JP2022187378A - Integrated composite of metal and resin and manufacturing method of the same - Google Patents

Abstract

To provide a composite made by ejection bonding of a non-aluminum metal piece such as steel material, SUS steel, and titanium alloy, and a high crystallinity thermoplastic resin, where bonding force between a metal part and a resin molded product part is sufficiently large.SOLUTION: An integrated composite of metal and resin is made by bonding a surface of a metal material and a crystalline thermoplastic resin composition through ejection molding operation. The metal material is one kind selected from steel material, stainless steel, titanium alloy, etc. The crystalline thermoplastic resin composition has heat resistance against a melting point of 200°C or higher. The ejection bonding is performed in a state in which a water-soluble high molecular weight amine-based compound is adsorbed on a surface before the ejection bonding. A bonded part of the integrated composite has shearing bond strength of about 39 MPa or more. The high molecular weight amine-based compound is triethanolamine or tetra-sodium salt of EDTA.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to an integrated composite of metal and resin and a method for producing the same. More specifically, it is manufactured by injection joining non-aluminum metal materials such as steel and Ti alloys with heat-resistant thermoplastic resin compositions, and can be used as parts and structural materials for machines and equipment. and a resin integrated composite and a method for producing the same.

Joining techniques for strongly joining metals and synthetic resins are required not only in the parts manufacturing industry for automobiles, home appliances, industrial equipment, etc., but also in a wide range of industrial fields, and many adhesives have been developed for this purpose. Such joining technology such as adhesion is a basic technology in all manufacturing industries. There have also been conventional researches and various proposals for bonding methods that do not use an adhesive. Among them, the inventors of the present invention (hereinafter referred to as "the inventors") developed, proposed, and named "NMT (abbreviation for Nano Molding Technology)" and "New NMT (New Nano Molding Technology). abbreviated)”. NMT is a technology for bonding aluminum alloy flakes having chemically treated surfaces with a resin composition whose main component is a crystalline thermoplastic resin. This joining is performed by injecting a molten crystalline thermoplastic resin into an Al alloy piece that has been inserted into an injection mold in advance, molding the resin part, and simultaneously joining the resin molded product and the Al alloy piece. It is a composite manufacturing technology that integrates by In addition, the new NMT, which has improved this, is a bonding technology that extends not only to aluminum alloy pieces but also to all metal types.The difference from NMT is the basic surface treatment method for metals before inserting into the injection mold. Different theory. The technique of joining a solid material such as a metal material and a thermoplastic resin by injection molding, and the technique related to the technique, are called "injection joining" or "injection joining technology" by the present inventors. there is

Among the injection-bonded products (integrated composites) created using this NMT and new NMT as the basic technology, injection-bonded products manufactured from aluminum alloy materials and specific PPS-based resin compositions are Bonding force between resins is as high as about 40 MPa. The bonding strength of this injection-bonded product hardly deteriorates even after being exposed to a temperature of 85° C. and a humidity of 85% for 8,000 hours. Moreover, it has been found that if a specific shape structure is adopted for this injection-bonded product, it can withstand temperature impact tests of -50°C/+150°C for 3,000 cycles (Patent Documents 4 and 5). In subsequent research and development, the following facts were found regarding new injection-bonded products of an aluminum alloy material and a specific polyamide-based resin composition. That is, this injection-bonded product has a very strong bonding force of about 50 to 55 MPa between metal and resin. The bonding strength between them hardly deteriorates even after being exposed to a temperature of 85° C. and a humidity of 85% for 1,000 hours. Moreover, it has been found that if the resin structure of the injection-bonded product has an appropriate shape structure, it can withstand a temperature shock test of -50°C/+150°C for 3,000 cycles (Patent Document 13). In this way, injection joints using aluminum alloy materials and heat-resistant crystalline thermoplastic resins called engineering plastics, super engineering plastics, etc. are subject to high humidity environments, temperature changes, and temperature shocks thousands of times. It is already possible to create something that can be used practically enough even in an environment such as a cycle.

On the other hand, the following results were obtained for the injection-bonded composite of non-aluminum metal material and crystalline thermoplastic resin. That is, as the resin material of this composite, "SGX120 (manufactured by Tosoh Corporation (head office: Tokyo, Japan), product name: Susteel" is used as the PPS resin, and AZ31Mg alloy, C1100 is used as the non-aluminum metal material. What happens to the joint strength of this injection joint when copper, SUS304 stainless steel, SUS430 stainless steel, SPCC (cold rolled steel plate), 64Ti alloy, etc. are used. In the case of an injection-bonded product (test piece shown in FIG. 1) in which the above-described new NMT-treated material and the above PPS resin are bonded to each of the non-aluminum metal materials, the shear bonding strength between the metal and the resin is A bonding strength of about 40 MPa is obtained. In short, if the above PPS-based resin "SGX120" is used as the resin material, and the chemical conversion treatment proposed by the present inventors, NMT, or new NMT injection joining technology is used, the joining between the resin portion and the metal piece can be achieved. It has already been found that the force can be about 40 MPa regardless of whether the metal is an Al alloy material or a non-aluminum metal material, and these have already been used and put into practical use.

If the resin material is a polyamide-based resin instead of the PPS-based resin "SGX120", using "CM3506G50 (manufactured by Toray Industries, Inc. (headquartered in Tokyo, Japan))" as the resin material, metal material When an Al alloy is used for the injection-bonded product (the test piece in FIG. 1), the resulting injection-bonded product has a very high shear bond strength of 50 to 55 MPa (Patent Document 12). However, according to the findings of the present inventors, the non-aluminum metal material is estimated to have a maximum value of about 40 MPa, and the bonding strength is clearly weaker than that of the Al alloy material. The reason why the above-mentioned high bonding strength exceeding about 50 MPa was generated in the injection-bonded product with the Al alloy is that the mixture ratio of the semi-aromatic polyamide resin and the aliphatic polyamide resin as the injection-bonding resin material This was the result of searching for the optimum resin composition through trial and error testing of the compositional ratio of the resin side, such as optimizing . Therefore, at this time, the above-mentioned "CM3506G50", which is a polyamide-based resin, was selected as the most excellent material for injection joining as a polyamide-based resin. Therefore, the present inventors consider that the above "CM3506G50" is the optimum resin composition at present as a polyamide resin commercially available for injection joining, and this resin and the above-mentioned new NMT Injection bonded with various non-aluminum metals treated. However, the shear bond strengths of the various injection-bonded products obtained were quite low.

This point will be explained in a more comprehensible manner. That is, by the new NMT treatment method, non-aluminum metals such as SUS304 stainless steel, SUS430 stainless steel, SPCC (cold rolled steel plate), 64Ti alloy, etc. are chemically treated, and then injection-bonded with the above PPS resin "SGX120". was joined to The shear bond strength of the injection-bonded products obtained by this bonding was all about 40 MPa, so the new NMT treatment method, which is a chemical conversion treatment method for each metal piece, is a well-improved chemical conversion treatment method. It was judged. That is, specifically, when the surface is chemically treated faithfully according to the "new NMT" theory described later, it has a fine uneven surface with a period of 1 to 5 μm and an ultrafine uneven surface with a period of 10 to 100 nm. The only requirement is to have However, in the experiment, at this time, an operation was added to add a larger rough surface with a period of 20 to 50 μm, that is, a matte surface, which is this rough surface. By adding this improvement operation, the bonding strength between the metal and the resin increased, and the aforementioned shear bonding strength of about 40 MPa was obtained. In short, a fine uneven surface is formed on a matte surface, which is a large rough surface, and an ultrafine uneven surface is formed on this fine uneven surface. It was possible to increase the existence (formation) density (surface area) of Various non-aluminum metal species were subjected to the new NMT treatment for forming the most improved surface shape, and then injection-bonded with the polyamide resin "CM3506G50".

However, in this injection bonding, even the highest shear bonding strength was about 45 MPa for 64Ti alloy. Moreover, when a plurality of injection-bonded products were simultaneously injection-bonded and the injection-bonded products were fractured under tension, the bonding strength was measured and varied widely from about 20 to 45 MPa depending on the individual. In short, it can be seen from these experimental results that it is much more difficult to secure a high injection joining strength when using a polyamide-based resin than when using a PPS-based resin. This was not the case when using NMT-treated Al alloy pieces. I was reminded of the inferences made by myself (the details of the difference between NMT and the new NMT will be described later). Similar cases to the injection joining technology using the above polyamide resin "CM3506G50" have also occurred with polyetheretherketone resin (hereinafter referred to as "PEEK") and polyaryletherketone resin (hereinafter referred to as "PAEK"). rice field. That is, when a PEEK or PAEK-based resin composition is used as an injection resin, and an improved NMT type treatment (for example, NMT7, NMT8 treatment, etc.) Al alloy is used as a metal material, the injection-bonded product (see FIG. 1 The shear bonding strength of all the specimens shown) reached about 50 MPa or more, and even reached 55 to 57 MPa.

On the other hand, when injection-bonded products were created using non-aluminum metals, the highest shear bonding strength was 20 to 50 MPa for 64Ti alloy. , etc., the joining force is considerably low, on the order of 10 MPa. In short, if the types of resins are listed in order of ease of production of injection bonded products having high bonding strength, roughly speaking, PBT, PPS, polyamide, and PAEK including PEEK are presumed. Based on the above premises, in the experience and knowledge of the present inventors, the PBT and PPS systems have already reached the level of perfection, and the highest level of bonding strength has been obtained, but the polyamide system has reached the level of perfection with Al alloys. Although it has reached the level of non-aluminum metals, it is still incomplete, and although Al alloys have reached the level of completion in the PAEK system, non-aluminum metals are still far away. In other words, in Al alloys that can be subjected to NMT-type surface chemical conversion treatment, PEEK and PAEK resins, which have the highest heat resistance among general-purpose and practically used high-strength resins, can be used. Regarding non-aluminum metals that use the new NMT type surface treatment, PPS resin has been completed, but there is still room for improvement after triamide resin in the above order, and PAEK resin is a long way off. That was the result.

The outlines of NMT, NMT2, NMT5 to NMT8 proposed by the present inventors and referred to in the present invention will be described below.
(NMT (abbreviation for Nano molding technology))
The inventors defined the following 4 or 5 conditions as necessary conditions for establishing the aforementioned NMT, which is an injection joining technique using an Al alloy. First, regarding the Al alloy side, the following conditions (1) and (2) are necessary conditions. Chemically treating the Al alloy surface so as to satisfy these two points is named "NMT treatment".
(1) The entire surface is covered with ultrafine recesses with a diameter of 20 to 50 nm.
(2) A water-soluble amine compound is chemically adsorbed on the surface layer.
Next, the following two or three points are necessary conditions for the injection resin composition side.
(3) The resin composition to be used is a resin composition containing a highly crystalline thermoplastic resin as a main component.
(4) The highly crystalline thermoplastic resin chemically reacts with amine-based molecules at high temperatures.
(5) Even if the resin composition is a subcomponent resin that is compatible with the main component resin or a resin that is not compatible with the main component resin, it can be transformed into the main component resin by adding the third component resin. Contains a resin that can be compatible or partially compatible with
The above (1) to (4) are essential requirements, and if the above condition (5) is added, the injection joining force becomes stronger. The practical NMT satisfies the above conditions (1) to (5) and selects hydrazine hydrate as the above (2) amine compound.

(NMT2, NMT5-NMT8)
The present inventors discovered that a polybutylene terephthalate (hereinafter referred to as "PBT")-based resin composition can provide a composite with strong bonding strength by injection bonding to an NMT-treated Al alloy. After that, as disclosed in Patent Document 1, the present inventors discovered that a PPS-based resin composition can also be injection-bonded to an NMT-treated Al alloy. Next, Patent Document 2 discloses a technique of injection joining a polyamide-based resin composition to an NMT-treated Al alloy. Then, in Patent Document 3, the surface treatment method of Al alloy was improved to develop the "NMT2" treatment method, and the injection joining strength between this treated product and the above-mentioned PBT-based resin, PPS-based resin, and polyamide-based resin found to improve. In particular, the PPS-based resin used product has a shear bond strength of about 40 MPa, and even if the injection-bonded product is placed at a temperature of 85 ° C. and a humidity of 85% for 6,000 to 8,000 hours or more, the shear bond strength is about 37 to 37. It was shown for the first time that a metal/resin integrated product with the highest heat and humidity resistance can be obtained while maintaining a pressure of 40 MPa. The inventors named this technology NMT2.

Although NMT2 was recognized as the highest level of injection joining technology for Al alloy and PPS resin, subsequent tests and experiments revealed that there were still problems. That is, if the aluminum alloy is stored for 10 days or more after being treated with NMT2 and then the PPS-based resin injection bonding process is performed, the wet heat resistance of the shear bonding strength tends to decrease. The most extensive use of NMT2 was in the production of aluminum alloy housings for smartphones. The number of production required in this actual production increased rapidly, and when we produced accordingly, we had a large number of injection molding machines and responded to the injection bonding process, but after finishing the NMT2 treatment process, all processed products were processed in 10 days. It became difficult to clean up in the next process within. As a countermeasure, the NMT2 treatment method was improved, and chemical conversion treatment methods named NMT5, NMT7, NMT8 treatment methods, etc. for various Al materials were developed and proposed. When used in these new treatment methods, the effective storage days described above are effective even in summer for four weeks or longer (Patent Document 4). In addition, the present inventors have studied the shape of the injection bonded product of the NMT-type treated Al alloy described in Patent Document 4 and the PPS resin, and when the resin is made into a specific shape, the bonding strength is - We have found and disclosed a shape that does not have any adverse effect on the joint structure even after a 3,000-cycle temperature shock test at 50° C./+150° C. (Patent Document 5).

(New NMT (abbreviation of New Nano molding technology))
In NMT and subsequent NMT-type injection joining techniques, as described above, the final step of surface treatment includes a step of chemically adsorbing amine-based molecules. Since the Al alloy material strongly chemisorbs amine-based molecules, this NMT-like chemical treatment is effective, and it is the key technology for the injection joining technology of NMT, NMT2 to NMT8. That is, metal materials other than aluminum alloy materials do not chemically adsorb amine-based molecules or adsorb them weakly, and therefore the NMT treatment does not exhibit its effect. However, research and development of the resin composition to be used has progressed from research on improving the injection bonding strength in NMT, and if an improved resin composition for injection bonding is used, even if there is no chemisorbed amine molecule, Injection bonding has become possible only by chemical conversion treatment for forming an appropriate fine uneven surface for each surface shape of various metal materials. That is, the present inventors have invented and disclosed a new NMT, which is a technique that enables injection bonding of various metal materials and resin compositions even on surface-treated materials that do not contain amine-based molecular adsorbates (Patent Documents 6 to 10). ). In short, the new NMT is an injection joining technology that can be used for almost all types of practical metals supplied to the market, such as Mg alloys, Al alloys, copper and copper alloys, stainless steel, general steel materials, and special steel plates. The highly crystalline thermoplastic resin is the same as the injection bonding resin for NMT.

According to the definitions of the present inventors, the following five points are necessary conditions for establishing the "new NMT". Of these, the following three points are necessary conditions for the metal materials used. Chemical treatment that satisfies these three points ((1) to (3) below) is called "new NMT treatment". Namely
(1) The metal material has a rough surface with a period of 0.8 to 10 μm,
(2) having a fine uneven surface shape with a period of 5 to 300 nm (preferably 50 to 100 nm) on the rough surface;
(3) the surface layer is covered with a hard ceramic thin layer such as a metal oxide or metal phosphate;
The following two points are necessary conditions for the resin to be injected. Namely
(4) using a resin composition containing a highly crystalline thermoplastic resin as a main component;
(5) In the resin composition, a resin compatible with the main component resin or a resin incompatible with the main component resin is used as a secondary component resin other than the highly crystalline thermoplastic resin that is the main component. Even if there is, it further contains a resin that promotes even partial compatibility with the main component resin as a third component resin.

New NMTs have been developed for all metal species, but the most technological achievements have been for Al alloys. That is, the present inventors have named NMT5-Ano and NMT7-Ano treatment methods named by the present inventors for those including anodizing treatment, which is an Al alloy surface treatment, and further hydrogen peroxide We have developed and proposed NMT5-Oxy and NMT7-Oxy treatment methods including water treatment in the final stage. Among these, injection-bonded products with PPS resin have extremely high resistance to moist heat in the bonding strength between the metal and resin, and the intermediate material storage time from surface treatment to injection bonding is 4 weeks or more. A good product was obtained without any problem even after several months and one year (Patent Document 4). In addition, with respect to titanium alloys, stainless steels, and general steels, the new NMT processing method for each of them has been improved, and high shear bonding strength can be obtained in injection bonding using PBT and PPS resins.

WO2004/041532 JP 2007-182071 WO2012/070654 JP 2019-188651 JP 2019-217704 WO2008/069252 WO2008/081933 WO2008/047811 WO2008/078714 WO2009/011398 JP 2006-315398 Patent application 2020-176274 JP 2018-111277 JP 2019-217704

In the background art as described above, the present invention is a composite of a non-aluminum material and a resin, and has been developed by what means to increase the bonding strength between the non-aluminum material and the resin. As described above, with respect to the surface shape of the metal side, the present inventors believe that the surface shape formed by the new NMT treatment method is the most suitable surface shape proposal. Regarding polyamide resins, the strength of injection bonding between non-aluminum metals is currently limited, but on the resin side, the commercially available polyamide resin "CM3506G50" has been found to be the most suitable for injection bonding, so improvements will be made in the future. The only issue to be addressed is the drastic improvement of the metal surface treatment method. That is, with regard to various non-aluminum metal materials, many efforts have already been made to improve the new NMT treatment method for injection joining. , and a process for enlarging the actual surface area, which is called ultra-fine unevenness with a period of 10 to 100 nm, has already been performed. Therefore, it was determined that what the present invention should do is to eliminate the difference between the NMT treatment and the new NMT treatment method, and that the only thing left is to add the adsorption operation of the amine-based molecule to the new NMT treated product. In short, the "innovative idea" that should be done is to forcibly adsorb a large amount of amine molecules and amine compounds to non-aluminum metal materials that do not have a clear chemical adsorption power for amine molecules. . Specifically, a large amount of the metal is physically adsorbed on the metal surface, and as a result, a metal-treated piece is produced in which a phenomenon similar to that of the NMT-treated product occurs.

Therefore, as a method for increasing the amount of adsorption, of course, if the metal materials to be injection-joined are non-aluminum metals, strong chemical adsorption cannot be expected, so a method of coping with a physical adsorption operation is conceivable. That is, the present inventors expanded the definition of NMT, which refers to water-soluble amine-based molecules, and expanded the scope to include water-soluble amine-based molecules and amine-based compounds. On that basis, we initially attempted to search for compounds that are as heavy as possible, that is, compounds with large molecular weights and masses, and generally speaking, molecules with higher boiling points have larger physical adsorption amounts. After that, it was decided to include things such as Na soaps or Na salts of amino acids whose boiling points cannot generally be measured. Among those selected, if a certain amount of adsorption can be obtained at normal temperature, it can withstand a high temperature of about 150°C to which a metal piece is subjected when it is inserted into an injection joining mold in the injection joining process. I guessed that it might be possible. Also, when PEEK-based resin, PAEK-based resin, or the like is used as the resin for injection joining, the mold temperature is 180 to 190°C. If amine-based molecules, amine-based compounds, etc. that are physically adsorbed on non-aluminum metal pieces are placed under such high temperatures, they may decompose or desorb before the injection joining operation begins. be. However, it was predicted that amine-based molecules and amine-based compounds that can withstand the above-mentioned high temperatures would exist if they were searched accurately. In addition, in NMT, hydrazine hydrate (N ₂ H ₄ ·H ₂ O: molecular weight 50) is used as the water-soluble amine-based molecule, and this is chemically adsorbed on the Al alloy piece, and the Al alloy piece and PEEK A shear bond strength of 50 MPa or more is easily obtained by injection bonding with the system resin.

In the prior invention proposed by the present inventors, it has been found that Al alloy and amine-based molecules strongly chemisorb, and the mold temperature at this time is 180 to 190°C. Therefore, if the adsorptive power is strong, even amine-based molecules are not easily desorbed even at temperatures approaching 200°C. Therefore, we selected a heavy-weight amine-based compound and expected van der Waals force (intermolecular attractive force) proportional to mass even if its chemical adsorption force is very weak. In short, we considered an injection joining technology that utilizes such a physical adsorption phenomenon. The inventors of the present invention have named this new technology a new type of NMT, that is, "SNMT (abbreviation for Special Nano Molding Technology)" in the present invention (details will be described later).

The metal/resin injection-bonded product (composite) obtained according to the present invention is not only useful as a vehicle body or component member for mobile machines such as automobiles, but also useful as a product that can be used in all kinds of machines and equipment. be. On the other hand, the aforementioned injection-bonded products of PPS-based resin and Al alloy (Patent Documents 4 and 5) were intended to be used in mobile machines such as automobiles. This is because these injection joints (composites) are lightweight and have a high joint strength of about 40 MPa between the Al alloy and the resin molding, and the joint has resistance to heat and humidity, and can withstand several thousand cycles of temperature impact tests. This is because it has a long-term durability that can withstand even Therefore, in the belief that the invention of injection-bonded products using this PPS-based resin and Al alloy can be used as it is as a composite for automobiles, the present inventors have proposed the above-mentioned Patent Documents 4 and 5. The idea was to complete and terminate the research and development of the proposed invention. This is because the most important thing for moving machine parts is high strength and light weight. be. However, it did not receive the expected interest from those skilled in the art of automotive manufacturing, which they viewed as most important.

The composites using the PPS-based resins described in Patent Documents 4 and 5 have not been adopted by automobile manufacturers and the like. One of the reasons for this is fire accidents that occur in automobile accidents and the like. Polyamide resins, bumpers, polyolefin resins used in plastic gasoline tanks, etc., both burn without emitting toxic gases. In contrast, PPS produces sulfurous acid gas, and PVC resin produces hydrochloric acid gas. Drivers and passengers left in the burning car will breathe toxic fumes. The present inventors changed the generally used resin material to a polyamide resin or the like, instead of the almost complete composite of PPS resin and metal. The present invention was invented against the above background, and achieves the following objects.
An object of the present invention is to integrate a metal and a resin in which an integrated composite of a non-aluminum metal material such as steel, stainless steel, and titanium and a crystalline thermoplastic resin is bonded with a shear bonding strength of about 39 MPa or more. An object of the present invention is to provide a composite and a manufacturing method thereof.
Another object of the present invention is to find an optimum compound to be adsorbed on the joint surface of metal materials in order to strongly bond non-aluminum metal materials such as steel, stainless steel and titanium to crystalline thermoplastic resins. Another object of the present invention is to provide an integrated composite of metal and resin and a method for producing the same.
Still another object of the present invention is to provide an integrated composite of steel, stainless steel, titanium, and other non-aluminum metal materials and a crystalline thermoplastic resin that can withstand -50°C/+150°C temperature shock 3,000 cycle tests. An object of the present invention is to provide an integrated composite of a metal and a resin that can withstand even a high temperature, and to provide a method for producing the same.

The present invention employs the following means to solve the above problems.
The integrated composite of metal and resin of the present invention 1 is
An integrated composite of metal and resin, in which a metal material having a surface-treated surface and the surface and a crystalline thermoplastic resin composition are joined by an injection molding operation,
The metal material is one selected from steel, titanium alloy, and stainless steel, and the surface is chemically treated,
On the surface after the chemical conversion treatment, a rough surface with a period of 20 to 50 μm is formed when observed with an electron microscope at a magnification of 1000, and a fine uneven surface with a period of 0.5 to 5 μm is formed on the rough surface when observed with an electron microscope at a magnification of 10,000. And, it has a fine irregularity period with an ultrafine uneven surface with a period of 10 to 100 nm when observed with an electron microscope at 100,000 times,
The crystalline thermoplastic resin composition has heat resistance of a melting point of 200° C. or higher,
The joint of the integrated composite obtained by integrating the crystalline thermoplastic resin composition by the injection molding with the water-soluble high molecular weight amine compound adsorbed on the surface has a shear joint strength of 39 MPa. It is characterized by having the above.

The metal-resin integrated composite of Invention 2 is characterized in that, in the metal-resin integrated composite of Invention 1, the high-molecular-weight amine-based compound is triethanolamine or an EDTA derivative. do.
The metal-resin integrated composite of Invention 3 is the metal-resin integrated composite of Invention 1 or 2, wherein the steel is general steel, and the stainless steel is austenitic stainless steel and ferrite. It is characterized by being a special steel containing stainless steel.

The metal-resin integrated composite of Invention 4 is the metal-resin integrated composite of Inventions 1 to 3, wherein the crystalline thermoplastic resin composition contains 70% by weight of polyphenylene sulfide in the resin content. As described above, the resin composition contains 30% by weight or less of the modified polyolefin resin and 5% by weight or less of the third component resin, and the composition contains 15 to 25% by weight of the short glass fibers, and the shear bonding strength is , 39 to 43 MPa.

The metal-resin integrated composite of Invention 5 is the metal-resin integrated composite of Inventions 1 to 3, wherein the crystalline thermoplastic resin composition contains 10 semi-aromatic polyamides in the resin content. The resin composition contains an aliphatic polyamide in an amount of 90% by weight or more and an aliphatic polyamide in an amount of 25% by weight or more, and the shear bonding strength is 45 to 65 MPa. It is characterized by

The metal-resin integrated composite of Invention 6 is the metal-resin integrated composite of Inventions 1 to 3, wherein the crystalline thermoplastic resin composition contains 80 polyether ether ketone in the resin content. It is a resin composition containing up to 100% by weight and 0 to 20% by weight of polyetherimide, and is characterized by having a shear bonding strength value of 50 MPa or more.

The method for producing an integrated composite of metal and resin of the first invention is a method for producing an integrated composite of metal and resin of the inventions 1 to 6,
After the chemical conversion treatment of the surface,
The rough surface, the fine uneven surface, and the ultra-fine uneven surface are formed by sequentially immersing the metal material in an acid-base aqueous solution or an oxidizing-reductive aqueous solution, or
First, after forming the rough surface and the fine uneven surface by physical roughening treatment by shot blasting, after forming the ultrafine uneven surface by chemical treatment,
The surface is immersed in a triethanolamine aqueous solution with a concentration of 0.1-0.5% for 1-60 minutes, further washed with pure water or an ultra-diluted triethanolamine aqueous solution with a concentration of 5-50 PPM, and then dried. and the metal material for injection joining.

The method for producing an integrated composite of metal and resin according to the second aspect of the present invention is the method for producing an integrated composite of a metal and a resin according to the first to sixth aspects of the present invention,
After the chemical conversion treatment of the surface,
The rough surface, the fine uneven surface, and the ultra-fine uneven surface are formed by sequentially immersing the metal material in an acid-base aqueous solution or an oxidizing-reductive aqueous solution, or
First, after forming the rough surface and the fine uneven surface by physical roughening treatment by shot blasting, after forming the ultrafine uneven surface by chemical treatment,
The surface is immersed in an aqueous solution of 4Na salt of EDTA with a concentration of 0.1 to 0.5% for 1 to 60 minutes, and then pure water or an acetic acid aqueous solution with a concentration of 0.05 to 0.5%, or After washing with an aqueous solution of 4Na of ultra-diluted EDTA with a concentration of 50 PPM, it is dried to obtain the metal material for injection joining.

Hereinafter, each configuration, technical background, etc. of the above-described present invention will be specifically described.
[About "SNMT (abbreviation of Special Nano mold technology)" of the present invention]
The new injection joining technology proposed by the present invention, ie, the "new type NMT", that is, the "SNMT" of the present invention will be described. SNMT is simply a method of treating non-aluminum metal materials for injection joining and a chemical conversion treatment method of metal surfaces. As for the surface treatment method for joining metal and resin by injection molding, in the opinion of the present inventors, strong chemical adsorption of amine-based molecules is clearly confirmed only in Al alloys, and therefore the above-mentioned The NMT treatment method is effective only for Al alloys. For non-aluminum metal materials, the present inventors recognized that only the new NMT treatment method described above could be used for injection joining technology, but the joining force did not reach the ideal strength. In order to overcome this, in the present invention, the adsorbate to be adsorbed on the metal surface has a chemical adsorption force that is too weak and almost non-existent, that is, rather than being bound by chemical affinity, physical adsorption or weak chemical adsorption force. We also adopted a strategy of increasing the molecular weight and formula weight to test measures to expand the physical adsorption force. And this strategy worked. This physical adsorption force expansion measure is a chemical conversion treatment method named "New NMT" or "SNMT" described in this section, and is a necessary condition such as the metal surface and the resin used.

The following six points are necessary conditions for establishing the "SNMT" according to the present invention. Among them, the following four points are necessary conditions for the metal materials used. Chemical conversion treatment that satisfies these four points (requirements (a) to (d) below) is called "SNMT treatment". Namely
(a) The metal material has a rough surface with a period of 20 to 50 μm, in other words, a “matte surface”;
(b) having fine irregularities with a period of 0.8 to 5 μm on the rough surface;
(c) having an ultra-fine uneven surface with a period of 10 to 100 nm on the fine uneven surface;
(d) The surface layer is covered with a hard ceramic thin layer such as a metal oxide or metal phosphate, and furthermore has a high boiling point or a large molecular weight amine molecule or amine having a plurality of polar groups. that the system compound is adsorbed,
On the injection resin side, the following two points are necessary conditions. Namely
(e) the resin composition to be used is a resin composition containing a highly crystalline thermoplastic resin as a main component; As a secondary component resin, a resin that is compatible with the main component resin, or a resin that is incompatible with the main component resin, and further a third component resin that is partially compatible with the main component resin. containing resin to advance.

The above three requirements (a, b, and c) include the above-mentioned new NMT treatment (1) and (2), as well as a roughening treatment (requirement a) for a matte surface. However, the current new NMT processed products for various metals, whether they are aluminum alloys or non-aluminum metals, are being made matte in order to increase the perfection of injection joining strength, so please check it. , only confirmed. In addition to requirement (d) above, requirement (3) for the new NMT treatment requires a ceramic thin layer on the surface layer of the metal material, and in addition, the adsorption state of amine-based molecules and compounds with a large molecular weight is required. and that is the biggest feature of this processing method. There are two types of substances that have been confirmed to be effective as high-molecular-weight amine-based molecules and high-formula-weight amine-based compounds. The lightweight class is triethanolamine, and the other is heavy-weight EDTA (ethylenediaminetetraacetic acid). specifically EDTA.4Na, EDTA.2Na (2Na), or a 4Na salt denoted as EDTA(4Na). As the high-molecular-weight amine-based molecule or amine-based compound of the present invention, specifically, various amino acids other than those mentioned above can be conceived. In fact, it is sufficient to confirm the performance of injection bonding tests using polyamide resin compositions and PEEK resin compositions for injection bonding using non-aluminum metal pieces. It can be commercialized.

That is, the injection-bonded product (specimen) that the inventor most wanted to acquire was an injection-bonded product using titanium alloy and PEEK resin, but this was not successful with the use of triethanolamine. The use of 4Na was successful. The injection joining force it also obtained showed a strong joining force in excess of about 60 MPa. The same thing did not occur when the metal material was changed from the titanium alloy piece to the steel piece. Also, when EDTA or EDTA.2Na was used instead of EDTA.4Na, no strong bonding strength was obtained. It is presumed that amine compounds with large molecular weights and formula weights have a wide variety of steric properties, and even if they are physically adsorbed, they change depending on which part of the compound is attached to the metal piece. It goes without saying that good results are not necessarily obtained simply by saying that a large molecular weight or formula weight is sufficient. In short, the conditions we state in our SNMT theory are necessary, not sufficient. However, the thought process itself that comes up with the necessary conditions is of utmost importance. Once the necessary conditions are fixed, I can come up with 10 or 100 items that match it. A person skilled in the art can find even one compound that can be put into practical use from the viewpoint of work, environmental safety, productivity, etc. by experimentally testing them one after another, and the selection of these compounds is based on the above technical idea. It is easy to search with

In addition, the requirements (e) and (f) of the conditions on the resin side are the requirements (3) and (5) under the NMT conditions, and the requirements (3) and (4) under the new NMT conditions described above. Substantially identical, NMT, New NMT and SNMT also define that the same resin compositions are effective. Strictly speaking, however, requirement (4) of the NMT conditions means that non-hydrophilic polyolefin-based resins, fluorine-based resins, and the like cannot be used as resin species. Although the description is omitted, both the new NMT and SNMT are the same in that the polyolefin resin cannot be used as the main component resin in the resin composition used. The reason for this is that most of the surface of the metal material itself is hydrophilic because a metal oxide thin film layer such as a natural oxide layer is formed thereon. All high-strength crystalline thermoplastic resins other than one polyolefin resin are hydrophilic and not lipophilic. Hydrophilic substances have a certain degree of chemical affinity with each other, and therefore, in a metal piece that satisfies the requirements (a to c) of the SNMT referred to in the present invention, the existence of the ultrafine uneven surface itself with a period of several nanometers is unlikely. The surface area is very large, and the numerical value obtained by dividing the actual surface area value by the apparent area is estimated to be 3 or 4 digits or more, but it is very large.

In short, if the surface of the metal piece can be made into a complex double-triple ultra-fine uneven surface shape, it is an oxide (requirement d) to the depth of the ultra-fine recesses on the hydrophilic ultra-fine uneven surface. The concept of injection joining theory, including the present invention, is that a resin composition that penetrates, crystallizes, and solidifies should exhibit the highest joining force. In NMT and SNMT, the amine molecules adsorbed on the surface of the metal material are in a supercooled state to the depths of the ultrafine recesses, and while maintaining the liquid phase, the resin flow smoothly penetrates without solidifying. Helpful. That is, hydrazine hydrate can be used in NMT, and a water-soluble amine-based substance with a large mass that can be expected to have physical adsorption properties can be used in SNMT. Triethanolamine and an EDTA derivative have actually been confirmed to have the effect in experiments. However, the substance that can be used in the present invention is not limited to this substance, and many other chemical substances can be used if chemically searched as an amine-based substance with a large mass.

[Water-soluble amine compounds used in SNMT and adsorption theory]
The amine-based compound referred to in the present invention refers to a high-molecular-weight amine-based compound. In the process of developing the SNMT proposed in the present invention, the first water-soluble amine-based molecule used was triethanolamine, and in the previously developed NMT, the water-soluble amine-based molecule was hydrazine hydrate. However, the SNMT of the present invention does not use hydrazine hydrate as its amine-based molecule. The reason for this is that when a hydrazine hydrate aqueous solution is used as an immersion liquid for chemically etched aluminum alloys, although the strength is not ideal as expected, injection bonding provides a reasonable bonding strength for a fully crystalline thermoplastic resin containing PEEK. was taken. However, with regard to non-aluminum metal materials, none of the injection-bonded products to which the hydrazine hydrate solution was adsorbed could achieve the target bonding strength. In short, although it is certain that Al alloy and hydrazine hydrate are abnormally strongly chemisorbed, it can be said that the present inventors' estimation is correct that they are chemically reacted rather than chemisorbed. On the other hand, with regard to non-aluminum metal materials, the chemical adsorption force with hydrazine hydrate is at a general level, or is much weaker than the situation that occurs with aluminum alloy materials, and as a result, the mold temperature during injection joining is It is thought that when the temperature is raised to (140° C. for most resin species), the total adsorptive power (the sum of the chemical adsorptive power and the physical adsorptive power) decreases and hydrazine hydrate is desorbed.

In short, even non-aluminum metal materials are polar because their surface layers are covered with a natural oxide layer and most of them are hydrophilic metal oxides. If the water-soluble amine-based molecule adhering to this is a polar substance such as hydrazine hydrate or triethanolamine, the adsorptive force generated between them is not only the physical adsorptive force, but also the chemical adsorptive force, which is generated if there is mass. However, with regard to non-aluminum metal materials, the chemisorption power itself is obviously weaker than when using an Al alloy, and there is no choice but to rely on the physical adsorption power. When placed under high temperature, the chemisorption force can decrease or increase, but the physical adsorption force, which relies on van der Waals force (intermolecular attraction force), is only proportional to the molecular mass, and if the temperature rises, It decreases because the detachment force prevails. Therefore, it is easier to understand if these are seen only in a physically adsorbed state. Therefore, hydrazine hydrate, which has a weak physical adsorptive power, cannot be used in the SNMT treatment, but triethanolamine could be used. Furthermore, triethanolamine does not fulfill its function in SNMT, in which a PEEK-based resin composition is used as an injection resin for which the injection joining reaction does not proceed unless the mold temperature during injection joining is as high as 180 to 200°C. However, in the experiments of the present invention, titanium alloys were the only applicable metal species when an EDTA derivative having a large molecular weight was used, but the effect was obtained in a prominent manner. Therefore, when high injection joining strength with PEEK resin is required for various steel materials other than titanium alloys, it is preferable to apply those subjected to SNMT treatment using high-molecular-weight amino acids.

[New Composite with Dissimilar Materials Joined by Injection Joining]
From the above experimental results and considerations, all practical crystalline thermoplastic resins and non-aluminum metal materials can be strongly bonded, so the following three types of bonding techniques can be predicted.
(1) One is to generalize SNMT as an injection joining technology using metal pieces and crystalline thermoplastic resin as a joining technology between dissimilar members, and to join solid objects other than metals with high hardness. It is to develop as a new injection joining technology.
(2) The other is to insert any solid material including metal materials as two materials to be bonded, insert them as a pair facing each other in the injection mold of the injection molding machine, and insert them into the gap between the two materials. , a method of injecting a crystalline thermoplastic resin to produce an integrated product of all three. In short, it is a new joint structure in which the injected crystalline thermoplastic resin functions as a kind of adhesive (see FIGS. 8 and 9, which will be described later).
(3) Yet another prediction is that the SNMT theory is slightly relaxed, and the uneven surface shape of the surface is roughened with a period of 20 to 50 μm (matte if it is a metal) and a fine uneven surface with a period of several μm. , that is, omitting the condition of forming an ultra-fine uneven surface with a period of 10 to 100 nm, the solid that is the object of injection resin for injection joining can be easily obtained even if it is not a metal material.
These requirements (1) to (3) are the same as the first-mentioned "injection joining technology in which a solid material having a high hardness is used instead of a metal piece". By relaxing the SNMT conditions of the present invention, injection joining technology can cover not only metal materials but also inorganic materials such as stone, pottery, and glass, organic materials such as wood, and even plastic molded products. That's what it means. The application of SNMT proposed by the present invention can also provide the possibility of expanding into new technology and new fields in such fields as miscellaneous goods and the restoration of cultural assets such as Kintsugi.

[Range of metal materials referred to in the present invention]
The metal material (non-aluminum material) referred to in the present invention is one selected from steel materials, titanium alloys, and stainless steels. The reason for this is determined by whether or not the SNMT process according to the present invention can reproduce the surface shape according to SNMT. As described above, the question is whether or not SNMT reliably provides a high injection joining force when the metal material is roughened and an ultra-fine uneven surface with a minimum uneven surface period of 10 to 100 nm is formed. That is, SNMT-treated products of all metal types are inserted into an injection-bonding mold, PBT, PPS, and polyamide-based injection-bonding resins are injected into the mold, and the water-soluble amine compound used in the SNMT treatment is triethanol. If it were an amine, would it give the highest injection bond strength of all the metals used? Experimental results are not necessarily applicable to all cases. It concerns C1100 copper, and the SNMT treatment was not suitable for pure copper-based metals. Pure copper-based products can be used up to the new NMT-treated products.To put it simply, in the case of PBT-based and PPS-based resins, the use of new NMT-treated products allows the use of PBT-based resins and PPS-based resins to achieve the highest level of injection. A conjugate was obtained. However, it is not possible to obtain a high-strength injection-bonded product of a polyamide-based resin or a PEEK-based resin. The reason for this is that the final step of the roughening treatment of the copper material is a step of immersion in an oxidation promoting liquid, which produces an ultrafine uneven surface with a period of 10 to 100 nm and a large number of whiskers. It has an ultra-fine uneven surface. After all, the reaction is to create fine features of copper oxide on the surface, and since the surface is treated for injection joining, the entire surface becomes a blackened product of cupric oxide.

This black copper oxide thin layer is quite hard, and if the resin penetrates deep into the ultrafine recesses and solidifies, the composite exhibits high shear bonding strength. Therefore, the injection-bonded structure of PPS-based resin and copper material is used as a complete encapsulant or the like for encapsulating copper electrodes of LIBs (lithium ion batteries). However, in injection joining with polyamide-based resin or PEEK-based resin, C1100 copper treated with the new NMT alone cannot be used because crystallization begins before the resin reaches the bottom of ultra-fine recesses. Therefore, we tried to physically adsorb these by immersing them in a 0.2% aqueous solution of triethanolamine. It's gone. Briefly, triethanolamine reduced a thin layer of copper oxide and changed the color from black to pink (cupric oxide was reduced to cuprous oxide). And the same thing happened when it was immersed in an aqueous solution of EDTA.4Na. Amine-based molecules that were supposed to be adsorbed were digested. Copper is a metal species that is easily oxidized and reduced in a low temperature range, and is not suitable for the NMT theory or the SNMT theory, and is a rare metal species that follows the new NMT theory. As can be understood from the above description, the metallic material referred to in the present invention does not include a copper material.

Another consideration is SPCC (cold rolled steel). When SPCC is injection-bonded to PEEK, PEEK-based resin, or the like, the new NMT cannot necessarily bond with high bonding strength. Injection bonding between SPCC and the polyamide resin "CM3506G50" described above showed optimum bonding strength in SNMT using triethanolamine. In the case of injection joining using PEEK resin, which has a high temperature range, Ti alloy showed favorable results with corresponding EDTA/4Na, and SUS304 steel showed slightly better results. According to the evaluation of the present inventors, not only SPCC, but also SUS430 is not a favorable result. The salt (Na) structure does not necessarily give good results with any metal species. However, even if the present inventors invented and proposed SNMT, the injection joining force can approach the maximum value, although the current SNMT consists only of Al alloys and 64Ti alloys, but those skilled in the chemical field As such, it is a satisfactory result. This is because applications where PEEK, PAEK, etc. should be used are areas in which wear resistance, heat resistance, corrosion resistance, etc. are emphasized, and Ti alloys are thought to be the most suitable metals for use in these areas. is. However, it is unknown what kind of metal species will be required in the future for injection-bonded products that use PEEK, PAEK, etc. However, as mentioned above, we have developed a new water-soluble amine compound that can be used with all metal species. You can deal with it by looking for it.

[Injection joining operation and annealing treatment of the present invention]
The injection joining used in the present invention involves creating a mold for injection joining, inserting a surface-treated metal piece into the opened mold, closing the mold, and injecting the resin. is a known technique, not a special technique. If I dare say it, it is the mold temperature and the holding pressure time. The mold temperature should be within the temperature range recommended by the resin manufacturer, but basically it is better to set it higher. Specifically, when using the PPS-based resin "SGX120" and the polyamide-based resin "CM3506G50", the mold temperature is preferably around 140°C. Also, in the case of PAEK resin, the temperature was set at 180 to 190°C. The other is pre-injection time and holding pressure time. If the insert is large, for example, 1 kg or more, instead of inserting it and closing the mold and immediately moving to the injection operation, wait about 30 to 90 seconds so that the temperature of the insert is almost the same as the mold temperature. At about the same time, it is necessary to start the injection operation of the molten resin composition. The reason is the same as the setting of the mold temperature. As for the subsequent holding pressure time, the crystallization speed during rapid cooling seems to be slightly slow in the above "CM3506G50", so the time from the start of injection to the end of holding pressure was set to about 30 seconds. Also, the injection temperature when PEEK resin is used is 370 to 380° C., which is rather high. That is, PEEK is said to have a melting point of around 340° C., but the fluidity was poor in experiments unless the injection temperature was 370° C. or higher.

Highly crystalline thermoplastic resins such as PPS, polyamide, and PBT can be injection molded and joined smoothly at a temperature of about 10°C above their melting points, even if their melt viscosities are sufficiently low. rice field. According to the manufacturer's specifications, PEEK requires an injection temperature that is about 30°C higher than its melting point. It may be better to think of it as a crystalline resin. Of course, the obtained injection-bonded product is not allowed to cool as it is, but is heat-treated (annealed) at a temperature of 170 to 190° C. for about 1 hour within several hours to crystallize the resin. is sufficiently advanced, all steps of the injection joining process are finished. In the previous section, it was stated that the injection-bonded product should be obtained by setting the time from resin injection to the end of holding pressure to approximately 30 seconds, but the injection-bonded product after such an annealing treatment is subjected to the annealing treatment.

[Method of implementing temperature shock 3,000 cycle test and its evaluation method]
It is a temperature shock test of the integrated composite of metal and resin of the present invention (hereinafter also referred to as “integrated composite” or “injection bonded product”) and its manufacturing method. In the composite of the non-aluminum metal material of the present invention and the above-mentioned PPS resin "SGX120", the target value of the shear bonding strength is set to about 40 to 42 MPa, which is slightly higher by adopting the SNMT treatment method. did. We have succeeded in acquiring full-fledged injection joining technology using non-aluminum metal materials, the above-mentioned polyamide resin "CM3506G50", and non-aluminum metal materials and PEEK resin. Examples of applications of these injection-bonded products are automobile parts, and they are used as materials for parts of all mobile machines including aircraft, mobile robots, and drones. That is, it can be used for housings, parts, etc. of general machines used indoors and outdoors, and a composite material of metal and resin for this purpose can be provided. However, for mobile machines such as automobiles and airplanes, it is necessary to consider temperature shocks, and it is necessary to withstand severe temperature shocks. As for automobiles, if the place of use is extreme cold Alaska or Siberia, the temperature will be -50°C in winter, and in the scorching desert, the outer plate of the car will be +80°C. Even indoors, if it is left unattended, it can reach +100°C in sunlight. In the case of aircraft, there is the -50°C environment in the stratosphere, while the wing of an aircraft waiting at a tropical airport can be +100°C. In short, in terms of automobiles, there are parts that require temperature shock 3,000 cycles of 50°C/+150°C, such as parts around the engine room and parts near the main lamp in Alaska, Siberia, etc., and automobiles and aircraft. -50°C/+80°C temperature shock 3,000 cycle test is required for some parts such as the body and wing structure of

The injection-bonded product of the above-described PPS-based resin “SGX120” and the above-described NMT2-8-treated Al alloy, that is, the shear bond strength of the test piece shown in FIG. An injection joint that exhibited strength was obtained. Regarding the shape of this injection-bonded product made of PPS-based resin and Al alloy, how should the structure be designed so that the injection-bonded product with that shape can sufficiently withstand the -50°C/+150°C temperature shock 3,000-cycle test? also need guidance. The present inventors proposed and disclosed a structural example for this purpose (Patent Document 5). In the composite of the present invention, the target injection-bonded product is different from the injection-bonded product of the Al alloy described in Patent Document 5 and the polyamide-based resin "CM3506G50". The composite of the present invention is composed of SNMT-treated non-aluminum metal and the PPS resin "SGX120", or SNMT-treated non-aluminum metal and the polyamide-based resin "CM3506G50", or SNMT-treated non-aluminum metal and PEEK. It is an injection-bonded product made of a system resin, and these are different only in the materials used in the injection-bonded products used. In short, with the resin structure exactly the same as that described in Patent Document 5, these injection-bonded products can also withstand the -50°C/+150°C temperature shock 3,000-cycle test. Therefore, the test method described in Patent Document 5 will be described as it is below.

[Temperature shock test and resin part thickness, composition, etc.]
First, the type of injection joint is determined. For example, the object is determined such that an injection joint of SNMT-treated SUS304 steel and the polyamide resin "CM3506G50" is subjected to a temperature shock 3,000 cycle test. Then, more than ten injection-bonded specimens of the test piece shown in FIG. 1 are made. Using a router, which is a cutting machine, several pieces, which are 1/3 of that, were cut into the shape shown in FIG. be a thing Then, using a router, several pieces, which are 1/3 of the original test piece shown in FIG. 1, were scraped into the shape shown in FIG. Make the part thickness 1 mm thick. In this work, more than a dozen test pairs were prepared for temperature shock cycle testing. That is, although the basic shape is the test piece shown in FIG. 1, the thickness of the resin portion on the back of the bonding surface was processed into three types of 3 mm thick, 2 mm thick, and 1 mm thick. All of them were subjected to a -50°C/+150°C temperature shock 3,000 cycle test.

After the 3,000-cycle test is completed, the test piece is removed from the testing machine and left for about one day. First, the resin part thickness is 3 mm, which is the test piece shown in FIG. As preliminary knowledge, the linear expansion coefficient of this metal part is 0.8×10 ⁻⁵ K ⁻¹ for Ti alloy, 1.1×10 ⁻⁵ K ⁻¹ for general steel plate and ferritic stainless steel, It is about 1.6×10 ⁻⁵ K ⁻¹ for austenitic stainless steel. One resin part joined to this is about 4.0 × 10 ^-5 K ^-1 in the case of the above "SGX120", and about 2.5 × 10 ^-5 K ^-1 in the case of the above polyamide resin "CM3506G50". , about 8.0×10 ⁻⁵ K ⁻¹ for a 95:5 mixture of PEEK and PEI. Therefore, the metal side is (0.8-1.6)×10 ^-5 K ^-1 and the resin side is (2.5-8.0)×10 ^-1 for all of the composite combinations of the present invention. ⁵ K ⁻¹ , and the coefficient of linear expansion is always smaller on the metal side than on the resin side. Among them, the composite of the polyamide resin "CM3506G50" and SUS304 steel has the smallest linear expansion coefficient difference, which is about 0.9×10 ⁻⁵ K ⁻¹ . With this linear expansion coefficient difference, even if the test piece shown in FIG. It is assumed that there is no resin adhesion at two of the four sides, and the bonding strength is lost to 30 MPa or less.

The inventors of the present invention conducted temperature shock 3,000 cycle tests at -50 ° C./+150 ° C. with many kinds of Al alloys and PPS resins before the previous invention (Patent Document 5), Al alloys and polyamide resins. FIG. 6 shows the state of delamination due to temperature impact on the joint surface at that time. Fig. 6 shows an injection-bonded product in which the metal plate is an Al alloy plate and the injection resin is the above-mentioned PPS resin "SGX120". This is a diagrammatic representation of the state of The test piece shown in FIG. 5, which is an injection-bonded product having a resin thickness of 1 mm at the bonding portion, did not cause peeling at all on the bonding surface (see FIG. 6(b)). It is shown that peeling was observed at one corner or two corners of the joint surface of the injection-bonded product with the resin of the test piece shown in FIG. 4 having a thickness of 2 mm (see FIG. 6(d)). 1, 4 and 5 and their resin thicknesses of 3 mm, 2 mm and 1 mm were subjected to the same temperature shock 3,000 cycle test. The pieces were put into the temperature shock tester at the same time. In this long-term temperature shock cycle test, a slight peeling portion was observed in the resin portion having a thickness of 1 mm. The joint surface of the resin with a thickness of 3 mm is peeled off from the four corners and spreads, and finally a circular joint surface remains in the center.

Since the Al alloy is not used as the metal material in the present invention, the difference in coefficient of linear expansion between the metal material and the resin material shows that the Al alloy shown in the previous invention (Patent Document 13) and the polyamide resin "CM3506G0" The linear expansion coefficient difference is considerably larger than that of the injection-bonded product. From this test result, it can be estimated that the injection-bonded article of the present invention, which does not peel off for a long period of time, has a thickness of 0.5 to 0.8 mm, which is 1 mm or less for the resin portion to be bonded to the metal. The results of the temperature shock 3,000 cycle test of these composites show that those with high injection joining strength are not necessarily resistant to temperature shock. On the other hand, the greater the difference between the coefficient of linear expansion of the resin material itself and the coefficient of linear expansion of the metal material, the more likely it is that the joint surface will peel off at an early stage due to fatigue fracture. As a countermeasure, the resin portion should be made soft so as to follow the expansion and contraction of the metal material. If the resin portion is hard, peeling will occur early. That is, it can be said that when the resin portion is highly flexible in material mechanics, the resin portion easily expands and contracts following the expansion and contraction of the metal material, and is resistant to temperature impact. Furthermore, it can be said that the shear bonding strength of the injection bonding force is about 42 MPa in the experiment when the above PPS resin "SGX120" is used, but when the above polyamide resin "CM3506G50" is used, it is about 64 MPa. is to become

The difference between 40 MPa and 64 MPa is related to the GF content contained in the resin composition, the former having a GF content of 20% and the latter having a GF content of 33.3%. and its shear bond strength is 42 MPa for the former and 64 MPa for the latter, with a ratio of 1:1.5. Both ratios are in good agreement, and the higher the GF content, the stronger and tougher the resin, and the higher the injection joining strength. However, making the joint stronger and tougher means that the material becomes harder in terms of material mechanics, but in the temperature shock test, the edge with the greatest thermal deformation becomes easy to peel off. That is, if the strength of the injection joint strength depends on the GF content, the resin will become harder, so the effect will be offset and not very useful. Therefore, whether a material is strong or weak against a temperature shock test is mostly affected by the difference in coefficient of linear expansion between the metal material and the resin material. In the case of the product of the present invention, which clearly has a large difference in coefficient of linear expansion, peeling as shown in FIG. 6 should not occur, and a greater change should occur. For example, when a Ti alloy having a low linear expansion coefficient is used as the metal material, the linear expansion coefficient difference is large regardless of what resin material is used. For this reason, even if the resin thickness is 1 mm as shown in FIG. 5, peeling occurs at the ends of the four corners of the joint when subjected to a temperature shock test of 3,000 cycles. Even if this resin thickness is set to 0.8 mm, the problem may not be solved. However, there is no way to confirm this except by making a product with a resin thickness of 0.8 mm and conducting a verification test.

That is, in the combination of the composite of the present invention, the metal side (titanium material, Ti alloy, general steel, ferritic stainless steel, austenitic stainless steel) is (0.8 to 1.6) × 10 ^-5 K ^{- 1} , and the resin side is (2.5 to 5)×10 ⁻⁵ K ⁻¹ , and the difference in linear expansion coefficient between the resin side and the metal side is large regardless of what resin is used. In particular, when a Ti alloy, general steel, or ferritic stainless steel is used as the metal material, the difference in coefficient of linear expansion increases. When a temperature shock test of -50°C/+150°C was conducted for 3,000 cycles, the test piece having the shape shown in FIG. In this case, as mentioned above, the reason for making and checking resin thickness up to 0.8 mm is that the limit for mass production of wide sheet-like products by injection molding is about 0.8 mm in thickness. This is because it is the common sense of engineers. Making a sheet-like material with a thickness of 0.5 mm itself is not impossible with injection molding. However, as a mold for injection joining, there is a possibility that the injection resin temperature will be low at the end of the molten resin flow (the injection joining force may be low at the end), which is not realistic. , because the resin thickness is limited to 0.8 mm.

Another reason is that, as explained in the temperature shock cycle test, even if the resin thickness is reduced to 1 mm, the results in the 3,000 cycle test are not good. determined that it could not withstand the temperature shock. However, in this experiment, the judgment was based on the premise of a temperature shock test of 3,000 cycles at -50°C/+150°C, which may have been too severe for practical experimental conditions. If the field of use of this composite is, for example, the engine room of an automobile or the like, or it can be placed away from equipment that emits high temperatures, such as a light-emitting device, no problem will arise. If the natural environment is only severe, even if it is used in automobiles, it can withstand temperature shocks of -50°C/+80°C for 3,000 hours. In short, it is sufficient to conduct a test that can withstand the required specifications depending on the application in which the composite is used.

On the other hand, even if there is a large difference in the coefficient of linear expansion between metal and resin, if there is a large temperature difference between summer and winter due to the natural environment, it is possible to bond injection-bonded objects (composites) that are unified by bonding force. It does not necessarily mean that cracks or peeling occurs on the surface. That is, a moderate temperature change does not generate a large load or a low load on the joint surface. However, in the temperature shock test, which is an artificial load, the temperature change rate is fast and repeated, so the environment is such that creep stress does not occur or is low. In this temperature shock test, it is considered whether or not there is a temperature range in which the internal stress is zero near the joint surface between metal and resin. Essentially, what is the moment when the internal stress generated near the joint surface of metal and resin becomes zero several days after the start of the temperature shock several thousand cycle test? Before the creep test, it means the room temperature before the start of the temperature shock test. The time the cage remains exposed to its room temperature is 30 minutes.

Then, when moving between the compartments of the high-temperature room and the low-temperature room, they once enter a separate room with a partition. In this separate room, the time required to converge to the predetermined high temperature and low temperature is repeated for about 5 minutes, and one cycle of the temperature shock test is about 70 minutes after all. After the temperature shock test starts, it is estimated that the center temperature of the temperature change, for example, around +50°C for the temperature shock test of -50°C/+150°C, and around +15°C for the temperature shock test of -50°C/+80°C. , is considered to be the temperature at which the internal stress of the injected joint is zero. Since the deviation from the central temperature is 100° C. for the former and 65° C. for the latter, the temperature change is 65% against the former 100%, which is a reduction of 35%. Under this latter condition (reduction of 35%), peeling of the joint surface does not occur if the resin thickness is set to 0.8 to 1.0 mm even for all combinations of injection-bonded products (composites) of the products of the present invention. It can be assumed that the In any case, it can be clearly seen by performing the above-described experiment of 3,000 cycles of temperature shock.

From the above considerations, in any case, the maximum temperature and minimum temperature actually required are set appropriately, and the temperature shock test is performed for 3,000 cycles, and the resin thickness of the test piece shown in FIG. If there is no peeling on the joint surface of the injection joint of 0.0 mm, the joint area of the injection joint with a resin thickness of 1.0 mm can withstand the temperature shock 3,000 cycle test. Show that you get It was determined that the test piece shown in FIG. 5 with a resin thickness of 1.0 mm should be able to withstand the temperature shock 3,000 cycle test. It was determined that the same durability would be obtained if the shapes shown in later-described FIGS. Regardless of the shape and lamination, the key is that the thickness of the resin at the joint should be about 1.0 mm or less. Therefore, when the thickness of the resin is limited to 0.8 mm, the structures of the joints are as shown in FIGS. Even so, if it is determined that the resin cannot withstand 3,000 cycles of temperature shock unless the resin thickness is 0.8 mm or less, it is recommended to use it in a range in which the temperature range in the temperature shock test is lowered. In order to search for the conditions, it is preferable to test the test piece shown in FIG. 5 by a temperature shock test. Other test methods are also conceivable, but are not mentioned as they are not the subject of the present invention.

On the other hand, when improving the resin material resistant to temperature shock, when using the above-mentioned polyamide resin "CM3506G50", the GF content is not 33.3% by weight, but the GF content is 25% by weight or 11% by weight. There is a method to lower the percentage. When the test piece shown in FIG. 1 is used to measure the shear bond strength, it may decrease from the original 50 to 65 MPa to 40 MPa, 20 MPa, etc., but for example, the shape shown in FIG. 8 with a resin thickness of 1.0 mm ( Laminated product), the left and right ends of this shape were cut, the left and right metal pieces were pulled apart, and the shear bond strength was measured. However, it has a strong shear bonding strength of 45 MPa or more. If this joining structure is adopted, a soft resin material can be adopted without being limited to the above "CM3506G50". If the shapes shown in FIGS. 5, 7, 8, and 9 are adopted, the temperature shock 3,000 cycle test can be withstood.

[Measurement of shear bond strength]
ISO19095 defines methods for measuring the shear bond strength (tensile lap-shear strength) and tensile bond strength (tensile strength) between the metal part and the resin molding in injection-bonded products. A method of tensile breaking a test piece with a tensile tester and measuring the shear bond strength, and a method of tensile breaking a test piece with the shape shown in Fig. 2 with a tensile tester and measuring the tensile bond strength are stipulated. It is This shear bonding strength measurement method is the one used by the present inventors in Patent Documents 6 to 10, while the tensile bonding strength measurement method has been used by the present inventors since around 2015 after various developments. It started. None of them can be measured by the methods stipulated in JISK6849 and JISK6850, which are conventional methods for measuring adhesive strength and bonding strength. , and ISO-related national governmental organizations.

In the integrated composite of metal and resin of the present invention, the shear bonding strength between the non-aluminum metal material such as steel, stainless steel and titanium material and the crystalline thermoplastic resin could be firmly bonded to about 39 MPa or more. In addition, in the method for producing an integrated composite of metal and resin of the present invention, when the non-aluminum metal material and the crystalline thermoplastic resin are injection-joined, the non-aluminum metal material and the crystalline thermoplastic resin are adsorbed to the joint surface of the metal material in order to increase the joint strength. We have found the optimal compound that can Furthermore, the integrated composite of the present invention was able to withstand a temperature shock test of -50°C/+150°C for 3,000 cycles.

FIG. 1 is an external view of a test piece for measuring shear bonding strength between a metal part and a resin part in an integrated composite of metal and resin specified in ISO19095. FIG. 2 is an external view of a test piece for measuring the tensile joint strength between a metal part and a resin part in an integrated composite of metal and resin specified in ISO19095. FIG. 3 is an external view of an auxiliary jig used when measuring the shear bonding strength of an integrated composite of metal and resin specified in ISO19095. FIG. 4 is an external view of the test piece shown in FIG. 1, in which a portion of the resin portion is scraped off and the joint portion has a thickness of 2.0 mm. FIG. 5 is an external view of the test piece of FIG. 1, in which a portion of the resin portion of the joint portion is scraped off to have a thickness of 1.0 mm. Fig. 6 shows the test specimens shown in Figs. 4 and 5, which were prepared from an A5052Al alloy piece treated with NMT2 and an injection-bonded product made of PPS resin "SGX120", and subjected to a temperature shock test of -50°C/+150°C for 3000 cycles. FIG. 10 is a diagram showing a change in the joint surface as a result. In FIG. 6(a), the joint thickness is 1.0 mm, and in FIG. 6(b), the joint thickness is 2.0 mm. FIG. 7 shows one example of the shape of the integrated composite according to the present invention, in which a large boss stands on a thick metal plate with high rigidity. FIG. 7(a) is a plan view, and FIG. 7(b) is a front view. FIG. 8 shows one example of the shape of the integrated composite body according to the present invention, which is an example of an integrated composite body in which the resin portion is bonded between two metal plates and laminated. FIG. 9 shows an example in which Al alloy pins for heat conduction are arranged between the metal plates in the integrated composite of FIG.

Hereinafter, embodiments of the present invention will be described using a specific injection-bonded article (an integrated composite of metal and resin). FIG. 7 shows one example of the shape of the injection-bonded product according to the present invention, which is a basic shape in which a large boss stands on a thick metal plate with high rigidity. FIG. 7(a) is a plan view, and FIG. 7(b) is a front view. The injection joint 1 consists of a metal rectangular plate 2 made of a non-aluminum metal plate and having an injection path hole, and a main body 3 of a resin molding integrally joined thereto. The metal plate 2 has a length and width of 100 mm and a thickness of 3 mm. The resin body 3 has a cylindrical portion 4 at its center, and four ribs 5 are erected along the cylindrical portion 4 at equal angles on the outer peripheral surface of the resin body 3 . The outer periphery of the resin body 3 is annularly supported by a central pedestal 6 having a thickness of 2 mm and a rectangular shape of 50 mm. A peripheral pedestal 7 is annularly formed so as to surround the outer circumference of the central pedestal 6 . The peripheral pedestal 7 is formed in a rectangular shape with a width of 10 mm, a thickness of 1 mm and a thickness of 70 mm. That is, the injection bonded product 1 made of metal and resin is formed with a central pedestal 6 and a thinner peripheral pedestal 7 in order to maintain the bonding strength between the resin central portions 4, 5 and the metal rectangular plate 2. . This injection joint 1 was prepared by manufacturing an injection mold, inserting a chemically treated rectangular metal plate 2 into this injection mold, and injecting the aforementioned PPS-based composition "SGX120".

Before the metal rectangular plate 2 is inserted, it is subjected to the aforementioned SNMT treatment according to the present invention. Since the cylindrical portion 4 on the metal rectangular plate 2 is surrounded by the thin outer peripheral pedestal 7 and the central pedestal 6 at the central portion, the difference in thermal expansion can be absorbed. The most important value here is the thickness of the outer peripheral base of 1 mm. The results that do not occur are referred to as the thin outer peripheral pedestal 7 described above. Therefore, if the result of the temperature shock test performed in advance is to obtain a thickness of the resin portion of 1 mm or less, the thickness of the outer peripheral pedestal obtained in FIG. By reducing the upper and lower temperature difference between the high temperature and the low temperature, the test piece of FIG. 5 or a similar one with a resin thickness of 0.8 mm as shown in FIG. A good place to start is to test and see what is possible.

FIG. 8 is an example of a laminate that is an injection-bonded article according to the present invention. This is an example in which two SUS304 steel plates are joined by injection joining with a polyamide resin. This laminate is manufactured by inserting two SNMT-treated SUS304 steel plates into an injection mold with a gap of 1.0 mm, and injecting a polyamide resin into the gap to join them. In this example, the aforementioned "CM3506G50" was used as the polyamide resin. FIG. 9 shows an example in which two SUS304 steel plates are injection-joined with a polyamide-based resin in the same manner as the laminate in FIG. This is an example of use in the case of a part or case where a temperature difference occurs between two SUS304 steel plates due to heat transfer or radiant heat. This is an example of an injection-bonded product in which two SUS304 steel plates are connected with an Al alloy pin. The heat of the SUS304 steel plate heated to a high temperature is conducted to the SUS304 steel plate of a low temperature through the Al alloy pin and is averaged, so that the load due to the thermal expansion of the joint can be reduced.

EXAMPLES Examples of the present invention will be described in detail below as experimental examples, and evaluation and measurement methods for integrated composites (test pieces) obtained from experimental examples will be described.
(a) Measurement of bonding strength In the present invention, the breaking strength when the injection-bonded product (FIGS. 1 and 2) is tensile-broken with a tensile tester is used as an index of bonding strength (shear bonding strength, tensile bonding strength). . However, the auxiliary jig shown in FIG. 3 was used in the measurement of the shear bond strength. As the tensile tester used, "AG-500N/1kN (manufactured by Shimadzu Corporation (head office: Kyoto, Japan))" was used, and the tensile strength was measured at a tensile speed of 10 mm/min. This measurement method is based on ISO19095.

[Experimental example A] Metal material surface treatment method [Experimental example A1-1] New NMT treatment of shot-blasted SPCC (cold-rolled steel plate) (reference example)
A number of 18 mm x 45 mm x 1.6 mm thick rectangular pieces were machined from a commercially available 1.6 mm thick SPCC plate. The ends of these SPCC pieces were roughened by shot blasting with white alumina powder ("WA"#150). Next, an aqueous solution containing 10.0% aluminum degreasing agent "NA-6 (manufactured by Meltex Co., Ltd. (head office: Tokyo, Japan)" is placed in a water tank equipped with an ultrasonic vibrating tip and heated to 60°C. was immersed for 5 minutes, and then washed with public tap water (Ota City, Gunma Prefecture) (hereinafter referred to as tap water). Next, a 5.0% sulfuric acid aqueous solution adjusted to 60° C. was prepared in another tank, and after the steel slab was immersed in this for 4 minutes, it was washed with pure water (hereinafter referred to as water washing). Next, an aqueous solution of ammonium monohydrogen difluoride with a concentration of 5% at 65° C. was prepared in another tank, and the steel slabs were immersed in this for 25 minutes and then washed with water. Next, 1.0% concentration ammonia water was prepared in another tank, and the steel pieces were immersed in this for 1 minute and then washed with water. Next, in another tank, an aqueous solution containing 2.0% potassium permanganate, 1.0% acetic acid, and 0.5% sodium acetate hydrate at 45°C was prepared. After soaking the pieces for 20 minutes, they were washed with water. Next, it was immersed for 7 minutes in a water washing bath in which an ultrasonic oscillation end was set and washed with water. These steel slabs were placed in a hot air dryer set at 80° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A1-2] SNMT treatment of shot-blasted SPCC A large number of rectangular pieces of 18 mm x 45 mm x 1.6 mm thick were machined from a commercially available 1.6 mm thick SPCC plate. The ends of these billets were roughened by a shot blasting machine using white alumina powder ("WA"#150). Next, in a water tank equipped with an ultrasonic vibrating end, an aqueous solution containing 10.0% of the aluminum degreasing agent "NA-6" was heated to 60°C, and these steel pieces were immersed for 5 minutes and then washed with tap water. . Next, an acidic ammonium fluoride aqueous solution with a concentration of 5.0% at 65° C. was prepared in another tank, and the steel pieces were immersed in this for 1 minute and then washed with water. Next, 1.0% concentration ammonia water was prepared in another tank, and the steel pieces were immersed in this for 1 minute and then washed with water. Next, in another tank, an aqueous solution containing 2.0% potassium permanganate, 1.0% acetic acid, and 0.5% sodium acetate hydrate at 45°C was prepared. After soaking the pieces for 5 minutes, they were washed with water. Next, it was immersed for 7 minutes in a water washing bath in which an ultrasonic oscillation end was set and washed with water. Next, a 1.0% hydrogen peroxide solution was prepared in another tank, and the steel pieces were immersed in the water for 0.5 minutes and then washed with water. Next, in another tank, a triethanolamine aqueous solution having a concentration of 0.2% at 40° C. is prepared, the steel piece is immersed for 30 minutes, and then the prepared triethanolamine is added to 25 PPM in another tank. The steel billet was placed in ultra-diluted water containing the steel and moved up and down for washing. It was pulled out of the ultra-diluted water tank, subjected to a simple draining operation, placed in a hot air dryer set at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A1-3] SNMT2 treatment of shot-blasted SPCC From a commercially available 1.6 mm thick SPCC plate, a large number of rectangular pieces of 18 mm x 45 mm x 1.6 mm thick were machined. The ends of these billets were roughened by a shot blasting machine using white alumina powder ("WA"#150). Next, an aqueous solution containing 10.0% of the degreasing agent for aluminum "NA-6" was heated to 60°C in a water tank equipped with an ultrasonic vibration end, and the steel slab was immersed in this for 5 minutes and then washed with tap water. did. Next, an aqueous solution containing acidic ammonium fluoride at a concentration of 5.0% at 65° C. was prepared in another tank, and the steel slab was immersed in this for 1 minute. Next, 1.0% concentration ammonia water was prepared in another tank, and the steel pieces were immersed in this for 1 minute and then washed with water. Next, in another tank, an aqueous solution containing 2.0% potassium permanganate, 1.0% acetic acid, and 0.5% sodium acetate hydrate at 45°C was prepared. After soaking the pieces for 5 minutes, they were washed with water. Next, it was immersed for 7 minutes in a washing bath in which an ultrasonic oscillation end was set, and then washed with water. Next, prepare an aqueous solution of EDTA (4Na) with a concentration of 0.4% at 40° C. in another tank, immerse the steel billet for 30 minutes, and then transfer the prepared 0.1 % concentration aqueous solution of acetic acid, and washed by immersing it several times. After these treatments were completed, the steel slab was placed in a warm air dryer set at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A1-4] SNMT2 treatment of SPCC A number of rectangular pieces of 18 mm x 45 mm x 1.6 mm thick were machined from a commercially available 1.6 mm thick SPCC plate. Next, in another tank, an aqueous solution containing 10.0% of the degreasing agent for aluminum "NA-6" was heated to 60° C., and these steel slabs were immersed for 5 minutes and then washed with tap water. Subsequent liquid treatment was carried out in the part near the end described in Experimental Example A1-3, that is, "In another tank, 2.0% concentration of potassium permanganate at 45° C., 1.0% concentration of acetic acid and 0% An aqueous solution containing sodium acetate hydrate with a concentration of 5% was prepared, and after immersing the billet in this for 20 minutes, it was washed with water, and then immersed in a washing bath in which an ultrasonic oscillation end was set for 7 minutes. and washed with water.", and after that, the following treatment was performed. That is, next, an aqueous solution of EDTA (4Na) with a concentration of 0.4% at 40° C. was prepared in another tank, the steel billet was immersed for 30 minutes, and then the 50 ppm concentration prepared in another tank was prepared. EDTA (4Na) aqueous solution, and washed several times. It was placed in a hot air dryer at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A1-5] SNMT2 treatment of SPCC (reference example)
A number of 18 mm x 45 mm x 1.6 mm thick rectangular pieces were machined from a commercially available 1.6 mm thick SPCC plate. Subsequent liquid treatment was performed near the end of Experimental Example A1-3, namely, "In a separate tank, 2.0% concentration of potassium permanganate, 1.0% concentration of acetic acid and 0.0% concentration of acetic acid at 45°C were added to another tank." An aqueous solution containing 5% sodium acetate hydrate was prepared, and the steel piece was immersed in this solution for 20 minutes, washed with water, and then immersed in a washing bath in which an ultrasonic oscillation end was set for 7 minutes and then washed with water. The processing is the same up to the part ".", and the processing after that is as follows. That is, in another tank, an aqueous solution of EDTA (2Na) having a concentration of 0.2% at 40° C. was prepared, and the steel billet was immersed in the water for 10 minutes and then washed with water. It was placed in a hot air dryer at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental example A2-1] New NMT treatment of shot-blasted SUS430 steel (reference example)
A large number of 18 mm×45 mm×1.5 mm thick rectangular pieces were machined from a commercially available 1.5 mm thick SUS430 steel plate. The ends of these billets were roughened by a shot blasting machine using white alumina powder (known in the industry as "WA" No. 150). Next, the steel billets were immersed in an aqueous solution containing 10% of the degreasing agent for aluminum "NA-6" at 60° C. for 5 minutes, and then washed with tap water. Next, an aqueous solution containing 10% sulfuric acid and 1.0% acidic ammonium fluoride at 50° C. was prepared in another tank, and the steel slab was immersed in this solution for 0.5 minutes and then washed with water. Next, it was immersed for 7 minutes in a water washing bath in which an ultrasonic oscillation end was set and washed with water. Next, an aqueous solution containing 0.5% acidic ammonium fluoride and 5.0% sulfuric acid at 50° C. was prepared in another tank, and the steel slab was immersed in this solution for 3 minutes and then washed with water. . Next, a 3.0% nitric acid aqueous solution at 40° C. was prepared in another bath, and the steel slabs were immersed in this for 3 minutes and then washed with water. Next, in another tank, an aqueous solution containing 2.0% potassium permanganate, 1.0% acetic acid, and 0.5% sodium acetate hydrate at 45°C was prepared. After soaking the pieces for 2 minutes, they were washed with water. Next, an aqueous solution containing 2.0% concentration of potassium permanganate and 3.0% concentration of caustic potassium at 70° C. was prepared in another tank, and the steel pieces were immersed in this for 15 minutes and washed with water. Next, an aqueous solution containing hydrogen peroxide at a concentration of 1.0% was prepared in another tank, the steel slab was immersed in this for 0.5 minutes, and then washed with water. It was placed in a hot air dryer at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A2-2] SNMT treatment of shot-blasted SUS430 steel A large number of rectangular pieces of 18 mm x 45 mm x 1.5 mm thick were machined from a commercially available 1.5 mm thick SUS430 stainless steel plate. The ends of these billets were subjected to a roughening operation with a shot blasting machine using white alumina powder ("WA" No. 150). The subsequent liquid treatment is a part close to the treatment of the final step described in Experimental Example A2-1, that is, "next, in another tank, 2.0% concentration of potassium permanganate at 45 ° C. and 1.0% potassium permanganate. An aqueous solution containing acetic acid at a concentration of 0.5% and sodium acetate hydrate at a concentration of 0.5% was prepared, and after the steel billet was immersed in this for 2 minutes, it was washed with water." treated. That is, next, a 1.0% hydrogen peroxide aqueous solution was prepared in another tank, and the steel slabs were immersed in the water for 0.5 minutes and then washed with water. Next, an aqueous solution containing 0.2% triethanolamine was prepared in a water washing bath set at 40° C., the steel plate pieces were immersed therein for 30 minutes, and then washed with an aqueous solution containing 50 ppm concentration of triethanolamine. After completion of these treatments, it was placed in a hot air dryer at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A2-3] SNMT2 treatment of shot-blasted SUS430 steel A large number of 18 mm × 45 mm × 1.5 mm thick rectangular pieces were machined from a commercially available 1.5 mm thick SUS430 stainless steel plate. The ends of these billets were subjected to a roughening operation with a shot blasting machine using white alumina powder ("WA" No. 150). Subsequent liquid treatment is a portion close to the final step described in Experimental Example A2-2, that is, "next, in another tank, 2% concentration of potassium permanganate at 45° C., 1% concentration of acetic acid, and 0.5% concentration of acetic acid are added to another tank. An aqueous solution containing a 5% concentration of sodium acetate hydrate was prepared, and the steel billets were immersed in the solution for 2 minutes and then washed with water.", and the subsequent steps were as follows. That is, next, a 1.0% concentration hydrogen peroxide aqueous solution was prepared in another tank, and the steel slab was immersed for 0.5 minutes and washed with water. Next, an aqueous solution containing 0.4% EDTA (4Na) was prepared in a washing tank set at 40°C, the steel plate pieces were immersed therein for 30 minutes, and then washed with an aqueous solution containing 50 ppm concentration of EDTA (4Na). . After this washing, the steel plate pieces were placed in a warm air dryer set at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental example A3-1] New NMT treatment of shot-blasted SUS304 stainless steel (reference example)
A large number of 18 mm×45 mm×1.5 mm thick rectangular pieces were machined from a commercially available 1.5 mm thick SUS304 stainless steel plate. The ends of these billets were roughened by a shot blasting machine using white alumina powder ("WA" No. 150). Next, the steel billets were immersed in an aqueous solution containing 10% of the degreasing agent for aluminum "NA-6" at 60° C. for 5 minutes, and then washed with tap water. Next, an aqueous solution containing 1% acidic ammonium fluoride and 10% sulfuric acid at 65° C. was prepared in another tank, and the steel slabs were immersed in this solution for 6 minutes and washed with water. Next, an aqueous solution containing 0.5% acidic ammonium fluoride and 5.0% sulfuric acid at 50° C. was prepared in another tank, and the steel slabs were immersed in this solution for 20 minutes and washed with water. Next, a 3.0% nitric acid aqueous solution at 40° C. was prepared in another bath, and the steel slabs were immersed in this for 3 minutes and then washed with water. Next, it was immersed for 7 minutes in a water washing bath in which an ultrasonic oscillation end was set and washed with water. Next, an aqueous solution containing 5.0% concentration of sodium chlorite and 10.0% concentration of caustic soda at 55° C. was prepared in another tank, and the steel slab was immersed for 6 minutes and then washed with water. . It was placed in a hot air dryer at 80° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A3-2] SNMT Treatment of SUS304 Steel A large number of rectangular pieces of 18 mm×45 mm×1.5 mm thick were machined from a commercially available 1.5 mm thick SUS304 stainless steel plate. Next, the steel billets were immersed in an aqueous solution containing 10% of the degreasing agent for aluminum "NA-6" at 60° C. for 5 minutes, and then washed with tap water. After that, in the same process as in Experimental Example A3-1, "An aqueous solution containing sodium chlorite with a concentration of 5.0% and caustic soda with a concentration of 10.0% at 55°C was prepared in another tank, and the steel slab was It is the same process until it is immersed for a minute and washed with water.", and the post-process is the following process. That is, next, a 1.0% hydrogen peroxide solution was prepared in another tank, and the steel slab was immersed in it for 0.5 minutes. Next, in another tank, a triethanolamine aqueous solution with a concentration of 0.2% at 40° C. is prepared, the steel piece is immersed for 30 minutes, and then the prepared triethanolamine is added to another tank. The billet was placed in the ultra-diluted water containing 25 PPM and washed by moving it up and down. After this washing, it was lifted out of the tank, drained, placed in a hot air dryer set at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A3-3] SNMT2 Treatment of SUS304 Steel A large number of 18 mm×45 mm×1.5 mm thick rectangular pieces were machined from a commercially available 1.5 mm thick SUS304 stainless steel plate. Next, the steel pieces were immersed in an aqueous solution containing 10% of the degreasing agent for aluminum "NA-6" at 60° C. for 5 minutes in a water tank equipped with an ultrasonic vibrator, and then washed with tap water. After that, in the same manner as in Experimental Example A3-2, "An aqueous solution containing 5% concentration of sodium chlorite and 10% concentration of caustic soda at 55°C was prepared in another tank, and the steel billet was immersed for 6 minutes and washed with water. .” and continue with the following. That is, next, a 1.0% hydrogen peroxide solution was prepared in another tank, and the steel slab was immersed in it for 0.5 minutes. Next, prepare an aqueous solution of EDTA (4Na) with a concentration of 0.2% at 40° C. in another tank, immerse the billet for 30 minutes, and then add acetic acid with a concentration of 0.1% in another tank. A steel piece was placed in an aqueous solution containing and washed by moving it up and down. It was removed from the tank, drained, placed in a hot air dryer at 67°C for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental example A4-1] New NMT treatment of 64Ti alloy (reference example)
A number of 18mm x 45mm x 1.5mm rectangular pieces were machined from 64Ti alloy. An aqueous solution containing 10.0% of the degreasing agent for aluminum "NA-6" was heated to 60° C. in a bath, and the alloy flakes were immersed for 5 minutes and then washed with tap water. Next, an aqueous solution containing 5% acidic ammonium fluoride at 65° C. was prepared in another bath, and the alloy flakes were immersed in this solution for 3 minutes and washed with water. Next, an aqueous solution containing 1% acidic ammonium fluoride and 10.0% sulfuric acid at 65° C. was prepared in another tank, and the steel slabs were immersed in this solution for 6 minutes and washed with water. Next, a 3% nitric acid aqueous solution adjusted to 40° C. was prepared in another bath, and the alloy flakes were immersed for 3 minutes and washed with water. Next, an aqueous solution containing 2.0% concentration of potassium permanganate and 3.0% concentration of caustic potassium at 70° C. was prepared in another tank, and the alloy flakes were immersed in this for 30 minutes and washed with water. Next, an aqueous solution containing sodium chlorite with a concentration of 5.0% and caustic soda with a concentration of 10.0% at 55° C. was prepared in another tank, and the steel slab was immersed in this solution for 20 minutes and then immersed. washed with water. This was placed in a warm air dryer set at 80° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A4-2] SNMT of 64Ti alloy
A number of 18mm x 45mm x 1.5mm rectangular pieces were machined from 64Ti alloy. An aqueous solution containing 10.0% of the degreasing agent for aluminum "NA-6" was heated to 60° C. in a bath, and the alloy flakes were immersed for 5 minutes and then washed with tap water. Next, an aqueous solution containing 5.0% acidic ammonium fluoride at 65° C. was prepared in another bath, and the alloy flakes were immersed in this solution for 5 minutes and then washed with water. Next, a 3.0% nitric acid aqueous solution at 40° C. was prepared in another bath, and the alloy pieces were immersed in the solution for 3 minutes and then washed with water. Next, an aqueous solution containing 2% potassium permanganate and 3% caustic potassium at 70° C. was prepared in another tank, and the alloy flakes were immersed in this for 30 minutes and then washed with water. Next, an aqueous solution containing 5% sodium chlorite and 10% caustic soda at 55° C. was prepared in another tank, and the steel slabs were immersed in this solution for 10 minutes and then washed with water. Next, it was immersed for 7 minutes in a water washing bath in which an ultrasonic oscillation end was set and washed with water. Next, in another tank, a triethanolamine aqueous solution having a concentration of 0.2% at 40° C. was prepared, the steel piece was immersed for 60 minutes, and then the prepared triethanolamine was added to 25 PPM in another tank. The steel billet was placed in the ultra-diluted water containing the steel and moved up and down for washing. It was taken out of the tank, drained, placed in a warm air dryer set at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental Example A4-3] SNMT2 treatment of 64Ti alloy A number of 18mm x 45mm x 1.5mm rectangular pieces were machined from 64Ti alloy. An aqueous solution containing 10% of the degreasing agent for aluminum "NA-6" was heated to 60° C. in a bath, and the alloy flakes were immersed for 5 minutes and then washed with tap water. Next, an aqueous solution containing 5.0% acidic ammonium fluoride at 65° C. was prepared in another bath, and the alloy flakes were immersed in this solution for 5 minutes and washed with water. Next, a 3.0% concentration nitric acid aqueous solution at 40° C. was prepared in another tank, and the alloy flakes were immersed for 3 minutes and washed with water. Next, an aqueous solution containing 2.0% concentration of potassium permanganate and 3.0% concentration of caustic potassium at 70° C. was prepared in another tank, and the alloy flakes were immersed in this for 30 minutes and washed with water. Next, an aqueous solution containing sodium chlorite with a concentration of 5.0% and caustic soda with a concentration of 10.0% at 55° C. was prepared in another tank, and the steel slab was immersed in this solution for 10 minutes and then immersed. washed with water. Next, it was immersed for 7 minutes in a water washing bath in which an ultrasonic oscillation end was set and washed with water. Next, prepare an aqueous solution of EDTA (4Na) with a concentration of 0.4% at 40° C. in another tank, immerse the steel billet for 10 minutes, and then transfer the prepared 0.1 % concentration aqueous solution of acetic acid and washed by moving it up and down. It was removed from the tank, drained, placed in a hot air dryer at 67°C for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental example A5-1] NMT8 treatment of A6061Al alloy (reference example)
A number of 18 mm x 45 mm x 1.5 mm rectangular pieces were machined from a 1.5 mm thick A6061 Al alloy plate. An aqueous solution containing 10.0% of the degreasing agent for aluminum “NA-6” was heated to 60° C. in a bath, and the Al alloy piece was immersed for 5 minutes and then washed with tap water. Next, a 10.0% aqueous solution of caustic soda at 40° C. was prepared in another tank, and the alloy flakes were immersed for 1 minute and washed with water. Next, an aqueous solution containing 5.0% hydrochloric acid and 1.0% hydrated aluminum chloride at 40° C. was prepared in another bath, and the alloy flakes were immersed for 1 minute and then washed with water. Next, an aqueous solution containing 10.0% sulfuric acid and 2.0% acidic ammonium fluoride at 40° C. was prepared in another bath, and the alloy flakes were immersed in this solution for 1 minute and then washed with water. Next, a 1.5% caustic soda aqueous solution adjusted to 40° C. was prepared in another tank, and the alloy flakes were immersed for 2 minutes and then washed with water. Next, a 3.0% concentration nitric acid aqueous solution at 40° C. was prepared in another bath, and the alloy pieces were immersed in the solution for 1.5 minutes and then washed with water. Next, an aqueous solution of hydrazine hydrate having a concentration of 3.5% at 60° C. was prepared in another tank, and the alloy flakes were immersed in this for 1 minute. Next, an aqueous solution of hydrazine hydrate having a concentration of 0.5% at 33° C. was prepared in another tank, and the alloy flakes were immersed in this for 4.5 minutes and washed with water. Next, a 1.0% hydrogen peroxide solution was prepared in another tank, and the alloy flakes were immersed for 1 minute and then washed with water. Next, an aqueous triethanolamine solution having a concentration of 0.2% was prepared, and the alloy flakes were immersed in the solution for 15 minutes and washed with water. The obtained alloy flakes were placed in a hot air dryer set at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental example A5-2] SNMT treatment of A6061Al alloy (reference example)
90% or more of the processing method of this Al alloy piece is the same as the NMT8 processing method. That is, the parts concerned with shaping the surface are substantially identical. That is, after the A6061Al alloy piece of 18 mm × 45 mm × 1.5 mm was produced, the degreasing process and the final chemical etching process were completed, that is, the chemically adsorbed hydrazine hydrate was immersed in a thin hydrogen peroxide solution. , completely decomposing the chemisorbed hydrazine molecules and then washing with water are exactly the same as other SNMT treatments. Therefore, it is described after that. That is, after washing with water, a triethanolamine aqueous solution having a concentration of 0.2% is prepared, the alloy piece is immersed for 15 minutes, and then washed with water. The obtained alloy flakes were dried in a hot air dryer set at 67° C. for 15 minutes, wrapped in aluminum foil and stored.

[Experimental example A5-3] SNMT treatment 2 of A6061Al alloy (reference example)
The processing method of this Al alloy piece is almost the same as the SNMT processing method, but the amine compound is a processing method using an EDTA derivative instead of triethanolamine, and the same SNMT2 processing method as described above is used. Therefore, from the degreasing step to the final chemical etching step, that is, the step of immersing the chemically adsorbed hydrazine hydrate in a dilute hydrogen peroxide solution to completely decompose the hydrazine molecules, and then washing with water. are the same. Therefore, it is described after that. That is, after washing with water, an EDTA aqueous solution having a concentration of 0.2% was prepared at 55° C., the alloy flakes were immersed for 15 minutes, and then washed with water. It was placed in a warm air dryer set at 67° C. for 15 minutes to dry, wrapped in aluminum foil and stored.

[Experimental example B] Preparation of injection-bonded product and measurement of bonding force [Experimental example B1] Shear bond strength of injection-bonded product: When using polyamide resin Various surface-treated metal pieces obtained in Experimental examples A1 to A4 were injection molded. It was inserted into a mold, and the above-described polyamide resin "CM3506G50" was injected for injection joining to obtain an injection-jointed product as a test piece shown in FIG. The injection temperature at this time was 300°C, and the mold temperature was 140°C. The obtained injection-bonded product was annealed by placing it in a hot air dryer at 170° C. for 1 hour. Table 1 shows the shear bond strength of the obtained test pieces. The method for measuring the shear bond strength is the result of putting the test piece of the test piece shown in FIG. 1 in accordance with ISO 19095 in the auxiliary jig shown in FIG. Average value.

表１に記載したのはＳＰＣＣ、ＳＵＳ４３０、ＳＵＳ３０４、及び、６４Ｔｉ合金に対して、最も優れていると判断した新ＮＭＴ型の処理品とＳＮＭＴ処理をした金属片使用の射出接合物の試験結果（せん断接合強度）を示したものである。表中のせん断接合強度は、３個の平均値を示したものであり、高い接合強度は表示値より何れも高い。ただ、新ＮＭＴ処理品は明らかにＳＮＭＴ処理品より劣る。更に言えば、トリエタノールアミンを使用したＳＮＭＴは、表１に示したように、ここで行った全非アルミ金属に対して接合強度を高くすることに成功した。更に、吸着物の耐熱性を高めようとして、新たに採用したＥＤＴＡ・４Ｎａは、そう単純な結果を示さず、「ＳＮＭＴ２」の表示で示したように、６４Ｔｉ合金だけが最高の結果を生んだだけで、他に対しては効果なく、特にＳＰＣＣに関しては酷い結果を示した。

Table 1 shows the test results of injection-bonded products using the new NMT-type treated products and SNMT-treated metal pieces that were judged to be the best for SPCC, SUS430, SUS304, and 64Ti alloys ( Shear bond strength). The shear bonding strength in the table shows the average value of three pieces, and the high bonding strength is higher than the indicated value. However, the new NMT treated product is clearly inferior to the SNMT treated product. Furthermore, SNMT using triethanolamine, as shown in Table 1, was successful in increasing bond strength to all non-aluminum metals performed here. Furthermore, EDTA 4Na, which was newly adopted to increase the heat resistance of the adsorbate, did not show such a simple result. However, it had no effect on others, and showed terrible results especially with respect to SPCC.

[Experimental example B2] Shear bond strength of injection-bonded product: when using PEEK-based resin As injection resins, PEEK "90G (marketed by Victrex Japan Co., Ltd. (Headquarters: Tokyo, Japan))" and PEI "ULTEM9075 (SHPP Japan) (headquarters: Tokyo, Japan)" was dry-blended at a weight ratio of 95:5. Various SNMT-treated metal pieces obtained in Experimental Examples A1-2, A2-2, and A3-2, and SNMT2-treated pieces obtained in A1-3, A2-3, A3-3, and A4-3 Various metal pieces were inserted into an injection mold, and the above PEEK-based resin was injected as an injection resin to obtain an injection-bonded product of the test piece shown in FIG. At this time, the injection temperature was 360°C and the mold temperature was 180°C. The obtained injection-bonded product was annealed by placing it in a hot air dryer set to 170° C. for 1 hour. Table 2 shows the shear bond strength of the obtained injection-bonded product.

As can be seen from the results in Table 2, the treated products using triethanolamine (SNMT treated products) are not good at all when the injection resin is changed to PEEK resin. This is thought to be because, as mentioned above, the mold temperature and the resin injection temperature for making an injection-bonded article using polyamide resin were raised by 40° C. or more, and the adsorbed substances were desorbed at this high temperature in the case of triethanolamine. Therefore, we tried heavier EDTA and EDTA derivatives, but EDTA (4H), which is almost insoluble in water, was tried to be adsorbed at a liquid temperature of 70°C, but as a result, the injection joining force could not be increased. , and EDTA (2Na) were also soluble in water, but did not give results either. Therefore, "SNMT2" uses EDTA (3Na), which is a complete salt but has sufficient water solubility. The result was that only 64 Ti gave an extraordinarily high effect, giving a maximum shear bond strength of 64 MPa. The result of this SNMT2 is abnormal as shown in Table 2, and although it is not good except for 64Ti, SUS304 has a figure of 20 MPa, and it is a surprisingly bad result for SPCC, which is a ferritic stainless steel and general steel material. Met. Although it is expected that the cause of this strange result is the three-dimensional shape of the amine compound used, that is, the EDTA.4Na salt, the correct theoretical elucidation has not been made.

However, it has been mentioned that non-aluminum metals excluding copper, in addition to Al alloys, exhibited high injection bondability when using the above-described polyamide resin "CM3506G50" as the injection resin. Therefore, according to the present invention, a high-performance injection joining technique between metal and resin involving all-crystalline thermoplastic resins other than PEEK and PAEK resins has been established. In addition, in the injection joining technology using PEEK or PAEK resins, which are super heat-resistant resins, there are all-Al alloys and 64Ti alloys as metal alloys capable of exhibiting a shear joint strength of 50 to 65 MPa. clarified. That is, in the production of composites made of metals and resins for parts and members of mobile machines, mainly automobiles, the combination of (general steel, stainless steel, Ti alloy, Al alloy) x (polyamide resin) and (Ti alloy) A combination of x (PEEK, PAEK resin) satisfies the highest specifications required for the present composite.

[Experimental example B3] Shear bond strength of injection-bonded product: when PPS resin is used This example discloses the non-aluminum metal materials and polyamide resins shown in Tables 1 and 2, and the PEEK/PEI mixed resin. There are not only successful and unsuccessful cases of injection joints with I would like to show the usefulness of the new injection joining called "new type NMT" that was newly developed. The latest new NMT-treated non-aluminum metal material and the above PPS resin "SGX120" injection-bonded product (test piece shown in Fig. 1) has a shear bond strength of about 40 MPa, and the injection-bonded product already using "SGX120" However, in order to confirm that the "SNMT" disclosed this time is always a superior technology to the new NMT, we also disclose the test results for injection-bonded products using PPS-based resin. Keep

The SNMT-treated metal pieces obtained in Experimental Examples A1-2, A2-2, A3-2, and A4-2 were inserted into an injection mold, and the PPS resin "SGX120" was injected as the injection resin, An injection-bonded product of the test piece shown in FIG. 1 was obtained. The injection temperature at this time was 300°C, and the mold temperature was 140°C. The obtained injection-bonded product was annealed by placing it in a hot air dryer set to 170° C. for 1 hour. Table 3 shows the shear bond strength of the obtained injection-bonded products. According to ISO 19095, the test piece shown in FIG. 1 was placed in the auxiliary jig shown in FIG.

As is clear from Table 3, the integrated product of the test piece shown in FIG. All shear bond strength values of 41 to 42 MPa are sufficiently high. In short, it showed 41 to 42 MPa, which is considered to be the upper limit of the shear bonding strength of the injection-bonded product using the above "SGX120". As the melting point of the heat-resistant crystalline resin, a numerical value set by the present inventors was set to 200° C. or higher. In this sense, among the thermoplastic resins used in the manufacture of various machines, the resin group with a melting point of 200°C or higher is considered to be around 290°C for PPS, around 210°C for PA66, and around 340°C for PEEK. is a specific resin material type used by In short, the "SNMT" used in the present invention is currently sufficiently effective for PPS resins and PA66 resins for non-aluminum metals. It can be seen that it can be used as an injection joining technique for combinations of crystalline thermoplastic resins above 200°C.

Claims (8)

An integrated composite of metal and resin, in which a metal material having a surface-treated surface and the surface and a crystalline thermoplastic resin composition are joined by an injection molding operation,
The metal material is one selected from steel, titanium alloy, and stainless steel, and the surface is chemically treated,
On the surface after the chemical conversion treatment, a rough surface with a period of 20 to 50 μm is formed when observed with an electron microscope at a magnification of 1000, and a fine uneven surface with a period of 0.5 to 5 μm is formed on the rough surface when observed with an electron microscope at a magnification of 10,000. And, it has a fine irregularity period with an ultrafine uneven surface with a period of 10 to 100 nm when observed with an electron microscope at 100,000 times,
The crystalline thermoplastic resin composition has heat resistance of a melting point of 200° C. or higher,
The joint of the integrated composite obtained by integrating the crystalline thermoplastic resin composition by the injection molding with the water-soluble high molecular weight amine compound adsorbed on the surface has a shear joint strength of 39 MPa. An integrated composite of a metal and a resin, characterized by having the above. An integrated composite of the metal and resin according to claim 1,
The integrated composite of metal and resin, wherein the high-molecular-weight amine-based compound is triethanolamine or an EDTA derivative. The integrated composite of metal and resin according to claim 1 or 2,
The integrated composite of metal and resin, wherein the steel material is general steel, and the stainless steel is special steel including austenitic stainless steel and ferritic stainless steel. An integrated composite of metal and resin according to claim 1 selected from claims 1 to 3,
The crystalline thermoplastic resin composition is a resin composition containing 70% by weight or more of polyphenylene sulfide, 30% by weight or less of modified polyolefin resin, and 5% by weight or less of a third component resin in the resin content, and A composition containing 15 to 25% by weight of the total fiber,
An integrated composite of metal and resin, characterized in that the shear bonding strength is 39 to 43 MPa. An integrated composite of metal and resin according to claim 1 selected from claims 1 to 3,
The crystalline thermoplastic resin composition is a resin composition containing 10% by weight or more of semi-aromatic polyamide and 90% by weight or less of aliphatic polyamide in the resin content, and 25% by weight or more of the total short glass fiber. is a composition comprising
The integrated composite of metal and resin, characterized in that the shear bonding strength is 45 to 65 MPa. An integrated composite of metal and resin according to claim 1 selected from claims 1 to 3,
The crystalline thermoplastic resin composition is a resin composition containing 80 to 100% by weight of polyetheretherketone and 0 to 20% by weight of polyetherimide in the resin content,
The integrated composite of metal and resin, wherein the shear bonding strength value is 50 MPa or more. A method for manufacturing a metal-resin integrated composite according to one of claims 1 to 6,
After the chemical conversion treatment of the surface,
The rough surface, the fine uneven surface, and the ultra-fine uneven surface are formed by sequentially immersing the metal material in an acid-base aqueous solution or an oxidizing-reductive aqueous solution, or
First, after forming the rough surface and the fine uneven surface by physical roughening treatment by shot blasting, after forming the ultrafine uneven surface by chemical treatment,
The surface is immersed in a triethanolamine aqueous solution with a concentration of 0.1-0.5% for 1-60 minutes, further washed with pure water or an ultra-diluted triethanolamine aqueous solution with a concentration of 5-50 PPM, and then dried. A method for manufacturing an integrated composite of a metal and a resin, characterized in that the metal material for injection joining is obtained by heating the metal material. A method for manufacturing the integrated composite of metal and resin according to one of claims 1 to 6,
After the chemical conversion treatment of the surface,
The rough surface, the fine uneven surface, and the ultra-fine uneven surface are formed by sequentially immersing the metal material in an acid-base aqueous solution or an oxidizing-reductive aqueous solution, or
First, after forming the rough surface and the fine uneven surface by physical roughening treatment by shot blasting, after forming the ultrafine uneven surface by chemical treatment,
The surface is immersed in an aqueous solution of 4Na salt of EDTA with a concentration of 0.1 to 0.5% for 1 to 60 minutes, and then pure water or an acetic acid aqueous solution with a concentration of 0.05 to 0.5%, or A method for producing an integrated composite of a metal and a resin, comprising: washing with an aqueous solution of 4Na of ultra-diluted EDTA having a concentration of 50 PPM, and then drying the metal material for injection joining.

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