JP2018111277A - Jointed composite of metal and resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite of a metal alloy piece and a PEEK resin composition strongly joined to each other, which is adapted to various devices that require high heat resistance and also mechanical strength.SOLUTION: A composite is prepared by injecting and joining PEEK resin into/to metal, the metal comprising a rough surface formed by a chemical and physical surface treatment, having a ruggedness period from micron order to dozens micron order and wholly covered with a complex rough surface formed by adding a superfine uneven surface having a period of 30 to 100 nm on the rough surface. However, for an AI alloy which has been already subjected to anode oxidation, the rough surface having the ruggedness period from the micron order to the dozens micron order is not always needed. Joining force is increased by the presence of a concave part into which resin readily flows, and by injecting a PEEK resin composition having a superfine uneven surface having at least a period of 30 to 100 nm, the superfine uneven surface containing PEI in about 10% contributing fixation of PEEK.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal / resin joint integrated body used for a mobile machine, an electric device, a medical device, a general machine, and other devices. More specifically, it is used for structural parts such as automobiles, aircrafts, marine parts and the like, and main bodies, and is composed of metal and polyether ether ketone resin (hereinafter referred to as “PEEK”) as main components. The present invention relates to an integrated joint.

  Technology for integrating metal and synthetic resin is required from a wide range of industrial fields such as automobiles, home appliances, parts manufacturing industries such as industrial equipment, and many adhesives have been developed for this purpose. Among these, very good adhesives are commercially available. However, rational joining methods that do not use an adhesive have been studied and have already been put into practical use and commercialized. That is, for non-ferrous metals such as magnesium, aluminum, copper, titanium and their alloys, and stainless steel, general steel, and special steel sheets that have been surface-treated such as aluminum-plated steel sheets and galvanized steel sheets. In this method, a high-strength engineering resin is integrated without an adhesive. Many of these are joining techniques proposed by the present applicant. In this joining technique, a surface-treated metal shape is inserted into an injection mold, a specific thermoplastic resin composition is injected to mold a resin portion, and at the same time, the molded product and the metal shape are fixed. Method (hereinafter referred to as “injection joining”) (Patent Documents 1 to 9).

JP 2003-200453 A JP2007-050630 WO2008 / 069252 WO2008 / 081933 WO2008 / 047811 WO2008 / 078714 WO2009 / 011398 WO2009 / 084648 WO2009 / 116484 WO2007 / 076023 JP2015-142960 WO2012 / 070654

  In recent years, composites (laminates) using PEEK have been required due to properties such as high mechanical strength and high heat resistance. As far as the applicant knows, regarding the injection joining technique using PEEK, there is no known technique regarding a specific injection joining technique related to PEEK. In the background as described above, the present invention achieves the following objects.

An object of the present invention is to provide a metal / resin joint integrated product in which a metal alloy piece and a PEEK resin composition are strongly joined and integrated.
Another object of the present invention is to provide a metal / resin joint integrated product that can be used for parts and structures of various devices that require mechanical strength, because the metal alloy piece and PEEK resin composition are strongly joined. There is to do.
Still another object of the present invention is to provide a metal / resin joint integrated product that can strongly reduce the weight of parts, structures, etc., by strongly joining a metal alloy piece and a PEEK resin composition.

  In addition, although the manufacturing method of these metal and resin joining integrated products is based on the injection joining method, this injection joining technology was standardized by ISO (International Organization for Standardization) in 2015. That is, this standard is the shape of injection joints (Overlapped test specimens) for measuring the joining force (tensile lap-shear strength) between the metal part and the resin molded part (Fig. 1). Yes (ISO 19095). In the present invention, an object having a shear bonding strength of 10 MPa or more obtained by this measuring method is an integrated object in which a metal and a resin are strongly bonded. That is, an injection-bonded product having a weak bonding force has no practical meaning, and in this case, it means that the injection-bonding is not judged to be successful.

The metal-resin joint integrated product of the present invention 1 is
A fine rough surface with a period of 100 to 1 μm is observed by observation with an electron microscope of 1,000 times and 10,000 times, and the entire surface is covered with ultrafine recesses having a diameter of 20 to 100 nm on the rough surface by observation with an electron microscope of 100,000 times. Aluminum material where uneven surface shape is observed, or
Anodized aluminum material in which a micro uneven surface shape is observed that is entirely covered with an ultrafine hole portion having an opening with a diameter of 30 to 100 nm by observation with an electron microscope 100,000 times;
Resin composition [A] containing only a polyether ether ketone resin as a resin component, or a heat resistant different resin which is a non-crystalline thermoplastic resin or semi-crystalline thermoplastic resin containing a polyether ether ketone resin as a main component resin. It is characterized in that it is formed by directly joining a polyether ether ketone resin composition [B] having a polymer as a secondary component resin.

The metal-resin joint integrated product of the present invention 2 is
A clear and three-dimensional complex rough surface with a period of 100 μm to several tens of μm and a period of several tens of μm to 1 μm is observed with an electron microscope of 1,000 times and 10,000 times, and on the rough surface with an electron microscope of 100,000 times of observation. A metal material in which a fine uneven surface shape covered with an uneven surface having a period of 50 to 100 nm is observed,
Resin composition [A] containing only a polyether ether ketone resin as a resin component, or a heat resistant different resin which is a non-crystalline thermoplastic resin or semi-crystalline thermoplastic resin containing a polyether ether ketone resin as a main component resin. It is characterized in that it is directly joined to an injection molded product of a polyether ether ketone resin composition [B] using a polymer as a secondary component resin.

  The metal-resin joint integrated product of the present invention 3 is characterized in that, in the present invention 2, the metal material is aluminum or titanium.

  In the present invention 1 to 3, the polyether ether ketone resin composition [B] is composed of 99 to 80% of the resin content of the polyether ether ketone resin according to the present invention. It is characterized in that 1 to 20% is occupied by a heat-resistant heteropolymer which is an amorphous thermoplastic resin or a semicrystalline thermoplastic resin.

1. Rough surface of metal surface (Theory of injection joining)
The injection joining technique using various metal materials described in Patent Documents 3 to 9, polyamide resin, polybutene terephthalate (hereinafter “PBT”), and polyphenylene sulfide (hereinafter “PPS”) resin composition is the invention of the present invention. Based on the “new NMT” theory defined by the authors. That is, the various metal materials have a necessary condition that they have a fine uneven surface with a period of 0.8 to 10 μm and a double uneven surface with an ultra fine unevenness with a period of 10 to 300 nm on the rough surface. . Further, the injection resin includes the above-described polyamide resin, PBT, or PPS, a high crystalline thermoplastic resin as a main component resin, and includes a different polymer that is compatible with each main component resin as a subcomponent resin. It was supposed to be. These are the “new NMT” theories.

  As shown in the examples, the present invention relating to PEEK deviates slightly from the requirements indicated by the “new NMT” theory. Generally speaking, the crystallization rate of the PEEK single resin during quenching was considerably high, and the crystallization rate decreased only slightly even when the resin composition was added with the secondary component resin. In short, it has been found that even if the resin side is devised, the injection joining force only shows a slight increase, and it is difficult to dramatically increase the joining force by improving the resin. In short, the rough surface shape on the metal side has a greater influence on the strength of the bonding force.

(Rough surface shape)
When the crystallization speed of the injected resin is high, the unevenness period of the rough surface is as large as several tens of μm, and the depth of the unevenness (height) is several μm level. It is easy to crystallize and solidify, and it is easy to get caught by these irregularities. In fact, an electron micrograph of the metal surface when a high bonding force was shown in the experimental example clearly showed this. What is important is the necessity of having an ultra-fine irregular surface with a period of 30 to 100 nm at the same time. The joint shape is formed by intruding into a large rough surface recess and solidifying, but the surface of the rough surface has an ultra fine uneven surface and is fixed so that the solidified resin does not slip.

  On the other hand, although it is a joining technique that can be used only with Al (aluminum) material, when it is performed by an improved anodizing treatment, an injection-joined article having a high joining force is obtained although it has a shape different from the above. Although it can be understood by observing an electron micrograph (FIG. 6), a rough surface having a large period of a micron order period or more is unclear, and a strong injection joining force is obtained although it has a metallic feeling visually. This is due to the large mouth having an opening diameter of 40 nm or more and a funnel shape below it, resulting in a hole structure. It was presumed that the surface fine shape of the anodic oxide formed into a clear pore-shaped aggregate would easily penetrate the resin.

  From these observations, all metal species can be applied to a clear and three-dimensional complex rough surface having a period of 100 μm to more than 10 μm and a period of more than 10 μm to 1 μm, and 10 A fine concavo-convex surface shape that is entirely covered with a concavo-convex surface having a period of 50 to 100 nm is observed on the rough surface by 10,000 times observation. When chemical etching is performed using a strong acid, it is easy to obtain a surface including a rough surface having a large period as described above, but it is difficult to form an ultra-fine irregular surface having a period of 100 nm or less in addition to this large period. At present, this is succeeded by Ti, Ti alloys, copper and aluminum plated steel sheets, and injection bonding can be confirmed with these except for copper. The ultra-fine irregularities of this copper were considered to be too small because it was a very fine irregular surface with a period of 10 to 20 nm by a multi-haired whisker, and with respect to PEEK injection bonding, the ultra-fine irregularities of a period of 30 to 100 nm Judged that it is necessary to have a surface.

  In recent years, it has been reported that laser technology is likely to be used to produce various metal pieces having both the above-described large periodic rough surface and an ultrafine irregular surface with a period of 30 to 100 nm (Patent Documents 10 and 11). The thing which seems to use this patent technology was supplied from Daicel Corporation (head office: Tokyo, Japan), and the present inventors confirmed that a high injection joining force was produced. In short, it has been confirmed that these rough surface shape creation methods are not limited to chemical treatment and electrolytic treatment, and it is only necessary to produce a physical treatment method such as laser.

2. PEEK-based resin composition PEEK and PEEK containing GF are commercially available from Victrex Japan Inc. (head office: Tokyo, Japan) under trademarks such as “90G”. According to the published technical data distributed by the company, “90G” is a resin component of PEEK alone, and the present inventors have stated that “PEEK [ A] ”. On the other hand, the PEEK resin composition, which clearly states that a different polymer has been added to form a compound, is not available in the company's commercial product, and in the examples of the present invention, the PEEK which is “90G” manufactured by the company is used separately. It is a PEEK resin composition prepared by dry blending a commercially available different polymer purchased by the present inventor. This was referred to as PEEK resin composition [B] in the text. That is, 20 to 2 parts by weight of polyetherimide (hereinafter “PEI”), polyethersulfone (hereinafter “PES”), and polyamideimide (hereinafter “PAI”) are added to 80 to 98 parts by weight of PEEK. Were dry blended and used as a PEEK resin composition.

3. Injection bonding and annealing (injection bonding process)
In the injection joining of the present invention, the aforementioned surface-treated metal piece is inserted into an injection mold, and the aforementioned PEEK resin is injected. In obtaining injection joints of various shapes, the injection molding conditions are actually finely adjusted, but the injection speed as this fine adjustment image is almost the same as in the case of normal PEEK resin injection molding. Although it is good, the mold temperature is preferably set high. The mold temperature used by the inventors in the injection joining process was 160 to 200 ° C. In the injection mold, it is important to provide gas venting also in the flow path part leading to the gate, and to pay sufficient attention so that the cavity part does not become an injection mold of a gas venting defective type.

(Necessity of annealing)
The obtained injection-bonded article should be “annealed” by heating in a hot air dryer set to 200 ° C. within the same day for about 1 hour. The intent is that the injection bonded product obtained by the above-described injection bonding suppresses the residual stress generated on the bonded surface with a strong bonding force after being released from the injection mold and then allowed to cool. The purpose of annealing is to make this residual stress zero once. In the thing which finished annealing and took out from the hot air dryer, resin part crystallization has already progressed enough, and even if it cools after that, both an aluminum material and a resin material will shrink according only to a linear expansion coefficient. Therefore, the stress remaining on the joint surface after cooling is smaller than that before annealing. When the product is commercialized and then left at room temperature for a long time, the residual stress becomes close to zero due to creep of the resin part.

4). Evaluation of injection joints (Measuring method of joining force)
As mentioned above, the injection joining technology was registered with ISO. That is, the shape of the measurement injection joint for measuring the shear joint strength between the metal part and the resin part in the injection joint (FIG. 1) and the measurement injection joint for measuring the tensile joint strength. The shape (Fig. 2) of (Butt welded test specimens) was defined. In addition, the injection-joint shown in FIG. 1 is not directly measured by measuring the shear joint strength by pulling and breaking its end portion, but it is housed in an auxiliary jig having the shape shown in FIG. The method to do is specified. The numerical values of the shear bonding strength described in the examples are based on this measuring method.

  As described in detail above, the metal / resin bonded integrated body of the present invention is a metal alloy piece and a PEEK resin composition that are strongly bonded and integrated. For this reason, it can be used as a composite material for parts and structures of various devices that require mechanical strength. As a result, it can contribute to weight reduction of parts, structures, and the like.

FIG. 1 shows a shape for measuring the shear bonding strength between a metal part and a resin part in an injection-bonded product of a metal piece and a resin. FIG. 2 shows a shape for measuring the tensile bonding strength between a metal part and a resin part in an injection-bonded product of a metal piece and a resin. FIG. 3 shows the shape of an auxiliary jig used when measuring the shear bonding strength between a metal part and a resin part in an injection-bonded product of a metal piece and a resin. FIG. 4 is an electron micrograph of an A6063Al alloy that has been “NMT2 treated”, where FIG. 4-1 is 1000 times, FIG. 4-2 is 10,000 times, and FIG. 4-3 is 100,000 times. FIG. 5 is an electron micrograph of an A6063Al alloy that has been “NMT5 treated”. FIG. 5-1 is 1000 times, FIG. 5-2 is 10,000 times, and FIG. 4-3 is 100,000 times. FIG. 6 is an electron micrograph of an A6063Al alloy that has been “anodized”. FIG. 6-1 is a thousand times, FIG. 6-2 is 10,000 times, and FIG. 6-3 is 100,000 times. FIG. 7 is an electron micrograph of an A6063Al alloy subjected to “NMT5-Oxi treatment”, FIG. 7-1 is 1000 times, FIG. 7-2 is 10,000 times, and FIG. 7-3 is 100,000 times. FIG. 8 is an electron micrograph of an A7075Al alloy subjected to “NMT5 treatment”. FIG. 8-1 is 1,000 times, FIG. 8-2 is 10,000 times, and FIG. 8-3 is 100,000 times. FIG. 9 is an electron micrograph of α-β type Ti alloy “KSTi-9 (Shinko)” subjected to “new surface treatment”, FIG. 9-1 is 1,000 times, and FIG. 9-2 is 10,000 times. 9-3 is 100,000 times. FIG. 10 is an electron micrograph of the A6063Al alloy subjected to the “laser scanning process”. FIG. 10-1 is 1,000 times, FIG. 10-2 is 10,000 times, and FIG. 10-3 is 100,000 times.

Hereinafter, embodiments of the present invention will be described by way of examples.
(A) Electron microscope observation SEM type electron microscopes “S-4800 (manufactured by Hitachi, Ltd. (head office: Tokyo, Japan))” and “JSM-6700F (manufactured by JEOL Ltd. (head office: Tokyo, Japan)) ) "And observed at 1-2 KV.
(B) Measurement of joint strength of composites Using a tensile tester “AG-500N / 1kN (manufactured by Shimadzu Corporation (head office: Kyoto, Japan))”, the shear joint strength was measured at a pulling speed of 10 mm / min. It was measured. The measuring method was based on ISO19095.

Next, examples and comparative examples of the composite according to the present invention will be described.
[Experimental Example 1] Surface treatment of A6063Al alloy (simple roughening treatment: reference)
A large number of 45 mm × 18 mm × 1.5 mm rectangular pieces were machined from the A6063Al alloy material. In order to degrease the alloy material, an aqueous solution containing 10% of an aluminum degreasing agent “NA-6 (Meltex Co., Ltd. (head office: Tokyo, Japan))” in the tank was set to 60 ° C. After the alloy piece was immersed for 5 minutes, it was washed with tap water (Ota City, Gunma Prefecture). Next, a 1% hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 1 minute and washed with water. Next, a 1.5% concentration aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 8 minutes, and then washed with water. Next, a 3% concentration nitric acid aqueous solution at 40 ° C. was prepared in another tank, immersed in this for 3 minutes, and then washed with water. These were wrapped together with clean aluminum foil, and further sealed in a plastic bag.

[Experimental Example 2] Surface treatment of A6063Al alloy (NMT2)
A large number of 45 mm × 18 mm × 1.5 mm rectangular pieces were machined from the A6063Al alloy material. For the degreasing treatment of this alloy material, an aqueous solution containing 10% of an aluminum degreasing agent “NA-6 (Meltex Co., Ltd. (head office: Tokyo, Japan))” in the tank was set to 60 ° C. After being immersed for 5 minutes, this was washed with tap water (Ota City, Gunma Prefecture). Next, a 1% hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 1 minute, and then washed with water. Next, a 1.5% concentration aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 8 minutes, and then washed with water. Next, a 3% concentration nitric acid aqueous solution at 40 ° C. was prepared in another tank, immersed in this for 3 minutes, and then washed with water. Next, prepare a 3.5% strength hydrated hydrazine aqueous solution at 60 ° C. in another tank, immerse in this for 1 minute, and then add 0.5% concentration at 33 ° C. in another tank. After being immersed in a hydrated hydrazine aqueous solution for 2.5 minutes, this was washed with water. And this was put into the warm air dryer set to 67 degreeC for 15 minutes, and the Al alloy piece which finished the said process was dried. Wrapped together with clean aluminum foil, and put it in a plastic bag and stored it sealed. These treatments are surface treatment methods for Al materials, which the inventors call “NMT2 treatment”, and are treatment methods according to Document 12.

  One A6063Al alloy piece that had undergone the same treatment was subjected to an electron microscope. The observation results were photographed and shown in FIGS. 4-1 to 4-3. These are electron micrographs of 1000 times, 10,000 times, and 100,000 times, respectively. It can be seen from FIG. 4-2 that there is a gentle rough surface with a period of 1 to 3 μm, and from FIG. 4-3 it can be seen that the entire surface is covered with a recess having an outer diameter of 20 to 30 nm. Moreover, when the A6063Al alloy piece which performed the same process is surface-analyzed by XPS, a nitrogen atom will be observed. This indicates that the hydrazine molecules used in the final treatment remained as they were chemisorbed.

[Experimental Example 3] Surface treatment of A6063Al alloy (NMT2-Oxi: Reference)
A large number of 45 mm × 18 mm × 1.5 mm rectangular pieces were machined from the A6063Al alloy material. Using these, the same treatment as in Experimental Example 2 was performed. However, the hot air dryer which carried out the process of Experimental Example 2, was immersed for 1 minute in the hydrogen peroxide solution of 1.5% density | concentration for 1 minute without drying after the last water washing, and was 67 degreeC. And dried for 15 minutes. This was wrapped together with clean aluminum foil, and further sealed in a plastic bag. This is a surface treatment method for an Al material referred to as “NMT2-Oxi treatment” as referred to by the present applicant (Taisei Plus Co., Ltd.). In short, when viewed with an electron microscope, the surface shape is the same as that of the “NMT2” treated product, but the adsorbed hydrazine molecules are destroyed by hydrogen peroxide, resulting in an Al alloy piece with no adsorption of amine-based molecules.

[Experimental Example 4] Surface treatment of A6063Al alloy (NMT5 treatment)
A large number of 45 mm × 18 mm × 1.5 mm rectangular pieces were machined from the A6063Al alloy material. For the degreasing treatment of this alloy material, an aqueous solution containing 10% of an aluminum degreasing agent “NA-6 (Meltex Co., Ltd. (head office: Tokyo, Japan))” in the tank was set to 60 ° C. After being immersed for 5 minutes, this was washed with tap water (Ota City, Gunma Prefecture). Next, a 10% strength aqueous caustic soda solution at 50 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 1 minute, and then washed with water. Next, an aqueous solution containing 5% concentration hydrochloric acid and 1% concentration aluminum chloride at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 1 minute, and then washed with water. Next, it was immersed in an aqueous solution containing 10% sulfuric acid and 45% ammonium hydrogen fluoride fluoride at 45 ° C. for 1 minute, and then washed with water. Next, a 1.5% concentration aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 8 minutes, and then washed with water.

  Next, a 3% concentration nitric acid aqueous solution at 40 ° C. was prepared in another tank, immersed in this for 3 minutes, and then washed with water. Next, prepare a 3.5% hydrated hydrazine aqueous solution at 60 ° C. in another tank and immerse in this for 1 minute, and then add 0.5% water at 33 ° C. in another tank. After being immersed in a hydrazine aqueous solution for 2.5 minutes, this was washed with water. And it put into the warm air dryer set to 67 degreeC for 15 minutes, and dried the Al alloy piece which finished the said process. Wrapped together with clean aluminum foil, and put it in a plastic bag and stored it sealed.

  This is a surface treatment method for Al material called “NMT5 treatment” named by the present applicant, and is a treatment method developed in recent years. The difference from the NMT2 treated product shown in Experiment 2 (Fig. 4) is clear in Fig. 5-1 (thousand times electron micrograph), but the existence of a rough surface with a period of several tens of microns is obvious, and a large cycle This rough surface was firmly formed in this experimental product. However, the electron micrograph (FIG. 5-3) at 100,000 times is substantially the same as Experimental Example 2.

[Experimental Example 5] A6063Al alloy surface treatment (anodizing treatment)
A large number of 45 mm × 18 mm × 1.5 mm rectangular pieces were machined from the A6063Al alloy material. For the degreasing treatment of this alloy material, an aqueous solution containing 10% of an aluminum degreasing agent “NA-6 (Meltex Co., Ltd. (head office: Tokyo, Japan))” in the tank was set to 60 ° C. After being immersed for 5 minutes, this was washed with tap water (Ota City, Gunma Prefecture). Next, a 1% hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 1 minute, and then washed with water. Next, a 1.5% concentration aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 8 minutes, and then washed with water. Next, a 3% concentration nitric acid aqueous solution at 40 ° C. was prepared in another tank, immersed in this for 3 minutes, and then washed with water. Up to this point, the surface treatment method described in Example 2 is the same.

  Next, anodic oxidation at 18 V was performed for 20 minutes with a 10% aqueous phosphoric acid solution, and then washed with running water of ion-exchanged water for 60 minutes. And it put into the warm air dryer set to 67 degreeC for 30 minutes, and also put into the 80 degreeC warm air dryer for 30 minutes, and dried. Wrapped together with clean aluminum foil, sealed in a plastic bag and stored. One A6063Al alloy piece that had undergone the same treatment was subjected to an electron microscope. This electron micrograph is shown in FIG. From the 1,000 times and 10,000 times photographs (FIGS. 6-1, 6-2) of this electron micrograph, it seems that there is no large uneven surface having a period of micron order or more, and the 100,000 times photograph ( From FIG. 6-3), it was observed that the presence of holes (holes) that were not shown in FIGS. That is, it is in the form of a collection of holes having an outer diameter of 30 to 50 nm, and when FIG. 6-3 is enlarged, a hole is formed in a funnel shape from the opening toward the inside (deep part) of the hole. The shape was narrow in diameter. In short, it was not just a recess, but a shape with a hole with a mouth. In addition, when the surface treatment similar to this experiment example is performed by changing the Al alloy type, it is known that the opening diameter reaches 100 nm depending on the alloy type.

[Experimental example 6] Surface treatment of aluminum plated steel sheet (NMT5-Oxi treatment)
A 0.5 mm thick aluminum-plated steel sheet “Alster Steel Sheet (Nisshin Steel Co., Ltd. (head office: Tokyo, Japan))” was cut to produce a large number of 18 mm × 45 mm × 0.5 mm rectangular pieces. For the degreasing treatment of this alloy material, an aqueous solution containing 10% of an aluminum degreasing agent “NA-6 (manufactured by Meltex Co., Ltd. (head office: Tokyo, Japan))” at 60 ° C. After being immersed for 5 minutes, this was washed with tap water (Ota City, Gunma Prefecture). Next, an aqueous solution containing 5% concentration hydrochloric acid and 1% concentration hydrated aluminum chloride at 40 ° C. was prepared in another tank, and a steel plate piece was immersed in this for 2 minutes, and then washed with water. Next, it was immersed in an aqueous solution containing 10% sulfuric acid at 45 ° C. and 2% ammonium hydrogen fluoride fluoride at 45 ° C. for 0.5 minutes, and then washed with water. Next, a 1.5% strength aqueous caustic soda solution at 40 ° C. was prepared in another tank, immersed in this for 4 minutes, and then washed with water. Next, it was immersed in a 3% concentration nitric acid aqueous solution at 40 ° C. for 3 minutes in another tank.

  Next, the smut was removed by dipping for 5 minutes in a washing tank having an ultrasonic oscillation end. Next, it was again immersed in a 3% concentration nitric acid aqueous solution at 40 ° C. for 0.5 minutes. Next, after preparing a 3.5% concentration hydrated hydrazine aqueous solution at 60 ° C. in another tank and immersing in this for 1 minute, then in another tank, 0.5% concentration at 40 ° C. After being immersed in an aqueous hydrazine solution of 2 minutes, this was washed with water. Next, hydrogen peroxide solution having a concentration of 3% was prepared in another tank, and the alloy pieces were immersed in this for 1 minute and washed with water. Then, it was dried for 15 minutes in a hot air dryer set at 67 ° C., and then dried in a hot air dryer set at 100 ° C. for 30 minutes. This was immersed for 3 minutes in a washing tank with an ultrasonic oscillation end to remove the smut, and then placed in a hot air dryer set at 80 ° C. for 15 minutes for drying. These were wrapped together in clean aluminum foil, which was further sealed in a plastic bag.

  One aluminum-plated steel sheet that had been subjected to the same treatment was subjected to an electron microscope. This observation result was photographed and shown in FIG. FIGS. 7A and 7B are electron micrographs of 1000 times and 7X, respectively. The rough surface condition on the micron order is well seen, which is far more severe than the rough surface of the Al alloy material described above. From the 100,000 times electron micrograph shown in FIG. 7-3, it can be seen that the entire surface is entirely covered with a recess having a diameter of about 20 nm.

[Experimental Example 7] Surface treatment of A7075Al alloy (super extra duralumin) (NMT5 treatment)
A large number of 45 mm × 18 mm × 1.5 mm rectangular pieces were machined from the A7075Al alloy material. For the degreasing treatment of this alloy material, an aqueous solution containing 10% of an aluminum degreasing agent “NA-6 (manufactured by Meltex Co., Ltd. (head office: Tokyo, Japan))” at 60 ° C. After being immersed for 5 minutes, this was washed with tap water (Ota City, Gunma Prefecture). Next, a 10% caustic soda aqueous solution at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 1 minute and washed with water. Next, an aqueous solution containing 5% concentration hydrochloric acid and 1% concentration hydrated aluminum chloride at 40 ° C. was prepared in another tank, and the alloy pieces were immersed in this for 1 minute and washed with water. Next, a 1.5% strength aqueous caustic soda solution at 40 ° C. was prepared in another tank, immersed in this for 8 minutes and washed with water. Next, a 3% concentration nitric acid aqueous solution at 40 ° C. was prepared in another tank, immersed in this for 1 minute and washed with water. Next, prepare a 3.5% hydrated hydrazine aqueous solution at 60 ° C. in another tank and immerse in this for 1 minute, and then add 0.5% hydration at 33 ° C. in another tank. It was immersed in an aqueous hydrazine solution for 2.5 minutes and washed with water.

  Next, the alloy pieces that had been subjected to the above treatment were dried for 15 minutes in a hot air dryer set at 67 ° C. Wrapped together with clean aluminum foil, which was then placed in a plastic bag and sealed. This treatment method is one of the surface treatment methods for Al materials called “NMT5 treatment” named by the present applicant. One of the A7075Al alloy pieces that had undergone the same treatment was subjected to an electron microscope. The observation results are shown in FIG. These are electron micrographs of 1000 times, 10,000 times, and 100,000 times. It can be seen from FIG. 8-3 that the ultrafine recess diameter is 30 to 60 nm. The diameter of the recess is larger than that of the A6063 treated with NMT2 (FIG. 4-3) and the A6063 treated with NMT5 (FIG. 5-3).

[Experimental Example 8] Surface treatment of Ti alloy (latest processed product)
A large number of rectangular pieces having a size of 18 mm × 45 mm × 1 mm were cut from a 1 mm thick plate material of an α-β type titanium alloy “KSTi-9 (manufactured by Kobe Steel, Ltd. (head office: Hyogo, Japan))”. This was degreased by a conventional method and then washed with clean water. Next, a 1.5% strength aqueous caustic soda solution at 40 ° C. was prepared in another tank, and the titanium piece was immersed in this for 1 minute, and then washed with water. Next, in a separate tank, 3% of the titanium piece was placed in an aqueous solution of a 2% concentration activator “KA3” (manufactured by Metal Chemical Engineering Laboratory (head office: Tokyo, Japan)) at 65 ° C. After being immersed for a minute, this was washed with water. Next, the titanium piece was immersed in a 3% concentration nitric acid aqueous solution at 40 ° C. for 3 minutes, and then washed with water. Next, it was immersed in an aqueous solution containing 5% concentration sodium chlorite and 10% concentration sodium hydroxide at 55 ° C. for 10 minutes, and then washed with water. Next, it was placed in a warm air dryer set at 80 ° C. for 15 minutes for drying. Such a surface treatment was carried out and packaged and stored in clean aluminum foil. An electron micrograph of this Ti alloy piece is shown in FIG. FIGS. 9A and 9B are electron micrographs of 1000 times and 10,000 times, but it can be clearly seen that a very severe uneven shape is generated on the micron order. What is noticed is the 100,000 times photograph shown in FIG. 9-3, in which a mesh pattern having a major and minor diameter of 50 to 100 nm was observed on the surface.

[Experimental Example 9] Surface treatment of A6063Al alloy (laser processing)
The A6063Al alloy material was machined into a large number of 45 mm × 18 mm × 1.5 mm rectangular pieces, degreased, and then roughened by the laser scanning method at the aforementioned Daicel Co., Ltd. Obtained by them and conducted an injection joining test using PEEK resin. An electron micrograph of this Al alloy piece is shown in FIG. FIGS. 10-1 and 10-2 are electron micrographs of 1000 times and 10,000 times. From these, the existence of a rough surface shape including valley-shaped concave portions having a period of 10 to 100 μm is known, and FIG. The existence of an ultra-fine irregular surface shape having a major axis and a minor axis of 30 to 100 nm was also evident from a double electron micrograph.

[Experimental Example 10] Injection joining process The following resins were obtained from various companies. PEEK is "90G (Victrex Japan Inc. (head office: Tokyo, Japan)"), PEI is "Ultem 9075 (SABIC Japan GK (head office: Tochigi, Japan))", and PES is "Suika Excel PES4800G ( “Sumitomo Chemical Co., Ltd. (head office: Tokyo, Japan)” and PAI are “Toron 4203L (Solvay Specialty Polymers Japan (head office: Tokyo, Japan))”. Compounding was performed by a dry blend method.

  1 A mold for injection joining to make a shaped object is attached to an injection molding machine, the mold temperature is set to 185 ° C., the injection temperature is set to 380 ° C., the mold is opened, and various metals of Experimental Examples 1 to 9 The piece was inserted, the mold was closed, and immediately the above-mentioned PEEK pellets and the compound resin by the dry blend were injected. The obtained injection-bonded product was placed in a hot air dryer set at 200 ° C. for 1 hour within the day of the injection-joining experiment, annealed and allowed to cool, and then placed in the auxiliary jig shown in FIG. The shear bond strength was measured using a machine.

[Experimental Example 11] Measurement of Shear Bond Strength of Injection Bonded Article The shaped article shown in FIG. 1 was mounted on the jig shown in FIG. 3, and a tensile test was performed using a testing machine. The tensile test was performed in a measurement chamber adjusted to 23 ° C. The results are shown in Tables 1-4. The data in Table 1 shows the shear joint strength of PEEK single resin “90G (Victrex Japan Inc.)” and metal injection joint. It is found that the metal NMT2 treated product of Experimental Example 2 is around 40 MPa, and the NMT5 product of Experimental Example 4 is around 50 MP, and the bonding strength of the one having a large unevenness depth (height) in the micron order cycle becomes larger. did. In addition, the difference between Experimental Example 2 and Experimental Example 3 (no amine adsorption) shows that there is a significant difference in the adsorbate of amine-based molecules, although both exhibit high bonding strength.

  The Alster steel plate treated with NMT5-Oxi (Experimental Example 6) also had an equivalent joining force. On the other hand, the NMT2 treated product of A7075Al alloy (Experimental Example 7) had 45 MPa, and the bonding force was slightly higher than that of the A6063Al alloy NMT2 treated product (Experimental Example 2). Probably because the diameter of the ultrafine recess was larger than A7075.

  Anodization (Experimental Example 5) also had an equivalent joining force. The reason why sufficient strength was obtained even without micron-order irregularities is thought to be because the diameter of the ultra-fine irregularities is larger than that of the NMT system and the resin is easy to enter because of the clear hole shape.

The laser scanning process (Example 9) also had an equivalent joining force. The laser-processed surface has a large rough surface that exceeds the matte so that it can be judged even with the touched feeling, and further has an ultra-fine unevenness that can be confirmed with an electron micrograph of 100,000 times. It seemed natural to make an injection joint.

  On the other hand, instead of “90G (Victrex)”, which is the only resin component of PEEK, this is a mixed resin in which 15% by weight of PEI “ULTEM 9075 (SABIC Japan GK (Headquarters: Tochigi, Japan))” is dry blended. The results are also shown in the second half of Table 1. According to this, the joining force increased in any case by using the mixed resin. However, all surface treatment methods showed a slight increase. It was close to 60 MPa for high objects. On the other hand, a Ti alloy has a bonding force of 30 MPa or less even when a mixed resin is used. Although the fine uneven surface shape is similar in Experimental Example 6 and Experimental Example 8 in that the rough surface shape is three-dimensional and intense, the reason for the considerably different bonding force is not well understood.

  Regarding all the metal materials, when the PPS resin “SGX120 (Toso Co., Ltd. (head office: Tokyo, Japan))” was used, the shear bonding strength was about 40 MPa, which was seen as the upper limit value. However, the upper limit cannot be seen from Table 1. Since it is presumed that it is probably about 60 MPa at the maximum, it can be seen that the ability to be joined (ability to obtain injection joining force) of various metal materials is in the middle level except for the experimental examples 4 and 5. Therefore, these values may increase considerably if the resin viscosity at the time of contact with the metal is somewhat lowered, such as raising the mold temperature to 200 ° C. That is, although the difference between Experimental Example 6 and Experimental Example 8 is large, the shape of the concavo-convex surface is quite similar, so it will be a little closer if the injection joining conditions are increased.

Tables 2, 3, and 4 show the results when the types and mixing ratios of different polymers used for dry blending were changed.

Table 4 shows PEEK and PES (Poly Ether Sulphone) “Sumika Excel PES4800G (Sumitomo Chemical Co., Ltd. (head office: Tokyo, Japan))”, Table 5 shows PAI (Poly Amide Imide ( Table 5 shows the results of “Tolon 4203L (Solvay Specialty Polymers Japan Co., Ltd. (head office: Tokyo, Japan))” with the results of the resin composition mixed with polyamideimide)). In any case, the effect of compounding a different polymer was inferior to that of PEI.

Claims (4)

A fine rough surface with a period of 100 to 1 μm is observed by observation with an electron microscope of 1,000 times and 10,000 times, and the entire surface is covered with ultrafine recesses having a diameter of 20 to 100 nm on the rough surface by observation with an electron microscope of 100,000 times. Aluminum material where uneven surface shape is observed, or
Anodized aluminum material in which a micro uneven surface shape is observed that is entirely covered with an ultrafine hole portion having an opening with a diameter of 30 to 100 nm by observation with an electron microscope 100,000 times;
Resin composition [A] containing only a polyether ether ketone resin as a resin component, or a heat resistant different resin which is a non-crystalline thermoplastic resin or semi-crystalline thermoplastic resin containing a polyether ether ketone resin as a main component resin. A metal-resin joint integrated product, which is formed by directly joining a polyether ether ketone resin composition [B] using a polymer as a secondary component resin. A clear and three-dimensional complex rough surface with a period of 100 μm to several tens of μm and a period of several tens of μm to 1 μm is observed with an electron microscope of 1,000 times and 10,000 times, and on the rough surface with an electron microscope of 100,000 times of observation. A metal material in which a fine uneven surface shape covered with an uneven surface having a period of 50 to 100 nm is observed,
Resin composition [A] containing only a polyether ether ketone resin as a resin component, or a heat resistant different resin which is a non-crystalline thermoplastic resin or semi-crystalline thermoplastic resin containing a polyether ether ketone resin as a main component resin. A metal-resin joint integrated product, which is formed by directly joining a polyether ether ketone resin composition [B] using a polymer as a secondary component resin. In the metal-resin joint integrated product according to claim 2,
The metal material is aluminum or titanium. A metal-resin joint integrated product, wherein: In the metal-resin joint integrated body according to claim 1 selected from claims 1 to 3,
In the polyether ether ketone resin composition [B], 99 to 80% of the resin component is a polyether ether ketone resin, and 1 to 20% is an amorphous thermoplastic resin or a semicrystalline thermoplastic resin. Metal / resin joint integrated product characterized by the fact that the heat-resistant different polymer occupies it.