and injection molding was repeated for 20 cycles to prepare 20 aluminum member-PPS resin composition member composites of the lid material. Then, the permeation evaluation of the aluminum member-PPS resin composition member composite with the penetrant for the penetrant inspection test was performed. At that time, the reference value of the weight increase rate per 1 square centimeter of the joint area was set to 2.0 mg. The weight increase rate per square centimeter of the joint area of the test piece-shaped aluminum member-PPS resin composition member composite shows a variation in the range of 1.6 to 2.5 mg, and exceeds the standard value of 2.0 mg. Nine were detected and eliminated. The weight increase rate per square centimeter of the joint area of the aluminum member-PPS resin composition member composite of the lid material shows a variation in the range of 1.6 to 2.9 mg, and those exceeding the standard value of 2.0 mg are 11 Individuals were detected and eliminated.

Next, the test piece subjected to the penetrant inspection test was evaluated for joint strength according to ISO 19095. The bonding strength was 33 MPa to 43 MPa. On the other hand, the bonding strength of the excluded composite was 16 to 28 MPa, which was inferior to the bonding strength with the metal, and ink penetrated into the fracture surface. Moreover, the result of the airtightness evaluation of the aluminum member-PPS resin composition member composite of the lid material was good. On the other hand, the excluded complex was a complex having poor airtightness due to the generation of bubbles.

Therefore, next, the injection time was extended from 0.1 second to 1 second, and the aluminum (A1050) test piece was set in a mold having a mold temperature of 150 ° C., and the cylinder temperature was 310 ° C. and the holding pressure was 50 MPa. The molding conditions were controlled to a holding time of 5 seconds, and a poly (p-phenylene sulfide) resin composition dried at 120 ° C. for 5 hours was injection-molded with an injection time of 1 second, and the aluminum member-PPS resin composition member composite was formed. Was repeatedly injection-molded with a cooling time of 30 seconds to prepare 20 more aluminum member-PPS resin composition member composites. Further, insert molding was performed in the shape shown in FIG. 1 under the same molding conditions as the test piece, and injection molding of the lid material was repeated for 20 cycles to prepare 20 more aluminum member-PPS resin composition member composites of the lid material.

The weight increase rate per square centimeter of the joint area of the obtained aluminum member-PPS resin composition member composite was stable in the range of 0.4 to 1.0 mg, and none exceeded the standard value. .. The bonding strength was stable in the range of 38 MPa to 40 MPa, and the penetration of ink into the fracture surface was extremely small. Further, the weight increase rate per 1 square centimeter of the joint area of the aluminum alloy member-PPS resin composition member composite of the lid material is stable in the range of 0.5 to 1.2 mg, and the airtightness of the lid material is evaluated. As a result, no bubbles were generated and the result was good.

The metal member-polyarylene sulfide resin member composite of the present invention has no defects such as voids on the joint surface, is excellent in airtightness on the joint surface, and is also excellent in impact resistance, light weight, and mass productivity. It is useful as a complex of transportation equipment such as automobiles and aircraft.

Claims (7)

Metal member formed by directly integrating the metal member and the polyarylene sulfide resin member by injection molding-A metal containing a penetrating liquid for a penetration flaw detection test on the joint surface between the metal member of the polyarylene sulfide resin member composite and the polyarylene sulfide resin member. It is a member-polyarylene sulfide resin member composite, and the weight increase rate of the metal member-polyarylene sulfide resin member composite by the penetrant for penetration flaw detection test is 2 mg or less per 1 square centimeter of joint area. Characteristic metal member-polyarylene sulfide resin member composite. The metal member-polyarylene sulfide resin member composite according to claim 1, wherein the metal member is a metal member having a surface that has been physically and / or chemically treated. The polyarylene sulfide resin member is further added to 100 parts by weight of the polyarylene sulfide resin, ethylene-α, β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α, β-unsaturated glycidyl carboxylic acid. 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 The claim is characterized by containing 1 to 40 parts by weight of at least one modified ethylene-based copolymer selected from the group consisting of a maleic anhydride graft-modified ethylene-α-olefin copolymer. Item 2. The metal member-polyylene sulfide resin member composite according to Item 1 or 2. A method for producing a metal member-polyarylene sulfide resin member composite, which comprises undergoing at least the following steps (1) to (3).
(1) Step: A molten polyarylene sulfide resin is directly integrated with a metal member in an injection molding die by injection molding to form a metal member-polyarylene sulfide resin member composite, and a metal member-polyarylene sulfide resin member composite. The process of measuring the weight of a body.
(2) Step; The penetrant for penetrant inspection test is brought into contact with the joint surface of the metal member-polyarylene sulfide resin member composite whose weight has been measured by the step (1), and the penetrant for penetrant inspection test is applied to the joint surface. The process of penetrating and measuring its weight.
(3) Step; A step of calculating a weight increase rate from the weight measured in the (2) step, and selecting and recovering a metal member-polyarylene sulfide resin member composite in which the weight increase rate is within a reference value. In the step (2), when the penetrant for penetrant inspection is permeated into the joint surface, the pressure is reduced to 1 mmHg or less or pressurized to 0.1 MPa or more, and then the weight is measured under atmospheric pressure. The method for producing a metal member-polyarylene sulfide resin member composite according to claim 4. The metal member-polyarylene sulfide resin member composite according to claim 4 or 5, wherein the reference value of the weight increase rate in the step (3) is 2 milligrams per 1 square centimeter of the joint area. Production method. When a metal member-polyarylene sulfide resin member composite whose weight increase rate is out of the standard value is generated in the step (3), the polyarylene sulfide resin drying temperature and poly, which are injection molding conditions in the step (1), are formed. Any of allylene sulfide resin drying time, injection molding temperature, injection molding mold temperature, injection molding time, injection molding mold holding pressure, injection molding mold holding time, metal member-polyallylen sulfide resin member composite cooling time. The method for producing a metal member-polyarylene sulfide resin member composite according to any one of claims 4 to 6, wherein one or more molding conditions are controlled.