JP5295738B2 - Adhesive composite containing metal alloy and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To increase an adhesive force at a temperature of 80-90&deg;C or above and to improve the heat resistance of an adhesive in an adhesion composite containing metal alloy. <P>SOLUTION: A metal shape object 21 obtained by NAT treatment in which the surface (1) has a roughness of micron order and (2) is covered with an ultra-fine unevenness of several tens nm order, and (3) an environmentally stable metal oxide or metal phosphate thin layer is formed on the surface and another similarly treated metal shape object or an FRP adherend 22 are adhered to each other by an epoxy adhesive 23, cured, and united. The epoxy adhesive contains inorganic powder having a center of particle size distribution of 5-20 &mu;m and 0.3-3 mass% of ultra-fine inorganic powder 100 nm or below in particle size as a filler. A fracturing dispersion method is used in order to dissolve the aggregation of the ultra-fine inorganic powder, and a fine powder type thermoplastic resin is added as a filler. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an adhesive composite including a metal alloy and a manufacturing method thereof, and more particularly to an adhesive composite including a metal alloy used in a mobile machine, an electric device, a medical device, a general machine, and the like, and a manufacturing method thereof. More specifically, in the present invention, as a new basic part, a metal part and a metal part are integrated, or metal and fiber reinforced plastic (hereinafter referred to as “FRP (abbreviation of Fiber reinforced plastics)”) are epoxy-based. The present invention relates to a composite that is firmly bonded and integrated with an adhesive and its manufacturing technology. In particular, the present invention relates to a composite for use in a mobile machine that has improved heat resistance compared to the case of using a normal epoxy adhesive and is expected to contribute most in practical use, and a manufacturing technique thereof.

  Technology for integrating metal and resin is required in all parts and materials manufacturing industries such as aircraft, 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 now a common bonding technique.

  On the other hand, bonding methods that do not use an adhesive have also been studied. An example is a method in which light metals such as magnesium, aluminum and 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 with resin molding by a method such as injection (hereinafter referred to as “injection joining”), polybutylene terephthalate resin (hereinafter referred to as “PBT”) or polyphenylene sulfide resin which is a thermoplastic resin for an aluminum alloy Manufacturing techniques for injection joining (hereinafter referred to as “PPS”) have been developed (see, for example, 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 4, 5, 6, 7, and 8).

  The principle of injection joining in Patent Document 1 is said to be as follows. The aluminum alloy is immersed in a dilute aqueous solution of a water-soluble amine compound, and the aluminum alloy is finely etched by the weak basicity of the aqueous solution. Further, in this immersion, adsorption of amine compound molecules on the surface of the aluminum alloy occurs simultaneously. The aluminum alloy thus treated is inserted into an injection mold, and the molten thermoplastic resin is injected at a high pressure.

  At this time, a chemical reaction occurs when the thermoplastic resin and the amine compound molecules adsorbed on the aluminum alloy surface are encountered. This chemical reaction suppresses a physical reaction in which the thermoplastic resin is rapidly cooled in contact with an aluminum alloy maintained at a low mold temperature to crystallize and solidify. As a result, the resin is delayed in crystallization and solidification, and in the meantime, it can sink into the recesses on the ultrafine aluminum alloy surface. This makes it difficult for the thermoplastic resin to peel off from the aluminum alloy surface even when subjected to external force. That is, the resin molded product formed with the aluminum alloy is firmly bonded. In other words, it can be said that the chemical reaction and the physical reaction are in a competitive relationship, and in this case, since the chemical reaction is given priority, strong injection joining occurs.

  In fact, it has been confirmed that PBT and PPS that can chemically react with an amine compound can be injection-bonded with the aluminum alloy. The inventors called this injection joining mechanism the “NMT (Nano molding technology)” theory (hypothesis).

  In addition to the NMT theory, there is another known technique in which chemical etching is performed in advance, and then a metal part is inserted into a mold of an injection molding machine and injection molding is performed using a thermoplastic resin material (for example, patents). Reference 3). Although this technique is poor as a joining method and is insufficient as compared with the joining by the “NMT”, the present inventor who is also a proponent of the NMT theory because the NMT theory shows an effect only in an aluminum alloy. They also thought that new joint technology should be developed for injection joining to metals other than aluminum alloys.

  As a result of proceeding with development for such a purpose, the present inventors have arrived at a new technology “new NMT” theory. That is, the present inventors have come up with conditions for injection joining without chemical adsorption of amine compounds on the metal alloy surface, in other words, without obtaining special exothermic reaction or assistance of any chemical reaction. This can be demonstrated with various metal alloys, as described below.

  The injection joining theory based on the new NMT theory requires at least the following conditions. The first condition is to use a hard highly crystalline resin, that is, to use PPS, PBT, or polyamide resin. In addition, it is necessary to make these compositions further improved for injection joining. Another condition is that the surface layer of the metal part inserted into the mold is strong and hard and has a specific surface shape.

  For example, when a magnesium alloy is used as a raw material and its shape is used, a magnesium alloy that is still covered with a natural oxide layer has low corrosion resistance. Therefore, the surface of the magnesium alloy is converted to metal oxide, metal carbonate, or metal. By using phosphorous oxide, a surface covered with a ceramic material having high hardness can be obtained. A magnesium alloy part having a ceramic surface layer and an uneven surface on the order of microns could meet the above conditions.

  Theoretically, the case where these surface-treated magnesium alloy shaped articles are inserted into an injection mold is considered as follows. Since the mold and the inserted magnesium alloy shape are kept at a temperature 100 ° C. or more lower than the melting point of the resin to be injected, the injected resin is rapidly cooled as soon as it enters the flow path in the mold, and the magnesium metal part There is a high possibility that the temperature is below the melting point when approaching.

  If any crystalline resin is rapidly cooled from the molten state to below the melting point, it does not instantly crystallize and solidify, but it is a short time, but the molten state below the melting point, that is, the time for the supercooled state There is. When the diameter of the concave portion on the magnesium alloy shaped article is relatively large, such as about 1 to 10 μm, the resin can enter within a limited time during which microcrystals are generated from supercooling. Further, even if the number density of the generated polymer microcrystal group is still small, the resin can enter if it is a large recess. Since the size of a microcrystal, that is, a crystallite having a shape when an alignment state is generated from a molecular chain that has been moving irregularly to the molecular chain, is estimated to be several nanometers to 10 nm when estimated from a molecular model. It is.

  Therefore, it is difficult to say that microcrystals can easily penetrate into ultrafine concave portions having a diameter of 10 nm, but if the concave portion has a concave and convex surface with a period of several tens of nanometers, there is a possibility that the head of the resin flow is slightly pushed. However, since innumerable microcrystals are generated at the same time, the viscosity of the resin flow rapidly rises at the point where it is in contact with the tip of the injection resin or the metal mold surface. As a result, if a resin whose crystallization speed during quenching is slowed down with a special compound is used, if the depth is 1 to 10 μm and the depth is about 0.5 to 5 μm, which is half the period, The molten resin can penetrate to the bottom of the recess, and if there are further ultrafine irregularities with a period of about 10 to 100 nm on the inner wall surface of the recess, the resin flow head should be slightly inserted into the recesses of the gaps of the ultrafine irregularities. It seemed to be possible.

  Coincidentally, when the surface of the magnesium alloy subjected to the chemical conversion treatment was observed with an electron microscope, an ultrafine irregular surface with a period of 10 to 50 nm was observed, and it was confirmed that the ultrafine surface structure as described above was present. When resin injection is performed when there is a metal part having a surface of the same shape as well as a magnesium alloy, the resin flow has large concave portions of micron order (that is, unevenness with a period of 1 to 10 μm, and the uneven height difference thereof. If the resin crystallizes and solidifies in this large recess, if it can penetrate to the bottom of a thing (up to about half the cycle) and be caught in a hard ultrafine uneven portion in that large recess It can be estimated that it is quite difficult to pull this out.

  In fact, aiming at such a shape, alloy parts of copper, titanium and steel materials are manufactured by etching and chemical treatment, and improved PPS resin (PPS resin compound that can reduce the rate of PPS molecular crystallization during quenching) When injection bonding, a considerably strong bonding force was generated. The surface of the alloy-shaped product was a ceramic crystallite group such as a metal oxide or an amorphous layer by oxidation or chemical conversion treatment, and was a hard and durable spike. In other words, the ultra-fine irregularities work like spikes in the micron-order recesses, and even if a strong peeling force is applied to the resin part, the solidified resin part does not come out in the large recesses. A strong bond between the resins was obtained.

  The improved PPS resin described above will be described. That is, in injection molding, the resin composition is rapidly cooled from the molten state to a temperature below the melting point by injection. If a resin composition prepared so as to slow down the crystallization rate during rapid cooling is available, it will take time to enter the fine recesses on the metal alloy part inserted into the mold. This will produce a stronger bonding force. This is an important and necessary condition for a resin composition suitable for injection joining.

  Based on the above concept, the present inventors chemically etched the shape of magnesium alloy and other metal alloys as described above, and further ceramicized and hardened the surface layer by surface treatment such as chemical conversion treatment. It has been found that a hard crystalline resin having a special composition is injection-bonded to obtain high bondability (Patent Documents 4 to 8). In each document, the bonding conditions are described in detail for each metal type, but the common idea is the new NMT theory described above. In short, it can be seen from Patent Documents 4 to 8 that the new NMT theory is a general theory that is not trapped by metal species.

The almost final conditions of the new NMT theory are described. First of all, regarding a metal alloy, it is a basic requirement that the surface be provided with the following (1) to (3) by chemical treatment corresponding to the metal alloy type. That is,
(1) An uneven surface with a height difference of up to about half of the period in a period of 1 to 10 μm, that is, a surface having a micron-order roughness,
(2) The inner wall surface of the recess is an ultra fine uneven surface with a period of 10 to 500 nm, most preferably with a period of 50 to 100 nm,
(3) The surface should be covered with a thin layer of a ceramic hard phase. Specifically, the surface should be covered with a thin layer of an environmentally stable metal oxide or metal phosphate. about,
It is. These are schematically illustrated as shown in FIG. Assuming that the liquid resin composition has infiltrated into the metal alloy as described above and has been hardened after the intrusion, the metal alloy base material and the cured resin are bonded very firmly.

  The injection joining of thermoplastic resin will be described below with this new NMT theory. When a hard and highly crystalline thermoplastic resin composition that can slow down the crystallization and solidification rate during rapid cooling is injected, the resin composition injected into the injection mold is cooled to a temperature below the melting point. Even for a while, it is in a supercooled liquid state.

  Therefore, if the metal alloy is inserted in advance into the injection mold, it can easily penetrate into the concave portion (1) having a micron-order roughness. Furthermore, although it is not perfect, it can penetrate to a certain extent into the recesses of the ultrafine irregularities of (2). After that, the crystallization progresses at a high speed and solidifies. As a result, the resin that has entered and solidified into the recesses having a roughness on the order of microns is caught by the ultrafine irregularities in (2), and the ultrafine irregularities in (3) Because it is very hard, it is firmly stopped as if it was spiked and cannot be pulled out from the recess. This is an injection joining technique using a thermoplastic resin (Patent Documents 4 to 8).

  If the bonding mechanism of the new NMT theory is correct, it can be expected that strong bonding will be produced by bonding using a solventless one-component thermosetting adhesive. In other words, the liquid resin approaches the surface-treated metal alloy according to the new NMT theory and enters the micron-order concave portion, and also enters the concave portion of the ultra-fine unevenness on the inner wall surface of the concave portion. If it is hardened, it can be inferred that the solidified resin cannot be pulled out of the recess due to the spike effect and a strong bond can be obtained. However, it is considered that the viscosity of the liquid resin in the environment (pressure and temperature) determines the extent to which the liquid resin can enter the gaps of the ultra-fine irregularities.

  Thus, while considering that the liquid viscosity when uncured is an important matter, the present inventors surface-treated metal alloy pieces by a method based on the new NMT theory, and commercially available general-purpose one-part epoxy. The metal alloy pieces were bonded to each other using a system adhesive. As a result, it was confirmed that the strong adhesion of 50 to 70 MPa was generated by the shear breaking force and the tensile breaking force.

  However, it was devised after applying the adhesive. That is, the process of putting the adhesive coated material into a desiccator and making it almost vacuum, and then returning to normal pressure was repeated. Although the pressure difference was 1 atm or less, the liquid adhesive was considered to easily enter the recesses on the metal surface. Thereafter, the applied metal alloys were fixed with clips or the like and heated to be cured. With the addition of this soaking step, a strong metal alloy bond that was not seen in the past was obtained. The present inventors have called this technique “NAT (abbreviation of Nano adhesion technology)”, and have made it clear that this is a technique for joining an adhesive different from the technique using injection molding (Patent Documents 9 to 16).

  The one-component adhesive is preferable in NAT because the gelation of the adhesive molecules does not progress in the pre-curing operation such as coating and subsequent dyeing operation, and it adheres to the gaps of (2) ultra fine irregularities on the metal. This is because agent molecules can penetrate to some extent. Even when a two-component thermosetting adhesive is used, the bonding strength is improved by using a metal alloy that has been surface-treated according to the present invention. However, in many cases, the improvement in bonding strength is not dramatic. Most two-component adhesives start to gel from the moment the hardener component is added to the main liquid and mixed. As the gelation progresses, there is little penetration of the resin component into the gaps between the ultra-fine irregularities in (2). Become.

In short, when a two-component adhesive is used, the adhesive force often changes depending on the elapsed time after mixing the curing agent, which may be inferior in stability and reproducibility. However, even epoxy resin adhesives that use two-component adhesives and generally known acid anhydrides as curing agents, these take a long time to start gelation and are expensive when proceeding skillfully. Adhesive strength was obtained. It is known that NAT can be effectively treated as a one-component adhesive as long as the two-component adhesive can reduce the gelation rate.
JP 2004-216425 A WO2004-055248 JP 2001-225352 A 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. 2007-185547 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 Japanese Patent Application No. 2007-325736 Japanese Patent Application No. 2007-336378 Japanese Patent Application No. 2007-325737

  The present inventors use commercially available one-component thermosetting epoxy adhesives and use NAT to identify metal pieces or metal pieces and carbon fiber reinforced plastics (hereinafter referred to as “CFRP (Carbon-fiber reinforced plastics)”). ), I realized that there was a problem to be solved in the process of commercialization and commercialization. There were two major points, one of which was the heat resistance of the adhesive.

  In other words, it is the curing agent type that is directly related to the heat resistance of the cured epoxy adhesive. Specifically, among the amine-based curing agents, the adhesive strength in the order of dicyandiamide, imidazoles, and aromatic diamines. It is known to increase heat resistance. However, since aromatic diamines are solid, the resulting thermosetting resin composition is solid rather than pasty at room temperature. This makes it difficult to use as an adhesive for NAT. That is, in the case of NAT, it is necessary to allow the liquid adhesive to penetrate to the bottom of the micron-order concave portion on the metal surface at a low pressure of about 1 atm.

  However, if the temperature to be raised is high, gelling and curing will start and it will be difficult to adjust the temperature during operation. In the end, thermosetting epoxy resin compositions using aromatic diamines are currently unsuitable for NAT adhesives. We considered using an acid anhydride (generally a liquid) as a curing agent to make it a heat-resistant adhesive, but one of the objects of the present invention is co-curing adhesion between a metal alloy and CFRP (in the industry related to adhesion, Normal solid-to-solid adhesive bonding is called “co-bond”, and one or both of them are adhesive-bonding uncured material such as prepreg is called “co-curing” type of adhesive, so co-curing is “co-curing” In addition, the curing agent system should be selected from the group of amine compounds according to CFRP, and acid anhydrides were excluded. In the end, dicyandiamide and imidazoles were specifically examined as curing agents. Therefore, one of the objectives of this NAT improvement was "to increase the heat resistance of the adhesive as much as possible by devising the filler without relying on a curing agent".

  Another problem is that the adhesive strength between the metal alloy and CFRP is inferior to the adhesive strength obtained by bonding metal alloys to each other. I was particularly worried about the inferiority of cocure adhesion. Since the adhesive to be used is the same, the above-described difference cannot occur if the breakage occurs between the adhesive and the metal alloy or the breakage occurs in the adhesive curing phase.

  In fact, when the fracture surface obtained by shearing and breaking the metal alloy piece and the CFRP bonded material by the Cocure method is observed, the resin phase is exposed on both surfaces, and therefore the present inventors have cured the epoxy adhesive. It was judged that there was a break between the phase and the CFRP matrix resin cured phase. Both were both epoxy resins and co-cured, but I was surprised to find that their joints were unexpectedly brittle. Assuming that this judgment is correct, the present inventors have inferred that to increase the bonding force between the two cured product phases, the difference in physical properties between the cured products should be reduced.

  That is, the composition characteristic of the current epoxy resin for CFRP matrix resin is high toughness. Since carbon fiber is responsible for the strength of the CFRP material, if the adhesion between the carbon fiber and the matrix resin can be made high, the matrix resin requires flexibility and impact resistance rather than strength and hardness.

  From this viewpoint, specifically, an epoxy resin composition in which rubber powder (for example, fine particles made from synthetic rubber latex), a powder of a thermoplastic resin, and the like are mixed and dispersed has recently been used. Assuming these, the present inventors also thought that if the bonding partner is not a metal alloy but a cured epoxy resin containing elastomer particles, the adhesive to be used must also be changed. Therefore, the second improvement target is to remodel the adhesive in consideration of the difference in physical properties with CFRP.

The present invention has been made to solve the above-mentioned problems, and an adhesive composite containing a metal alloy according to claim 1 of the present invention has a surface with a roughness of micron order by chemical etching and 5 to 5. A metal shape having a shape covered with an ultrafine irregular surface with an irregular period of 500 nm and a thin layer of metal oxide or metal phosphate formed on the surface, and adhesion to the metal shape Adhering material to be joined and adhesive that is applied to an adhesive surface between the metal shaped article and the adherend is cured to integrally bond the metal shaped article and the adherend. An adhesive composite comprising a metal alloy comprising a hardened layer, wherein the adhesive is a thermosetting epoxy adhesive, and an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler. together comprise a particle size of 0.3 to 3 wt% 100 following the ultrafine inorganic powder m, it is intended to include carbon nanotubes 0.02-0.2 wt%.

  The adhesive composite containing the metal alloy according to claim 2 that cites claim 1 of the present invention is one in which the adhesive further contains 1 to 10% by mass of thermoplastic resin powder as a filler.

An adhesive composite containing a metal alloy according to claim 3 which refers to claim 2 of the present invention is such that the thermoplastic resin powder is polyethersulfone.

An adhesive composite containing a metal alloy according to claim 4 which refers to any one of claims 1 to 3 of the present invention is such that the ultrafine inorganic powder is fumed silica.

An adhesive composite comprising a metal alloy according to claim 5 quoting any one of claims 1 to 4 according to the present invention is such that the adhesive is contained in an epoxy resin using a sand grind mill type wet pulverizer. It was produced by dispersing in high quality.

In an adhesive composite including a metal alloy according to claim 6 which refers to any one of claims 1 to 5 of the present invention, the surface of the metal shape has a roughness of micron order by chemical etching. And a shape covered with an irregular micro-protrusion surface with an irregular period that is a recess or protrusion having a diameter of 10 to 100 nm and an equivalent depth or height, and the surface does not contain sodium ions and has a thickness of 2 nm or more It is a metal shape product made of an aluminum alloy in which an aluminum oxide thin layer is formed.

An adhesive composite containing a metal alloy according to claim 7 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can, The surface has a roughness on the order of microns by chemical etching, and is covered with an extremely fine irregular surface in a form in which rods having a diameter of 5 to 20 nm and a length of 20 to 200 nm are intricately complicated, and The metal shape is made of a magnesium alloy having a thin layer of manganese oxide formed on the surface.

An adhesive composite containing a metal alloy according to claim 8 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can, The surface has a micron-order roughness due to chemical etching, and an ultrafine shape in which spherical objects having a diameter of 5 to 20 nm and a rod-like protrusion having a length of 10 to 30 nm and an infinite number of 80 to 100 nm in diameter are stacked irregularly. It is a metal shape made of magnesium alloy having a shape covered with an uneven surface and having a thin layer of manganese oxide formed on the surface.

The adhesive composite comprising a metal alloy according to claim 9 of the present invention has a shape in which the surface has a micron-order roughness by chemical etching and is covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can, The surface has a roughness on the order of microns by chemical etching and is covered with an ultrafine uneven surface having a shape in which 20 to 40 nm particles and / or indefinite polygonal shapes are stacked, and the surface The metal shape is made of a magnesium alloy in which a thin layer of manganese oxide is formed.

An adhesive composite containing a metal alloy according to claim 10 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching, and the fine or uneven surface has pore openings or recesses having an average diameter or major axis and minor axis of 10 to 150 nm at irregular intervals of 30 to 300 nm. This is a metal shape made of a copper alloy having a shape that is almost entirely covered with a surface, and in which a thin layer of cupric oxide is mainly formed on the surface.

An adhesive composite comprising a metal alloy according to claim 11 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching and is an ultrafine concavo-convex shape in which convex portions having an average diameter or major axis and minor axis of 10 to 200 nm are mixed and exist on the entire surface, and mainly on the surface The metal shape is made of a copper alloy in which a thin layer of cupric oxide is formed.

The adhesive composite containing a metal alloy according to claim 12 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching, and has an average of 10 to 150 nm in diameter or major axis and minor axis. The metal shape is made of a copper alloy in which almost the entire surface is covered and a thin layer of cupric oxide is mainly formed on the surface.

The adhesive composite containing a metal alloy according to claim 13 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching, and has an ultra-fine uneven shape with a shape in which particles with a diameter of 10 to 20 nm and an indefinite polygon with a diameter of 50 to 150 nm are mixed and stacked. The metal shape is made of a copper alloy that is covered and in which a thin layer of cupric oxide is mainly formed on the surface.

The adhesive composite containing a metal alloy according to claim 14 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching and is almost entirely covered with an ultra-fine irregular shape in which particles having a diameter of 20 to 70 nm and irregular polygonal shapes are stacked, and the surface is oxidized by metal. It is a metal shape made of stainless steel in which a thin layer of the object is formed.

The adhesive composite containing a metal alloy according to claim 15 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a surface roughness of micron order by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching, and is almost entirely covered with an ultra-fine irregular 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 continues indefinitely. And a metal shape made of steel having a thin layer of either manganese oxide, chromium oxide, zinc phosphorous oxide, or zinc and calcium phosphorous oxide formed on the surface. It is a thing.

The adhesive composite containing a metal alloy according to claim 16 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching, a height of 80 to 150 nm, a depth of 80 to 500 nm, a width of several hundred to several thousand nm, and an extremely fine uneven shape with an infinitely wide step. It is a metal shaped product made of steel that is covered and on which a thin layer of manganese oxide, chromium oxide, zinc phosphate, or zinc and calcium phosphate is formed. It is what I did.

An adhesive composite containing a metal alloy according to claim 17 of the present invention has a surface covered with an ultrafine irregular surface having an irregular period of 5 to 500 nm and having a roughness on the order of microns by chemical etching. And a metal shaped article having a thin layer of metal oxide or metal phosphate formed on the surface, an adherend that is adhesively bonded to the metal shaped article, the metal shaped article, and the deposition An adhesive composite comprising a metal alloy comprising: an adhesive cured layer that hardens an adhesive applied to an adhesive surface with a material and integrally bonds the metal shape and the adherend. The adhesive is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and a particle size of 0.3 to 3 mass% and a particle size of 100 nm or less. comprising ultrafine inorganic powder, wherein a shaped metal can The surface has a roughness on the order of microns by chemical etching, a height of 50 to 100 nm, a depth of 80 to 200 nm, a width of several hundred to several thousand nm, and an extremely fine uneven shape with an infinitely wide step. It is a metal shaped product made of steel that is covered and on which a thin layer of manganese oxide, chromium oxide, zinc phosphate, or zinc and calcium phosphate is formed. It is what I did.

According to claim 18 of the present invention, there is provided a method of manufacturing an adhesive composite including a metal alloy, wherein a plurality of the same or different metal alloy materials are mechanically processed to form a metal shape having a predetermined shape, and the predetermined The surface of the metal shaped product having a shape is an ultrafine concavo-convex surface covered with an ultrafine concavo-convex shape having an irregular period of 5 to 500 nm, and the ultrafine concavo-convex surface has a maximum roughness with a mountain-valley average interval RSm of 1 to 10 μm. Surface treatment process for performing various liquid treatments including chemical etching so that the height Rz is a surface having a larger roughness with a roughness of 0.2 to 5 μm, and the center of epoxy resin, curing agent, particle size distribution is 5 and inorganic fine powder of less inorganic powder and the particle size 100nm of 20 [mu] m, to prepare at least comprising a thermosetting epoxy adhesive carbon nanotubes 0.02-0.2 wt% which the metal shaped The step of applying to the object and the metal shape object made of the same or different kind of metal alloy coated with the above-mentioned thermosetting epoxy adhesive are bonded together, fixed, and all uncured resin is gelled and cured by heating. And integrating the two.

According to a nineteenth aspect of the present invention, there is provided a method of manufacturing an adhesive composite including a metal alloy, the step of forming a metal shape having a predetermined shape by mechanically processing a metal alloy material, and the metal shape having the predetermined shape. The surface of the object is an ultra-fine uneven surface covered with an ultra-fine uneven shape with an irregular period of 5 to 500 nm, and the ultra-fine uneven surface has a mean roughness RSm of 1 to 10 μm and a maximum roughness height Rz of 0. Surface treatment process for performing various liquid treatments including chemical etching so that the surface has a larger uneven shape with a roughness of 2 to 5 μm, and the center of particle size distribution as an epoxy resin, a curing agent, and a filler is 5 to 20 μm. Preparation of the inorganic powder and inorganic fine powder having an average particle size not greater than 100nm of the ultrafine filler, a thermosetting epoxy-based adhesive containing at least carbon nanotubes 0.02-0.2 wt% A step of applying this to the metal shape, a step of preparing a fiber reinforced plastic prepreg having the epoxy resin composition as a matrix resin into a predetermined shape by cutting and laminating, and the like, and the thermosetting epoxy adhesive And a step of combining and fixing the applied metal shaped article and prepreg shaped article together, and gelling and curing all uncured resins by heating to integrate them together.

According to claim 20 of the present invention, there is provided a method for producing an adhesive composite including a metal alloy, wherein a metal alloy material having a predetermined shape is formed by mechanically processing a metal alloy material; The surface of the object is an ultra-fine uneven surface covered with an ultra-fine uneven shape with an irregular period of 5 to 500 nm, and the ultra-fine uneven surface has a mean roughness RSm of 1 to 10 μm and a maximum roughness height Rz of 0. A surface treatment process for performing various liquid treatments including chemical etching so that the surface has a larger uneven shape with a roughness of 2 to 5 μm, and a cured product of fiber reinforced plastic using an epoxy resin composition as a matrix resin. a step of preparing to place the roughening to be bonded, an epoxy resin, a curing agent, the center of the particle size distribution following inorganic powder and the particle size 100nm of 5~20μm inorganic ultrafine powder, 0.02 A step of applying this to prepare a 0.2 wt% thermosetting comprising at least a carbon nanotube epoxy adhesive to the shaped metal and the cured shaped article of the fiber-reinforced plastic, the thermosetting epoxy adhesive And a step of combining and fixing the applied metal shape and the cured shape of the fiber reinforced plastic while pressing them, gelling and hardening all uncured resin by heating, and integrating them.

Method for producing a bonded composite according to claim 21 comprising a metal alloy to cite any one of claims 18 to 20 of the present invention, the prepreg or cured shaped article of the metal shaped article and / or fiber-reinforced plastic After the step of applying the adhesive, the coated material is housed in a sealed container, and the operation of pressure reducing the inside of the container and then pressurizing is repeated, and the step of soaking the adhesive into the material surface is added.

According to a method of manufacturing an adhesive composite containing a metal alloy according to claim 22 which refers to any one of claims 18 to 21 of the present invention, the filler is dispersed in the manufacturing process of the thermosetting epoxy adhesive. In order to proceed, a sand grind mill type wet pulverizer is used.

  Even in the bonding technique previously disclosed in the patent application by the present inventors that made it possible to bond metal alloys to each other and metal alloys and epoxy-based FRP with a strong adhesive force, the heat resistance of the adhesive force is an unresolved issue, In addition, the metal alloy as the adherend had already reached the maximum performance at the stage of the bonding technique disclosed in the above patent application, and the adhesive force could be said to depend on the performance of the adhesive itself. Then, as a result of examining to improve the heat resistance performance of the epoxy adhesive, the adhesive strength at 100 to 150 ° C. or less could be increased by 10 to 30 MPa from the present by adding an ultrafine inorganic filler to the epoxy adhesive.

  The metal alloy composite of the present invention and the manufacturing method thereof are metal alloy parts, or a metal alloy and FRP that are strongly integrated and have excellent heat resistance. Can be provided. If the metal alloy is a high-strength aluminum alloy such as ultraduralumin or a heat-resistant titanium alloy, a structural member that is extremely lightweight and characteristic as an aircraft or automobile member can be manufactured by integrating with the CFRP. That is, if the end portion of the composite is a metal alloy portion, it can be screwed and bolted, which is very convenient, and at the same time, can be made into a part with a constant design, and inexpensive mass production is possible.

  The present invention provides a solution for increasing the heat resistance of an adhesive and remodeling an adhesive, which are problems in forming an adhesive composite including a metal alloy by NAT. First, the characteristics of the adhesive desired to form the adhesive composite containing the metal alloy by NAT of the present invention and the examination contents thereof will be described, and further, the form of actually forming the adhesive composite containing the metal alloy Will be described.

[A] Features of the adhesive in forming an adhesive composite containing a metal alloy by NAT As a result of various studies on the adhesive composition, the following basic policy was adopted. That is, as the basic composition of the adhesive,
1) Be sure to include inorganic fillers (talc, clay),
2) including carbon nanotubes that the inventors have previously developed for NAT,
3) Add an ultrafine inorganic filler such as fumed silica (the reason will be described later)
4) Aiming at ensuring similarity with CFRP, blending with CFRP matrix resin, polyethersulfone (hereinafter referred to as “PES”) powder of amorphous thermoplastic resin, which is often used recently,
It was. In addition, current adhesive manufacturers usually use an automatic mortar or kneader to formulate inorganic fillers, etc., but the present inventors have used the latest used to disperse carbon nanotubes in the past. Since the mold wet pulverizer gave good dispersion results,
5) Standard use of sand grind mill for mixing epoxy resin and all fillers,
It was.

  In addition, although it is the ultrafine inorganic filler of 3), it should not be filled from a simple idea. I inferred the mechanism of destruction and made the theoretical hypothesis of destruction, which will be described later, and hoped for the experiment. In other words, the first evaluation of the adhesive performance performed by the present inventors was the shear breaking force value of the NAT-treated A7075 aluminum alloy (also referred to as “super-super duralumin”) pieces, but dicyandiamide was used as a curing agent. Despite the strength of 65-70 MPa at room temperature when using a commercially available one-part epoxy adhesive, the shear breaking strength at high temperatures of 100 ° C. and 150 ° C. is 15-20 MPa and 6-7 MPa. Also dropped significantly.

  Moreover, in the commercially available adhesive which used the imidazole type compound as the hardening | curing agent, it was about 15 MPa at 150 degreeC, although it was 50-60 MPa in the break test at normal temperature. An epoxy adhesive using an imidazole compound as a curing agent is called a heat-resistant adhesive, which is certainly stronger at a higher temperature than a dicyandiamide-used product. It is known that the hardness of the cured resin decreases rapidly as it approaches the glass transition point (Tg), and the Tg of the cured epoxy resin using dicyandiamide or imidazole as a curing agent is 100 to 140 ° C. If you don't do it, you can clear it up.

  However, the present inventors thought that the mechanism of why the adhesive strength decreases when the cured epoxy resin becomes soft at high temperatures should be inferred in more detail. By this reasoning, it was expected that a clue to improve the adhesive strength at high temperatures of epoxy adhesives using dicyandiamide and imidazoles to some extent could be obtained. The commercially available one-component epoxy adhesive using dicyandiamide as a curing agent is “EP106NL (manufactured by Cemedine)”, and the commercially available one-component epoxy adhesive using an imidazole compound as a curing agent is “EP160”. (Cemedine).

  As a result of inferences below, the direct cause of the joint breakage at high temperature is “the suppression of the spike on the inner wall surface of the micron-order recess on the NAT-treated metal alloy becomes ineffective due to the softening of the cured adhesive” I came up with a hypothesis. In fact, when the fracture surface was observed, the amount of the resin remaining on the metal side was less than that at the normal temperature. This is considered to indicate that the resin part is not broken in the vicinity of the entrance to the recess but is simply removed.

  If the hypothesis is correct, it can be expected that when a large amount of inorganic filler is contained in the resin portion solidified in the micron-order concave portion, it is difficult to come off to some extent and the adhesive strength is improved. Furthermore, in the micron-order recesses, vertical recesses (recesses having an inlet diameter smaller than the inner diameter) should also be seen. If the resin part contains a large amount of inorganic filler, the cured product will be removed from the recesses. It should not be easy to escape. The inorganic filler referred to here is one that favors micron-order concave portions, and must be ultrafine particles having a particle size of at least 0.1 μm (100 nm) or less. From this reasoning, the addition plan of the above-mentioned inorganic ultrafine filler (3) was examined.

  The target for improving heat resistance is that the shear breaking force between A7075 pieces bonded with an adhesive containing dicyandiamide as a curing agent may be about 60 to 70 MPa at room temperature (current commercial adhesive level), and 40 MPa at 100 ° C. It was hoped that it would be above (15-25 MPa for current commercial adhesives). Further, in the adhesion between A7075 pieces and CFRP, an average value of the shear strength at normal temperature and a shear breaking strength of 60 MPa or more (30 to 34 MPa for both current-curing adhesives and co-bonds) was expected. With this goal, trials and errors were repeated by preparing adhesives by changing the composition ratio in the material composition. As a result, the value was far above the target for Cobond and slightly below the target for Cocure. Regardless of whether the above hypothesis is correct or not, the adhesive force was obviously improved and the present invention was achieved.

  That is, an integrated product of A7075 aluminum alloy piece and CFRP piece was obtained by cocure adhesion using the improved adhesive according to the present invention and a commercially available CFRP prepreg, and when subjected to a tensile breaking test, a shear breaking force of 40 to 45 MPa was obtained. It was. On the other hand, a CFRP piece was prepared from the CFRP prepreg under the curing conditions as instructed by the manufacturer, and the harder conditions determined by the inventors were added twice and again. When this CFRP piece and NAT-treated A7075 aluminum alloy piece are co-bonded with the above-mentioned adhesive, the shear breaking force reaches 60 to 70 MPa, which is equivalent to the adhesion force between the A7075 aluminum alloy pieces. I was able to.

  Further, the integrated product of CFRP piece and A7075 aluminum alloy piece produced by co-curing also reached 45 to 50 MPa when heated again at 180 ° C. for several hours. Such a phenomenon may be due to the CFRP prepreg material used, but the curing conditions for maximizing the adhesion between the carbon fiber and the matrix resin are different from the curing conditions for achieving the highest performance as a CFRP material. I thought it was.

  That is, if the prepreg is solid, it can be assumed that the cocure adhesion between the CFRP and the NAT-treated metal alloy can sufficiently achieve a shear breaking force of 60 to 70 MPa by using an improved epoxy adhesive. . This is because, although there were some process improvements, the co-bonding method of CFRP pieces and A7075 aluminum alloy pieces stably yielded a shear breaking force of 60 to 70 MPa, which is the adhesion of A7075 aluminum alloy pieces to each other by the same adhesive. This is because the shear breaking force measured in the experiment was exactly the same level. Therefore, if improved research on prepregs and improved curing conditions are made, cobond and cocure should be at the same level.

  In addition, the present inventors think about the reason why the adhesive force in the simple cocure bonding performed at first remains at 35 to 40 MPa. These conditions are shown in the Examples, and by observing the broken pieces obtained by pulling and breaking the cocure product, it was possible to find the place to be the starting point of breakage. That is, when an integrated sample of the A7075 aluminum alloy piece and CFRP by the Cocure method was broken and the fracture surface on the aluminum alloy side was observed, carbon fibers were always attached to those having a shear fracture strength of about 40 MPa or more. In short, the adhesive improvement made by the present inventors solved the problem of adhesion between the CFRP matrix resin and the epoxy adhesive, and the starting point of the breakage shifted to peeling between the carbon fiber and the matrix resin.

  At the time of manufacturing the prepreg, first, a carbon fiber bundle or a carbon fiber cloth is surface-treated to obtain a parent epoxy type. After that, it is a normal prepreg manufacturing process that both sides are sandwiched between matrix resin sheets and integrated with a hot roll to form a prepreg. Since the adhesion between the carbon fiber and the matrix resin after curing is a very important factor, the surface treatment method of the carbon fiber has been extensively studied. Therefore, I was surprised to see the actual state of carbon fiber peeling in the above-mentioned cocure product, but since NAT did not exist in the past, it may have been 40MPa level, and the prepreg used by chance was the best carbon It may not have been subjected to a fiber surface treatment method.

  A somewhat interesting phenomenon is the same as the A7075 / CFRP integrated product by the Cocure method with a shear breaking force of about 40 MPa. Then, the shear fracture strength improved to 43 MPa when 43 MPa and two reheatings were applied. Since the present inventors are not a prepreg manufacturer, they do not understand the contents and theory of fiber processing at all, but as described above, the curing conditions required for the prepreg itself and the temperature conditions that maximize the adhesion between the carbon fiber and the matrix resin. May not match.

  Therefore, correctly, it would be necessary to have a prepreg manufacturer provide a prepreg with the best carbon fiber treatment and obtain experimental results using that material. Of course, the same can be said for bonding by the cobond method. It is strange to re-fire the integrated product obtained by co-curing many times in order to get high adhesion data, and to re-fire the CFRP material before bonding in order to obtain a strong co-bond adhesion demonstration value. Because it is strange.

  The bottom line is not to do the best carbon fiber surface treatment, but to use a balanced CFRP prepreg that can be cured in one step, whether it is cocure or cobond. It is thought that it should be made. In short, a CFRP prepreg material that prevents the surface layer portion from being broken even if a maximum shearing force of about 100 MPa is applied to the bonding surface on the CFRP surface by one-time bonding / heat curing as described above. I want to receive it. Perhaps this already exists, but we have not yet encountered it.

  Now, when bonding CFRP pieces by the co-bond method, the edges are polished several times with various sandpapers of # 100 to # 2000, and the resulting product is washed with tap water, various aqueous solutions, various solvents, etc. After drying, an adhesive was applied. After the application, the same pressure reduction and pressure treatment as that normally performed by NAT was performed, and the adhesive was soaked into the rough surface of the CFRP material. As a result of trial and error in many combinations, it was found that the roughening seemed to be a good result with a polished article with # 100 sandpaper, and it was suitable to make a fairly rough surface. Then, it seems that it is optimal that the subsequent washing is immersed in an aqueous solution containing a surfactant that has been heated and sonicated, and then thoroughly washed with pure water or tap water and dried at 80 to 90 ° C. It was.

  If the adhesive according to the present invention is used, the processed CFRP piece can be bonded without any problem. That is, when the A7075 aluminum alloy piece and the CFRP piece are co-bonded, a shear breaking force equivalent to that obtained when the A7075 aluminum alloy pieces are bonded to each other can be obtained, and the carbon fiber is very small on the fracture surface on the aluminum alloy side. Either attached or not attached at all. In short, it can be said that the other parts were more robust because it breaks at around 70 MPa if it breaks starting from the breakage of the cured adhesive near the surface of the aluminum alloy. In this case, the carbon fiber should not basically adhere to the aluminum alloy side, but it is rubbed with a coarse sandpaper of # 100, and there are many places where the carbon fiber is exposed. Therefore, it seems that some carbon fiber residue remains on the aluminum alloy side.

  Furthermore, the greatest advantage obtained by the present invention is ensuring heat resistance. As mentioned above, since dicyandiamide was mainly used as the curing agent, the adhesive strength at high temperature was not reduced suddenly. However, if it is better to add an ultrafine inorganic filler, it is 60 MPa at 100 ° C. A shear breaking force was obtained. This was a surprising value for the inventors. I don't know if the above-mentioned failure theory is correct or for a completely different reason, but the numerical value is very high, and it is a strong adhesive strength not seen in the past.

[B] Formation of Adhesive Composite Containing Metal Alloy An embodiment of actually forming an adhesive composite containing a metal alloy by NAT will be described in detail.
(1) Metal alloy shaped article The metal alloy shaped article referred to in the present invention, that is, a metal alloy used as an adherend in the above-mentioned NAT is 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, since mercury is naturally liquid, it is not relevant to the present invention, but soft metal species such as lead are also excluded from the metal species considered by the present inventors. 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.

  In the present invention, the metal alloy species that are useful for NAT are considered to be alloy species mainly composed of magnesium, aluminum, copper, titanium, and iron. Hereinafter, these will be described. However, the NAT theory does not limit the metal species, and moreover, it does not limit the metal itself. However, it is practically not easy to simultaneously provide the three conditions of making the non-metal a surface condition of roughness, ultra-fine uneven surface, and high hardness, which are NAT conditions. In short, since NAT discusses adhesion by anchor effect theory by defining only the surface shape and its surface thin layer hardness, it is not limited to at least the following metal alloy types.

  Patent Document 9 describes an aluminum alloy, and Patent Document 10 describes a magnesium alloy. Patent Document 11 describes a copper alloy, and Patent Document 12 describes a titanium alloy. Patent Document 13 describes stainless steel, and Patent Document 14 describes general steel materials. Patent Document 15 describes a brass alloy. Patent Document 16 describes an aluminum plated steel sheet. Regarding these metal alloy types arranged from aluminum alloys to special 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.

(2) Chemical etching of metal alloy materials There are various types of corrosion, including general corrosion, pitting corrosion, and fatigue corrosion. You can choose. 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 can be totally corroded by oxidizing agents such as hydrogen peroxide that have been made strongly acidic, and titanium alloys can be corroded entirely by special acids such as oxalic acid or hydrofluoric acid. And are often found in patent literature. Some metal alloys that are actually sold in the market, such as pure copper-based copper alloys and pure titanium-based titanium alloys, have a purity of 99.9% or more and cannot be said to be alloys. included. Most of the materials that are actually used in the world are mixed with various other elements in order to obtain characteristic physical properties, and few of them are pure metals, and are substantially alloys.

  That is, most of the target metals alloyed from pure metals have improved corrosion resistance without deteriorating the original metal properties. Therefore, in many cases, the target chemical etching cannot be performed even in the case of using an acid base or a specific chemical substance 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 9 describes aluminum alloy, Patent Document 10 describes magnesium alloy, Patent Document 11 describes copper alloy, Patent Document 12 describes titanium alloy, Patent Document 13 relates to stainless steel. Description, Patent Document 14 describes general steel materials, Patent Document 15 describes brass alloys, and Patent Document 16 describes aluminum plated steel sheets. For special 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. For details, refer to these patent documents, but to explain the points that are generally common as the work actually performed, when obtaining a metal alloy shape, first immerse it in an aqueous solution in which a commercially available degreasing agent for each metal is dissolved. Degrease and wash 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 referred to as preliminary acid cleaning or preliminary base cleaning. However, 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. In the case of a metal species that is particularly corrosive in a basic aqueous solution such as an alloy, 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 the chemical etching is previously attached (adsorbed) to the metal alloy, 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.

(3) Surface hardening treatment, fine etching Depending on the type of metal alloy, fine etching on the nano-order is performed at the same time by performing the above chemical etching, and depending on the type of alloy, the natural oxide layer on the surface becomes thicker than the original and hardening treatment is performed. May have already been processed. 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 metal alloy after chemical etching is reacted with a oxidant or chemical conversion treatment or chemical conversion treatment for the purpose of surface hardening treatment or surface stabilization treatment, the resulting surface is made ultra fine irregularities by chance. The surface layer that appears to be manganese oxide formed when a magnesium alloy is subjected to chemical conversion treatment with a potassium permanganate aqueous solution is a complex of rod-like crystals having a diameter of 5 to 10 nm that can be finally identified with a 100,000-fold electron microscope. 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 serves as a fine etching operation.

  The same is true for copper alloys, and when a hardening treatment is performed to change the surface to cupric oxide by oxidation under basic conditions, the surface of a pure copper-based copper alloy has a circular or circularly distorted hole opening. It becomes a peculiar fine uneven surface. A copper alloy that is not a pure copper type is not a concave shape, but is continuous with a particle having a diameter of 10 to 150 nm or an indefinite polygonal shape. Even in this case, most of the surface is covered with cupric oxide, and hardening and fine unevenness occur simultaneously.

  Details of general steel materials 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 when 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 is necessary to go and check the durability of the bond. In a short period of at least 4 weeks, the bonding strength of a steel material (actually SPCC: cold rolled steel material) bonded with a phenol resin adhesive without chemical conversion treatment decreased sharply. However, the general steel (SPCC) subjected to the chemical conversion treatment did not deteriorate from the initial adhesive force under these conditions.

  In addition, in the experience of the present inventors, when the surface treatment and the ultra fine unevenness creation treatment that also improved the corrosion resistance by performing a chemical conversion treatment, generally, if the film thickness of the chemical conversion treatment layer is thick, the adhesive strength may decrease. I know 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 layers are thickened with 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) produced by chemical conversion treatment and the cured epoxy 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 bonded material should be improved. However, if the chemical conversion film is thickened, the adhesive strength itself is lowered. The degree of balance is probably left to commercial research and development after using the present invention.

(4) Epoxy adhesive / resin component The epoxy adhesive will be described. The curable resin component consists of an epoxy resin and a curing agent. Both can be easily obtained from the market. As for epoxy resins, bisphenol-type epoxy resins, polyfunctional polyphenol-type epoxy resins, alicyclic epoxy resins, and the like are commercially available. In addition, various types of polyfunctional epoxy resins in which an epoxy group is combined with a polyfunctional compound, for example, a polyfunctional compound or oligomer having a plurality of hydroxyl groups or amino groups, are commercially available. The majority of all epoxy resins used in ordinary commercial adhesives are liquid and low viscosity bisphenol type epoxy resin monomer types. In the present invention, a bisphenol type epoxy resin monomer is mixed in a majority to ensure low viscosity as an adhesive.

  On the other hand, the ability to cure is in amine compounds, phenol resins, acid anhydrides, etc., but amine compounds are used in the present invention. The reason is that the amine curing agent system is usually used for CFRP prepregs. The object of the present invention is not only to strongly bond metal alloys to each other but also to strongly bond metal alloys and CFRP by a co-curing method. This is because, unlike the co-bonding method, the co-curing method can simultaneously achieve adhesion with a metal alloy and molding and hardening as a CFRP member, so that it is considered more rational than the co-bonding method as an industrial CFRP member mass production method. Since it is necessary for cocure to use the same kind of curing agent as the matrix resin of CFRP prepreg (which is also a kind of one-component epoxy resin adhesive), the use of an amine-based adhesive was a condition.

  That is, the curing agent used in the present invention is an amine compound, specifically, dicyandiamide, an imidazole compound, or an aromatic diamine compound. Aliphatic amine compounds are not preferred. This is because when an aliphatic amine compound is used as a curing agent, gelation often starts in a normal temperature range. However, any gel can be used as long as gelation does not start immediately at room temperature, and it is applied to and soaked into a NAT-treated metal alloy within several hours after mixing of the curing agent. A part of the alicyclic amine compound can be used as such a product. That is, it is a composition marketed as a curing agent for a two-component epoxy resin composition having a long pot life, and heating at about 100 ° C. is effective for curing. Such a curing agent is cataloged and marketed as a mixed amine containing alicyclic amine as a main component, and can be used. However, it is necessary to apply and soak the work with a time limit.

(5) Epoxy resin adhesive / inorganic filler The filler will be described. Adhesives usually contain an inorganic filler, which plays an important role. In other words, according to the current fracture theory, a small local fracture occurs first in a small part of the stress concentration area or in a weak intensity area near the stress concentration area before the object breaks. It is thought that the fracture increases the stress concentration of the adjacent minute part and proceeds to the chain of local fracture. This is a mechanism theory that the chain of microfracture expands, the size of the fractured portion is not microscopic and becomes a large crack, and finally it is completely fractured, and in the adhesive system, the adherends are peeled off.

  Actually, the strength of the cured adhesive is not uniform as a whole, and it is always strong and weak on a micro level. Therefore, if the fractures are easily chained, the microfracture almost reaches a complete fracture, and the complete fracture is determined only by the strength value at a microscopically weak part. Therefore, even if the local breakage of the weakest minute part occurs, if this is not linked, the incident does not occur until the local breakage occurs in the next weakest minute part, and the adhesive force is improved as a result. The current fracture theory is that the presence of an inorganic filler having a diameter of several μm to several tens of μm is very effective in stopping local fracture even if it occurs locally.

  Therefore, the structural adhesive always includes an inorganic filler. Commercially available epoxy adhesives usually contain several percent or more of powders of silica, clay (clay, kaolin), talc, alumina, etc. having a particle size of several μm to several tens of μm. The details of the inorganic filler to be added are important company secrets of the adhesive manufacturer only because they affect the adhesive performance, and are not known to the present inventors. Therefore, the present inventors used in the experiment only clay and talc for which fine powder can be purchased from the city.

  The present inventors had a handicap that there was no detailed know-how regarding the inorganic filler, but the experiment was carried out on the assumption that the amount could be offset by using the latest wet pulverizer as the filler disperser. In other words, the surface properties (ie, affinity with epoxy resin) seem to be important for the selection of the inorganic filler, and the inventors have lacked practical knowledge, but the dispersion has been updated. We expected the possibility that the affinity between the epoxy resin and the filler could be improved by using a mold wet pulverizer to achieve a certain mechanochemical effect.

(6) Epoxy resin adhesive / ultra fine inorganic filler The most important thing in the present invention is that the situation around the interface made with NAT is assumed, and the possible failure phenomenon is inferred there, and the failure theory related to NAT. I thought of the hypothesis. That is, since the unevenness present on the surface of the NAT-treated metal alloy is a minimum of 1 to 10 μm and an unevenness of 1 μm period, the existing inorganic filler having a particle size of several μm or more can hardly be inserted into the recess. . Therefore, the filler that involves only the fracture theory in NAT is a fine filler that can enter a 1 μm recess, and specifically has a particle size of 0.1 μm (100 nm) or less. This is the greatest feature of the adhesive used in the present invention, and is therefore a necessary condition but also has a large actual effect. Although there is no effect at room temperature, the adhesive force can be improved by 10 to 30 MPa at 100 ° C. as compared with an adhesive not containing an ultrafine inorganic filler.

  Our hypothesis is that ultrafine inorganic fillers are useful in situations where the adhesive is placed under high temperature and the environmental temperature approaches the glass transition point of the cured adhesive and softens and the adhesive strength decreases rapidly. is there. That is, when the cured epoxy adhesive by NAT was hit by a strong peeling stress at high temperature, it was presumed that there were two locations where the mutation first occurred. FIG. 16 schematically shows a metal alloy part bonded with NAT and a cured adhesive product. 40 represents a metal alloy phase of a metal alloy piece, 41 represents a ceramic phase, and 42 represents a cured adhesive product phase. One of the candidate locations where the mutation occurs is near the entrance of the micron-order concave portion shown in FIG. If it breaks here, it can be strengthened by adding the CNT already disclosed by the present inventors (Patent Document 17). However, the effect of improving the adhesive strength was greatest near room temperature, and no clear additive effect was observed at high temperatures. The amount of CNT added that is effective at room temperature is 0.2% by mass or less, especially from 0.005 to 0.1% by mass, as seen from the experimental value.

  Another candidate for destruction is in a micron-order recess, and the cured adhesive in the recess becomes soft at high temperatures and the spike grip loosens, that is, the shape is somewhere in contact with the spike. It was decided that slip would occur due to deformation such as collapse. If the slip at this microinterface advances in a chain along the interface, the spike effect disappears and the anchor effect possessed by this micron-order recess becomes zero. As a result, the degree of stress concentration on the concave group around the concave portion increases, and the same thing occurs next in the peripheral concave portion. Eventually, the cured adhesive will come out of the micron-order recesses and float, leading to breakage. It should be bad if the spike slips.

  Even if it is desired to maintain the hardness and strength of the adhesive cured product in contact with the spike, the resin hardness decreases at high temperatures, and so there is no choice but to rely on fillers. However, since the concave / convex period of the spike portion is on the order of several tens of nanometers, an ultrafine filler with a diameter of several nanometers is required. Unfortunately, ultrafine powder with a diameter of several nanometers is not found in the world, and even if it exists, it will be difficult to uniformly disperse it in the adhesive. Therefore, it is assumed that the slip progresses in the vicinity of the spike, the effect of the spike disappears, and the adhesive cured product convex portion in the micron order concave portion has already floated about several tens of nm. A schematic diagram of this situation is shown in FIG.

  In this case, in order to prevent the chain from being transmitted to the surrounding micron-order recesses, the floated distance does not become more than several tens of nanometers and stops at the backlash. The conditions to stop are that the shape of the recess is an under shape and the opening is narrower than the internal diameter, and that the hardened adhesive contained in the recess on the metal alloy side does not collapse as a whole and does its best without breaking , Both. Based on this hypothesis, Ando, one of the present inventors, predicted the usefulness of ultrafine inorganic fillers for NAT adhesives.

  In other words, since the concave portion on the NAT-treated metal alloy side is obtained by a chemical etching method, it is not a straight hemispherical shape or V-shaped groove shape, that is, a bowl-shaped concave portion whose opening is narrower than the inside or a concave opening direction is vertical. It is assumed that there is a so-called under-shaped concave portion that has an oblique direction, not a direction, with a reasonable probability. When an adhesive in which an ultrafine filler having a particle size of several tens to several hundreds of nanometers penetrates into such under-shaped recesses and solidifies, the cured adhesive present in these recesses can be easily obtained. Will not break into pieces.

  For example, when a strong vertical peeling force is applied, the cured polymer in the adhesive is slightly softened due to high temperature, and the effect of the spike is reduced, so the micron-order concave portion where the strongest force is applied near the stress concentration point In, it is considered that the polymer part in contact with the inner wall spike slides and the effect of the spike is lost. If such a concave portion has the above-described under shape, the cured adhesive in the concave portion is unfixed and floats by several tens of nm. That is, if the concave portion has an under structure, the central portion of the adhesive cured product in the concave portion will not float and will not come off unless the central portion of the cured adhesive is greatly broken.

  FIG. 17 schematically shows the joint surface just before breakage, where 50 is a metal alloy phase of a metal alloy piece, 51 is a ceramic phase, 52 is a cured adhesive phase, and 53 is peeled off. Although the space is shown, only the three concave portions at the center of the five micron-order concave portions arranged side by side are in a state where the anchor does not work, and are in the form of floating several tens of nm. However, since the entire cured adhesive is softened at a high temperature, it is somewhat elastic and the two recesses at the end in the figure are not lifted by being dragged to the center three. That is, even if the effect of the spike disappears and the destruction phenomenon occurs in the three recesses, it is considered that it is difficult to proceed to the chain destruction once it stops at this level of destruction. It is a hypothesis of time.

  In other words, even if the anchor effect is lost at the weakest part of the infinite number of micron-order recesses, the anchoring effect is lost by generating a play of about several tens of nanometers. It is also an idea that adhesion can be maintained until destruction. The filler to be added according to this hypothesis was an ultrafine inorganic filler of 100 nm or less. It is based on the idea that if they enter the micron-order recess, the hardness at that portion is maintained, and even if the spike function is somewhat lowered, it will not easily come out of the recess. Fumed silica is easily available as an ultrafine inorganic filler having a particle size of 100 nm or less.

  These ultrafine inorganic powders are essential fillers for the present invention. There are two types of fumed silica. One is ultra-fine fused silica recovered from the exhaust gas in the reduction process that uses silica (silicon oxide) sand as a raw material to obtain metallic silicon. The other is vaporized and combusted silicon tetrachloride to form ultrafine fused silica, which is commercially available under the trademark “Aerosil”. Aerosil that has been surface-treated is also commercially available, and the present inventors have used a hydrophobic treatment. The fumed silica obtained by the combustion treatment is not necessarily highly hydrophilic, but the hydrophobic treatment is considered to have better affinity with the epoxy resin.

  Normally, powders with particle sizes smaller than micron order are agglomerated, and Aerosil is actually an agglomerated product. The agglomeration force becomes stronger as the powder becomes ultrafine powder, and the agglomeration cannot be solved and the dispersed state assumed in the present invention cannot be achieved as long as it is put into an adhesive and kneaded in an automatic mortar. Therefore, it is necessary to apply to a disperser after addition to the epoxy resin. This will be described later. From the experimental results, the filling rate of the ultrafine inorganic filler is preferably 0.3% by mass or more, particularly preferably 0.3 to 3% by mass. When added in excess of 3% by mass, not only was the viscosity increased and it was difficult to use, but when used, the adhesive strength remained unchanged or decreased, although no clear reason was known.

(7) Epoxy resin adhesive / elastomer type filler In the present invention, it is preferable to add an elastomer component as a filler. Various vulcanized rubbers, powder rubbers modified on the surface of various vulcanized rubbers, various raw rubbers, modified rubbers modified from various raw rubbers, vinyl chloride resin (hereinafter “PVC”), vinyl acetate resin (hereinafter “PVA”), polyvinyl formal Resin (hereinafter “PVF”), ethylene vinyl acetate resin (hereinafter “EVA”), polyolefin resin, polyethylene terephthalate resin (hereinafter “PET”), various polyamide resins (hereinafter “PA”), polyethersulfone resin (hereinafter referred to as “PET”) "PES"), polyurethane resin, thermoplastic polyester elastomer (hereinafter "TPEE"), thermoplastic polyurethane elastomer (hereinafter "TPU"), thermoplastic polyamide elastomer (hereinafter "TPA"), thermoplastic polyolefin elastomer (hereinafter "TPO"). )) Etc. are elastomer components as referred to in the present invention. .

  Some of these are not usually elastomers, but the cured epoxy resin is hard and the thermoplastic resin is soft. These increase the toughness of the cured product due to its softness. Preference is given to blending these as fine powder having a particle size of 10 to 20 μm and further improving the surface to a parent epoxy resin mold. Since it is an amino group or a hydroxyl group that reacts with the epoxy resin at a high temperature, it is an effective modification treatment to have these at the end of the elastomer. Moreover, since the present invention seeks an adhesive that exhibits a strong adhesive force not only at room temperature but also at a slightly high temperature, an excessively soft material is not preferred. Taking these into account, those that are readily available include PVF that is prone to hydroxyl groups, urethane resins with hydroxyl groups at the ends, PAs with countless amino groups, and PES with intentionally hydroxyl groups. is there.

  It is preferable that the elastomer type filler has a filling rate of 3 to 10% of the adhesive. Specifically, a method of classifying a particle size product obtained by pulverizing an elastomer component and using this is first considered. Actually, it is difficult to obtain the above-mentioned substances having low hardness as a finely pulverized product of 10 μm level with a pulverizer, and it is difficult to obtain a good yield. However, it is not so easy to obtain a high yield by reducing the particle size to several tens of μm. However, it may be fortunate that there is a way to use a larger particle size for another purpose. That is, when PES is pulverized, it can be used as a filler for heat-resistant elastic paints, and since this application is great, finely pulverized products of the order of 10 μm that are co-produced are also supplied as commercial products. In the experimental example of the present invention, commercially available PES powder was purchased and used.

  In addition, for synthetic rubbers and thermoplastic resins obtained by emulsion polymerization, there is a method to obtain powder by cutting off moisture and dehydrating latex materials obtained after finishing the polymerization process so that they do not adhere to each other. is there. Few products are manufactured as adhesive fillers, but as special functional chemicals, special coating materials used in printing inks and special paints, electronic device parts such as liquid crystal displays, and medical uses. It is used for. Of course, these can also be used.

  Whether or not the addition of any elastomeric powder is effective should not be selected theoretically, but should be determined through experimentation. With this additive, a clear result is usually not obtained by observation of the adhesive strength that breaks the adhesive between the NAT-treated metal pieces. Of course, it is not preferable that the adhesive strength between metal alloy pieces is reduced by using an adhesive containing elastomer powder, but if the adhesive strength does not decrease, the first barrier is a pass. This tensile fracture test is preferably performed not only at room temperature but also at 100 ° C. or 150 ° C. Then, an adhesive of the metal alloy piece and CFRP is prepared by co-curing, and the adhesive force is measured. In this experiment, if there is an additive effect, it should be judged that it can be used, and the details of the composition ratio should be examined.

(8) Dispersion of epoxy resin adhesive / filler As described above, the basic composition of the adhesive used in the present invention is an epoxy resin, a curing agent, an inorganic filler having an average particle size of 10 μm, and a particle size of 100 nm or less. Ultrafine inorganic filler, thermoplastic resin powder having an average particle size of 5 μm to 20 μm. Especially, ultrafine inorganic filler is dispersed when mixed and kneaded by an automatic mortar or kneader, which is a conventional mixing and kneading method. It ’s not mixed.

  Since the ultrafine inorganic filler having a particle size of 100 nm or less and the CNT are aggregated, it is necessary to break and disperse, and therefore, a wet pulverizer is preferably used. In particular, the use of the latest wet pulverizer such as a sand grind mill is preferable. Furthermore, not only ultrafine inorganic fillers, but also normal inorganic fillers and thermoplastic resin powders should be put into a sand grind mill at the same time to obtain good dispersion. It is preferable to adopt. However, the operation of the wet pulverizer is accompanied by heat generation. When trying to mix and disperse using a sand grind mill etc. including a hardener, an accident will occur unless the temperature of the grinding chamber is strictly controlled. That is, the wet pulverizer cannot be operated unless the viscosity of the liquid material is lowered to some extent, and even if the temperature is increased and the viscosity is lowered and the operation is started, if the heat generation in the pulverization chamber is not controlled well, the heat generation due to gelation is added. Runaway, solidify the crushing chamber and make the crusher unusable. Therefore, it is preferable to mix up the filler using a wet pulverizer without adding a curing agent, and then add a curing agent and knead using a kneader or the like.

  Ultimately, it is considered that it can be used in the form of a paste at room temperature, which is slightly thickened on a metal piece and melts and spreads into a liquid state when placed at 70 ° C. for about 1 minute. Whether the curing agent is dicyandiamide, imidazole or aromatic diamine, gelation starts at about 100 ° C., and therefore it is judged that the maximum temperature that can be handled is about 70 ° C. This may change in future improvement studies. If the obtained adhesive is put in a refrigerator and stored at 5 degrees or less, there is no problem for more than half a year. If the curing agent is a mixture of alicyclic amines and the gelation proceeds slowly even at room temperature, the kneading time should be about 5 minutes and the coating and soaking process described below should be performed. Preferably within a few hours. And this adhesive should not be stored.

(9) Adhesive application and subsequent treatment The adhesive obtained as described above is applied to a necessary portion of the metal alloy piece. Brush painting or spatula painting may be used. After that, put it in a vacuum vessel or a pressure vessel preheated to 50 to 70 ° C., and after reducing the pressure to several tens of mmHg after several minutes, put it in several seconds, and then return to normal pressure by adding air, It is preferable that the pressure be several tens of atmospheres. The reason why the coated material is warmed is to make the viscosity of the adhesive 10 or less Pa seconds or less. The higher this temperature is, the lower the viscosity is. However, when the temperature is too high, gelation starts and it is disadvantageous for securing adhesive force. These depend on how the gel temperature of the adhesive is predicted.

  Then, it is preferable to repeat the cycle of pressure reduction and pressure increase. The air between the adhesive and the metal alloy escapes under reduced pressure, and the adhesive easily enters the ultrafine recesses on the metal surface when returned to normal pressure. In actual mass production, using high-pressure air using a pressure vessel leads to increased costs both in terms of equipment and costs. It is economical to do this several times. It is preferable to take it out from the container or bag, put it in a storage place at a temperature below room temperature, and enter the next step within a short time.

(10) Adhering material: Adhesion between metal alloys When adhering metal alloys of the same type, two metal alloy pieces coated with an adhesive are produced in the above-mentioned process, and they are tie-bonded and fastened with a clip or the like. What is necessary is just to heat-harden in a dryer. When using a different type of metal for the adherend, apply an epoxy adhesive to the adherend side metal alloy according to the method described in the above section after applying a surface treatment in accordance with NAT. After the above processing is performed, they may be tied together and fastened with a clip or the like, and similarly heat cured.

  As the curing agent of the adhesive is an alicyclic amine-based compound, dicyandiamide, imidazole-based compound, or aromatic diamine-based compound, heating is performed by putting the above-mentioned thing in a hot air dryer, Usually, the adhesive component is melted at about 90 ° C. for about 30 minutes, heated to 120 ° C. and held for about 30 minutes, heated to 135 ° C. and further heated for 30 minutes, further raised to 165 ° C. for 30 minutes. When the temperature was further raised to 180 ° C. for 30 minutes, the entire adhesive and CFRP prepreg handled by the present inventors could be cured without problems. Since the optimum temperature condition varies depending on each composition, it is not limited to the above. However, since the condition allows curing of any one-component epoxy adhesive, CFRP prepreg, the experiment can be easily performed.

(11) Adhering material: FRP semi-cured product or prepreg and adhesion method FRP includes glass fiber reinforced plastic (hereinafter referred to as “GFRP”), aramid fiber reinforced plastic (hereinafter referred to as “AFRP”), CFRP, and the like. is there. The present invention discusses FRP using an epoxy resin as a matrix, and all FRPs using glass fiber, carbon fiber, aramid fiber and other reinforcing fibers can be applied as long as the matrix resin is an epoxy resin. . Here, CFRP using an epoxy resin will be specifically described, and the description will be replaced with other FRP.

  Most commercially available CFRP prepregs are epoxy resin-based products and can be used after confirmation. The CFRP prepreg is obtained by pressing carbon fibers into a matrix resin composed of an epoxy resin composition containing at least the same epoxy resin and a curing agent as the basic one-component epoxy adhesive. Most commercially available CFRP prepregs are kneaded with a kneader or roll after adding an elastomer type filler to an epoxy resin and a curing agent, and finally formed into a sheet with a roll. The current method for producing CFRP prepregs is to sandwich a carbon fiber woven fabric with two sheets and pass through a heating roll while defoaming them to form a sheet.

  In addition, in order to enhance the adhesion with the matrix resin, the carbon fiber cord or the carbon fiber cloth is subjected to some treatment to improve the adhesion with the matrix resin, such as being dipped in an organic solvent liquid containing an epoxy resin and dried in advance. . Details are an important secret of the prepreg maker and I don't know at all. When Japanese patents are investigated, published patents describing this relationship appear after 1985, and no patents are seen after 2005. Therefore, it seems that the classic one is already used, but I don't know what this is.

  A CFRP prepreg is cut into a required shape and is laminated in a required shape to form a prepreg laminate. However, when stacking multiple unidirectional prepregs (prepregs from weaving fabrics with many warps and very little wefts), the final CFRP plate material can be obtained by overlapping the directions or tilting the angles. It is said that there is a lot of know-how in the assembly because the direction of the strength of the steel can be controlled. Carbon fiber plain weaves have the same number of warp and weft yarns, and are said to have the same strength in all directions when overlapping prepregs, for example, by changing the angle by 45 degrees. In short, the required number of sheets and how to stack them are designed in advance, and each prepreg is cut accordingly, and the preparation is completed by stacking as designed.

(12) Lamination of prepreg and method for producing composite The FRP prepreg is placed on the metal alloy part to which the above-mentioned epoxy adhesive is applied. If heated well in this state, the epoxy resin adhesive and the epoxy resin in the prepreg are once melted and subsequently cured. In order to join firmly, it heats in the state which pressed both, and the air contained in between needs to be expelled at the time of resin melting. For example, a pedestal matched to the shape opposite to the surface to be joined of the metal alloy shaped object is prepared in advance, and after placing an aluminum foil or polyethylene film, the metal alloy part is placed, and a large number of prepregs are placed. A polyethylene film is laid on the prepreg, a fixing member according to the shape of the final product prepreg separately manufactured with a structural material or the like is placed, and a heavy object is further placed thereon, so that pressing and fixing during heat curing can be performed.

  Of course, not only gravity but also various methods can be used because both of them can be cured while being pressed. In aircraft members, the entire assembly as described above is sealed in a heat-resistant film bag (bag) and heated while being decompressed so that the internal air is forcibly removed when all the epoxy is melted. Since the prepreg is tightened when the air escapes to some extent, it is a mechanism to send the air into the bag and harden it under pressure. Since the present inventors have no experimental equipment to do so, the experiment was conducted with the expectation that the air in the prepreg would be considerably removed by the pressure pressed when the epoxy component was melted.

  Heating is performed by placing the entire structure in a hot air dryer or autoclave, usually at 90 ° C for about 30 minutes, raised to 120 ° C and held for 30 minutes, then raised to 135 ° C and heated for another 30 minutes. The temperature was raised to 165 ° C. every 30 minutes and further raised to 180 ° C. for 30 minutes. Although the curing conditions originally vary depending on the epoxy component and the curing agent component, the detailed composition of the commercially available prepreg is unknown to the present inventors. Allow to cool, remove the mold, and remove the molded product. If an aluminum foil or polyethylene film is used as described above so that the mold can be released, it is peeled off.

(13) Example of Measurement of Adhesive Strength A method for measuring the adhesive strength of an adhesive between metal alloys used in the present invention or an adhesive adhesive between a metal alloy and FRP will be described below. FIG. 13 is a cross-sectional view of a firing jig for firing for bonding a metal alloy and FRP. FIG. 14 is a test piece of the metal alloy resin composite 10 in which the metal alloy piece and CFRP are produced by cocure bonding with the firing jig 1. The firing jig 1 is a fixing jig for firing the metal alloy plate 11 and the prepreg 12. The mold body 2 has an open upper surface and a recess 3 formed in a rectangular parallelepiped shape. A through hole 4 is formed at the bottom.

  A protrusion 6 of the bottom plate 5 is inserted into the through hole 4. The protrusion 6 protrudes from the bottom surface 7 of the mold body 2. The bottom surface of the mold body 2 is mounted on the mold base 8. In a state where the bottom plate 5 is inserted and placed in the recess 3 of the mold body 2, the metal alloy resin composites 10 and 20 in which the metal alloy pieces 21 and the CFRP 22 are joined as shown in FIG. In general, the composites 10 and 20 are manufactured by the following procedure. First, a release film 17 is laid on the entire upper surface of the bottom plate 5. The metal alloy piece 11 and the plate-like spacer 16 are placed on the release film 17. The required prepreg 12 is laminated on the spacer 16 and the end of the metal alloy piece 11. The prepreg 12 is obtained by cutting a commercially available product with scissors.

  After the prepreg 12 is laminated, a release polyethylene film piece 13 is further laminated on the aluminum alloy plate 11 and the prepreg 12. On top of this, PTFE (polytetrafluoroethylene resin) blocks 14 and 15 are placed as weights. Further, if necessary, a several kg weight (not shown) is placed thereon. In this state, the prepreg is cured and allowed to cool, and then the weight and the pedestal 8 and the like are removed, and the lower end of the protrusion 6 is pressed against the floor surface. The metal alloy resin composite 10 (see FIG. 14) joined with CFRP can be taken out. Since the spacer 16 and the release films 17 and 13 are non-adhesive materials, they can be easily peeled off from the CFRP.

  Examples of the present invention will be described below. FIG. 15 illustrates a shape in which metal alloy pieces are bonded to each other with an adhesive. The metal alloy piece was processed by the surface treatment method according to the present invention, and the adhesive used was also in accordance with the present invention. The metal alloys are joined together at the joining surface 33. The fine uneven surface on the metal alloy is bonded with an epoxy adhesive. Moreover, FIG. 14 represents the test piece for joint strength measurement obtained by joining a metal alloy piece and FRP with an epoxy adhesive as described above.

[Measurement equipment]
The equipment used for measurement etc. 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 Microscope Observation An SEM type electron microscope “S-4800 (manufactured by Hitachi, Ltd.)” and “JSM-6700F (JEOL)” were used and observed at 1 to 2 KV.
(C) Scanning probe microscope observation “SPM-9600 (manufactured by Shimadzu Corporation)” was used. This is a dynamic force type scanning probe microscope.
(D) X-ray diffraction analysis (XRD analysis)
“XRD-6100 (manufactured by Shimadzu Corporation)” was used.
(E) Measurement of Bonding Strength of Composite Material Using a tensile tester “AG-10kNX (manufactured by Shimadzu Corporation)”, the shear breaking force was measured at a pulling speed of 10 mm / min.
(F) Dispersion of filler (use of wet pulverizer)
A sand grind mill “Minitsu Air (manufactured by Ashizawa Finetech)” using zirconia beads having a diameter of 0.1 to 0.5 mm as sand was used.

Next, an experimental example of the joining system will be described for each type of metal piece.
[Experiment 1] (Surface treatment of aluminum alloy)
A commercially available 3 mm thick A7075 plate (manufactured by Kobe Steel) was obtained and cut into a large number of 45 mm × 15 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% concentration hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the alloy plate material was immersed in this for 1 minute and washed with water. Next, a 1.5% concentration aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the above alloy plate material was immersed for 4 minutes and washed with water.

  Subsequently, a 3% concentration aqueous nitric acid solution at 40 ° C. was prepared in another tank, and the alloy plate material 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 alloy plate material was immersed in this for 2 minutes and washed with water. Next, a 5% hydrogen peroxide aqueous solution was set to 40 ° C., and the alloy sheet was immersed 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. An A7075 piece subjected to the same treatment was observed with an electron microscope and 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. In addition, when roughness data was taken with a scanning probe microscope, the mean valley interval (RSm) was 3 to 4 μm, and the maximum height (Rz) was 1 to 2 μm.

[Experiment 2] (Surface treatment of aluminum alloy)
A commercially available 1.6 mm thick A5052 plate (manufactured by Sumitomo Light Metal Industry Co., Ltd.) 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% concentration hydrochloric acid aqueous solution at 40 ° C. was prepared in another tank, and the alloy plate material was immersed in this for 1 minute and washed with water. Next, a 1.5% strength aqueous caustic soda solution at 40 ° C. was prepared in a separate tank, and the above alloy plate material was immersed for 2 minutes and washed with water. Subsequently, a 3% concentration aqueous nitric acid solution at 40 ° C. was prepared in another tank, and the alloy plate material 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 alloy plate material 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. When the A5052 piece treated in the same way was observed with an electron microscope, it was found that the A5052 piece was covered with a recess having a diameter of 30 to 100 nm. FIG. 2 shows an electron micrograph of 10,000 times and 100,000 times. In addition, roughness data was obtained by applying a scanning probe microscope. According to this, the mean valley interval (RSm) was 2.0 to 3.4 μm, and the maximum height (Rz) was 0.2 to 0.5 μm.

[Experiment 3] (Surface treatment of magnesium alloy)
A commercially available 1 mm thick AZ31B plate material (manufactured by Nippon Metal Co., Ltd.) 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% concentration hydrated citric acid aqueous solution at 40 ° C. was prepared in another tank, and the alloy plate material was immersed in this 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 alloy plate was dipped 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 sealed in a plastic bag. Observation of this treated AZ31B piece with an electron microscope reveals that 5 to 10 nm diameter rod-like crystals are intricately entangled and their lumps are gathered together with a diameter of about 100 nm, and the gathering forms ultra fine irregularities. There was a part covered with the shape. Two types of the 100,000 times electron micrographs are shown in FIG. Further, when the roughness was observed by scanning with a scanning probe microscope, the mean interval between ridges and valleys referred to in JIS, that is, the average value (RSm) of the uneven period was 2 to 3 μm, and the maximum roughness height (Rz) was 1-1. It was 5 μm.

[Experimental Example 4] (Surface treatment of copper alloy)
Tough pitch copper (C1100: manufactured by Kobe Steel), which is a commercially available 1 mm thick pure copper-based copper alloy, 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% 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 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 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 sealed and stored in a plastic bag.

  A piece of C1100 treated in the same way 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. Further, when observed with an electron microscope of 100,000 times, a hole or opening having a diameter or an average of a major axis and a minor axis having an average of 10 to 150 nm is present on the entire surface at irregular intervals of 30 to 300 nm. It was covered. The 10,000 times and 100,000 times electron micrographs are shown in FIG.

[Experimental Example 5] (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 to obtain a copper alloy piece as the metal plate 1. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” in a tank was made 60 ° C. to obtain a degreasing aqueous solution. The said copper alloy board | plate material was immersed here for 5 minutes, degreased | defatted, and washed well with water. Subsequently, an aqueous solution containing 20% of an etching material for copper alloy “CB5002 (made by MEC)” at 25 ° C. and 18% of 30% hydrogen peroxide was prepared in another tank, and the copper alloy piece was added to this for 15 minutes. It was immersed and washed with water. Next, an aqueous solution containing 10% caustic soda and 5% 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 after reaching 65 ° C. 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 piece was placed in a hot air dryer at 90 ° C. for 15 minutes and dried. Wrapped in aluminum foil and stored.

  FIG. 5 shows 10,000 times and 100,000 times electron micrographs of the C5191 piece treated in the same manner, but when observed with an electron microscope of 100,000 times, convex portions having an average diameter or major axis and minor axis of 10 to 200 nm are mixed. It was an ultra-fine concavo-convex shape existing on the entire surface, and was completely different from the fine structure of tough pitch copper, which is pure copper. Moreover, when it applied to the scanning probe microscope, the ridge-and-valley average space | interval (RSm) said by JIS was 1-3 micrometers, and the maximum roughness height (Rz) was 0.3-0.4 micrometer.

[Experimental example 6] (Surface treatment of copper alloy)
A small amount of commercially available 0.7-mm-thick iron-containing copper alloy “KFC” (manufactured by Kobe Steel) 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% of an etching material for copper alloy “CB5002 (made by MEC)” at 25 ° C. and 18% of 30% hydrogen peroxide was prepared, and the copper alloy piece 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 sealed and stored in a plastic bag.

  The same treated KFC copper alloy piece 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 7] (Surface treatment of copper alloy)
Commercially available 0.7 mm thick special copper alloy “KLF5 (manufactured by Kobe Steel)” plate material 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% of an etching material for copper alloy “CB5002 (made by MEC)” at 25 ° C. and 18% of 30% hydrogen peroxide was prepared, and the copper alloy piece 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 sealed and stored in a plastic bag.

  A piece of KLF5 copper alloy treated in the same way 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, a shape in which a particle size of 10 to 20 nm and an indefinite polygonal shape of 50 to 150 nm are mixed and stacked together, that is, a lava plateau slope-like ultra fine uneven shape. Almost the entire surface was covered. The 10,000 times and 100,000 times electron micrographs are shown in FIG.

[Experiment 8] (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 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)” in a tank was made 60 ° C. to obtain a degreasing aqueous solution. The titanium alloy plate was immersed in the aqueous solution for 5 minutes to degrease and washed thoroughly with water. Next, 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. is prepared in another tank, and the titanium alloy The 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.

  The KS40 titanium alloy pieces subjected to the same treatment were observed with an electron microscope and a scanning probe microscope. From the observation with an electron microscope, a curved continuous mountain-shaped projection having a width and height of 10 to several hundred nm and a length of several hundred to several μm stands on the surface with an interval period of 10 to several hundred nm. It was found to have an ultra fine uneven surface. This 10,000 times 100,000 times electron micrograph is shown in FIG. Moreover, by observation with a scanning probe microscope, the mean valley interval (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 9] (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 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)” in a tank was made 60 ° C. to obtain a degreasing aqueous solution. The titanium alloy plate was immersed in the aqueous solution for 5 minutes to degrease and washed thoroughly with water. Next, a 1.5% aqueous solution of caustic soda at 40 ° C. was prepared in a separate tank, immersed for 1 minute and washed with water. Next, an aqueous solution in which 2% by weight of a commercially available general-purpose etching reagent “KA-3 (manufactured by Metalworking Technology Laboratories)” was dissolved was prepared at 60 ° C. in another tank, and the titanium alloy piece was immersed in this for 3 minutes. Wash thoroughly with ion-exchanged 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 piece 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.

  The KSTi-9 titanium alloy piece treated in the same manner was observed with an electron microscope and a scanning probe microscope. The results of observation with an electron microscope of 10,000 times and 100,000 times are shown in FIG. In addition to the portion very similar to the electron microscopic observation photograph 8 of Experimental Example 8, many dead leaf-like portions that are difficult to express were seen. Moreover, according to the scanning analysis by a scanning probe microscope, the average valley / slope RSm was 4 to 6 μm, and the maximum roughness height Rz was 1 to 2 μm.

[Experimental Example 10] (Stainless steel surface treatment)
1 mm thick plate material of commercially available stainless steel SUS304 / 2B (manufactured by Takasago Iron Works Co., Ltd.) 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)” in a tank was made 60 ° C. to obtain a degreasing aqueous solution. The stainless steel plate material was immersed in the aqueous solution for 5 minutes for degreasing and thoroughly washed with water. Subsequently, an aqueous solution containing 1% ammonium difluoride and 5% 98% sulfuric acid at 65 ° C. was prepared in another tank, and the stainless steel piece was immersed in this for 4 minutes and washed thoroughly with ion-exchanged water. . Next, it was immersed in a 3% nitric acid aqueous solution at 40 ° C. for 3 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.

  Observation of the SUS304 piece subjected to the same treatment with an electron microscope and a scanning probe microscope was performed. From observation with an electron microscope, it was covered with a super fine uneven shape of a laminar slope slanted shape, that is, a shape in which particles having a diameter of 30 to 70 nm and indefinite polygonal shapes were stacked. This electron micrograph is shown in FIG. In the scanning analysis of the scanning probe microscope, the mean valley interval (RSm) was 1 to 2 μm, and the maximum height difference (Rz) was 0.3 to 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 were 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.

[Experimental Example 11] (Surface treatment of general steel materials)
A commercially available 1.6 mm thick cold rolled steel “SPCC” plate was purchased and cut into a large number of 18 mm × 45 mm rectangular pieces to form steel pieces. Drill holes in the ends of this steel piece, pass through copper wires coated with vinyl chloride to dozens, and bend the copper wires so that the steel pieces 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. was immersed in the tank for 5 minutes and washed with tap water (Ota City, Gunma Prefecture). Next, a 1.5% aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the steel piece 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 a steel piece 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 observation result of the SPCC steel slab treated with the same treatment by a 100,000 times electron microscope, it is almost an ultra-fine concavo-convex shape in which the height and depth are 80 to 200 nm and the width is several hundred to several thousand nm infinite steps. It can be seen that the entire surface is covered. It can be seen that the pearlite structure is exposed and the chemical conversion treatment layer is very thin. 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.

[Experiment 12] (Surface treatment of general steel)
A commercially available 1.6 mm thick hot rolled steel “SPHC” plate was purchased and cut into a large number of 18 mm × 45 mm rectangular pieces to obtain steel pieces. Drill holes in the ends of this steel piece, pass through copper wires coated with vinyl chloride to dozens, and bend the copper wires so that the steel pieces 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. was immersed in the tank for 5 minutes and washed with tap water (Ota City, Gunma Prefecture). Next, a 1.5% aqueous solution of caustic soda at 40 ° C. was prepared in another tank, and the steel piece was immersed for 1 minute and washed with water. Next, an aqueous solution containing 10% 98% sulfuric acid at 65 ° C. and 1% ammonium hydrogen fluoride and 1% was prepared in another tank, and a steel piece was immersed in this for 2 minutes and washed thoroughly with ion-exchanged water. Next, it was immersed in 1% ammonia water at 25 ° C. for 1 minute and washed with water, then at 55 ° C., 80% normal phosphoric acid was 1.5%, zinc white was 0.21%, and sodium silicofluoride was 0%. It was immersed in an aqueous solution containing 16% and 0.23% basic nickel carbonate for 1 minute and thoroughly washed with water. This was placed in a hot air dryer at 90 ° C. for 15 minutes and dried.

  From the observation results of the SPHC steel slab, which was processed in the same manner, with a 100,000-fold electron microscope, it was found to be an extremely fine concavo-convex shape having a height and depth of 80 to 500 nm and a width of several hundred to several tens of thousands of stairs. It was found that the entire surface was covered, and this was also a pearlite structure. This electron micrograph 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] (Adhesive: Aerosil)
An epoxy resin “JER828 (manufactured by Japan Epoxy Resin Co., Ltd.)” whose main component is a monomer type of bisphenol-type epoxy resin, and a polymer bisphenol epoxy resin “JER1003 (Japan Epoxy Resin) having a molecular weight of about 1300 which is a solid. ) ”, Polyfunctional phenol novolac type epoxy resin“ JER154 (made by Japan Epoxy Resin Co.) ”, aniline type trifunctional epoxy resin“ JER630 (made by Japan Epoxy Resin Co., Ltd.) ”, average particle size of about 15 μm PES powder “PES4100MP (manufactured by Sumitomo Chemical Co., Ltd.)”, multi-walled carbon nanotube “MCNT (manufactured by Nanocarbon Technologies)” having a diameter of about 50 nm, and hydrophobized fumed silica having an average particle diameter of 16 to 20 nm "Aerosil R805 (Japan "Erosil Co., Ltd."), fine talc "Hymicron HE5 (manufactured by Takehara Chemical Industry Co., Ltd.)" with an average particle size of 8-12 μm, calcined kaolin clay "Satinton 5 (Takehara Chemical Co., Ltd.) with an average particle size of 10-15 µm ) ”, Fine powdered dicyandiamide“ DICY7 (manufactured by Japan Epoxy Resin Co., Ltd.) ”which is a curing agent for epoxy resin, and 3- (3,4-dichlorophenyl) -1,1-dimethyl which is the curing aid. Urea “DCMU99 (Hodogaya Chemical Co., Ltd.)” was obtained.

  60 parts of “JER828”, 20 parts of “JER1003”, 10 parts of “JER154”, 10 parts of “JER630” are placed in a beaker and heated in a hot air dryer at 130 ° C. to heat the solid type “JER1003” At the same time of melting, the whole was homogenized by stirring. Then, it stood to cool and stored as an epoxy resin liquid.

  A sand grind mill “Minitsu Air (manufactured by Ashizawa Finetech Co., Ltd.)” filled with 80% of the grinding chamber capacity with 0.3 mm diameter zirconia beads was prepared, and an open tank with a circulation pump and a stirrer was connected to the inlet side. . On the other hand, the exit of the sand grind mill was opened to an open tank. The above epoxy resin liquid was reheated to 60 ° C. to lower the viscosity, 350 g was put into an open tank, and the mill was started after the grinding chamber was completely filled with a circulation pump. Since the mill has a water cooling line, water flow was adjusted so that the inside of the grinding chamber was 50-60 ° C. The peripheral speed of the mill rotor was set to 11 to 12 m / sec.

  Thereafter, 10 g of “Hi-micron HE5” was gradually added to the open tank to circulate and grind, and then “Aerosil R805” was added in the same manner as 1.6 g. This was followed by circulating pulverization for about 5 minutes. Then, 16 g of “PES4100MP” was gradually added, and then wet pulverization (substantially dispersion operation) was continued for 40 minutes. The outlet of the mill was directed from the open tank to the polyethylene bottle, and a mixture containing 4.5 parts of PES, 2.9 parts of fine talc and 0.5 part of Aerosil was obtained in a polyethylene bottle with respect to 100 parts of the total epoxy resin. Next, 5 parts of the curing agent “DICY7” was taken into 108 parts of the mixture in a beaker and well kneaded with a glass rod, and then 3 parts of the curing aid “DCMU99” was taken and kneaded well again. Next, the beaker was covered with aluminum foil, allowed to stand at room temperature for 50 hours, a kind of aging was carried out, taken back into a plastic bottle and stored in a refrigerator at 5 ° C. The name of this adhesive was “PES, T3, A0.5”.

[Experimental Example 14] (Adhesive: Aerosil and CNT)
An adhesive was prepared in the same manner as in Experimental Example 13, but 350 g of epoxy resin was put into an open tank of a sand grind mill, and after filling the whole with a circulation pump, the mill was started and then put into the open tank. In addition to 16 g of PES4100MP, 10 g of fine talc “Hymicron HE5”, 2 g of fumed silica “Aerosil R805”, it was 0.3 g of CNT “MCNT”. A mixture containing 4.5 parts of PES, 2.9 parts of fine talc, 0.5 part of Aerosil, and 0.07 part of CNT was obtained from 100 parts of the total epoxy resin. Subsequently, 5 parts of “DICY7” and 3 parts of “DCMU99” were added to 108 parts of the mixture in a beaker in the same manner as in Experimental Example 13, and kneaded at 40 ° C. for 5 minutes. This was allowed to stand at room temperature for 50 hours, and then taken in a polyethylene bottle and stored in a refrigerator at 5 ° C. The name of this adhesive was “PES, T3, A0.5, C0.07”.

[Experimental Example 15] (Adhesive: Comparison)
An adhesive was prepared in exactly the same manner as in Experimental Example 13, but an adhesive was produced in which fumed silica “Aerosil R802” was not added. That is, the mixture before adding the curing agent dicyandiamide contained 4.5 parts of PES and 2.9 parts of fine talc based on 100 parts of the total epoxy resin. The name of the obtained adhesive was “PES, T3”.

[Experimental Example 16] (Adhesive)
Adhesives were made in exactly the same manner as in Experimental Example 13, but different adhesives were produced except that the PES powder “PES4100MP” was not added. That is, the mixture before adding the curing agent “DICY7”, etc. contained 2.9 parts of fine talc “Hymicron HE5” and 0.5 part of “Aerosil R805” based on 100 parts of the total epoxy resin. It was. The name of the obtained adhesive was designated as “T3, A0.5”.

[Experimental Example 17] (Adhesive: Comparison)
An adhesive was made in exactly the same way as in Experimental Example 16, but fumed silica “Aerosil R802” was not added. That is, the mixture before adding the curing agent dicyandiamide contained 2.9 parts of fine powder talc “High Micron HE5” based on 100 parts of the total epoxy resin. The name of the obtained adhesive was designated as an adhesive “T3”.

[Experiment 18] (Adhesion experiment: A7075 aluminum alloy)
Six A7075 aluminum alloy pieces having a thickness of 45 mm × 15 mm × 3 mm were produced by the method shown in Experimental Example 1, and the adhesive “PES, T3, A0.5” obtained in Experimental Example 13 was applied to the ends of the small pieces. I attached. This was put in a large-scale desiccator which had been preheated for 30 minutes in a hot air dryer preliminarily set at 60 ° C., covered, and the inside was reduced to 30 mmHg or less using a vacuum pump. The pressure was returned to normal pressure every few minutes under reduced pressure. This decompression / return to normal pressure operation was repeated three times, after which the desiccator was opened and the aluminum alloy piece was taken out. Then, the adhesive application surfaces were butted together so that the adhesion area was 0.6 to 0.7 cm ² , and then fixed with two clips to form three sets. This was placed in a hot air dryer set at 90 ° C. After maintaining at 90 ° C. for 30 minutes, the temperature was raised to 120 ° C., and after 30 minutes, the temperature was raised to 135 ° C. and held at this temperature for 30 minutes. Thereafter, the temperature was further raised to 165 ° C. and held for 30 minutes, further raised to 180 ° C. for 30 minutes, and the hot air dryer was turned off and allowed to cool until the next day.

  The obtained integrated product was subjected to a tensile fracture test at normal temperature, 100 ° C., and 150 ° C. The shear rupture force was divided by the adhesion area to calculate three sets of shear rupture forces, and the average value was obtained. The result was 68.9 MPa at room temperature, 55.1 MPa at 100 ° C., and 17.1 MPa at 150 ° C. .

[Experimental Example 19] (Adhesion experiment)
Adhesive hardening of the A7075 aluminum alloy pieces obtained in Experimental Example 1 using the adhesive “PES, T3, A0.5, C0.07” obtained in Experimental Example 14 to measure the shear breaking force by NAT A test sample was prepared. That is, the experiment proceeded in exactly the same way as in Experimental Example 18 except that the adhesive used was “PES, T3, A0.5, C0.07”, and the shear fracture strength was measured. The average shear breaking force at room temperature was 77.1 MPa, the average under 100 ° C. was 54.0 MPa, and the average under 150 ° C. was 16.0 MPa. At room temperature, it is about 10 MPa higher than Experimental Example 18, and the addition of CNTs helps to improve the adhesive strength near room temperature, but the effect is not apparent at high temperatures.

[Experimental Example 20] (Adhesion experiment: comparison)
The A7075 aluminum alloy pieces obtained in Experimental Example 1 were bonded and cured using the adhesive “PES, T3” obtained in Experimental Example 15 to prepare a test sample for measuring the shear breaking force by NAT. That is, the experiment proceeded in exactly the same way as in Experimental Example 18 except that the adhesive used was “PES, T3”, and the shear fracture strength was measured. The average shear breaking force at normal temperature was 68.8 MPa, the average shear breaking force at 100 ° C. was 32.0 MPa, and the average shear breaking force at 150 ° C. was 10.2 MPa. Compared with Experimental Example 18, it does not contain aerosil, but it seems that there is almost no difference at room temperature, and it is greatly reduced at 100 ° C. and 150 ° C. The effect of adding Aerosil is not well understood at room temperature, but the adhesion at high temperature was clearly improved.

[Experiment 21] (Adhesion experiment)
The A7075 aluminum alloy pieces obtained in Experimental Example 1 were bonded and cured using the adhesive “T3, A0.5” obtained in Experimental Example 16 to prepare a test sample for measuring the shear breaking force by NAT. That is, the experiment was conducted in exactly the same manner as in Experimental Example 20 except that the adhesive used was the adhesive “T3, A0.5”, and the shear breaking strength was measured. The average shear breaking force at room temperature was 68.5 MPa, the average shear breaking force at 100 ° C. was 50.2 MPa, and the average shear breaking force at 150 ° C. was 17.3 MPa. Compared to Experimental Examples 18 and 19, there was no significant difference at 100 ° C.

[Experimental example 22] (Adhesion experiment: comparison)
The A7075 aluminum alloy pieces obtained in Experimental Example 1 were bonded and cured using the adhesive “T3” obtained in Experimental Example 17 to prepare a test sample for measuring the shear breaking force by NAT. That is, the experiment proceeded in exactly the same manner as in Experimental Example 20 except that the adhesive used was the adhesive “T3”, and the shear breaking strength was measured. The average shear breaking force at room temperature was 67.1 MPa, the average shear breaking force at 100 ° C. was 32.0 MPa, and the average shear breaking force at 150 ° C. was 7.3 MPa. Although it differs from Experimental Examples 18 and 19 in that it does not contain any ultrafine inorganic filler, the adhesive strength was greatly reduced at high temperatures.

[Experimental Examples 23 to 33] (Adhesion experiment)
The metal alloy pieces obtained in Experimental Examples 2 to 12 were bonded and cured using the adhesive “PES, T3” and the adhesive “PES, T3, A0.5”, and various metal alloy pieces were sheared by NAT. A test sample for measuring the breaking force was prepared. These were each broken at room temperature and 100 ° C., and the shear breaking force was measured and averaged. The results are shown in Table 1.

  As is apparent from Table 1, the data at 100 ° C. is roughly 25-30 MPa for “PES, T3” and rapidly rises to 40-50 MPa for “PES, T3, A0.5” regardless of the type of metal alloy. Compared with the whole, the experimental value of the alloy piece having a thin thickness or slightly softness was low, and titanium alloys having a slightly inferior surface property were slightly lower than others.

[Experimental Example 34] (Preparation of complex with CFRP)
A CFRP prepreg “Pyrofil TR3110 (manufactured by Mitsubishi Rayon Co., Ltd.)” was obtained, and a large number of 45 mm × 15 mm pieces were cut out. The adhesive “PES, T3, A0.5” produced in Experimental Example 13 was applied to the end of the A7075 aluminum alloy piece subjected to the surface treatment obtained in Experimental Example 1, and further put into a desiccator to reduce pressure / normally. The operation of pressure return was added 3 times. A bonded body of an aluminum alloy piece and CFRP is produced using the firing mold 1 shown in FIG. In the molds 2 and 5, a release film 17 of 0.05 mm polyethylene film was laid, and the aluminum alloy piece 11 and the PTFE spacer 16 described above were placed. A 45 mm × 15 mm CFRP prepreg “Pyrofil TR3110 (manufactured by Mitsubishi Rayon Co., Ltd.)” that had been cut earlier was stacked and placed in a thickness of 3 mm. Further, a release film 14 made of a polyethylene film was placed on top of the aluminum alloy piece 11.

  A PTFE spacer 13 and a block 15 were placed and placed in a hot air dryer. Therefore, a 5 kg iron weight 18 is placed on the PFTE spacers, blocks 13 and 15, and the dryer is energized. The temperature is raised to 90 ° C. for 30 minutes, then raised to 120 ° C. for 30 minutes, The temperature was raised to 135 ° C. every 30 minutes, further raised to 165 ° C. every 30 minutes, then raised to 180 ° C. every 30 minutes, and the electricity was turned off and the door was closed and left to cool. The next day, the product was taken out from the dryer, the molded product was released from the firing mold 1, and the polyethylene film was peeled off to obtain a composite 10 of aluminum alloy and CFRP shown in FIG. The same operation was repeated to obtain six integrated objects 10 which are composites of aluminum alloy pieces and CFRP.

  A tensile break test was conducted on the second day after joining. The CFRP portion was sandwiched between two 1 mm thick SUS304 stainless steel pieces that were sanded and fixed by sandwiching them with a chuck plate. The maximum shear breaking force at room temperature was 38.0 MPa, but the average was 35.8 MPa. When the fracture surface was observed, there was a slight amount of carbon fiber residue attached to the aluminum alloy side. Moreover, the average shear breaking force under 100 degreeC was 23.2 MPa, and the carbon fiber residue did not adhere to the aluminum alloy side.

[Experimental Example 35] (Preparation of complex with CFRP)
The experiment proceeded in exactly the same way as in Experimental Example 34, and the CFRP piece and the A7075 aluminum alloy piece were integrated by cocure bonding with an adhesive “PES, T3, A0.5”. Three pairs were obtained, put in a hot air dryer at 90 ° C. every 30 minutes, raised to 135 ° C. every 30 minutes, raised to 165 ° C. every 30 minutes, further raised to 180 ° C. and held for 1 hour. I put it out.

  The next day, it was taken out from the hot air dryer and subjected to a tensile breaking test at room temperature. As a result, the shear breaking strength was 43.0 MPa at the maximum and 42.8 MPa on the average, which was improved from Experimental Example 34. Furthermore, when the fracture surface was observed, carbon fiber residue adhered to the aluminum alloy side. Peeling occurred between the carbon fiber and the matrix resin, and this was considered to be the starting point for fracture. And this can be said for this prepreg used, but it was found from the relationship with Experimental Example 34 that the adhesive force between the carbon fiber and the matrix resin was improved by tightening the curing conditions.

[Experimental example 36] (Preparation of composite of adhesive and CFRP: clay filler)
An adhesive was prepared in exactly the same manner as in Experimental Example 13, but fine powder talc “Hi-micron HE5 (manufactured by Takehara Chemical Industries)” was not used as the inorganic filler, but instead “Satinton 5 (Takehara Chemical Industries, Ltd.) of calcined kaolin clay. Used). The name of the adhesive was “PES, KC3, A0.5”.

  The adhesive “PES, KC3, A0.5” produced above was applied to the end of the A7075 aluminum alloy piece subjected to the surface treatment obtained in Experimental Example 1. Otherwise, the experiment proceeded in exactly the same way as in Experimental Example 35, and three pairs of A7075 aluminum alloy and CFRP composite 10 were obtained. A tensile fracture test was performed on the seventh day after joining. The CFRP portion was sandwiched between two 1 mm thick SUS304 stainless steel pieces that were sanded and fixed by sandwiching them with a chuck plate. The shear breaking strength at normal temperature was 41.2 MPa on average. This result was close to Experimental Example 35.

[Experimental Example 37] (Creation of a complex with CFRP: Cobond)
A CFRP prepreg “Pyrofil TR3110 (manufactured by Mitsubishi Rayon Co., Ltd.)” was obtained, and a large number of 45 mm × 15 mm pieces were cut out. A CFRP rectangular body is produced using the firing mold 1 shown in FIG. A mold release film 17 of 0.05 mm polyethylene film is laid in the molds 2 and 5, and a PTFE piece of the same shape is placed instead of the metal alloy piece usually placed at the position 11, and a PTFE spacer 16 is further provided. Placed. A 45 mm × 15 mm CFRP prepreg “Pyrofil TR3110 (manufactured by Mitsubishi Rayon Co., Ltd.)” that had been cut earlier was laminated and placed in a thickness of 3 mm. Further, a release film 14 made of a polyethylene film was placed on top of the PTFE piece 11.

  A PTFE spacer 13 and a block 15 were placed and placed in a hot air dryer. Therefore, a 5 kg iron weight 18 is placed on the PFTE spacers, blocks 13 and 15, and the hot air dryer is operated to raise the temperature to 90 ° C. for 30 minutes, and then to 120 ° C. for 30 minutes. The temperature was raised to 135 ° C. every 30 minutes, further raised to 165 ° C. every 30 minutes, raised to 180 ° C. every 30 minutes, the operation of the hot air dryer was stopped, and the door was allowed to cool with the door closed. . The next day, the product was taken out from the hot air dryer, the molded product was released from the baking mold 1, and the polyethylene film was peeled off to obtain a CFRP rectangular body. This operation was repeated to obtain many CFRP pieces.

  After 3 days, a part of the CFRP piece obtained above was put again in a hot air dryer, and every 30 minutes at 90 ° C, then heated to 135 ° C and kept for 30 minutes, and further heated to 165 ° C and 30 minutes Then, the temperature was raised to 190 ° C. and allowed to cool every 30 minutes. This was called a twice-baked product. The obtained twice-baked product was baked again under the same conditions after 3 days. This was called a third-degree baked product.

  The end of the CFRP piece obtained by the above operation was firmly rubbed with a # 100 sandpaper several times to roughen it. This CFRP piece was immersed in a 60 ° C. degreasing tank used in Experimental Example 1 with ultrasonic waves for 5 minutes, washed thoroughly with pure water, and dried at 90 ° C. for 15 minutes. The adhesive “PES, T3, A0.5” produced in Experimental Example 13 was applied to the roughened portion of the CFRP member. On the other hand, an A7075 aluminum alloy piece subjected to the surface treatment obtained in Experimental Example 1 was obtained, and the adhesive “PES, T3, A0.5” prepared in Experimental Example 13 was applied to the end portion thereof. Both the obtained CFRP piece with adhesive and the same A7075 aluminum alloy piece were put into a desiccator, and the operation of depressurization / return to normal pressure was added three times.

A pair was made by taking out from the desiccator, contacting the CFRP piece and the aluminum alloy piece with the adhesive application pieces as an adhesive surface of 0.6 to 0.7 cm ² and fixing with two clips. This pair was put into a hot air dryer, heated to 90 ° C. and held for 30 minutes, then heated to 135 ° C. for 50 minutes, further heated to 165 ° C. for 30 minutes and allowed to cool.

  A tensile break test was conducted on the second day after joining. The results are shown in Table 2. I don't know why, but how many times the CFRP piece is refired improves the adhesion between the carbon fiber and the matrix resin. The value was 71.8 MPa. The average value is also around 70 MPa, which is almost the same as the data (Experimental Example 18) of the adhesion between A7075 aluminum alloy pieces.

[Experimental Examples 38 to 42] (Creation of a complex with CFRP: cobond: including comparison)
The experiment was carried out in exactly the same way as in Experimental Example 37, but the adhesive used was a different one instead of the adhesive “PES, T3, A0.5”. In Experimental Example 41, a commercially available one-component epoxy adhesive “EP106NL (Cemedine)” using dicyandiamide as a curing agent, and in Experimental Example 42, a commercially available one-component epoxy adhesive “EP160 (using imidazoles) as a curing agent. Cemedine) ”was used. The curing conditions are the same as in Experimental Example 37. Table 3 shows an average value of the results of the tensile fracture test.

  From Table 3, when an adhesive containing aerosil is used, the adhesive strength at a high temperature is greatly improved, and an imidazole compound is used as a curing agent instead of dicyandiamide, which is commercially available as a heat-resistant adhesive "EP160 (produced by Cemedine)" It was found to be superior at 100 ° C. Further, the commercially available adhesive “EP106NL” used in Experimental Example 41 contained an inorganic filler, and the content was expected to be most similar to the adhesive “T3” of Experimental Example 40. The results were somewhat similar, but the results at high temperatures were slightly but the experimental example 40 seemed to be superior. If this is the case, it is assumed that the reason is that the epoxy resin recipe was appropriate. “EP106NL” is commercially available as a low-viscosity adhesive, and the content of the bisphenol A type epoxy resin monomer type in the epoxy resin may be higher than the recipe (60%) in this experiment. It can be said that the epoxy resin mixture used in this experimental series has a rather good composition ratio.

FIG. 1 is a 10,000 times and 100,000 times electron micrograph of an A7075 aluminum alloy obtained by etching with an aqueous caustic soda solution and fine etching with an aqueous hydrazine solution. FIG. 2 is an electron micrograph of 10,000 times that obtained by etching an A5052 aluminum alloy with an aqueous caustic soda solution and finely etching with an aqueous hydrazine solution. FIG. 3 shows two kinds of 100,000-magnification electron micrographs obtained by etching a AZ31B magnesium alloy with a citric acid aqueous solution and chemical conversion treatment with a potassium permanganate aqueous solution. FIG. 4 is an electron micrograph of 10,000 times and 100,000 times that obtained by etching a C1100 copper alloy with an aqueous solution of sulfuric acid and hydrogen peroxide and performing surface hardening treatment with an aqueous solution of sodium chlorite. FIG. 5 is an electron micrograph of 10,000 times and 100,000 times obtained by etching a C5191 phosphor bronze alloy with an aqueous solution of sulfuric acid and hydrogen peroxide and surface hardening with an aqueous solution of sodium chlorite. Fig. 6 shows 10,000 times and 100,000 times the electron microscope of “KFC (Kobe Steel)” copper alloy etched with sulfuric acid / hydrogen peroxide solution and surface hardened with sodium chlorite solution. It is a photograph. FIG. 7 shows 10,000 times and 100,000 times the electron microscope of “KLF5 (Kobe Steel)” copper alloy etched with sulfuric acid / hydrogen peroxide aqueous solution and surface hardened with sodium chlorite aqueous solution. It is a photograph. FIG. 8 is an electron micrograph of 10,000 times that obtained by etching “KS40 (manufactured by Kobe Steel)” pure titanium-based titanium alloy with an aqueous solution of 1 hydrogen diammonium fluoride. FIG. 9 is an electron micrograph of 10,000 times that obtained by etching a “KSTi-9 (manufactured by Kobe Steel)” α-β titanium alloy with an aqueous solution of 1 hydrogen diammonium fluoride. . FIG. 10 is an electron micrograph of 10,000 times and 100,000 times that obtained by etching SUS304 stainless steel with a sulfuric acid aqueous solution. FIG. 11 is an electron micrograph of 10,000 times and 100,000 times that obtained by etching a cold-rolled steel material “SPCC Bright” with an aqueous sulfuric acid solution. FIG. 12 is an electron micrograph of 10,000 times and 100,000 times that obtained by etching hot-rolled steel “SPHC” with a sulfuric acid aqueous solution. FIG. 13 is a cross-sectional view schematically showing a firing jig for bonding a metal piece and an FRP prepreg with a one-component thermosetting adhesive and curing them in a hot air dryer. FIG. 14 shows the shape of an integrated product obtained by cocure-bonding a NAT-treated metal alloy piece and FRP with a one-component epoxy adhesive. FIG. 15 shows the shape of an adhesive with a one-component epoxy adhesive between various metal alloy pieces that have been subjected to NAT processing. FIG. 16 is a schematic partial cross-sectional view showing a metal alloy surface structure in the new NMT theory and NAT theory. FIG. 17 is a schematic view when the joining surface of the NAT-treated metal alloy piece and the cured epoxy adhesive is on the verge of breaking.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Firing jig | tool 2 ... Mold body 3 ... Mold recessed part 4 ... Mold through-hole 5 ... Mold bottom plate 6 ... Bottom plate protrusion 7 ... Mold bottom surface 8 ... Base 10 ... Integrated object 11 of metal alloy piece and FRP 11 ... Metal alloy piece 12 ... FRP
DESCRIPTION OF SYMBOLS 13 ... Release film 14 ... PTFE block 15 ... PTFE block 16 ... PTFE spacer 17 ... Release film 20 ... Integrated metal alloy piece and FRP 21 ... Metal alloy piece 22 ... FRP
DESCRIPTION OF SYMBOLS 30 ... Composite of metal alloys 31 ... Metal alloy piece 32 ... Metal alloy piece 40 ... Metal alloy phase 41 of a metal alloy piece ... Ceramic layer 42 ... Hardened adhesive agent phase 50 ... Metal alloy phase 51 of a metal alloy piece ... Ceramic layer 52 ... Hardened adhesive phase 53 ... Space generated by peeling

Claims (22)

The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive complex comprising a metal alloy consisting of, wherein the adhesive is a thermosetting epoxy adhesive, with the center of the particle size distribution comprises an inorganic powder filler 5~20μm as a filler, 0 An adhesive composite containing a metal alloy characterized by containing ultrafine inorganic powder having a particle diameter of 100 nm or less of 3 to 3% by mass and carbon nanotubes of 0.02 to 0.2% by mass .   The adhesive composite containing the metal alloy according to claim 1, wherein the adhesive further contains 1 to 10% by mass of thermoplastic resin powder as a filler. The adhesive composite containing the metal alloy according to claim 2, wherein the thermoplastic resin powder is polyethersulfone. The adhesive composite containing the metal alloy according to any one of claims 1 to 3 , wherein the ultrafine inorganic powder is fumed silica. The adhesive composite containing the metal alloy according to any one of claims 1 to 4 , wherein the adhesive disperses the filler in the epoxy resin with high quality using a sand grind mill type wet pulverizer. An adhesive composite containing a metal alloy, wherein the composite is manufactured. Comparable in adhesive composite comprising a metal alloy according to any one of claims 1 to 5, wherein the shaped metal can surface in 10~100nm diameter with has a roughness of micron by chemical etching A thin aluminum oxide layer having a thickness of 2 nm or more, which is covered with an irregularly shaped ultra-fine irregular surface having irregular intervals or protrusions of a certain depth or height and does not contain sodium ions is formed on the surface. An adhesive composite containing a metal alloy, wherein the adhesive composite is a metal shape made of an aluminum alloy. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shape was covered with an ultra-fine irregular surface having a surface with a roughness on the order of microns by chemical etching and an infinite number of bar-shaped objects having a diameter of 5 to 20 nm and a length of 20 to 200 nm. An adhesive composite containing a metal alloy, characterized in that the metal alloy is made of a magnesium alloy having a shape and a thin layer of manganese oxide formed on the surface thereof. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal-shaped product has a surface roughness of micron order by chemical etching, and a spherical product with a diameter of 5 to 20 nm and an infinite number of rod-shaped protrusions having a length of 10 to 30 nm and a diameter of 80 to 100 nm. Adhesion including a metal alloy characterized by being a metal shape made of a magnesium alloy having a shape covered with super fine uneven surfaces of a stacked shape and a thin layer of manganese oxide formed on the surface Complex. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The shape of the metal shape is covered with an ultra-fine irregular surface having a surface with a roughness on the order of microns by chemical etching and a stack of 20 to 40 nm granular shapes and / or indefinite polygonal shapes. An adhesive composite containing a metal alloy, which is a metal shape made of a magnesium alloy and having a thin layer of manganese oxide formed on the surface. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The surface of the metal shape has a roughness on the order of microns by chemical etching, and the surface of the hole or recess having an average diameter or major axis / minor axis of 10 to 150 nm at irregular intervals of 30 to 300 nm. A metal shape made of a copper alloy having a shape in which almost the entire surface is covered with an ultra-fine uneven surface present in the surface, and a thin layer of cupric oxide is mainly formed on the surface. An adhesive composite containing an alloy. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shape is an ultra-fine concavo-convex shape in which the surface has a roughness on the order of microns by chemical etching and has an average of 10 to 200 nm in diameter or major axis and minor axis in a mixed manner. An adhesive composite containing a metal alloy, wherein the adhesive is a metal shape made of a copper alloy, and a thin layer of cupric oxide is mainly formed on the surface. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shape has a surface roughness of micron order by chemical etching, and the average of the diameter or major axis and minor axis is 10 to 150 nm. Including a metal alloy characterized by being a metal shape made of a copper alloy in which a substantially entire surface is covered with an ultrafine uneven shape of a shape and a thin layer of cupric oxide is mainly formed on the surface Adhesive complex. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shape has a micron-order roughness due to chemical etching, and has an ultrafine shape in which a granular shape having a diameter of 10 to 20 nm and an indefinite polygonal shape having a diameter of 50 to 150 nm are mixed and stacked. An adhesive composite containing a metal alloy, characterized in that the metal alloy is a metal shape made of a copper alloy, which is almost entirely covered with a concavo-convex shape, and in which a thin layer of cupric oxide is mainly formed on the surface. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shaped object has a surface with a micron-order roughness by chemical etching and is covered almost entirely with an ultra-fine irregular shape of a shape in which particles having a diameter of 20 to 70 nm and irregular polygonal shapes are stacked, An adhesive composite containing a metal alloy, characterized in that it is a metal shape made of stainless steel having a thin layer of metal oxide formed on the surface. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shape has a surface roughness of micron order by chemical etching, a height of 80 to 150 nm, a depth of 80 to 200 nm, a width of several hundred to several thousand nm, and an extremely fine unevenness having a shape with infinite steps. A metal made of a steel material that is almost entirely covered with a shape and on which a thin layer of either manganese oxide, chromium oxide, zinc phosphorus oxide, or zinc and calcium phosphate is formed An adhesive composite comprising a metal alloy, wherein the composite is a shape. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shape has a micron-order roughness by chemical etching, a height of 80 to 150 nm, a depth of 80 to 500 nm, a width of several hundred to several thousand nm, and an ultrafine shape having an infinite number of steps. Made of a steel material that is almost entirely covered with an uneven shape and on which a thin layer of manganese oxide, chromium oxide, zinc phosphorous oxide, or zinc and calcium phosphorous oxide is formed. An adhesive composite containing a metal alloy characterized by being a metal shape of the above. The surface has a roughness on the order of microns by chemical etching and is covered with an ultra-fine irregular surface with an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal shape in which a thin layer is formed;
An adherend bonded and bonded to the metal shape;
An adhesive cured layer that cures an adhesive applied to an adhesive surface between the metal shape and the adherend, and integrally bonds the metal shape and the adherend;
An adhesive composite containing a metal alloy comprising: an adhesive that is a thermosetting epoxy adhesive, and includes an inorganic powder filler having a particle size distribution center of 5 to 20 μm as a filler, and 0 .3-3 mass% ultrafine inorganic powder having a particle size of 100 nm or less,
The metal shape has a micron-order roughness by chemical etching, a height of 50 to 100 nm, a depth of 80 to 200 nm, a width of several hundred to several thousand nm, and an ultrafine shape having an infinite number of steps. Made of a steel material that is almost entirely covered with an uneven shape and on which a thin layer of manganese oxide, chromium oxide, zinc phosphorous oxide, or zinc and calcium phosphorous oxide is formed. An adhesive composite containing a metal alloy characterized by being a metal shape of the above. Forming a metal shape having a predetermined shape by machining a plurality of the same or different metal alloy materials;
The surface of the metal shaped object having the predetermined shape is an ultra-fine uneven surface covered with an ultra-fine uneven shape with an irregular period of 5 to 500 nm, and the ultra-fine uneven surface has an average interval between peaks and valleys RSm of 1 to 10 μm. A surface treatment step of performing various liquid treatments including chemical etching so that the surface having a larger uneven shape having a roughness with a maximum roughness height Rz of 0.2 to 5 μm,
Thermosetting epoxy-based adhesive comprising at least an epoxy resin, a curing agent, an inorganic powder having a particle size distribution center of 5 to 20 μm, an inorganic fine powder having a particle diameter of 100 nm or less, and 0.02 to 0.2% by mass of carbon nanotubes Producing an agent and applying it to the metal shape,
A process of laminating and fixing metal shapes made of the same or different metal alloys coated with the above-mentioned thermosetting epoxy adhesive, and unifying the entire uncured resin by heating to integrate the two. When,
The manufacturing method of the adhesive composite containing the metal alloy characterized by including. Forming metal shapes having respective predetermined shapes by mechanical processing of metal alloy materials;
The surface of the metal shaped object having the predetermined shape is an ultra-fine uneven surface covered with an ultra-fine uneven shape with an irregular period of 5 to 500 nm, and the ultra-fine uneven surface has an average interval between peaks and valleys RSm of 1 to 10 μm. A surface treatment step for performing various liquid treatments including chemical etching so that the maximum roughness height Rz is a surface having a larger roughness with a roughness of 0.2 to 5 μm,
Epoxy resin, curing agent, inorganic powder having a particle size distribution center of 5 to 20 μm as filler and inorganic fine powder having an average particle diameter of 100 nm or less as ultrafine filler , and 0.02 to 0.2% by mass Producing a thermosetting epoxy adhesive containing at least carbon nanotubes and applying it to the metal shape;
A step of preparing a fiber-reinforced plastic prepreg having an epoxy resin composition as a matrix resin into a predetermined shape by work such as cutting and lamination;
The step of fixing the above-mentioned thermosetting epoxy adhesive with the applied metal shape and prepreg shape together and fixing them, and gelling and curing all uncured resin by heating, and integrating both,
The manufacturing method of the adhesive composite containing the metal alloy characterized by including. Forming metal shapes having respective predetermined shapes by mechanical processing of metal alloy materials;
The surface of the metal shaped object having the predetermined shape is an ultra-fine uneven surface covered with an ultra-fine uneven shape with an irregular period of 5 to 500 nm, and the ultra-fine uneven surface has an average interval between peaks and valleys RSm of 1 to 10 μm. A surface treatment step for performing various liquid treatments including chemical etching so that the maximum roughness height Rz is a surface having a larger roughness with a roughness of 0.2 to 5 μm,
Preparing a cured shape of fiber reinforced plastic using an epoxy resin composition as a matrix resin and roughening a portion to be bonded;
Thermosetting epoxy system comprising an epoxy resin, a curing agent, an inorganic powder having a particle size distribution center of 5 to 20 μm, an inorganic ultrafine powder having a particle diameter of 100 nm or less, and at least 0.02 to 0.2% by mass of carbon nanotubes Producing an adhesive and applying it to the metal shape and the cured shape of the fiber reinforced plastic; and
Fixing the thermosetting epoxy adhesive applied metal shape and the cured shape of fiber reinforced plastic while pressing them together and heating them to gel and cure all uncured resin to integrate them,
For producing an adhesive composite containing a metal alloy In the manufacturing method of the adhesion composite containing the metal alloy according to any one of claims 18 to 20,
After the step of applying the adhesive to the above-described metal shape and / or fiber reinforced plastic prepreg or cured shape, the applied material is housed in a sealed container, and the operation of repeatedly depressurizing the inside of the container and then pressurizing is repeated. Added the process of soaking the adhesive on the material surface,
The manufacturing method of the adhesive composite containing the metal alloy characterized by the above-mentioned. In the manufacturing method of the adhesion composite containing the metal alloy according to any one of claims 18 to 21,
In order to advance the dispersion of the filler in the manufacturing process of the thermosetting epoxy adhesive described above, a sand grind mill type wet pulverizer is used.
The manufacturing method of the adhesive composite containing the metal alloy characterized by the above-mentioned.