JP2009061648A - Joint composite material including metal alloy and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a joint composite material in which various kinds of adherends are solidly united to a metallic component having a specified ultra-fine rugged surface formed on the surface of the metallic component with a phenol resin type adhesive. <P>SOLUTION: In the joint composite material including metal alloy, the metal part which has roughness of micron order formed by chemical etching, further, has a shape coated with the ultrafine rugged surface in the rough surface and has the surface as the thin layer of metal oxide or metal phosphate, and the adherend of friction material or the like are stuck to each other with one-component thermosetting resin adhesive such as phenol resin type adhesive, are united by hardening and, thereby, are solidly joined. The stuck composite material is effectively joined by repeating pressure reduction and pressure rising while being housed in a closed container. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a manufacturing technique for producing a mobile machine, an electric device, a medical device, a general machine, and other devices. The present invention also relates to a manufacturing method for producing a new basic part, and more specifically, a metal part and a metal part or a thermosetting resin molded product such as a phenol resin and a metal part are bonded with a phenol resin. The present invention relates to an adhesive composite that is firmly integrated using an agent and a manufacturing technique thereof.

  Technology for integrating metal and resin is required by various parts and materials manufacturing industries such as automobiles, home appliances, and industrial equipment, and many adhesives have been developed for this purpose. Among these are very good adhesives. For example, an adhesive exhibiting a function at room temperature or by heating is used for joining to integrate a metal and a synthetic resin, and this method is a general bonding technique at present.

  On the other hand, bonding methods that do not use an adhesive have also been studied. An example is a method in which magnesium, aluminum, light metals such as alloys thereof, and iron alloys such as stainless steel are integrated with a high-strength thermoplastic engineering resin without an adhesive. For example, as a method of joining simultaneously by injection or the like (hereinafter referred to as “injection joining”), a polybutylene terephthalate resin (hereinafter referred to as “PBT”) or a polyphenylene sulfide resin (hereinafter referred to as “PPS”) which is a thermoplastic resin for an aluminum alloy. ”) Has been developed (for example, see Patent Documents 1 and 2). In addition, it has been demonstrated that magnesium alloy, copper alloy, titanium alloy, stainless steel, and the like are injection-bonded using the same type of resin (see Patent Documents 3, 4, 5, and 6).

  All of these inventions are by the present inventors, but these are based on a relatively simple joining theory. This is why the joining theory was named the “NMT” (short for Nano molding technology) theory hypothesis, and the injection theory of all metal alloys was named the “new NMT” theory hypothesis. For example, the “NMT” theory can be applied to aluminum alloys. As one of the inventors of the present invention who proposes a hypothesis of the “new NMT” theory that can be used in a broader sense, Ando advocates the following. That is, in order to obtain injection bonding with strong bonding strength, conditions are required on both the metal alloy side and the injection resin side, and first, the following conditions are required on the metal side. That is, three conditions are necessary on the metal alloy side.

  The first condition is that the unevenness of the unevenness of 1 to 10 μm period is a rough rough surface up to about half of the period, that is, 0.5 to 5 μm by the chemical etching method. However, in practice, it is difficult to accurately cover the entire surface with the rough surface, and it is difficult for a chemical reaction that is not constant. Specifically, when viewed with a roughness meter, it is irregular in the range of 0.2 to 20 μm. Can draw a roughness curve with irregularities with a long period and a maximum height difference in the range of 0.2-5 μm, or by scanning analysis with the latest scanning probe microscope, according to JIS standard (JISB0601: 2001) As long as the average surface, that is, the roughness surface having a peak-valley average interval (RSm) of 0.8 to 10 μm and a maximum roughness height (Rz) of 0.2 to 5 μm, the roughness conditions shown above are substantially I think that it was satisfied.

  The inventors of the present invention called the “surface having a roughness on the order of microns” as an easy-to-understand definition because the ideal rough surface irregularity period is approximately 1 to 10 μm as described above. Furthermore, the second condition is that a fine uneven surface having a period of 10 nm or more, preferably about 50 nm, is formed on the inner wall surface of the concave portion having the above-mentioned roughness by adding a fine etching treatment, an oxidation treatment, a chemical conversion treatment or the like. Furthermore, the third condition is that the complex surface of the metal alloy is formed of a ceramic material, specifically, a metal oxide layer that is thicker than a natural oxide layer in a metal alloy type that is originally corrosion resistant. A metal alloy type (for example, a magnesium alloy or a general steel material) originally having a problem with corrosion resistance is a thin layer of a metal oxide or a metal phosphorus oxide generated by chemical conversion treatment.

  On the other hand, under the conditions on the resin side, it is possible to use a hard, highly crystalline thermoplastic resin that has a reduced crystallization rate during rapid cooling, such as by compounding another polymer suitable for these. Actually, a resin composition compounded with another polymer suitable for PBT or PPS, which is a crystalline hard resin, and glass fiber can be used. These can be used for injection joining with a general injection molding machine or injection mold, and this process will be described according to the hypothesis of the above-mentioned “new NMT” theory that the present inventors have named.

  The injected molten resin is introduced into a mold having a temperature of about 150 ° C. lower than the melting point, but is cooled in this flow path and is considered to be at a temperature lower than the melting point. That is, when the molten crystalline resin is rapidly cooled, even if the melting point is lower than the melting point, crystals are formed in zero hours and do not change to a solid. In short, the melted state and the supercooled state are present for a very short time while being below the melting point.

  As mentioned above, PBT and PPS with special compounds think that this supercooling time can be made a little longer, and before using this, a large increase in viscosity due to the formation of a large amount of microcrystals occurs on the order of microns. The microcrystals can penetrate into the recesses on the metal surface. Since it continues to cool after intrusion, the number of microcrystals increases rapidly with this, and the viscosity increases rapidly. However, whether or not the resin can reach the bottom of the recess depends on the size and shape of the recess.

  In the experiment results of the present inventors, the metal type is not selected, and a recess having a diameter of 1 to 10 μm, or a recess having a roughness of 1 to 10 μm, and the depth or height difference is up to about half of the period, It seemed to invade quite far. Furthermore, if the inner wall surface of the recess is rough, as seen from the second condition described above, a part of the resin also enters the gaps between the fine irregularities, and as a result, the pulling force on the resin side It seems that even if is added, it becomes difficult to get stuck. If this rough surface is a metal oxide as in the third condition, the hardness is high and a hook-like catch becomes effective.

Bonding itself is a problem of the resin component and the surface of the metal alloy. However, if reinforcing fiber or inorganic filler is contained in the resin composition, the linear expansion coefficient of the entire resin can be made close to that of the metal alloy, so Easy to maintain. In accordance with such a hypothesis, for example, a magnesium alloy, copper alloy, titanium alloy, stainless steel, etc. obtained by injection-bonding PBT or PPS resin with a shear breaking force of 200 to 300 Kgf / cm ² (about 20 to 30 N / mm ² = 20 to 30 MPa) or more and a tensile breaking force of 300 to 400 Kgf / cm ² (30 to 40 MPa) or more, and it has been confirmed that a strong integrated product is obtained.

  The present inventors believe that the “new NMT” theoretical hypothesis has been proved by the injection joining of many metal alloys, but this hypothesis is based on the fundamental part of polymer physics (polymer crystal formation). Inferences related to kinetics are fundamental, and verification by a large number of chemists and scientists is essential. For example, although the crystalline resin melted at the time of rapid cooling is independently discussed, the crystallization kinetics has not been discussed in the conventional polymer physics as to “whether the crystallization rate is really lowered”. The present inventors believe that this reasoning is correct, but it has not been verified from the front.

  That is, this injection joining is a high-speed reaction under high temperature and high pressure and cannot be directly measured. Moreover, the hypothesis is explained by a completely physical anchor effect theory about joining, and deviates slightly from conventional common sense. As far as the present inventors know, it seems that there are more descriptions about chemical factors in books edited by experts in current bonding.

  The present inventors stopped the direct confirmation experiment leading to the proof of the hypothesis from the experimental difficulty, and examined another method. That is, regarding the adhesive bonding, the “new NMT” theoretical hypothesis can be applied, and it was decided whether or not the high-performance adhesion phenomenon based on the similar theory could be demonstrated. That is, first, a commercially available general-purpose one-component epoxy adhesive was used to devise only the surface condition of the adherend, and an attempt was made to find out whether an unprecedented joining system could be found.

  With regard to adhesive bonding, effective technology has already been developed, and in particular, the use of such advanced technology is used in aircraft assembly. It is a technology that provides a surface treatment that gives corrosion resistance and subtle unevenness to an aluminum alloy and bonds it using a high-performance adhesive. However, when examining the adhesion method using a metal as an adherend in the conventional technology, the metal surface treatment methods, such as phosphorylation, chromateization, anodization, etc., which were developed more than 40 years ago, are still normal treatments. It was used as a law and the development seemed to be stagnant in recent years.

  On the other hand, the development of the adhesive itself has not appeared innovative since the mass production of instant adhesives began several decades ago and the second generation acrylic adhesives appeared brilliantly. In addition, with regard to adhesion theory, the trend of recent academic societies is that materials such as commercially available books and papers that contain both chemical explanations and physical explanations are not clear but are expected to develop further. The current situation is poor.

  The present inventors have made full use of an electron microscope having a resolution of several nanometers, and have discussed hypotheses regarding the above-mentioned “NMT” and “new NMT” injection joining while viewing high-resolution electron micrographs. As a result, the hypothesis based entirely on the anchor effect has been proposed. Therefore, it was anticipated that a new phenomenon would occur if it was carried out with an emphasis on physical aspects in the bonding theory of adhesive bonding.

  The procedure established in advance by the inventors regarding the experimental method of adhesive bonding is as follows. That is, a metal alloy having the same surface as that used in the “New NMT” injection joining experiment (a metal alloy satisfying the above three conditions) is first prepared, and a liquid one-part epoxy adhesive is applied to the metal piece. In this method, the adhesive is made to conform to the fine irregularities on the surface of the metal alloy by placing it under vacuum and returning to normal pressure, and then bonding and heating to cure.

  In such a case, since the epoxy adhesive having a certain viscosity can enter the large concave portion due to the roughness of the micron order on the surface of the metal alloy (the concave and convex portion according to the first condition described above) due to the liquid, the epoxy adhesive is thereafter It will harden | cure in this recessed part by heating. Actually, the inner wall surface of the recess is a fine uneven surface (the second condition described above), and the fine uneven surface is also a ceramic-like high hardness (the third condition described above). Then, the solidified epoxy resin is difficult to come out by being gripped by fine irregularities such as spikes.

  The present inventors have shown that this is not a hypothesis but a fact by demonstrating this in the same way as the hypothesis of the above-mentioned “NMT” and “new NMT” theory. In fact, these were first demonstrated by the present inventors in aluminum alloys, then in magnesium alloys, copper alloys, titanium alloys, stainless steels, and general steel materials (see Patent Documents 7, 8, 9, 10, 11, 12). ). By controlling the state of the surface of the adherend metal, various metal alloys could be bonded with unprecedented strength.

One idea of the present inventor, Ando, named the above-mentioned idea regarding adhesive bonding as “NAT (abbreviation of Nano adhesion technology)” and made it a theoretical hypothesis. According to “NAT”, for example, A7075 aluminum alloy pieces are surface-treated, and the A7075 pieces are subjected to 700 kgf / cm ² (about 70 N / mm ^{2) in} both shear and tension by using a commercially available general-purpose epoxy adhesive. == 70 MPa) A breaking force with an intense force of not less than 70 MPa was actually measured. The adhesives between the other metal alloys also had a strong breaking force of 50 Mpa (500 Kgf / cm ² ) or more in both shear and tension, except for soft pure copper-based copper alloys.

  In this development, the structure of the surface of the metal alloy that is considered to be the most ideal, that is, an ideal image on the side of the metal alloy determined by “NAT” was assumed as shown in FIG. In FIG. 4, the metal alloy side is 30, and the surface is a fine uneven surface formed in a plurality of groups with a width of 2 to 3 μm in diameter (C) and repeatedly formed as a whole. The depth has a concave portion whose diameter is about half of the diameter, and the inner wall surface is covered with fine irregularities having a period (A) of 50 nm in length. Moreover, the surface layer 31 is a ceramic layer having a thickness (B) of 10 nm or more, that is, a thin layer of metal oxide or metal phosphate. In the figure, 32 is a cured epoxy adhesive layer.

  The “NAT” hypothesis advocated by Ando in the patent groups of Patent Documents 7 to 12 is based on the use of a one-component epoxy adhesive. This is because it is good that the one-component epoxy adhesive is basically a solvent-free type and that the active adhesive component is not gelled at the time of application. In the case of a liquid adhesive, the adhesive penetrates into the micron-order concave portion at a pressure of about 1 atm, and also enters into the ultra-fine concave portion on the fine uneven surface of the order of several tens of nm on the inner wall surface of the concave portion. This is because there may be some intrusion.

  If the adhesive used is already gelled before it is applied to a metal alloy or the like, the molecular diameter of the active ingredient in the adhesive is increasing, making it difficult to enter the ultrafine recesses. . In that sense, two-component adhesives and resins, such as two-component epoxy adhesives and two-component unsaturated polyester cured resins, are subject to the condition that the technical features of "NAT" cannot be fully utilized. It was not included. Usually, in a two-component thermosetting adhesive, gelation starts at the moment when the main liquid and the hardener liquid are mixed. Immediately after mixing, even if it is a liquid material that cannot be visually judged and the increase in viscosity is not felt by finger touch, the molecular weight expansion due to gelation has begun. Absent.

  When a two-component adhesive is actually used, a comparison between a “NAT” -treated metal piece and a metal piece that has been pre-treated before bonding by a conventional method, the conventional metal piece is always “NAT”. "It shows a lower adhesive strength than the product, but in addition to that, it seems to be a problem that the adhesive strength varies greatly from experiment to experiment. Probably, the change in adhesive force due to the progress of gelation after mixing of the curing agent appears as poor reproducibility.

  In addition, in the original “NAT”, a one-component adhesive diluted with a solvent was not an adhesive to be used. That is, there is a phenol resin adhesive as such a one-component adhesive, and it is usually diluted twice with a solvent. If this is used to maximize the characteristics of "NAT", the timing of the solvent in the adhesive should be volatilized and the adhesive will become highly viscous even if it is volatilized after application. However, there is a point that is not known unless detailed experiments are performed such as whether the ultrafine recesses on the alloy can be firmly infiltrated.

  However, the phenol resin adhesive has a feature that the heat resistance is superior to the epoxy adhesive. Therefore, this time, we have developed a NAT for phenolic resin adhesives. Since the curing mechanism is in the dehydration condensation reaction, the specific method of adhesion itself is not as easy as epoxy. However, if an adhesive force close to that of an epoxy adhesive is shown by adding some ingenuity, the cured phenol resin itself has excellent water resistance in addition to heat resistance, and therefore a new use of NAT can be expected.

  The present invention has been developed by studying various problems as described above, and achieves the following objects. An object of the present invention is to provide an adhesive composite including a metal part which is improved in adhesiveness and excellent in heat resistance and water resistance by using a one-component phenolic resin adhesive, and a manufacturing technique thereof. The phenolic resin itself is used for friction materials (for example, brake pads), abrasives (grinding stones), molds (shell molds), building materials (heat-resistant foam, fire-resistant plates), resin parts (ash trays, other heat-resistant resin molded products). The A phenol-based adhesive is used when bonding these phenolic resin products and metal parts.

WO 03/064150 A1 WO 2004/041532 A1 Publication Japanese Patent Application No. 2006-329410 Japanese Patent Application No. 2006-281196 Japanese Patent Application No. 2006-345273 Japanese Patent Application No. 2006-354636 Japanese Patent Application No. 2007-62376 Japanese Patent Application No. 2007-106454 Japanese Patent Application No. 2007-100727 Japanese Patent Application No. 2007-106455 Japanese Patent Application No. 2007-114576 Japanese Patent Application No. 2007-140072

The present invention takes the following means in order to achieve the object.
The adhesive composite containing the metal alloy of the present invention 1
It has a micron-order roughness by chemical etching, and its surface is covered with a fine irregular shape with an irregular period of 5 to 500 nm, and its surface is made of metal oxide or metal phosphate. Metal parts that are thin layers;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 2
It has a micron-order roughness by chemical etching, and its surface has a shape covered with an ultrafine uneven surface that is a recess or protrusion having a diameter of 10 to 100 nm and an equivalent depth or height, and A metal part made of an aluminum alloy having a thin aluminum oxide layer having a thickness of 2 nm or more whose surface does not contain sodium ions;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 3
The surface has a roughness of micron order by chemical etching, and the surface thereof is covered with an ultrafine uneven surface in a form in which rods having a diameter of 5 to 20 nm and a length of 20 to 200 nm are complexed, and A metal part made of magnesium alloy whose surface has a thin layer of manganese oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 4
There is a roughness on the order of microns by chemical etching, and the surface is ultrafine in the shape of irregularly stacked spheres with a diameter of 5 to 20 nm and 10 to 30 nm long rod-shaped projections with a diameter of 80 to 100 nm. A metal part made of magnesium alloy having a shape covered with an uneven surface and having a thin layer of manganese oxide on its surface;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 5
It has a micron-order roughness due to chemical etching, and its surface is covered with an ultra-fine irregular surface formed by stacking 20 to 40 nm particle size objects and indefinite polygonal shapes, and the surface is Metal parts made of magnesium alloy having a thin layer of manganese oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 6
Ultra-fine irregularities with roughness on the order of microns by chemical etching, and the surface has hole openings or recesses with an average of 10 to 150 nm in diameter or major axis and minor axis at irregular intervals of 30 to 300 nm. A metal part made of a copper alloy whose surface is almost entirely covered with the shape and whose surface is mainly a thin layer of cupric oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 7
It has a micron-order roughness by chemical etching, and its surface is an ultrafine uneven shape in which convex portions having an average diameter or major axis and minor axis of 10 to 200 nm are mixed, and the surface is Metal parts made of copper alloy, which is mainly a thin layer of cupric oxide,
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 8
Ultra-fine irregularities with a roughness of micron order by chemical etching, and the surface is formed by continuous fusion of particle diameters or indefinite polygonal shapes with an average diameter or major axis and minor axis of 10 to 150 nm. A metal part made of a copper alloy whose surface is almost entirely covered with the shape and whose surface is mainly a thin layer of cupric oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 9
There is a roughness on the order of microns by chemical etching, and the surface is a super fine uneven shape of a shape in which a particle having a diameter of 10 to 20 nm and an indefinite polygon having a diameter of 50 to 150 nm are mixed and stacked. A metal component made of a copper alloy that is covered and whose surface is a thin layer of cupric oxide mainly;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 10
There is a roughness on the order of microns by chemical etching, and the surface is super fine with a height or width of 10 to 350 nm, and ridges or continuous ridges having a length of 10 nm or more on the entire surface in a cycle of 10 to 350 nm. A metal part made of a titanium alloy having a concavo-convex shape and whose surface is mainly a thin layer of titanium oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 11
By chemical etching, as seen with a scanning probe microscope, there is a roughness with an average interval between peaks and valleys (RSm) of 1 to 10 μm, a maximum roughness height (Rz) of 1 to 5 μm, and the surface has an area of 10 μm square. A metal part of an α-β type titanium alloy having a fine concavo-convex shape in which both a smooth dome-like shape and a dead leaf-like shape are observed, and a surface of which is a metal oxide thin layer mainly containing titanium and aluminum;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 12
It has a micron-order roughness due to chemical etching, and its surface is almost entirely covered with an ultra-fine irregular shape of a particle size 20 to 70 nm in diameter or an indefinite polygonal shape, and its surface. A stainless steel part metal part which is a thin layer of metal oxide,
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 13
It has a roughness of micron order by chemical etching, and its surface is an ultra fine uneven shape with a height of 80 to 150 nm, a depth of 80 to 200 nm, and a width of several hundred to several thousand nm that is infinitely long. A metal part made of steel material, the whole surface of which is covered and whose surface is one kind of thin layer selected from manganese oxide, chromium oxide, and zinc phosphorus oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 14
It has a micron-order roughness due to chemical etching, and its surface is an ultra-fine uneven shape with a height of 80 to 150 nm, a depth of 80 to 500 nm, and a width of several hundred to several thousand nm that is infinitely long. A metal part made of steel material that is almost entirely covered and whose surface is a thin layer of manganese oxide, chromium oxide, or zinc phosphorus oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

The adhesive composite containing the metal alloy of the present invention 15
It has a micron-order roughness due to chemical etching, and its surface is an ultra-fine uneven shape with a height of 50 to 100 nm, a depth of 80 to 200 nm, and a width of several hundred to several thousand nm and an infinite number of steps. A metal part made of steel material that is almost entirely covered and whose surface is one kind of thin layer selected from manganese oxide, chromium oxide, and zinc phosphorus oxide;
An adherend to be bonded to the metal part;
It consists of the adhesive layer which is the hardened | cured material of the 1-component thermosetting type resin adhesive which is apply | coated to the adhesive surface of the said metal component and the said adherend, and adhere | attaches both.

  In the adhesive composite containing the metal alloy of each of the present invention, the one-component thermosetting resin adhesive may be a phenol resin adhesive. Further, according to the present invention, in the adhesive complex including the metal alloy of each of the present invention, the adherend may be a metal part having the same property as the metal part.

  Furthermore, in the adhesive composite containing the metal alloy of each of the present invention according to the present invention, the adherend may be a cured product of a thermosetting resin composition using a thermosetting resin as a matrix. Further, in each of the present inventions, in the present invention, the cured product may be a cured product of a thermosetting resin composition using a phenol resin as a matrix. Further, the present invention is an adhesive composite comprising the metal alloy of each of the present invention, wherein the cured product is a friction obtained by solidifying a phenolic resin as a matrix and including a fiber material and an abrasion-resistant solid powder. It is a material.

The manufacturing method of the adhesive composite containing the metal alloy of the present invention 1
Forming a metal alloy material into a predetermined shape by mechanical processing;
The surface of the shaped metal alloy material is covered with fine irregularities having an irregular period of 5 to 500 nm, and the large irregularities constituted by the fine irregularities are represented by an average interval between peaks and valleys (RSm). A surface treatment step of performing various liquid treatments including chemical etching that gives a roughness of 1 to 10 μm and a maximum roughness height (Rz) of 0.2 to 5 μm;
Forming an adherend to be bonded to the shaped metal alloy material into a predetermined shape;
Applying a one-component thermosetting resin adhesive to the metal alloy material or the adherend;
The process comprises a step of bonding the coated surfaces of the metal alloy material and the adherend, and curing the one-component thermosetting resin adhesive and integrating the two by bonding.

  The manufacturing method of the adhesive composite containing the metal alloy of the present invention 2 is the manufacturing method of the adhesive composite containing the metal alloy of the first invention, wherein the one-component thermosetting resin adhesive is applied after the applying step. A step of storing a metal alloy material or the adherend in a hermetically sealed container and depressurizing and then pressurizing is added.

The manufacturing method of the adhesive composite containing the metal alloy of the present invention 3 is the manufacturing method of the adhesive composite including the metal alloy of the present invention 1 or 2, wherein the one-component thermosetting resin adhesive is a phenol resin-based adhesive. It is an agent.
[Surface observation and confirmation]
The roughness of the surface in the order of microns in the above-described invention is a numerical value analyzed and determined by observation with a scanning probe microscope. In addition, the observation of surface irregularities such as the fine irregularities described above is the shape and numerical value determined by analyzing a photograph with a magnification of 10,000 times, 100,000 times, or the like of an electron microscope. Hereinafter, each means constituting each invention described above will be described in detail for each element constituting the means.

[Metal alloy parts]
The metal alloy parts referred to in the present invention, that is, the metal alloys used as the adherend in the above-mentioned “NAT” are theoretically not limited in particular. All metal species may be used, but what is actually meaningful is a hard and practical metal species or alloy species. That is, mercury is naturally liquid at normal temperature and is not included in the alloy component of the present invention, but soft metal species such as lead are also excluded from the metal species considered by the inventor. Of course, alkali metal species and alkaline earth metal species (except for magnesium) that exist chemically but react actively in the atmosphere are also basically excluded.

  The inventors of the present invention consider that magnesium, aluminum, copper, titanium, and iron are the main alloy types that are substantially useful for “NAT”. Hereinafter, these will be described. However, the “NAT” theory does not limit the metal species, and moreover, it does not limit the metal itself. It is not easy to simultaneously provide the three conditions of making the nonmetal a condition of “NAT”, that is, the roughness, ultra-fine irregular surface, and high hardness surface layer. In short, “NAT” defines only the surface shape and the surface layer hardness and discusses the adhesion by the anchor effect theory, and is not limited to at least the following metal alloy types.

  Patent Document 7 describes an aluminum alloy. Patent Document 8 describes a magnesium alloy. Patent Document 9 describes a copper alloy. Patent Document 10 describes a titanium alloy. Patent Document 11 described stainless steel. Patent Document 12 describes general steel materials. Regarding these metal alloy types arranged from aluminum alloys to general steel materials, the section of [Metal Alloy Parts] in each of these patent documents is also applied to the present invention, and therefore, detailed description thereof is omitted. The individual contents are exactly the same in the present invention.

[Chemical etching of metal alloy materials]
There are various types of corrosion, such as general corrosion, pitting corrosion, and fatigue corrosion, but it is possible to select an appropriate etching agent by selecting a chemical species that causes general corrosion for the metal alloy and performing trial and error. According to literature records (for example, "Chemical Engineering Handbook (edited by Chemical Engineering Association)"), aluminum alloys are basic aqueous solutions, magnesium alloys are acidic aqueous solutions, stainless steel and general steel materials in general are hydrohalic acid such as hydrochloric acid, sulfurous acid, There is a record that the entire surface is corroded by an aqueous solution of sulfuric acid or a salt thereof.

  In addition, copper alloys with strong corrosion resistance are totally corroded by strong oxidizing agents such as hydrogen peroxide, and titanium alloys are specially corroded with special acids such as oxalic acid or hydrofluoric acid. It is often found in books and patent literature. The metal alloys actually sold on the market, such as pure copper-based copper alloys and pure titanium-based titanium alloys, have a purity of 99.9% or more and are difficult to say as alloys. Is included. Most of the materials that are actually used in the world are mixed with a wide variety of other elements in order to obtain characteristic properties, and few pure metal materials are substantially alloys.

  That is, most of the target metals alloyed from pure metals have improved corrosion resistance without degrading the original metal properties. Therefore, in the case of an alloy, the target chemical etching is often not possible even when using acid bases or specific chemical substances applied with reference to the literature as described above. In short, the use of the acid-bases and specific chemicals described above is fundamental, and in practice, the concentration of the acid-base aqueous solution to be used, the liquid temperature, the immersion time, and in some cases, appropriate by trial and error while devising the additive Chemical etching is performed.

  Speaking of chemical etching, Patent Document 7 describes aluminum alloy, Patent Document 8 describes magnesium alloy, Patent Document 9 describes copper alloy, Patent Document 10 describes titanium alloy, Patent Document 11 relates to stainless steel. Description, and Patent Document 12 described general steel materials. For general steel materials from aluminum alloys, it is advisable to check the [Chemical Etching] section of these patent documents. The present invention can be applied in exactly the same manner.

  Therefore, these patent documents should be referred to for details. To explain the points that are generally common as work actually performed, when a metal alloy shaped product is obtained, it is first immersed in an aqueous solution in which a commercial degreasing agent for each metal is dissolved, degreased and washed with water. This step is preferred and should always be performed because it removes most of the machine oil and finger grease deposited in the step of obtaining the metal alloy shape. Then, it is preferably immersed in a thinly diluted acid-base aqueous solution and washed with water.

  This is a process that the present inventors have called pre-acid cleaning and pre-base cleaning, and in the case of a metal species that corrodes with an acid such as general steel, it is immersed in a basic aqueous solution and washed with water, or an aluminum alloy For a metal species that is particularly corrosive in a basic aqueous solution, it is immersed in a dilute acid aqueous solution and washed with water. These are processes in which a solution opposite to the aqueous solution used for chemical etching is attached (adsorbed) to the metal alloy in advance, and the subsequent chemical etching starts without an induction period, so that the reproducibility of the process is remarkably improved. . Therefore, the preliminary acid cleaning and preliminary base cleaning steps are not essential, but are preferably employed in practice.

[Surface hardening treatment, fine etching]
Depending on the type of metal alloy, only the chemical etching described above is performed, and at the same time, nano-order fine etching is also performed. Further, depending on the type of alloy, the natural oxide layer on the surface is thicker than the original, and the curing process has been processed. There may be. For example, a pure titanium-based titanium alloy is also finely etched by performing only chemical etching. However, in many cases, it is necessary to perform fine etching or surface hardening treatment after forming a large uneven surface on the order of microns by chemical etching.

  Even at this time, we are often hit by unpredictable chemical phenomena. That is, this is an example in which, when a chemical etching is caused to react with an oxidant or the like or a chemical conversion treatment is performed for the purpose of surface hardening treatment or surface stabilization treatment, the resulting surface accidentally becomes ultrafine irregularities. The surface layer that appears to be manganese oxide formed when a magnesium alloy is subjected to a chemical conversion treatment with a potassium permanganate aqueous solution is a complex of 5 to 10 nm diameter rod-like crystals that are finally discriminated by a 100,000 times electron micrograph. This sample was analyzed by XRD (X-ray diffractometer), but diffraction lines derived from manganese oxides could not be detected.

  It is clear by XPS analysis that the surface is covered with manganese oxide. The reason why XRD could not be detected is that the crystal was a thin layer exceeding the detection limit. In short, the chemical conversion treatment for the magnesium alloy also served as a fine etching operation. The same applies to copper alloys, and when a hardening treatment is performed to change the surface to cupric oxide by oxidation under basic conditions, in pure copper-based copper alloys, the hole openings in the form of circular or distorted circles are formed on the surface. It occurs on one side and becomes a characteristic fine uneven surface. A copper alloy that is not a pure copper type is not a concave type, but is formed of a 10-150 nm diameter particle size product or an indefinite polygonal shape, resulting in a super fine uneven shape in which some are melted and stacked. Even in this case, most of the surface is covered with cupric oxide, and hardening and fine unevenness occur simultaneously.

  It is a general steel material whose details are still unknown. In many cases, fine unevenness is often made only by the chemical etching process, and the surface layer (natural oxide layer) was originally hard, so that it could not be used as it is for “NAT”. The problem is that the corrosion resistance of the natural oxide layer is not sufficient, so that corrosion starts before the bonding process, or the adhesive force decreases immediately if the environment after bonding is severe.

  Although there is a possibility that these can be prevented by chemical conversion treatment, since there is no precedent, there are tests that apply adhesives to a temperature shock test, tests that leave them in a general environment, tests that apply a coated product to a salt spray device, etc. It was necessary to go and check the durability of the bond. In a short period of at least 4 weeks, the steel material (actually SPCC: cold-rolled steel material) bonded with a phenol resin adhesive without any chemical conversion treatment showed a sharp decrease in bonding strength. However, the general steel (SPCC) subjected to the chemical conversion treatment did not deteriorate from the initial adhesive force under these conditions.

  In addition, according to the experience of the present inventors, when a chemical conversion treatment is performed and a surface treatment that also improves corrosion resistance or an ultrafine unevenness creation treatment is performed, generally, if the film thickness of the chemical conversion treatment layer is thick, the adhesive force decreases rapidly. I know that there are many. A strong adhesive force is observed when the thin layer is such that a diffraction line is not detected by XRD, such as the thin layer of manganese oxide adhered to the magnesium alloy. When the chemical conversion treatment layer is thickened with a phenol resin adhesive or an epoxy resin adhesive and subjected to a destructive test, the fracture surface is mostly between the metal phase and the chemical conversion film.

  In the experience of the present inventors, the bonding force between the thick film (chemical conversion film) prepared by chemical conversion treatment and the cured phenol resin adhesive was always stronger than the bonding force between the chemical conversion film and the internal metal alloy phase. That is, even with a general steel material, if the chemical conversion treatment time is further extended to thicken the chemical conversion treatment layer, the durability of the adhesive should be improved. However, if the chemical conversion film is thickened, the adhesive strength itself is lowered. The degree of balance is left to commercial research and development after using the present invention.

[One-component thermosetting resin adhesive / phenolic resin adhesive]
As already disclosed in the aforementioned patent document group, it has been demonstrated that a one-component epoxy adhesive exhibits a very high adhesive force. The present invention is a technique developed for the purpose of showing that this is not limited to epoxy adhesives. Specifically, it has been confirmed that a phenol resin adhesive exhibits excellent adhesive performance, and the details will be described below.

  As one-component thermosetting resin adhesives, urea resin-based, melamine resin-based, diallyl phthalate-based, and polyimide-based adhesives are known in addition to epoxy resin-based and phenol resin-based adhesives. An adhesive that can be substantially cured in a temperature range that is uncured and in a liquid state and can be further thermally cured by raising the temperature can be used as the adhesive of the present invention. Furthermore, it is necessary for the effectiveness of the present invention to be exhibited that the gelation progresses little or the gelation rate is low in the temperature range where the viscosity is about several tens of Pa seconds after melting.

  Following the epoxy resin adhesive, such a condition could be obtained for the phenol resin adhesive, but the present inventors are able to sufficiently exhibit the adhesive performance if other resin systems can be adjusted as such. It is clear from the contents of Patent Documents 1 to 12 that have been verified by the above. The phenol resin adhesive will be described below.

  An excellent phenol resin adhesive is commercially available. Even if you make your own, you can easily procure raw materials from commercial products. A phenolic resin is a polymer obtained by adding a catalyst to a mixture of phenol and formaldehyde and subjecting it to an addition condensation reaction. The molecular structure of resole and novolak differs depending on the raw material mixing ratio, catalyst, and heating conditions during the reaction. Become a seed phenolic resin. Although resole and novolak can be used as the adhesive raw material for the present invention, the basic is resol.

  Specifically, it utilizes the fact that resol is thermosetting and dissolves in organic solvents such as ketones and alcohols, and these solvents are added to resole to lower the viscosity and are used as an adhesive. Many commercially available products further improve adhesive properties by mixing a little epoxy adhesive. Some phenolic resin adhesives increase the epoxy adhesive content to nearly half of the adhesive component. Although it can be said that these use phenol resins as curing agents for epoxy adhesives (hardening agents that work at high temperatures), they are also treated as phenolic resin adhesives in the market.

  These are generally used in various ways such as phenol resin adhesives, thermosetting phenol resin adhesives, phenol resin adhesives, etc., but the present inventors have included them all as phenol resin adhesives. A feature common to all of these is that a dehydration condensation reaction is included in the reaction of gelation or curing and solidification. That is, water vapor is generated during gelation and solidification. This is an unfavorable property as an adhesive, and is also why a phenol resin adhesive is not used as a general-purpose adhesive. On the other hand, when the bonding method is devised and the foaming at the time of final solidification is suppressed and bonding can be performed reliably, the bonding layer is a phenol resin itself and has excellent heat resistance and water resistance.

  The present inventors used a phenol resin adhesive “110 (manufactured by Cemedine Co.)” that is widely used in Japan. It is a phenol resin product mixed with some epoxy adhesive, and 40 to 50% methyl ethyl ketone (hereinafter referred to as “MEK”) is also used as a solvent. This adhesive is considered to be a standard phenolic resin adhesive, and other similar adhesives are commercially available, but all of these can be used in the same manner.

  Moreover, adding a filler component, an elastomer component, or the like to these adhesives means that the linear expansion coefficient of the cured product is equivalent to that of a metal alloy or that of a cured phenol resin product. In particular, the elastomer component is preferable because it can be used as a relaxation agent when subjected to a temperature impact or a mechanical impact. That is, as an elastomer component, it is preferable to include 0 to 30 parts by mass with respect to a total of 100 parts by mass of the resin component (epoxy resin component + curing agent component) because the impact resistance and temperature impact resistance are improved. An excessive amount of 30 parts by mass or more is not preferable because the bonding force is reduced.

  One of the elastomer components is a vulcanized rubber powder having a particle size of 1 to 15 μm. When the diameter is several μm, even when the adhesive is applied, the ultrafine recess on the aluminum alloy is too large to enter, so that the anchor portion is not affected and remains in the adhesive layer. Therefore, it has a role of enduring temperature shock and physical shock without reducing the bonding force. Any kind of vulcanized rubber can be used. The other is the use of unvulcanized and semi-crosslinkable rubber and modified super engineering plastics. An example of a modified super engineering plastic is a hydroxyl-terminated polyethersulfone “PES100P (Mitsui Chemicals)”.

  Next, the filler will be described. An adhesive composition further comprising 0 to 100 parts by mass of a filler is preferred for use with respect to 100 parts by mass of the total resin content including the elastomer component. Examples of the filler used include carbon fiber, glass fiber, and aramid fiber in the reinforcing fiber system, and the powder filler includes calcium carbonate, mica, glass flake, glass balloon, magnesium carbonate, silica, talc, clay, And pulverized products of carbon fibers and aramid fibers.

  It is also preferable to add these elastomers and fillers to phenolic resin adhesives to obtain improved adhesives. Various commercially available kneaders can be used as this adjustment method, but the most faithful mixing method with good reproducibility is kneading with a ball mill. Kneading for several hours at a kneading speed such that the heat generation is about 40 ° C. Thereby, an adhesive composition having no problem in dispersion can be obtained. The adhesive composition is applied to a necessary portion of the metal alloy part obtained in the previous step. It does not matter if it is applied by brush coating or coating machine.

[Process after applying phenolic resin adhesive]
It is preferable to leave it for at least 1 hour after coating. During this time, the majority of the solvent contained in the adhesive volatilizes. Thereafter, the coated material is placed in a decompression vessel or a pressure vessel that has been heated to 50 to 70 ° C. in advance, and the pressure is reduced to near vacuum, and the mixture is placed for several minutes. After that, it is preferable to return to normal pressure by introducing air, or to set the pressure to several atmospheric pressure or several tens atmospheric pressure. Furthermore, it is preferable to repeat the pressure reduction and pressure increase cycle slowly. As a result, the solvent in the adhesive composition can be volatilized and removed, and the viscosity of the phenolic resin after most of the solvent has been removed can be greatly reduced. Under reduced pressure, the air between the adhesive and the metal alloy escapes, and the adhesive easily penetrates into the ultrafine recesses on the metal surface.

  In actual mass production, using high-pressure air using a pressure vessel leads to increased costs both in terms of equipment and costs, and rather, using a pressure-reducing vessel, pressure reduction / normal pressure return is performed several times. It is economical. In the case of the metal alloy of the present invention, when a desiccator previously heated to 60 ° C. was used as a decompression vessel, a sufficiently stable joining force could be obtained by three decompression / normal pressure return cycles. Then, it takes out from a container. Although it may be left as it is, it is preferable to enter the next step within several hours.

[Substrate: phenolic resin composition and molded product]
As the adherend used in the present invention, in addition to the metal alloy, a semi-cured product using a phenol resin or an uncured shaped product obtained by pressing can be used. The shaped object that is used after being pressed and shaped by a press will be described in detail. Brake friction materials, grindstones, various heat-insulating bakelite materials, and the like are products that are once shaped by a room temperature press or a warming press and then heat-cured. As the phenolic resin, both resole and novolak are used.

  Novolak is thermoplastic unlike resol, and usually a curing agent such as hexamethylenetetramine is used by mixing 10-15% by mass of novolac. It is said that there are two types of commercially available phenol resins for friction materials, that is, a resole-derived material and a novolac mixed with hexamethylenetetramine or the like, but it is not clearly shown. However, in any case, the temperature range from 90 to 130 ° C. does not lead to solidification, and the degree of polymerization and gelation progresses. Rather, this temperature range can be used for mixing of fillers and pre-molding by utilizing melt liquefaction.

  For example, for friction materials for brake parts, the phenol resin, inorganic powder fillers, aramid pulp, glass fiber reinforcing materials, vibration absorbing materials such as rubber powder, graphite and other highly heat conductive fillers, etc. Are often kneaded and pre-molded once at 90 to 130 ° C. Also, for grinding wheels, it is common to use a large amount of cemented carbide ceramic powder such as alumina, and to use heat-resistant building materials and heat insulating materials for the plate materials, such as inorganic powder fillers and glass fiber reinforcements. It is.

  For example, a recipe example of a brake pad compound that requires highly stable friction performance is often within the following range. That is, 15 to 20 parts by mass of phenol resin, 45 to 55% by mass of a filler such as calcium carbonate, barium sulfate, aluminum powder, and / or copper powder, and 5% by mass of a soft material such as rubber powder, an aramid that is a reinforcing material The pulp is 15 to 20% by mass, glass fiber is 10 to 20% by mass, and graphite is 0 to 5% by mass to make the whole 100 parts by mass.

  After these are mixed well, they are put into a preforming die (pressing press die) and shaped by press-pressing at a low temperature of about 100 atm. The preform is inserted into a hot press mold and heated to 180 to 200 ° C. while being pressurized, and the phenol resin is gelled and solidified to obtain a friction material. However, the brake pad needs to be integrated with the friction material and a steel material to be attached to a necessary portion. In short, it is necessary that the friction material preform and the mounting metal part can be strongly bonded with a phenol-based adhesive, and the present invention has been developed in view of its important purpose.

[Adhesion method between phenol resin preform and metal alloy piece]
Place the metal alloy part coated with the phenol resin adhesive described above in a hot air dryer, and at 90 to 100 ° C. for 10 to 30 minutes, specifically, instructions in the work instructions of the manufacturer of the phenol adhesive to be used Heat according to Preliminary heating for the polymerization, which is a process of proceeding with the majority of gelation (polymerization) by dehydration condensation of the phenol resin, water vapor is generated by dehydration condensation, and the adhesive layer repeats foaming and melting. When the set heating end time approaches, the foaming is moderated and the coating film becomes viscous and melted. The metal alloy piece taken out from the hot air dryer waits for the next process. It is preferable to perform this preparation first and enter the next bonding step.

  An example of an adhesion process is shown. This is also the method performed by the present inventors. A mold for heating press is prepared, the preformed product prepared in the previous section is inserted, and the metal alloy component coated with the prepolymerized phenol resin adhesive is placed on the preformed product at a position to be bonded. After placing the upper mold on the mold, the press is driven to pressurize the press mold. The press machine is a machine that can control the pressing force to be constant, and the pressure applied in the mold is 10 atm (about 1 MPa) or more, preferably 10 to 100 atm (1 to 10 MPa).

  The temperature is raised while keeping the pressure constant, and the phenol resin in the preform is dehydrated and condensed at 100 to 110 ° C. for several hours, and then the temperature is raised to 180 to 250 ° C. It is preferable that the solidification reaction is sufficiently advanced and then the heating is stopped and the mixture is allowed to cool. In the experiments by the present inventors, the temperature history as described above was passed, and the cooling of the mold was left to natural cooling. When the mold temperature dropped to 60 ° C., the pressure was released, and the mold was opened to release the integrated product.

  As described above in detail, the present invention provides a stable composite that is capable of bonding and bonding the same type of metal alloys, different metal alloys, or metal alloy materials and phenolic resin parts. It has become possible. Therefore, it is possible to manufacture useful products such as manufacturing brake pads, polishing parts that can be easily attached to various devices, and manufacturing heat-insulating functional parts with metal edges and joints. .

  In other words, by precisely designing and controlling the surface of the metal alloy, it is possible to dramatically increase the bonding strength with the phenolic resin, and use the bonding force to improve the performance of conventional products. It became a thing. Regarding the manufacturing method of the same metal and resin integrated product, the present inventors have already disclosed a new adhesion technique using an epoxy resin, but the present invention in which the resin type is replaced with a phenol resin-based material, It became possible to improve the heat resistance, solvent resistance, etc. of the single-layer bonded product. The present invention is a basic adhesion (fixing) technique, and can be applied and applied to a wide variety of techniques and industrial fields.

  Hereinafter, embodiments of the present invention will be described by way of examples. FIG. 1 is a cross-sectional view schematically showing a firing jig 1 of a hot press mold for bonding a metal piece 11 and a preformed product 12 containing a phenol resin with a phenol-based adhesive. FIG. 2 is an external view showing an adhesive composite 10 formed by adhering a metal piece 11 and a preformed product 12 which is a cured product of a phenol resin composition. In addition, what is shown to FIG.1, 2 is a test piece of the shape common to each embodiment demonstrated below. It is the figure which showed the structural example for applying both ends to a tensile testing machine and measuring shear fracture strength. FIG. 3 is a diagram showing a structural example of an adhesive complex 20 that is a test piece for measuring an adhesive force obtained by joining the metal alloy pieces 21 and 22 to each other with a phenol resin adhesive and joining the joint 23.

  The mold main body 2 is for bonding in which an upper surface is opened and a mold concave portion 3 is formed in a rectangular shape. A mold through hole 4 is formed at the bottom. A bottom plate protrusion 6 of a mold bottom plate 5 is inserted into the mold through hole 4. The bottom plate protrusion 6 protrudes outward from the mold bottom surface 7 of the mold body 2. A mold bottom surface 7 of the mold body 2 is mounted on a mold base 8.

  The firing jig 1 is an adhesive composite in which a metal piece 11 and a preform 12 are joined as shown in FIG. 2 in a state where the mold bottom plate 5 is inserted and placed in the mold recess 3 of the mold body 2. 10 is produced by firing. The joint portion of the metal piece 11 is subjected to a surface treatment to form a fine concavo-convex shape by the above-described chemical etching, and a treatment to make a thin layer of metal oxide or metal phosphate is performed.

  In general, the adhesive composite 10 is manufactured by the following procedure. First, a release film 17 is laid on the entire upper surface of the mold bottom plate 5. A metal piece 11 and a spacer 16 made of plate-like polytetrafluoroethylene resin (hereinafter referred to as “PTFE”) are placed on the release film 17. A preform 12 cut to a required size was placed on the PTFE spacer 16 and the end of the metal piece 11.

  A plate-like PTFE spacer 13 is placed on the metal piece 11. A release film 14, which is a release polyethylene film, is laminated on the spacer 13 and the preform 12 that are provided side by side. A PTFE block 15 is placed thereon as a weight. Further, a weight of several hundred grams is placed thereon. After putting in a baking furnace in this state, curing the phenol resin and allowing to cool, removing the weight 15, the weight 18, the pedestal 8 and the like and pressing the lower end of the bottom plate projection 6 against the floor surface, the bottom plate projection 6 is pressed against the floor surface, and only the mold body is lowered, and the adhesive composite 10 (see FIG. 2) obtained by joining the metal piece 11 and the preform 12 together with the release films 14 and 17 can be taken out.

  Since the PTFE spacers 13 and 16 and the release films 17 and 14 are non-adhesive materials, they can be easily peeled off from the metal piece 11 and the preform 12. In this example, 0.05 mm polyethylene film was cut into strips to form the release films 14 and 17 described above. Further, a weight 15 of a PTFE block was placed thereon as a presser, an iron weight 18 was placed on the dryer, and the temperature of the dryer was increased to 135 ° C.

  The mixture was heated at 135 ° C. for 40 minutes, further heated to 165 ° C. over 5 minutes, held at 165 ° C. for 20 minutes, and the electricity was turned off, and the door was left to cool. On the next day, the product was taken out from the dryer, and the molded product was released from the mold, and the release films 14 and 17 were peeled off to obtain an adhesive composite 10 shown in FIG. FIG. 3 is an external view showing a configuration of an adhesive complex 20 obtained by joining a second metal 22 of the same quality to a metal piece 21 with the same shape as FIG. The metal pieces 21 and 22 are subjected to the above-described surface treatment by chemical etching to form a fine concavo-convex shape, and a phenol resin adhesive is applied to the bonding portion 23 which is a bonded portion to form an adhesive layer, which is cured by firing. This is an adhesive composite 20. The results of the examples were obtained by the following experimental examples.

Specific examples will be shown in the experimental examples described later, but the equipment used for the measurement and the like is shown below.
(A) X-ray surface observation (XPS observation)
An ESCA “AXIS-Nova (Kuratos / Shimadzu Corporation)” in the form of observing constituent elements on a surface having a diameter of several μm in a depth range of 1 to 2 nm was used.
(B) Electron beam surface observation (EPMA observation)
An electron beam microanalyzer “EPMA1600 (manufactured by Shimadzu Corp.)” of a type in which constituent elements are observed in a range of several μm diameter to a depth of several μm was used.
(C) Electron Microscope Observation Using a SEM type electron microscope “JSM-6700F (JEOL)”, observation was performed at 1 to 2 KV.
(D) Scanning probe microscope observation “SPM-9600 (manufactured by Shimadzu Corporation)” was used.
(E) Measurement of Bonding Strength of Composite Body Using a tensile tester “Model 1323 (manufactured by Aiko Engineering Co., Ltd.)”, the shear breaking force was measured at a pulling speed of 10 mm / min. Next, an example of a joining system will be described for each type of metal piece according to an experimental example.

[Experiment 1] (Surface treatment of aluminum alloy)
A commercially available 1.6 mm thick A5052 plate was obtained and cut into a large number of 45 mm × 18 mm rectangular pieces. A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” was poured into water to form an aqueous solution at 60 ° C. and a concentration of 7.5%. The aluminum alloy sheet was immersed in this for 7 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution adjusted to 40 ° C. was prepared in another tank, and the aluminum alloy plate material was immersed in the tank for 1 minute and washed with water.

  Next, a 1.5% caustic soda aqueous solution at 40 ° C. was prepared in another tank, and the aluminum alloy plate material just before was immersed for 2 minutes and washed with water. Subsequently, a 3% concentration nitric acid aqueous solution at 40 ° C. was prepared in another tank, and the aluminum alloy sheet was immersed in the tank for 1 minute and washed with water. Next, an aqueous solution containing 3.5% monohydric hydrazine at 60 ° C. was prepared in another tank, and the aluminum alloy sheet was immersed in this for 2 minutes and washed with water.

  Subsequently, it put into the warm air dryer which was 67 degreeC for 15 minutes, and dried. After drying, the aluminum alloy sheets were wrapped together with aluminum foil, which was then stored in a plastic bag. Four days later, one of them was observed with an electron microscope and found to be covered with a recess having a diameter of 30 to 100 nm. An electron micrograph of 10,000 times and 100,000 times is shown in FIG. Another piece was subjected to a scanning probe microscope to obtain roughness data. According to this, the peak-valley average interval (RSm) was 1-2 μm, and the maximum height (Rz) was 0.3-0.5 μm.

[Experimental example 2] (Surface treatment of aluminum alloy)
A commercially available 3 mm thick A7075 plate was obtained and cut into a large number of 45 mm × 18 mm rectangular pieces. A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” was poured into water to form an aqueous solution at 60 ° C. and a concentration of 7.5%. The aluminum alloy sheet was immersed in this for 7 minutes and washed thoroughly with water. Subsequently, a 1% hydrochloric acid aqueous solution adjusted to 40 ° C. was prepared in another tank, and the aluminum alloy sheet was immersed in the tank for 1 minute and washed with water. Next, a 1.5% concentration aqueous solution of caustic soda at 40 ° C. was prepared in a separate tank, and the aluminum alloy plate material was immersed for 4 minutes and washed with water.

  Subsequently, a 3% concentration nitric acid aqueous solution at 40 ° C. was prepared in another tank, and the aluminum alloy sheet was immersed in the tank for 1 minute and washed with water. Next, an aqueous solution containing 3.5% monohydric hydrazine at 60 ° C. was prepared in another tank, and the aluminum alloy sheet was immersed in this for 2 minutes and washed with water. Subsequently, the aluminum alloy sheet was immersed in a 5% hydrogen peroxide aqueous solution at 40 ° C. for 5 minutes and washed with water. Subsequently, it put into the warm air dryer which was 67 degreeC for 15 minutes, and dried.

  After drying, the aluminum alloy sheets were wrapped together with aluminum foil, which was then stored in a plastic bag. When one of them was observed with an electron microscope, it was found to be covered with a recess having a diameter of 40 to 100 nm. An electron micrograph of 10,000 times and 100,000 times is shown in FIG. Another piece was subjected to a scanning probe microscope to obtain roughness data. According to this, the peak-valley average interval (RSm) was 3-4 μm, and the maximum height (Rz) was 1-2 μm.

[Experiment 3] (Surface treatment of magnesium alloy)
A commercially available 1 mm thick AZ31B plate was obtained and cut into a large number of 45 mm × 18 mm rectangular pieces. A commercially available magnesium alloy degreasing agent “Cleaner 160 (manufactured by Meltex Co., Ltd.)” was poured into water to form an aqueous solution at 65 ° C. and a concentration of 7.5%. The magnesium alloy sheet was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 1% hydrated citric acid aqueous solution having a temperature of 40 ° C. was prepared in another tank, and the magnesium alloy sheet was immersed in the tank for 6 minutes and washed with water.

  Next, an aqueous solution containing 1% concentration sodium carbonate and 1% concentration sodium hydrogen carbonate at 65 ° C. was prepared in another tank, and the above magnesium alloy sheet was immersed in water for 5 minutes and washed with water. Subsequently, a 15% strength aqueous caustic soda solution at 65 ° C. was prepared in another tank, and the alloy plate material was immersed in this for 5 minutes and washed with water. Subsequently, it was immersed in a 0.25% strength hydrated citric acid aqueous solution at 40 ° C. for 1 minute and washed in another tank. Next, it was immersed in an aqueous solution containing 2% potassium permanganate at 45 ° C., 1% acetic acid and 0.5% hydrated sodium acetate for 1 minute, washed with water for 15 seconds, and placed in a warm air dryer at 90 ° C. for 15 minutes. Dried and dried.

  After drying, the magnesium alloy sheet was wrapped together with aluminum foil, which was then placed in a plastic bag and sealed. Observation of one of them with an electron microscope reveals that the intricately entangled 5-10 nm diameter rod-like crystals and their lumps are gathered with a diameter of about 100 nm, and the gathering is covered with an ultra-fine uneven shape forming a surface. There was a part that was broken. The 100,000 times electron micrographs are shown in FIGS. In addition, when another one was scanned with a scanning probe microscope to observe the roughness, the mean interval between peaks and valleys, that is, the average value of the irregularity period (RSm) in JIS was 2 to 3 μm, and the maximum roughness height (Rz). ) Was 1 to 1.5 μm.

[Experimental Example 4] (Surface treatment of magnesium alloy)
A large number of 1 mm × 45 mm × 18 mm rectangular plate pieces were machined out from a die-cast product of a magnesium alloy for casting AZ91D. A commercially available magnesium alloy degreasing agent “Cleaner 160 (manufactured by Meltex Co., Ltd.)” was poured into water to form an aqueous solution at 65 ° C. and a concentration of 7.5%. The magnesium alloy sheet was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 1% malonic acid aqueous solution having a temperature of 40 ° C. was prepared in another tank, and the alloy plate material was immersed in the tank for 2.25 minutes and washed with water.

  Next, an aqueous solution containing 1% sodium carbonate and 1% sodium hydrogen carbonate at 65 ° C. was prepared in another tank, and the above magnesium alloy sheet was immersed for 5 minutes and washed with water. Subsequently, a 15% strength aqueous caustic soda solution at 65 ° C. was prepared in another tank, and the alloy plate material was immersed in this for 5 minutes and washed with water. Subsequently, it was immersed in a 0.25% strength hydrated citric acid aqueous solution at 40 ° C. for 1 minute and washed in another tank. Next, it was immersed in an aqueous solution containing 2% potassium permanganate at 45 ° C., 1% acetic acid and 0.5% hydrated sodium acetate for 1 minute, washed with water for 15 seconds, and placed in a warm air dryer at 90 ° C. for 15 minutes. Dried and dried.

  After drying, the magnesium alloy sheet was wrapped together with aluminum foil, which was then placed in a plastic bag and sealed. When one of them was observed with an electron microscope, it was observed with a magnification of 100,000 times, and a shape in which 20 to 40 nm particle diameters and indefinite polygonal shapes were stacked, that is, a shape covered with an ultra-fine uneven surface of lava plate slope It was found that it was covered with. A photograph is shown in FIG. Further, when another one was scanned with a scanning probe microscope and the roughness was observed, the mean interval between peaks and valleys, that is, the average value (RSm) of the concave / convex period in JIS was 3 to 5 μm, and the maximum roughness height (Rz). ) Was 1.5 to 2.5 μm.

[Experimental Example 5] (Surface treatment of copper alloy)
A commercially available tough pitch copper (C1100) plate material, which is a pure copper-based copper alloy with a thickness of 1 mm, was obtained and cut into a large number of 45 mm × 18 mm rectangular pieces. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” was immersed in water at 60 ° C. for 5 minutes and then washed with water, and then 1.5% caustic soda at 40 ° C. It was immersed in an aqueous solution for 1 minute, washed with water, and washed with a preliminary base. Next, an aqueous solution containing 20% and 18% of 30% hydrogen peroxide was prepared for an etching material for copper alloy “CB5002 (manufactured by MEC)” at 25 ° C., and the copper alloy piece was immersed in this for 10 minutes and washed with water. .

  Next, an aqueous solution containing 10% of caustic soda at 65 ° C. and 5% of sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the copper alloy sheet was immersed for 1 minute and washed with water. Next, it was immersed in the etching tank for 1 minute and washed with water, and then immersed in the oxidation treatment tank for 1 minute and washed with water. Subsequently, it put into the warm air dryer which was 90 degreeC for 15 minutes, and dried. After drying, the copper alloy sheets were wrapped together with aluminum foil, which was then stored in a plastic bag.

  One of them was subjected to a scanning probe microscope. As a result, the mean valley interval (RSm) in JIS was 3 to 7 μm, and the maximum roughness height (Rz) was 3 to 5 μm. In addition, when observed with an electron microscope of 100,000 times, the average of the diameter or major axis and minor axis is about 10 to 150 nm, and the apertures or recesses are irregular intervals of 30 to 300 nm, and the surface of the ultra-fine irregularities present on the entire surface is almost uniform. The entire surface was covered. The 10,000 times and 100,000 times electron micrographs are shown in FIG.

[Experimental Example 6] (Surface treatment of copper alloy)
A commercially available phosphor bronze (C5191) plate material having a thickness of 0.8 mm was purchased and cut into 18 mm × 45 mm rectangular pieces, and this phosphor bronze metal plate was used as a copper alloy plate material. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” in the tank was used as a degreasing aqueous solution at 60 ° C. The said copper alloy board | plate material was immersed here for 5 minutes, degreased | defatted, and washed well with water. Subsequently, an etching solution for copper alloy “CB5002 (manufactured by MEC)” at 25 ° C. is prepared in a separate tank, and an aqueous solution containing 20% and 18% of 30% hydrogen peroxide is prepared. It was immersed for a minute and washed with water.

  Next, an aqueous solution containing 10% caustic soda and 5% sodium chlorite was prepared as an aqueous solution for oxidation in another tank, and after the temperature of 65 ° C., the copper alloy sheet was immersed for 1 minute and washed with water. Next, it was again immersed in the previous etching solution for 1 minute and washed with water. Subsequently, it was immersed again in the aqueous solution for oxidation for 1 minute and washed with water. The copper alloy sheet was placed in a hot air dryer at 90 ° C. for 15 minutes and dried. Wrapped in aluminum foil and stored.

  The 10,000 times and 100,000 times electron micrographs are shown in FIG. 11. In the 100,000 times electron microscope observation, the average of the diameter or the major axis and the minor axis is 10 to 200 nm. It was a fine concavo-convex shape and was completely different from the fine structure of tough pitch copper, which is pure copper. Moreover, one piece was applied to the scanning probe microscope. As a result, the mean valley interval (RSm) in JIS was 1 to 3 μm, and the maximum roughness height (Rz) was 0.3 to 0.4 μm.

[Experimental Example 7] (Surface treatment of copper alloy)
A commercially available plate material made of copper alloy “KFC (manufactured by Kobe Steel)” containing 0.7 mm thick iron was obtained and cut to obtain a large number of 45 mm × 18 mm rectangular copper alloy plate materials. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” in a tank is set to 60 ° C., the copper alloy plate material is immersed in this for 5 minutes, and then washed with water. It was immersed in an aqueous 1.5% strength caustic soda solution for 1 minute, washed with water, and washed with a preliminary base.

  Next, an aqueous solution containing 20% of an etching material for copper alloy “CB5002 (manufactured by MEC)” at 25 ° C. and 18% of 30% hydrogen peroxide was prepared, and the copper alloy plate material was immersed in this for 8 minutes and washed with water. . Next, an aqueous solution containing 10% of caustic soda at 65 ° C. and 5% of sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the copper alloy sheet was immersed for 1 minute and washed with water. Next, it was immersed in the etching tank for 1 minute and washed with water, and then immersed in the oxidation treatment tank for 1 minute and washed with water. Subsequently, it put into the warm air dryer which was 90 degreeC for 15 minutes, and dried.

  After drying, the copper alloy sheets were wrapped together with aluminum foil, which was then stored in a plastic bag. One of them was subjected to a scanning probe microscope. As a result, the mean valley and valley interval (RSm) in JIS was 1 to 3 μm, and the maximum roughness height (Rz) was 0.3 to 0.5 μm. Further, when observed with an electron microscope of 100,000 times, the entire surface was covered with an ultra fine uneven shape in which convex portions having an average diameter or major axis and minor axis of 10 to 200 nm were mixed and present on the entire surface. The 10,000 times and 100,000 times electron micrographs are shown in FIG.

[Experimental Example 8] (Surface treatment of copper alloy)
A commercially available 0.7 mm-thick special copper alloy “KLF5 (manufactured by Kobe Steel)” was obtained and cut into a large number of 45 mm × 18 mm rectangular copper alloy sheets. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” in a tank is set to 60 ° C., the copper alloy plate material is immersed in this for 5 minutes, and then washed with water. It was immersed in an aqueous 1.5% strength caustic soda solution for 1 minute, washed with water, and washed with a preliminary base.

  Next, an aqueous solution containing 20% of an etching material for copper alloy “CB5002 (manufactured by MEC)” at 25 ° C. and 18% of 30% hydrogen peroxide was prepared, and the copper alloy plate material was immersed in this for 8 minutes and washed with water. Next, an aqueous solution containing 10% of caustic soda at 65 ° C. and 5% of sodium chlorite was prepared as an oxidizing aqueous solution in another tank, and the alloy plate was immersed for 1 minute and washed with water. Next, it was immersed in the etching tank for 1 minute and washed with water, and then immersed in the oxidation treatment tank for 1 minute and washed with water.

  Subsequently, it put into the warm air dryer which was 90 degreeC for 15 minutes, and dried. After drying, the copper alloy sheets were wrapped together with aluminum foil, which was then stored in a plastic bag. One of them was subjected to a scanning probe microscope. As a result, the mean valley and valley interval (RSm) in JIS was 1 to 3 μm, and the maximum roughness height (Rz) was 0.3 to 0.5 μm. In addition, when observed with an electron microscope of 100,000 times, it was found that the particle size of 10-20 nm and the indefinite polygonal shape of 50-150 nm were mixed and stacked, so to speak, ultra-fine, such as lava plate slope The entire surface was covered with an uneven shape. The 10,000 times and 100,000 times electron micrographs are shown in FIG.

[Experimental example 9] (Surface treatment of titanium alloy)
A commercially available pure titanium type titanium alloy JIS type 1 “KS40 (manufactured by Kobe Steel)” 1 mm thick plate material was obtained, and this was cut to obtain a large number of 45 mm × 18 mm rectangular titanium alloy plate materials. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” in a tank was set to 60 ° C., and this was used as a degreasing aqueous solution. The titanium alloy sheet was immersed in this degreasing aqueous solution for 5 minutes for degreasing and thoroughly washed with water.

  Subsequently, an aqueous solution containing 2% of a universal etching material “KA-3 (manufactured by Metalworking Technology Laboratories)” containing 40% of monohydrogen difluoride at 60 ° C. was prepared in another tank, The titanium alloy piece was immersed for 3 minutes and washed thoroughly with ion exchange water. Subsequently, it was immersed in a 3% nitric acid aqueous solution for 1 minute and washed with water. It put into the warm air dryer which was 90 degreeC for 15 minutes, and dried. After drying, the titanium alloy sheets were wrapped together with aluminum foil and stored in a plastic bag. One of them was cut and observed with an electron microscope and a scanning probe microscope.

  From observations with an electron microscope, a shape in which curved continuous mountain-shaped protrusions having a width and height of 10 to several hundred nm and a length of several hundred to several μm stand on the surface with an interval period of 10 to several hundred nm. It was found to have an ultrafine uneven surface. The 10,000 times and 100,000 times electron micrographs are shown in FIG. Moreover, by observation with a scanning probe microscope, the average interval between peaks and valleys (RSm) was 1 to 3 μm, and the maximum roughness height (Rz) was 0.8 to 1.5 μm. Further, from the analysis by XPS, a large amount of oxygen and titanium were observed on the surface, and a small amount of carbon was observed. From these, it was found that the surface layer was composed mainly of titanium oxide, and because it was dark, it was estimated to be a trivalent titanium oxide.

[Experimental Example 10] (Surface treatment of titanium alloy)
A 1 mm thick plate material of a commercially available α-β type titanium alloy “KSTI-9 (manufactured by Kobe Steel)” was cut to obtain a large number of 45 mm × 18 mm rectangular titanium alloy plate materials. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” in a tank was set to 60 ° C., and this was used as a degreasing aqueous solution. The titanium alloy sheet was immersed in this degreasing aqueous solution for 5 minutes for degreasing and thoroughly washed with water. Next, an aqueous solution of 1.5% concentration of caustic soda at 40 ° C. was prepared in another tank, immersed for 1 minute and washed with water.

  Next, an aqueous solution in which 2% by mass of a commercially available general-purpose etching reagent “KA-3 (manufactured by Metalworking Technology Laboratories)” is dissolved is prepared at 60 ° C. in another tank, and the titanium alloy plate material is immersed in this for 3 minutes. Washed well with ion exchange water. Since black smut was attached, it was immersed in 3% nitric acid aqueous solution at 40 ° C. for 3 minutes, then immersed in ion-exchanged water treated with ultrasonic waves for 5 minutes to remove the smut, and again into 3% nitric acid aqueous solution. It was immersed for 0.5 minutes and washed with water. Subsequently, it put into the warm air dryer which was 90 degreeC for 15 minutes, and dried. The obtained titanium alloy sheet was dark brown with no metallic luster. After drying, the titanium alloy sheets were wrapped together with aluminum foil and stored in a plastic bag.

  Two days later, one of them was observed with an electron microscope and a scanning probe microscope. The results of observation with an electron microscope at 10,000 times and 100,000 times are shown in FIG. In addition to the part very similar to FIG. 14 which is an electron microscopic observation photograph of Experimental Example 9, it is difficult to express this surface state, but many parts like dead leaves were observed. Further, according to the scanning analysis by the scanning probe microscope, the mean valley interval RSm was 4 to 6 μm, and the maximum roughness height Rz was 1 to 2 μm.

[Experimental example 11] (Stainless steel surface treatment)
A commercially available stainless steel SUS304 1 mm thick plate material was obtained and cut to obtain a large number of stainless steel plate materials having a rectangular shape of 45 mm × 18 mm. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” in the tank was used as a degreasing aqueous solution at 60 ° C. The stainless steel plate material was immersed in this degreasing aqueous solution for 5 minutes for degreasing and thoroughly washed with water. Subsequently, an aqueous solution containing 10% of 98% sulfuric acid at 60 ° C. was prepared in another tank, and the stainless steel plate material was immersed in this for 5 minutes and washed thoroughly with ion-exchanged water.

  Subsequently, it was immersed in a 5% hydrogen peroxide aqueous solution at 40 ° C. for 5 minutes and washed with water. It put into the warm air dryer which was 90 degreeC for 15 minutes, and dried. After drying, the stainless steel plate material was wrapped together with aluminum foil, which was then stored in a plastic bag. One of them was cut and observed with an electron microscope and a scanning probe microscope. From observation with an electron microscope, this surface is covered with a super fine uneven shape of a particle size of 30 to 70 nm in diameter or an indefinite polygonal shape, in other words, a lava plateau slope surface gala field shape, and its coverage rate Was about 90%. The 10,000 times and 100,000 times electron micrographs are shown in FIG.

  At the same time, in the scanning analysis of the scanning probe microscope, the mean valley interval (RSm) was 1-2 μm, and the maximum height difference (Rz) was 0.3-0.4 μm. Another one was subjected to XPS analysis. In XPS, element information of a portion shallower than the surface depth of about 1 nm can be obtained. From this XPS analysis, a large amount of oxygen and iron was observed on the surface, and a small amount of nickel, chromium, carbon, a very small amount of molybdenum and silicon were observed. From these, it was found that the surface layer was mainly composed of metal oxide. This analysis pattern was almost the same as SUS304 before etching.

[Experiment 12] (Surface treatment of general steel)
A commercially available 1.6 mm-thick cold rolled steel “SPCC Bright” plate was purchased and cut into a rectangular shape having a size of 18 mm × 45 mm, which was used as a steel plate. Holes are made in the ends of this steel plate, and copper wires coated with vinyl chloride are passed through to dozens, and the copper wires are bent and processed so that they do not overlap each other, so that all can be hung at the same time. did. An aqueous solution containing 7.5% of an aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” at 60 ° C. is immersed in a steel plate for 5 minutes and washed with tap water (Ota City, Gunma Prefecture). did.

  Next, a 1.5% aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the steel plate material was immersed for 1 minute and washed with water. Next, an aqueous solution containing 10% of 98% sulfuric acid at 50 ° C. was prepared in another tank, and the steel plate material was immersed in this for 6 minutes and sufficiently washed with ion-exchanged water. Next, it was immersed in 1% aqueous ammonia at 25 ° C. for 1 minute, washed with water, then at 45 ° C. 2% potassium permanganate, 1% acetic acid, 0.5% sodium hydroxide hydrate It was immersed in an aqueous solution containing 1 minute and washed thoroughly with water.

  This was placed in a hot air dryer at 90 ° C. for 15 minutes and dried. From the result of observation of the obtained steel sheet material with a 100,000 times electron microscope, it is an ultra-fine uneven shape with an infinite number of steps with a height and depth of 50 to 500 nm and a width of several hundred to several thousand nm. It can be seen that is covered. A photograph is shown in FIG. On the other hand, in the scanning analysis with a scanning probe microscope, roughness with a mountain-valley average interval RSm of 1 to 3 μm and a maximum roughness height Rz of 0.3 to 1.0 μm was observed.

[Experimental Example 13] (Adhesion between aluminum alloys)
A phenol resin adhesive “110 (manufactured by Cemedine)” was thinly applied with a brush to each of the 18 ends of the A5052 aluminum alloy sheet material prepared in Example 1. Thereafter, this was allowed to stand for 100 minutes, and then placed in a large desiccator that had been heated to 60 ° C. in advance, depressurized with a vacuum pump, and returned to normal pressure for 3 minutes. The cycle of returning to normal pressure and allowing to stand for 3 minutes, reducing pressure again and returning to the same normal pressure was repeated three times. Next, it was taken out from the desiccator, left in a hot air drier at 90 ° C. for 20 minutes and taken out.

And the pair which contacted the surfaces which apply | coated the adhesive agent was pinched | interposed with the clip, and preparation for adhesion | attachment was carried out like FIG. The adhesion area of both aluminum alloy plate materials was set to 0.7 to 0.8 cm ² . Nine pairs of aluminum alloy sheets sandwiched between two small clips were placed in a hot air dryer set at 180 ° C. and left for 1 hour to cure the adhesion. One week later, a tensile tester was used to break three pairs and measure the shear breaking strength. The average of the three sets was 290 Kgf / cm ² (28 MPa).

The remaining 6 pairs were allowed to stand in a hot air drier at 100 ° C. for 3 hours and then removed, and the 3 pairs were pulled and broken at 100 ° C. The average shear breaking force was 350 kgf / cm ² (34 MPa). Next, the hot air dryer was raised to 150 ° C. and allowed to stand for 30 minutes, and when the remaining 3 pairs were pulled and broken at 150 ° C., the average shear breaking force was 300 kgf / cm ² (29 MPa). In an experiment using a phenol resin adhesive, it was confirmed that the adhesive strength was higher and the heat resistance was higher at 100 to 150 ° C. than normal temperature.

[Experimental example 14] (Adhesion between aluminum alloys: comparative example)
On the other hand, the A5052 aluminum alloy was processed in the same manner as in Example 1 but until the degreasing step. Specifically, a product which was immersed in an aqueous solution of degreasing material for 7 minutes, washed with water and dried was prepared from these 6 pieces in the same manner as described above. Three pairs were obtained by bonding with a phenol resin adhesive “110”. Further, the sample was broken with a tensile tester in the same manner as described above, and the shear breaking force was measured. The average of the three pairs was 190 kgf / cm ² (19 MPa). This was nearly 100 kgf / cm ² lower than Experimental Example 13.

[Experimental Examples 15 to 25] (Adhesion between various metal alloys)
Phenol resin adhesive at each end of each of six A7075 aluminum alloys, two magnesium alloys, four copper alloys, two titanium alloys, SUS304, and SPCC metal alloy sheets prepared in Experimental Examples 2-12 “110 (Cemedine)” was applied thinly with a brush. This was allowed to stand for 100 minutes, and then placed in a desiccator that had been heated to 60 ° C. in advance, and the pressure was reduced with a vacuum pump for 3 minutes to return to normal pressure. The cycle of returning to normal pressure and allowing to stand for 3 minutes, reducing pressure again and returning to the same normal pressure was repeated three times.

Next, it was taken out from the desiccator, left in a hot air drier at 90 ° C. for 20 minutes and taken out. And the pair which contacted the surfaces which apply | coated the adhesive agent was pinched | interposed with the clip, and preparation for adhesion | attachment was carried out like FIG. The adhesion area of both metal alloy pieces was set to approximately 0.7 cm ² . Three pairs of aluminum alloy sheets sandwiched between two small clips were placed in a hot air dryer set at 180 ° C. and left for 1 hour to cure the adhesion. One week later, a tensile tester was used to break three pairs and measure the shear breaking strength. The average value for each of the three sets is shown in Table 1.

[Experimental examples 26, 29 to 35] (Adhesion between various metal alloys: Comparative example)
On the other hand, each of the A7075 aluminum alloy, the magnesium alloy 2 types, the copper alloy 4 types, the titanium alloy 2 types, the SUS304, and the SPCC metal alloy plate materials are treated in the same manner as in Experimental Examples 2 to 12, but the magnesium alloy and the SPCC are processed. Except for the degreasing process, specifically, a product which is immersed in a degreasing aqueous solution for 7 minutes, washed with water and dried is prepared, and the phenol resin adhesive “110” is prepared from these six pieces in the same manner as in Experimental Examples 13-25. To obtain 3 pairs. Furthermore, it fractured | ruptured with the tension test machine similarly to Experimental Examples 13-25, and the shear breaking strength was measured. The results are shown in Table 1.

[Experimental examples 27 and 28] (Adhesion between various metal alloys: Comparative example)
The following treatment was performed from each of 1 mm × 45 mm × 18 mm rectangular pieces of AZ31B and AZ91D. That is, a commercially available magnesium alloy degreasing agent “cleaner 160 (manufactured by Meltex Co., Ltd.)” was poured into water to form an aqueous solution at 65 ° C. and a concentration of 7.5%. The magnesium alloy sheet was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 10-fold diluted solution of a commercially available magnesium alloy etching material “Mgtreat E5109 (manufactured by Meltex Co., Ltd.)” at 40 ° C. was prepared in another tank, and each of the above-mentioned alloy plate materials was immersed in this for 6 minutes. Washed well with water.

  Next, prepare a 7.5% aqueous solution of a commercially available first smut treating agent “NE-6 (manufactured by Meltex Co.)” at 65 ° C. in another tank, and immerse the above alloy plate material for 5 minutes. And washed well with water. Subsequently, a 15% strength aqueous caustic soda solution at 65 ° C. was prepared in another tank, and the alloy plate material was immersed in this for 5 minutes and washed with water. Next, a 10-fold diluted aqueous solution of a commercially available manganese phosphate chemical conversion treatment agent “Magtreat MG5565 (manufactured by Meltex Co.)” at 45 ° C. was prepared in another tank, immersed in this for 2 minutes, and this was added for 15 seconds. It was washed with water and placed in a hot air dryer at 90 ° C. for 15 minutes to dry.

  The entire chemical conversion treatment method is a standard formulation of the treatment agent manufacturer (Meltex Co.) used in this experiment, and until this standard formulation is followed. After drying, the magnesium alloy sheet was wrapped together with aluminum foil, which was then placed in a plastic bag and sealed. Using this magnesium alloy sheet, it was bonded with an adhesive “110 (manufactured by Cemedine)” in the same manner as in Examples 16 and 17, and tensile ruptured to determine its shear rupture strength. The results are shown in Table 1.

[Experimental example 36] (Adhesion between various metal alloys: Comparative example)
A commercially available 1.6 mm-thick cold-rolled steel “SPCC Bright” plate was purchased and cut into a rectangular shape with a size of 18 mm × 45 mm, which was used as a number of steel plates. A hole is made in the end of this steel plate material, and a copper wire coated with vinyl chloride is passed through a plurality of pieces, and the copper wire is bent and processed so that the steel plate materials do not overlap each other, so that a plurality can be hung at the same time. I made it. An aqueous solution containing 7.5% of an aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” was set to 60 ° C., and the steel plate was immersed in this aqueous solution for 5 minutes, and then the tap water (Ota, Gunma) City).

  Next, prepare an aqueous solution in which 1.2% orthophosphoric acid, 0.21% zinc oxide, 0.23% basic nickel carbonate, and 0.16% sodium silicofluoride at 55 ° C are dissolved in another tank. The steel sheet was immersed in this aqueous solution for 2 minutes and washed with water. This is a standard method of zinc phosphate processing used for rust prevention of steel plate materials. Using this SPCC steel piece, it was bonded with an adhesive “110 (manufactured by Cemedine)” in exactly the same manner as in Example 25, and was subjected to tensile rupture to determine its shear rupture strength. The results are shown in Table 1 below.

  As is clear from Table 1, all showed high adhesive strength as compared with the conventional pre-adhesion standard treatment. From numerical values, it was 40-50 MPa for A7075 aluminum alloy, SUS304 stainless steel, SPCC steel, and the like, while copper alloys were low and felt to be proportional to the hardness of the material.

[Experimental example 37] (Preparation of preform using friction material recipe)
20 parts by mass of a commercially available phenolic resin “PGA-2473 (manufactured by Gunei Chemical Co., Ltd.)” for bar brake pads, 20 parts by mass of barium sulfate “Varico # 300 (manufactured by Nakami Hitech Co., Ltd.)”, calcium carbonate “SL300 (Takehara Chemical) Kogyo Co., Ltd.) ”10 parts by weight, copper powder“ electrolytic copper powder (manufactured by Nikko Materials) ”5 parts, aramid pulp“ KEVLAR pulp (manufactured by Toray DuPont) ”15 parts, steel fiber“ cut wool (Nihon Steel) Wool Co., Ltd.) ”15 parts by mass, cashew resin powder“ Cashew Polymer LB3111 (Tohoku Kako Co., Ltd.) ”10 parts by mass, graphite“ slag-like graphite CX-3000 (manufactured by Chuetsu Graphite Industries Co., Ltd.) ”5 parts by mass 100 parts by mass were mixed well.

  About 5 cc of the mixed powder was put into a 45 mm × 15 mm rectangular hot press die and pressed at 100 atm. After the temperature was raised to 90 ° C., it was maintained at 100 atm for 1 hour. When cooled and taken out from the press mold, a 45 mm × 15 mm × 7.1 mm rectangular brake pad preform was obtained.

[Experiment 38] (Production of metal alloy / friction material composite and its evaluation)
An A7075 aluminum alloy sheet obtained by the same method as in Experimental Example 2 was used. The aluminum alloy sheet was taken out, applied with a phenol resin adhesive “110 (Cemedine)”, and left for one and a half hours. It put into the desiccator previously heated at 60 degreeC, and reduced pressure to 5 mmHg or less with a vacuum pump, and left for 1 minute, and air was introduce | transduced into this and it returned to the normal pressure. When the pressure was returned to normal pressure, the operation of leaving it in this air for 5 minutes and then reducing the pressure was repeated three times, and the pressure was returned to normal pressure and taken out from the desiccator. It was left for 20 minutes in a hot air dryer set at 90 ° C. and taken out.

  On the other hand, the mold and jig shown in FIG. 1 were prepared. A material 17 cut with a fluororesin sealing tape was laid in the mold cavity, and the aluminum alloy plate was placed as 11 in the figure so that the adhesive-coated surface faced upward. Next to that, 16 plate materials having a thickness of 1.6 mm, which were cut out from the fluororesin block, were arranged as spacers. The preform of the brake pad composition prepared in Experimental Example 39 is placed on the spacer 16 as 12 in the figure, and a fluororesin plate-like material matching the thickness of the preform as a thickness of 7.1 mm is used as the spacer 13. Packed sideways.

On top of these, a cut piece of fluororesin seal tape was placed as a release film 14, and an upper mold 15 was placed thereon. It put in the hot air dryer in this form. Therefore, 5 kg of iron ingot was placed on the upper die 15 as a weight 18, and the dryer was energized and heated to 180 ° C. It was kept at 180 ° C. for 100 minutes, and was allowed to cool with the energization stopped and the door closed. On the next day, the product was taken out from the dryer, and the molded product was released from the mold, and the fluororesin tape was peeled off to obtain the shape shown in FIG. The same operation was repeated to obtain three integrated products. One week later, the sample was broken by a tensile tester and the shear breaking strength was measured. The average of the three was 380 Kgf / cm ² (37 MPa).

[Experimental Example 39] (Preparation of metal alloy / friction material composite and its evaluation)
A cold rolled steel SPCC plate obtained by the same method as in Experimental Example 13 was used. The SPCC plate material was taken out, applied with a phenol resin adhesive “110 (manufactured by Cemedine)”, and left for one and a half hours. The sample was put in a desiccator that had been heated to 60 ° C. in advance, and the pressure was reduced to 5 mmHg or less with a vacuum pump. After returning to normal pressure, the operation of leaving for 5 minutes and then reducing the pressure was repeated three times, and the pressure was returned to normal pressure and taken out from the desiccator. Thereafter, an integrated product of the friction material and SPCC was obtained in the same manner as in Experimental Example 38. One week later, it was subjected to a tensile tester and three pieces were broken and the shear breaking strength was measured. The average of the three sets was 420 kgf / cm ² (41 MPa).

FIG. 1 is a cross-sectional view schematically showing a firing jig for bonding a metal piece and a preformed product with a phenol resin adhesive and curing them in a hot air dryer. FIG. 2 is an external view showing an adhesive complex in which a metal piece and a preform are joined with a phenol resin adhesive. FIG. 3 is an external view showing an adhesive complex in which metal pieces are bonded to each other with a phenol resin adhesive. FIG. 4 is a schematic partial sectional view showing a theoretical configuration (NAT theory) to be bonded by using a one-component thermosetting adhesive. FIG. 5 is a 10,000 times and 100,000 times electron micrograph of an A5052 aluminum alloy piece etched with an aqueous caustic soda solution and finely etched with a hydrated hydrazine aqueous solution. FIG. 6 is a 10,000 times and 100,000 times electron micrograph of an A7075 aluminum alloy piece etched with a caustic soda solution and finely etched with a hydrated hydrazine solution. FIG. 7 is a 100,000 times electron micrograph of an AZ31B magnesium alloy piece etched with an organic carboxylic acid aqueous solution and subjected to chemical conversion treatment with a potassium permanganate aqueous solution. FIG. 8 is a 100,000 times electron micrograph of an AZ31B magnesium alloy piece etched with an organic carboxylic acid aqueous solution and subjected to chemical conversion treatment with a potassium permanganate aqueous solution. FIG. 9 is a 10,000 times and 100,000 times electron micrograph of an AZ91D magnesium alloy piece etched with an organic carboxylic acid aqueous solution and subjected to chemical conversion treatment with a potassium permanganate aqueous solution. FIG. 10 is a 10,000 times and 100,000 times electron micrograph of a C1100 tough pitch copper piece etched with sulfuric acid / hydrogen peroxide aqueous solution and oxidized with sodium chlorite aqueous solution. FIG. 11 is a 10,000 times and 100,000 times electron micrograph of a C5191 phosphor bronze piece etched with sulfuric acid / hydrogen peroxide aqueous solution and oxidized with sodium chlorite aqueous solution. FIG. 12 is a 10,000 times and 100,000 times electron micrograph of a “KFC (made by Kobe Steel)” copper alloy piece etched with sulfuric acid / hydrogen peroxide aqueous solution and oxidized with sodium chlorite aqueous solution. FIG. 13 is a 10,000 times and 100,000 times electron micrograph of a “KLF5 (manufactured by Kobe Steel)” copper alloy piece etched with sulfuric acid / hydrogen peroxide solution and oxidized with sodium chlorite solution. FIG. 14 is a 10,000 times and 100,000 times electron micrograph of a pure titanium-based titanium alloy KS-40 piece etched with an aqueous hydrogen difluoride ammonium solution. FIG. 15 is a 10,000 times and 100,000 times electron micrograph of an α-β type titanium alloy KSTI-9 piece etched with an aqueous solution of 1 hydrogen difluoride ammonium fluoride. FIG. 16 is a 10,000 times and 100,000 times electron micrograph of a stainless steel SUS304 piece etched with a sulfuric acid aqueous solution. FIG. 17 is a 10,000 times and 100,000 times electron micrograph of a cold rolled steel SPCC steel piece etched with a sulfuric acid aqueous solution and subjected to chemical conversion treatment with a potassium permanganate aqueous solution.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Baking jig 2 ... Mold main body 3 ... Mold recessed part 4 ... Mold through-hole 5 ... Mold bottom plate 6 ... Bottom plate projection 7 ... Mold bottom 8 ... Mold base 10 ... Adhesive composite 11 ... Metal piece DESCRIPTION OF SYMBOLS 12 ... Preliminary product 13 ... Spacer 14 ... Release film 15 ... Weight 16 ... Spacer 17 ... Release film 18 ... Weight 20 ... Adhesive complex 21 ... Metal piece 22 ... Metal piece 23 ... Joint part (phenol resin type) Hardened material layer of adhesive)

Claims (23)

It has a micron-order roughness by chemical etching, and its surface is covered with a fine irregular shape with an irregular period of 5 to 500 nm, and its surface is made of metal oxide or metal phosphate. Metal parts that are thin layers;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . It has a micron-order roughness by chemical etching, and its surface has a shape covered with an ultrafine uneven surface that is a recess or protrusion having a diameter of 10 to 100 nm and an equivalent depth or height, and A metal part made of an aluminum alloy having a thin aluminum oxide layer having a thickness of 2 nm or more whose surface does not contain sodium ions;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . The surface has a roughness of micron order by chemical etching, and the surface thereof is covered with an ultrafine uneven surface in a form in which rods having a diameter of 5 to 20 nm and a length of 20 to 200 nm are complexed, and A metal part made of magnesium alloy whose surface has a thin layer of manganese oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . There is a roughness on the order of microns by chemical etching, and the surface is ultrafine in the shape of irregularly stacked spheres with a diameter of 5 to 20 nm and 10 to 30 nm long rod-shaped projections with a diameter of 80 to 100 nm. A metal part made of magnesium alloy having a shape covered with an uneven surface and having a thin layer of manganese oxide on its surface;
An adherend to be bonded to the metal part;
An adhesive composite containing a metal alloy comprising the metal component and an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the adherend and adheres both . It has a micron-order roughness due to chemical etching, and its surface is covered with an ultra-fine irregular surface formed by stacking 20 to 40 nm particle size objects and indefinite polygonal shapes, and the surface is Metal parts made of magnesium alloy having a thin layer of manganese oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . Ultra-fine irregularities with roughness on the order of microns by chemical etching, and the surface has hole openings or recesses with an average of 10 to 150 nm in diameter or major axis and minor axis at irregular intervals of 30 to 300 nm. A metal part made of a copper alloy whose surface is almost entirely covered with the shape and whose surface is mainly a thin layer of cupric oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . It has a micron-order roughness by chemical etching, and its surface is an ultrafine uneven shape in which convex portions having an average diameter or major axis and minor axis of 10 to 200 nm are mixed, and the surface is Metal parts made of copper alloy, which is mainly a thin layer of cupric oxide,
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . Ultra-fine irregularities with a roughness of micron order by chemical etching, and the surface is formed by continuous fusion of particle diameters or indefinite polygonal shapes with an average diameter or major axis and minor axis of 10 to 150 nm. A metal part made of a copper alloy whose surface is almost entirely covered with the shape and whose surface is mainly a thin layer of cupric oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . There is a roughness on the order of microns by chemical etching, and the surface is a super fine uneven shape of a shape in which a particle having a diameter of 10 to 20 nm and an indefinite polygon having a diameter of 50 to 150 nm are mixed and stacked. A metal component made of a copper alloy that is covered and whose surface is a thin layer of cupric oxide mainly;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . There is a roughness on the order of microns by chemical etching, and the surface is super fine with a height or width of 10 to 350 nm, and ridges or continuous ridges having a length of 10 nm or more on the entire surface in a cycle of 10 to 350 nm. A metal part made of a titanium alloy having a concavo-convex shape and whose surface is mainly a thin layer of titanium oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . By chemical etching, as seen with a scanning probe microscope, there is a roughness with an average interval between peaks and valleys (RSm) of 1 to 10 μm, a maximum roughness height (Rz) of 1 to 5 μm, and the surface has an area of 10 μm square. A metal part of an α-β type titanium alloy having a fine concavo-convex shape in which both a smooth dome-like shape and a dead leaf-like shape are observed, and a surface of which is a metal oxide thin layer mainly containing titanium and aluminum;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . It has a micron-order roughness due to chemical etching, and its surface is almost entirely covered with an ultra-fine irregular shape of a particle size 20 to 70 nm in diameter or an indefinite polygonal shape, and its surface. A stainless steel part metal part which is a thin layer of metal oxide,
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . It has a roughness of micron order by chemical etching, and its surface is an ultra fine uneven shape with a height of 80 to 150 nm, a depth of 80 to 200 nm, and a width of several hundred to several thousand nm that is infinitely long. A metal part made of steel material, the whole surface of which is covered and whose surface is one kind of thin layer selected from manganese oxide, chromium oxide, and zinc phosphorus oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . It has a micron-order roughness due to chemical etching, and its surface is an ultra-fine uneven shape with a height of 80 to 150 nm, a depth of 80 to 500 nm, and a width of several hundred to several thousand nm that is infinitely long. A metal part made of steel material that is almost entirely covered and whose surface is a thin layer of manganese oxide, chromium oxide, or zinc phosphorus oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . It has a micron-order roughness due to chemical etching, and its surface is an ultra-fine uneven shape with a height of 50 to 100 nm, a depth of 80 to 200 nm, and a width of several hundred to several thousand nm and an infinite number of steps. A metal part made of steel material that is almost entirely covered and whose surface is one kind of thin layer selected from manganese oxide, chromium oxide, and zinc phosphorus oxide;
An adherend to be bonded to the metal part;
An adhesive composite comprising a metal alloy, comprising: an adhesive layer that is a cured product of a one-component thermosetting resin adhesive that is applied to the adhesive surface of the metal part and the adherend and adheres both . 16. One selected from an adhesive composite comprising a metal alloy according to claim 1 selected from claims 1-15.
The adhesive complex containing a metal alloy, wherein the one-component thermosetting resin adhesive is a phenol resin adhesive. 17. One selected from an adhesive composite comprising a metal alloy according to claim 1 selected from claims 1-16.
The adhesive composite comprising a metal alloy, wherein the adherend is a metal part having the same property as the metal part. 17. One selected from an adhesive composite comprising a metal alloy according to claim 1 selected from claims 1-16.
An adhesive composite containing a metal alloy, wherein the adherend is a cured product of a thermosetting resin composition using a thermosetting resin as a matrix. An adhesive composite comprising the metal alloy of claim 18.
An adhesive composite containing a metal alloy, wherein the cured product is a cured product of a thermosetting resin composition using a phenol resin as a matrix. An adhesive composite comprising the metal alloy of claim 19.
An adhesive composite containing a metal alloy, wherein the cured product is a friction material obtained by solidifying a phenolic resin as a matrix and containing a fibrous material and an abrasion-resistant solid powder. Forming a metal alloy material into a predetermined shape by mechanical processing;
The surface of the shaped metal alloy material is covered with fine irregularities having an irregular period of 5 to 500 nm, and the large irregularities constituted by the fine irregularities are represented by an average interval between peaks and valleys (RSm). A surface treatment step of performing various liquid treatments including chemical etching that gives a roughness of 1 to 10 μm and a maximum roughness height (Rz) of 0.2 to 5 μm;
Forming an adherend to be bonded to the shaped metal alloy material into a predetermined shape;
Applying a one-component thermosetting resin adhesive to the metal alloy material or the adherend;
An adhesive composite comprising a metal alloy comprising the steps of: bonding the applied metal alloy material to the adherend and bonding the adhesive surface of the adherend and curing the one-part thermosetting resin adhesive and integrating the two together by adhesion Manufacturing method. In the manufacturing method of the adhesion composite containing the metal alloy according to claim 21,
After the coating step, a step of storing the metal alloy material coated with the one-component thermosetting resin adhesive or the adherend in a hermetically sealed container and depressurizing, and then repeatedly performing the pressurizing operation is added. A method for producing a bonded composite comprising a metal alloy. In the manufacturing method of the adhesion composite containing the metal alloy according to claim 21 or 22,
The method for producing an adhesive composite containing a metal alloy, wherein the one-component thermosetting resin adhesive is a phenol resin adhesive.