WO2014112506A1

WO2014112506A1 - Process for producing metal-resin bonded object, and metal-resin bonded object

Info

Publication number: WO2014112506A1
Application number: PCT/JP2014/050531
Authority: WO
Inventors: 正憲遠藤; 祥成武村; 原田　聡; 奈保金子; めぐみ佐藤; 栄一郎中島; 圭司西村; 諒吉田; 令子高澤; みゆき吉田
Original assignee: 日本軽金属株式会社
Priority date: 2013-01-18
Filing date: 2014-01-15
Publication date: 2014-07-24
Also published as: CN104936763B; MY170538A; JPWO2014112506A1; JP6079791B2; JP2017109496A; CN104936763A

Abstract

Provided is a process for producing a metal-resin bonded object in which the metal member has been untied with the resin member constituted of a thermoplastic resin, the process being easier and versatile, being capable of imparting stable bonding strength to the bonded surfaces of the metal member and resin member, and giving no damage, etc. to the metal member, etc. of the metal-resin bonded object. The process, which is for producing a metal-resin bonded object by bonding a metal member to a resin member constituted of a thermoplastic resin, comprises: superposing beforehand a resinous bonding layer that comprises a thermoplastic resin having compatibility with the resin member and has a thickness of 0.01-9 mm, on the surface of the metal member which is to be bonded; and heating the surfaces to be bonded of the resinous bonding layer of the metal member and the resin member to compatibilize and bond the resinous bonding layer and the resin member.

Description

Method for producing metal-resin joined body and metal-resin joined body

The present invention provides a metal-resin bonded body for manufacturing a metal-resin bonded body in which a metal member and a resin member made of a thermoplastic resin are bonded by thermal welding and the metal member and the resin member are integrated. The present invention relates to a method and a metal-resin joined body produced by this method.

For joining thermoplastic resins, methods using an external heat source such as hot air welding, hot plate welding, laser welding, electromagnetic heating methods such as high frequency welding, electric heating methods such as hot wire welding, vibration welding, spin welding, etc. , A method that uses frictional heat generation such as ultrasonic welding, a method that uses the retained heat of a secondary injection resin such as injection welding, and so on. These heat welding techniques are known, and are used in various applications depending on the characteristics of each heat welding technique.

However, with regard to the bonding between different kinds of materials, especially the bonding between the metal member and the resin member, a method of bonding under pressure using an adhesive or the metal member is inserted into an injection mold and inserted. The mainstream method is to inject a molten thermoplastic resin toward the surface of the metal member, and simultaneously join the metal member and the resin member when molding the resin member, and use the technique of thermal welding. As for the method, the following proposals have been seen, but sufficient studies have not yet been made.

For example, in Patent Document 1, when a resin material made of a thermoplastic resin having a thickness of 0.1 mm or more and a metal material having a thickness of 0.1 mm or more are joined, a resin material is joined to the metal material. A resin thin film having a film thickness of 0.1 to 50 μm made of a thermoplastic resin compatible with the thermoplastic resin of the resin material is laminated on the surface, and the resin thin film of the metal material and the resin material are overlapped with each other to form a metal material. The cylindrical rotary tool is pressed from the side and rotated. At this time, the frictional heat generated between the rotary tool and the metal material is exchanged between the resin material in contact with the metal material and the resin thin film of the metal material via the metal material. There has been proposed a method in which bonding is performed by transmitting between the joining surfaces and mixing the two.

In Patent Document 2, a metal body having a lower melting point than that of the thermoplastic resin body is brought into surface contact with the thermoplastic resin body, and ultrasonic vibration is applied to the metal body to melt the metal body and soften the thermoplastic resin body. Then, a method has been proposed in which a molten metal body is diffused into a softened thermoplastic resin body to join the metal body and the thermoplastic resin body.

However, in the method of Patent Document 1, since the rotary tool is pressed against the surface of the metal material to generate frictional heat, the metal tool surface is rubbed by the rotary tool, and the appearance is impaired. In addition, the device configuration of the joining device using a rotating tool is complicated and large, and further, in processing such as press molding after joining a metal material and a resin material, it causes troubles such as cracks starting from friction marks. There's a problem.

Further, in the method of Patent Document 2, a metal material having a melting point lower than that of the thermoplastic resin body must be selected as the metal body, and there are severe restrictions on the metal material and resin material that can be joined by this method. There is a problem of poor versatility.

JP2009-279,858 Japanese Patent No. 3,352,708

Therefore, the present inventors joined a metal member and a resin member made of a thermoplastic resin to manufacture a metal-resin joined body in which the metal member and the resin member are integrated with a simpler method. As a result of intensive studies on the development of a method capable of providing stable bonding strength between the bonding surfaces between the metal member and the resin member, a resin bonding layer having a predetermined film thickness is previously formed on the metal member side. By providing, it is possible to effectively apply the thermal welding technology adopted in the joining technology between thermoplastic resins, particularly the thermal welding technology in which frictional heat is generated and heated by pressing and relative movement between the joined bodies. The present invention has been completed.

Accordingly, an object of the present invention is to provide a simpler and more versatile method for producing a metal-resin joined body in which a metal member and a resin member made of a thermoplastic resin are integrated. Stable joint strength can be imparted between the joint surfaces between the metal and the resin, and the metal member of the metal-resin joined body is not damaged and the subsequent of the obtained metal-resin joined body. It is an object of the present invention to provide a method for producing a metal-resin bonded body that does not cause problems such as cracking in processing such as pressing and bending.

Another object of the present invention is to provide a metal-resin bonded body manufactured by such a method, having a stable bonding strength between bonding surfaces and excellent in properties such as appearance.

That is, the present invention is a method of manufacturing a metal-resin bonded body by bonding a metal member and a resin member made of a thermoplastic resin, and a thermoplastic having compatibility with the resin member in advance on the bonding surface of the metal member. A metal-resin bonded body characterized by laminating a resin bonding layer having a thickness of 0.01 to 9 mm made of a resin, and bonding the bonding surface between the resin bonding layer of the metal member and the resin member by heat welding. It is a manufacturing method.
Further, the present invention is a metal-resin bonded body obtained by such a method.

In the present invention, as the metal member, those made of various metal materials can be used depending on the use of the metal-resin assembly to be produced. For example, an aluminum member made of aluminum or an aluminum alloy, or iron or iron alloy Or iron members made of alloy steel, etc., copper members made of pure copper, high copper alloys, brass, bronze, copper nickel alloys, etc., titanium members made of titanium or titanium alloys, etc., magnesium members made of magnesium or magnesium alloys, etc. Can be mentioned. Among these, the aluminum member has excellent conductivity, is lightweight and excellent in workability and heat dissipation, and can be suitably used for many applications.

Further, the resin member used in the present invention is not particularly limited as long as it is a thermoplastic resin and can be melted or softened under heating. Polyethylene, polypropylene, polystyrene, ABS resin, AS resin, polyvinyl chloride, acrylic Resins, polyvinyl acetate, polyamide resins, polyacetals, polyester resins, etc. can be exemplified, and preferably various kinds of materials because they are inexpensive, excellent in handling properties, easy to melt at low temperatures and excellent in workability. An olefin resin, more preferably an olefin resin such as polyethylene or polypropylene. In particular, since polyethylene has a low processing deformation temperature, the processing temperature at the time of joining can be lowered, the deformation surface of the joined surface of the joined body can be easily deformed, and polypropylene has a high tensile strength and is a metal. A high bonding strength can be stably imparted between the bonding surfaces between the member and the resin member.

The resin material for forming the resin bonding layer laminated on the bonding surface of the metal member is not particularly limited as long as it is a thermoplastic resin that is compatible with the resin member and melts or softens under heating. However, it is preferable to use various olefin-based resins because they are inexpensive, excellent in handling properties, easy to melt at low temperatures and excellent in workability. It is a resin, more preferably an olefin resin such as polypropylene or polyethylene.

The melting point difference between the melting point of the resin member and the melting point of the resin bonding layer is preferably 100 ° C. or less, and more preferably, the melting point difference is 50 ° C. or less. When the difference in melting point between the resin member and the resin bonding layer is 100 ° C. or more, the viscosity of the resin bonding layer is lowered before the resin member is melted when the pressure is applied to bond the resin member and the resin bonding layer. There is a concern that the resin bonding layer may flow out of the bonding surface before the layers are compatible.

In the present invention, the film thickness of the resin bonding layer laminated on the bonding surface of the metal member needs to be 0.01 mm or more and 9 mm or less. In particular, the method of thermal welding for bonding the resin member is a vibration. In the case of welding, it is preferably 0.1 mm or more and 9 mm or less, and in the case where the method of thermal welding for joining the resin members is ultrasonic welding, it is preferably 0.01 mm or more and 1 mm or less. It is good. Further, when the method of thermal welding for joining with the resin member is injection welding, the thickness is preferably 0.05 mm or more and 9 mm or less.

When vibration welding is selected, if the film thickness of the resin bonding layer is less than 0.1 mm, or conversely, if the film thickness is greater than 9 mm, it is sufficient between the bonding surfaces between the metal member and the resin member. May not be able to obtain a good bonding strength. Here, the reason why sufficient bonding strength cannot be obtained when the film thickness is less than 0.1 mm is not clear, but the film thickness of the resin bonding layer is thin and sufficient heat insulation effect does not occur, and heat welding is performed. During this process, the heat supplied between the joining surfaces easily flows out to the metal member side having excellent thermal conductivity, and is necessary and sufficient for joining between the joining surfaces between the resin joining layer of the metal member and the resin member. Therefore, it is considered that the compatibilization is difficult to occur, and as a result, sufficient bonding strength cannot be obtained. Also, the reason why sufficient bonding strength cannot be obtained when the film thickness is thicker than 8 mm is that the resin bonding layer does not bond uniformly to the metal member, so that high bonding strength is obtained when the resin member is bonded thereafter. It is thought that it is not possible.

On the other hand, when the ultrasonic welding is selected, when the film thickness of the resin bonding layer is less than 0.01 mm, or conversely, when the film thickness is greater than 1 mm, the bonding between the metal member and the resin member is performed. In some cases, sufficient bonding strength cannot be obtained between the surfaces. Here, the reason why sufficient bonding strength cannot be obtained when the film thickness is less than 0.01 mm is not clear, but the film thickness of the resin bonding layer is thin and sufficient heat insulation effect does not occur, and heat welding is performed. During this process, the heat supplied between the joining surfaces easily flows out to the metal member side having excellent thermal conductivity, and is necessary and sufficient for joining between the joining surfaces between the resin joining layer of the metal member and the resin member. Therefore, it is considered that the compatibilization is difficult to occur, and as a result, sufficient bonding strength cannot be obtained. However, in comparison with vibration welding where the frequency is low and heat easily escapes to the metal side, when ultrasonic welding is selected, bonding can be performed even in the range of 0.01 to 0.1 mm. On the other hand, the reason why sufficient bonding strength cannot be obtained when the film thickness is thicker than 1 mm is that the vibration attenuation in the plate thickness direction becomes large in ultrasonic welding, so that the vibration necessary to generate heat when the resin thickness increases. It is considered that the number cannot be obtained, and as a result, sufficient bonding strength cannot be obtained.

When injection welding is selected, if the thickness of the resin bonding layer is less than 0.05 mm, or conversely, if the thickness is greater than 1 mm, the bonding surface between the metal member and the resin member In some cases, sufficient bonding strength cannot be obtained. Here, the reason why a sufficient bonding strength cannot be obtained when the film thickness is thinner than 0.05 mm is that the melting heat of the molten resin that has reached the bonding surface diffuses to the metal member side having excellent thermal conductivity. In addition, it is considered that necessary and sufficient compatibilization is difficult to occur between the bonding surfaces between the resin bonding layer of the metal member and the resin member, and as a result, sufficient bonding strength cannot be obtained. On the other hand, the reason why sufficient bonding strength cannot be obtained when the film thickness is thicker than 8 mm is that the resin bonding layer is not uniformly bonded to the metal member, so that high bonding strength is obtained when the resin member is bonded thereafter. It is considered impossible.

In the present invention, before the metal member and the resin member are bonded by thermal welding, the resin bonding layer is laminated on the bonding surface of the metal member. A method for forming the resin bonding layer at this time is as follows. There is no particular limitation as long as the resin bonding layer having a thickness of 0.01 to 9 mm can be formed. For example, a resin sheet made of a thermoplastic resin having compatibility with the resin member is bonded to the bonding surface of the metal member. It may be formed.

In particular, the laminate bonding method of forming a resin bonding layer by bonding a resin sheet to a bonding surface of a metal member can reduce the cost of a resin bonding layer having a desired film thickness by using a resin sheet having a desired film thickness. In addition to being easy to form, there are advantages such as uniform film thickness and high surface smoothness. Here, in the present invention, the term “laminate adhesion” means that a resin sheet made of a thermoplastic resin is laminated on the surface of a metal member at a temperature not lower than the glass transition temperature and lower than the melting point under heat and pressure.

And in the case of forming the resin bonding layer on the bonding surface of the metal member by the laminate adhesion, in order to further improve the adhesion between the metal member and the resin sheet, prior to the formation of the resin bonding layer, Preferably, a hydration film is formed by cleaning the joining surface of the metal member with an acid aqueous solution and / or an alkaline aqueous solution, or treating the joining surface of the metal member in pure water or an alkaline solution at 50 ° C. or higher. Hydration treatment, zincate treatment that forms a zincate film by treating the joint surfaces of metal members in a zinc-containing alkaline solution, and trivalent that forms a chromate film by treating in a phosphate chromate solution at 50 ° C or higher A pretreatment consisting of one or two or more treatments selected from chromate treatment or the like is preferably performed.

Specifically, as the cleaning treatment for cleaning the bonding surface, for example, a metal member is immersed in an acid aqueous solution, then washed with water, then immersed in an alkaline aqueous solution, again immersed in an acid aqueous solution, and then washed with water. And a method of washing with a volatile organic solvent such as acetone. Specific examples of the hydration treatment for forming a hydrated film on the joint surface include a method of treating with pure water at 70 ° C. or higher. Furthermore, specific examples of the zincate treatment for forming a zinc-containing film on the joint surface include, for example, a method of treating with an alkaline zinc-containing solution. Furthermore, specific examples of the trivalent chromate treatment for forming a trivalent chromate film on the joint surface include a method of treating with a phosphoric acid chromate treatment solution.

In particular, in the case where the metal member is an aluminum member, the above-mentioned cleaning treatment is applied as a pretreatment to the joint surface before laminating, and in addition to the washing treatment, the hydration treatment, zincate treatment, It is preferable to perform a valent chromate treatment to form a hydrated film or a zinc-containing film, whereby the adhesion between the bonding surface of the aluminum member and the resin bonding layer can be further increased. The reason why the adhesion is improved by performing the pretreatment as described above is not necessarily clear, but is included in the OH group and the resin bonding layer present in the outermost layer of the hydrated film, zincate film, and trivalent chromate film. This is probably because a COOH group causes a dehydration reaction when the laminate is adhered, and forms a COO bond to bond firmly. In addition, the presence of a coating with low thermal conductivity on the surface layer compared to metal makes it difficult for the heat generated during heat welding to escape from the metal side, resulting in a gap between the bonding surface of the aluminum member and the resin bonding layer. It is considered that the adhesion of the material becomes higher.

In the present invention, the metal member prepared as described above is joined by so-called thermal welding, where the joint surface between the resin joint surface and the resin member of the metal member is heated and compatibilized to join them. A metal-resin bonded body is integrally manufactured. And as a method of joining by this thermal welding, depending on conditions such as the shape of the metal member and the resin member, the type and physical properties of the thermoplastic resin forming the resin joining layer and the resin member of the metal member, vibration welding, spin Heating by frictional heating such as welding, ultrasonic welding, etc., heating using an external heat source such as laser welding, hot press welding, hot air welding, hot plate welding, electromagnetic heating such as high frequency welding, electric heating such as hot wire welding, etc. It is possible to select and apply the most suitable method from various methods using the heat source and injection welding, but from the viewpoint of minimizing the thermal effect on the part other than the joining surface, it is preferable that the metal member be resin-bonded A joining method in which the joining surfaces of the layer and the resin member are pressed against each other, frictional heat is generated by relative motion, and the frictional heat is heated and compatibilized to join them. It is preferable that either one surface is heated by laser irradiation between the joint surfaces with the member to make them compatible and joined, and among these joining methods by frictional heat generation, the joining time is short and the productivity is low. From the viewpoint that the appearance of the bonded surface after bonding is high or is difficult to be impaired, a bonding method by vibration welding, ultrasonic welding or injection welding is more preferable.

Here, the above-described joining method by vibration welding is set in the vibration welding machine by superimposing the portions (joint surfaces) where the resin joining layer and the resin member of the metal member prepared as described above are to be joined to each other. In a state where the space between the joining surfaces is sufficiently pressurized, a reciprocating vibration having a predetermined frequency and a predetermined maximum amplitude is applied to the metal member side or the resin member side, and frictional heat generated between the joining surfaces by the reciprocating vibration is applied. In this method, the bonding surface between the resin bonding layer of the metal member and the resin member is heated, and the thermoplastic resin of the resin bonding layer and the resin member is made compatible to be bonded.

In addition, the above-described joining method by ultrasonic welding is performed by superposing the portions (joining surfaces) where the resin joining layer and the resin member of the metal member prepared as described above are to be joined to each other. In an ultrasonic welder), the electrical signal amplified by the oscillator is input to the piezo-electric element of the vibrator, and the electrical signal is converted into mechanical vibration energy by the piezo-electric element. The mechanical vibration energy is converted and transmitted between the joint surface between the resin joint layer of the metal member and the resin member via the horn of the resonator, and the resin joint layer of the metal member is generated by frictional heat generated between the joint surfaces. In this method, the bonding surfaces of the resin member and the resin member are heated to make the resin bonding layer and the thermoplastic resin of the resin member compatible with each other. This ultrasonic welding is advantageous for producing small and precise products. This vibration welding has almost no adverse effect such as damage upon joining to both the metal member and the resin member, and is advantageous when manufacturing a metal-resin joined body having a relatively large weight and volume. It is.

Further, the above-mentioned joining method by injection welding is performed by setting the metal member prepared as described above to a resin mold in an injection molding apparatus, then injecting molten resin, and heat of the molten resin. This is a method of joining by melting and compatibilizing the joining layer. The greatest feature of injection welding is that the cycle time is overwhelmingly shorter than other welding methods.

And in the joining method by the above-mentioned vibration welding, ultrasonic welding, or injection welding, the applied operating conditions depend on the type and physical properties of the thermoplastic resin forming the resin joining layer of the metal member and the resin member. Determined and set.
For example, in the case of thermally welding between the resin bonding layer of the metal member and the resin member by the vibration welding, the time for applying the reciprocating vibration (that is, the vibration applying time) is usually 0.2 seconds to 60 seconds, preferably Is preferably not shorter than 0.2 seconds and not longer than 15 seconds. If the vibration application time is shorter than 0.2 seconds, sufficient bonding strength may not be obtained. The strength does not increase further, the resin between the joint surfaces melts completely, flows out of the joint surface and becomes burrs, and as a result, the appearance defect of the joint and the thickness of the resin joint cannot be controlled. May occur.
In addition, when the resin bonding layer of the metal member and the resin member are thermally welded by injection welding, if the resin member is PP, a PP resin member such as a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. is generally injection molded. It is possible to join within the conditions.

According to the present invention, when manufacturing a metal-resin bonded body in which a metal member and a resin member made of a thermoplastic resin are integrated, it is more simple and versatile, and provides a stable bonding strength between bonded surfaces. In addition, it is possible to provide a method for producing a metal-resin joined body that does not damage the metal member of the metal-resin joined body.
In addition, it is possible to provide a metal-resin bonded body having a stable bonding strength between bonding surfaces and excellent in appearance and other characteristics at a low cost.

1A and 1B are a side view and a plan view for explaining metal members prepared in Examples and Comparative Examples of the present invention.

FIG. 2 is a side view and a plan view for explaining test pieces (metal-resin bonded bodies) prepared in Examples and Comparative Examples of the present invention.

FIG. 3 is an explanatory diagram for explaining a tensile force acting on a test piece when a shear tensile strength test is performed in Examples and Comparative Examples of the present invention.

FIG. 4 is an explanatory diagram for explaining a fracture mode generated in a test piece in a shear tensile strength test performed in Examples and Comparative Examples of the present invention.

<< Examples 1 to 13 and Comparative Examples 1 to 7 >>
Hereinafter, based on an Example and a comparative example, the manufacturing method of a metal-resin conjugate | zygote and metal-resin conjugate | zygote of this invention are demonstrated concretely.
In the following examples and comparative examples, an aluminum plate (aluminum member) made of an aluminum alloy plate (JIS A5052-H34) having a size of width 30 mm × length 90 mm × thickness 3 mm is used as the metal member. An olefin sheet having a width of 30 mm, a length of 90 mm and a thickness of 0.1 to 10 mm as a resin sheet for forming a resin bonding layer to be laminated on the bonding surface of the aluminum member (trade name: ADMER, manufactured by Mitsui Chemicals, Inc.) In addition, a polypropylene molded plate material (PP molded body) having a size of 30 mm width × 90 mm length × 3 mm thickness was used as the resin member.

[Pretreatment P1 of aluminum plate]
First, the aluminum plate was immersed in a 30 wt% nitric acid aqueous solution at room temperature for 5 minutes, then sufficiently washed with ion exchange water, then immersed in a 5 wt% sodium hydroxide solution at 50 ° C. for 1 minute, and further washed with water. A pretreatment was performed by immersing in a 30 wt% nitric acid aqueous solution at room temperature for 3 minutes and washing with water.

[Pretreatment of aluminum plate P2]
After the pretreatment P1 was completed, a hydration treatment was performed in which the aluminum plate was further immersed in pure water at 95 ° C. for 1 minute.

[Pretreatment of aluminum sheet P3]
After the pretreatment P1 was completed, a trivalent chromate treatment was performed in which the aluminum plate was further immersed in a phosphoric acid chromate solution at 50 ° C. for 10 seconds.

[Lamination of resin bonding layer on the bonding surface of aluminum plate]
On the aluminum plate after completion of the above pretreatment A or B, olefin sheets having different thicknesses are superposed on the entire surface of one side, and this is set in a hot press machine (As One hot press machine). As shown in FIG. 1, an aluminum resin laminated sheet 2 in which an olefin sheet (resin bonding layer) 2b was laminated on one side of the aluminum sheet 2a was produced by hot pressing under a condition of pressing at 30 ° C. for 30 seconds.
Table 1 shows the film thickness (mm) of the olefin sheet (resin bonding layer) used in each example and comparative example.

[Preparation of aluminum-resin bonded body by vibration welding]
Next, the above PP molded body (resin member) 3 is placed on the olefin sheet (resin bonding layer) 2b of the produced aluminum resin laminate 2 and this is welded to a vibration welding machine (manufactured by Seidensha: VL-1900 ), A reciprocating vibration with a frequency of 238.2 Hz and a maximum vibration of 1.6 mm was applied under conditions of a pressurizing force of 5 to 7 MPa and a vibration applying time of 0.1 to 10 seconds, and as shown in FIG. A test piece (metal-resin bonded body) 1 having a PP molded body bonded to the bonding surface was produced.
Table 1 shows the applied pressure (MPa) and the vibration application time (sec.) Applied in each example and comparative example.

[Shear tensile strength test]
For the test pieces (metal-resin bonded bodies) 1 of each Example and Comparative Example obtained as described above, using a shear tensile strength test apparatus (manufactured by Shimadzu Corporation: Autograph), as shown in FIG. A tensile force is applied between the aluminum member 2 side and the PP molded body 3 side to measure the breaking load (N) when each test piece breaks, and the test piece after this shear tensile strength test is shown in FIG. By examining which of the fracture forms A to C shown in Fig. 4 was broken, the shear tensile strength of each test piece was evaluated.
This shear tensile strength is evaluated in three stages: x: in the case of the fracture form A shown in FIG. 4, ◯: in the case of the fracture form B shown in FIG. 4, and ◎: in the case of the fracture form C shown in FIG. It was. The results are shown in Table 1.

[Deep drawability evaluation test]
Also, the aluminum plate (aluminum member) having a size of width 100 mm × length 100 mm × thickness 3 mm is used as a metal member, and resin sheet has a size of width 100 mm × length 100 mm × thickness 0.6 mm. Using the olefin sheet, and using the PP molded body having a size of width 100 mm × length 100 mm × thickness 3 mm as a resin member, for deep drawing in the same manner as in the above examples and comparative examples. Test specimens (metal-resin joints) were prepared, and for each of these deep drawing test pieces, a deep drawability evaluation tester (Ericsen Co., Ltd .: Eriksen Tester) was used. Each test piece was inserted into a wrinkle presser and pressed with a hemispherical punch under the conditions of a wrinkle presser pressure of 270 kg and a test speed of 3 notches to form each test piece into a complete cup shape. Thereafter, the entire test piece formed into a cup shape was observed in detail, and evaluated as ◯: no crack in each part and x: a crack in any part. The results are shown in Table 1.

<Test results and evaluation>
As is apparent from the results shown in Table 1 showing the results of the joint strength (shear tensile strength) test and the deep drawability evaluation test, in Comparative Examples 1 and 2 in which the film thickness of the olefin sheet (resin joint layer) is 0.05 mm In the case where the vibration application time during vibration welding is 0.5 seconds or 3 seconds, the fracture mode is A evaluation, and sufficient shear tensile strength cannot be obtained (Comparative Examples 1 and 2). On the other hand, in Examples 1 to 6 in which the film thickness of the resin bonding layer is 0.2 to 0.5 mm, the shear is applied regardless of the vibration application time (0.5 to 3 seconds) during vibration welding. Both tensile strength and deep drawability were good.

For Comparative Example 4 and Examples 7 to 12 in which the film thickness of the olefin sheet (resin bonding layer) is 1 mm, in the case of Comparative Example 4 in which the vibration application time during vibration welding is 0.1 seconds, In the case of Examples 7 to 11 in which the fracture mode is A evaluation, the shear tensile strength is insufficient, and on the contrary, the vibration application time during vibration welding is 0.5 to 10 seconds, all are shear tensile strengths. The deep drawability was good. From this, it was found that it is desirable to perform the vibration application time during vibration welding longer than 0.1 seconds.

Further, in Example 12 in which the film thickness of the olefin sheet (resin bonding layer) was 8 mm, both the shear tensile strength and the deep drawability were good, but the comparison was made with the resin bonding layer having a film thickness of 10 mm. In the case of Example 5, both the shear tensile strength and the deep drawability were insufficient.

In Example 13, a pretreatment P2 for further hydration was performed after the pretreatment P1 performed in the case of the above Examples 1 to 12. As a result, both the shear tensile strength and the deep drawability were good as compared with the case of only the pretreatment P1 (Comparative Example 3). From this, it was found that by providing a layer having low thermal conductivity on the aluminum surface layer, bonding is possible even with a film thickness of 0.1 mm. However, from the results of Comparative Example 7, even when the treatments of P1 and P2 are performed, a sufficient shear tensile strength is obtained when the film thickness of the olefin sheet (resin bonding layer) is 10 mm, as in Comparative Example 5. There wasn't.

<< Examples 14 to 15 and Comparative Examples 8 to 9 >>
Next, the above PP molded body (resin member) 3 is superimposed on the olefin sheet (resin bonding layer) 2b of the produced aluminum resin laminated sheet 2 and this is welded with an ultrasonic welding machine (TELSONIC: USP-2000). , Ultrasonic welding was performed under the conditions of a frequency of 20 kHz, an amplitude of 50%, and a welding time of 1 second. As shown in FIG. 2, a test piece in which a PP molded body was joined to the joining surface of an aluminum plate (metal -Resin bonded body) 1 was produced.

In Examples 14 and 15 and Comparative Examples 8 and 9, except that the joining method was changed to the ultrasonic welding shown above, Examples 1 to 13 including the shear tensile strength test and the deep drawability evaluation test were used. It carried out similarly.
Table 2 shows the evaluation results of the shear tensile strength test and the deep drawability evaluation test.

As is clear from the results shown in Table 2, in Comparative Examples 8 and 9, the fracture mode was A, and sufficient shear tensile strength was not obtained. On the other hand, in Examples 14 and 15, sufficient strength was obtained in both the shear tensile strength and deep drawability, and when the joining method is ultrasonic welding, the film thickness of the resin joining layer It was found that the range of 0.01 to 1 mm is suitable.

<< Examples 18 to 20 and Comparative Example 10 >>
Next, the produced olefin sheet (resin bonding layer) 2b of the aluminum resin laminate 2 is set in a mold in an injection molding machine (ST10R2V manufactured by NISSEI), and PP resin is injected in time (including pressure holding time) 5 Second, injection speed 60 mm / second, holding pressure 90 MPa, cylinder temperature 280 ° C., mold temperature 50 ° C., injection molding is performed, and the PP molded body is joined to the joining surface of the aluminum plate material as shown in FIG. A test piece (metal-resin bonded body) 1 was prepared.

In Examples 18 to 20 and Comparative Example 10, the same procedure as in Examples 1 to 17 was performed, including the shear tensile strength test and the deep drawability evaluation test, except that the joining method was changed to the injection welding shown above. did.
Table 3 shows the evaluation results of the shear tensile strength test and the deep drawability evaluation test.

As is clear from the results shown in Table 3, in Comparative Example 10, the fracture mode was A, and sufficient shear tensile strength was not obtained. In contrast, in Examples 18 to 20, sufficient strength was obtained in both the shear tensile strength and the deep drawability. When the joining method is ultrasonic welding, the film thickness of the resin joining layer is as follows. It was found that the range of 0.05 to 8 mm is suitable.

The method for producing a metal-resin bonded body of the present invention is a simple and versatile heat welding process in which a metal member and a resin member are integrated and a metal-resin bonded body having stable bonding strength is easily industrially produced. Can be manufactured.
In addition, the metal-resin bonded body of the present invention has a stable bonding strength at the bonding surface and is excellent in appearance and other characteristics, so it can be used for various sensor parts for automobiles, parts for home appliances, parts for industrial equipment. It can utilize suitably for manufacture of various components, such as.

DESCRIPTION OF SYMBOLS 1 ... Aluminum resin joined body, 2 ... Surface-treated aluminum base material, 3 ... PPS molded object (resin molded object), 4 ... Jig, 5 ... Load.

Claims

This is a method of manufacturing a metal-resin bonded body by bonding a metal member and a resin member made of a thermoplastic resin, and a film thickness of 0 made of a thermoplastic resin having compatibility with the resin member in advance on the bonding surface of the metal member. A method for producing a metal-resin bonded body, comprising: laminating a resin bonding layer of 0.01 to 9 mm, and bonding a bonding surface between the resin bonding layer of the metal member and the resin member by thermal welding.
2. The method for producing a metal-resin bonded body according to claim 1, wherein the resin bonding layer is formed in advance by bonding a resin sheet made of a thermoplastic resin having compatibility with the resin member.
3. The method for producing a metal-resin bonded body according to claim 2, wherein the resin bonding layer is formed by laminating and bonding a resin sheet to the surface of the metal member.
The pretreatment consisting of a washing treatment using an acid aqueous solution is performed on the surface of the metal member prior to the formation of the resin bonding layer by laminating and bonding the resin sheet. A method for producing a metal-resin bonded body.
Prior to the formation of the resin bonding layer by laminating the resin sheet, the surface of the metal member is subjected to a pretreatment consisting of a cleaning treatment using an acid aqueous solution, and then the surface of the metal member is hydrated, zincate treatment, 5. The method for producing a metal-resin bonded body according to claim 4, wherein any pretreatment selected from trivalent chromate treatment is performed.
In the joining method in which the thermal welding between the resin joining layer of the metal member and the resin member presses the joining surfaces of the resin joining layer and the resin member to each other, generates frictional heat by relative motion, and heats it. 6. The method for producing a metal-resin bonded body according to claim 1, wherein the metal-resin bonded body is provided.
The method for producing a metal-resin bonded body according to claim 6, wherein the bonding method by thermal welding is vibration welding, and the film thickness of the resin bonding layer is 0.1 to 9 mm.
7. The method for producing a metal-resin bonded body according to claim 6, wherein the bonding method by heat welding is ultrasonic welding, and the film thickness of the resin bonding layer is 0.01 to 1 mm.
The method for producing a metal-resin joined body according to claim 6, wherein the joining method by thermal welding is injection welding, and the film thickness of the resin joining layer is 0.05 to 9 mm.
The metal-resin bonding according to any one of claims 1 to 9, wherein the metal member is an aluminum member made of aluminum or an aluminum alloy, and the resin bonding layer and the resin member are an olefin resin. Body manufacturing method.
The method for producing a metal-resin bonded body according to claim 10, wherein the resin bonding layer and the resin member are polypropylene and / or polyethylene.
A metal-resin bonded body manufactured by the manufacturing method according to any one of claims 1 to 11.