JP2012066383A - Adhesive-bonded composite containing metal alloy, and manufacturing method for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite that is formed by combining a thermosetting resin molded product with a metal alloy shaped product by injection-bonding the thermosetting resin to metal alloys so as to have excellent corrosion resistance, weather resistance, and heat resistance.SOLUTION: A metal alloy piece 61 is subjected to NAT treatment as follows: (1) forming an uneven surface 72 where the roughness period is 1 to 10 μm and the height difference is up to about half of the roughness period, (2) forming ultra-fine irregularities with a period of 10 to 500 nm, most desirably 50 to 100 nm, on the inner-wall surfaces of the concaves, and (3) covering the surface with a thin layer of a hard ceramic phase. The composite is formed by integrating a metal alloy shaped product with a thermosetting resin molded product via an adhesive layer, by applying a one-pack epoxy adhesive, a phenol resin adhesive, or an unsaturated polyester-resin-based adhesive to insert the metal alloy piece applied with the adhesive into an injection mold, and injecting a thermosetting resin composition having the same kind as the adhesive into the mold.

Description

  TECHNICAL FIELD The present invention relates to an adhesive composite containing a metal alloy and a method for manufacturing the same, and more particularly, to an adhesive composite containing a metal alloy used in mobile machinery, electrical equipment, medical equipment, general machinery and other general manufacturing fields, and the manufacture thereof. Regarding the method. More specifically, the present invention relates to a new basic manufacturing technique. Specifically, a metal part and an injection-molded product of a thermosetting resin are combined with a phenol resin adhesive, an epoxy adhesive, or an unsaturated polyester resin system. With regard to composites firmly bonded and integrated through an adhesive and its manufacturing technology, in particular, the injection of a thermosetting resin into a mold after inserting an adhesive-coated metal alloy part into an injection mold The present invention relates to an adhesive composite containing a metal alloy obtained by means of injection joining, and a method for producing the same.

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

  Although these are techniques by the present inventors, the joining force has reached a high level of 25 to 30 MPa as a shear breaking force due to subsequent improvements. The joining theory has also been elucidated, and is the name of the present inventors. However, it is now known to metalworkers as “NMT” (short for Nano molding technology). In addition, the present inventors have demonstrated that magnesium alloys, copper alloys, titanium alloys, stainless steel, general steel materials, galvanized steel plates, etc. can be injection-bonded by using the same type of resin as used in NMT (patent document) 3, 4, 5, 6, 7, 8, 15, 16). These depend on another principle different from NMT, and the inventors named this injection joint “new NMT”.

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. thing,
It is. These are schematically illustrated as shown in FIG. In the figure, 70 is a metal alloy part, 71 is an uneven part on the surface of the metal alloy, 72 is a resin composition, A and B indicate the spacing and height of the ultra fine protrusions, and C is an uneven part larger than that. Cycle. 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.

  Generally speaking, an injection molding machine refers to a machine that injection-molds a thermoplastic resin composition, but there is also an injection molding machine that performs injection molding using a thermosetting resin composition as a raw material. In order to avoid confusion, it is daunted by the long name “injection molding machine for thermosetting resin”, and its basic structure has a temperature setting opposite to that of a general injection molding machine. That is, the injection temperature is set to a low temperature range of 70 to 100 ° C., and the mold temperature is set to a high temperature of 150 to 200 ° C. The raw material resin to be injected is a thermosetting resin composition, most of which are phenolic resin and unsaturated polyester resin thermosetting resin compositions. There is a thing.

  The composition of the unsaturated polyester resin composition for injection molding is at least 1) an unsaturated polyester resin or vinyl ester resin, 2) a styrene monomer, 3) an inorganic filler, and 4) an organic peroxide of a curing agent. Depending on the grade, there are compounds containing a reduced amount of styrene monomer, and some containing glass fibers. By selecting organic peroxides that have a slow decomposition rate, they can be stored for more than a month if stored refrigerated. On the other hand, many epoxy resin-based compositions are compounds containing an epoxy resin, an inorganic filler, and an amine-based or phenol resin-based curing agent and can be stored at room temperature. The phenol resin-based composition is usually a compound containing a novolac-type phenol resin, an inorganic filler, and a curing agent, hexamethylenetetramine (hereinafter referred to as “hexamine”), and can be stored at room temperature.

  The above-described thermosetting resin compositions for injection molding of unsaturated polyester resin type, epoxy resin type, and phenol resin type are usually supplied in the form of a powder mixture. Unlike those used for these injection molding machines, a bulk molding compound (Bulk) containing unsaturated polyester resin, styrenic monomer, short glass fiber, some inorganic filler, and organic peroxide as a curing agent. There is also a thermosetting resin composition for BMC molding machines, which is an abbreviation for molding compound, hereinafter referred to as “BMC”. As can be seen from the above composition, BMC is intended to obtain a GFRP material by injection molding. It contains a short glass fiber and has a high styrene monomer content, so it is somewhat difficult to handle. That is, an BMC molding machine is an injection molding machine in which a forced raw material pushing device is installed at the raw material inlet.

  Now, injection joining with the new NMT is a strong metal by inserting a metal alloy with a new NMT surface treatment into an injection mold and injecting the PBT or PPS resin of the specific composition described above into this mold. -Obtained an integrated resin. As a horizontal development of the new NMT, the present inventors tested at the same time whether similar injection joining could be obtained with a thermosetting resin composition instead of a thermoplastic resin composition. However, unfortunately it was not bonded at all, and the present inventors determined that injection bonding of thermosetting resin was impossible at all at that time. I will describe the situation at that time in detail.

  That is, the present inventors surface-treated various metal alloys according to the above-mentioned Patent Documents 1 to 8, and inserted the obtained metal alloy pieces into a mold attached to a thermosetting resin injection molding machine, An unsaturated polyester resin thermosetting resin composition for injection molding was injected. However, when the mold was opened, the resin molding and the metal piece were not joined at all, and they were separated and dropped. At that time, an epoxy resin thermosetting resin composition was similarly subjected to an injection bonding test, but it was not bonded at all. The reason for not joining was obvious from the observation of the resin molding, and in a word, the excess viscosity of the injection was the cause.

  In short, the nozzle temperature of the injection cylinder was set to 80 to 90 ° C. in order to melt the raw material resin. However, in this temperature range, the commercially available thermosetting resin composition for injection molding is in the form of a paste, but not so liquid. Absent. This paste-like material usually enters a mold heated to 150 to 180 ° C. at high pressure, but the viscosity of the paste tends to decrease at high temperature and gel hardening at high temperature proceeds at the same time. In addition, only a viscosity far from the micron-order recesses on the surface of the insert metal alloy piece can be obtained. In short, the original form of thermosetting resin injection molding is to press the resin composition that is solidifying into a mirror-finished mold without fine irregularities and complicated shapes at high pressure to obtain a shape with a beautiful surface appearance. I had no choice but to recognize. Of course, there is an improved compound for realizing a slightly precise shape for electrical parts, but the fluidity to completely transfer the fine irregularities with a period of several μm as shown in Patent Documents 3 to 8 is not possible. I found out that I could not have it. With this judgment, research and development in this direction was interrupted.

  At the same time, the new NMT, a technology for injection-bonding a thermoplastic resin to a metal alloy, changed its direction and led to a great discovery. In other words, this is a technique that the present inventors call “NAT (abbreviation of Nano adhesion technology)”. The basics of NAT are technologies to bond metal alloys to each other and metal alloys to CFRP with a one-component epoxy adhesive, and the basic technology that shows a strong adhesive strength of 70 to 80 MPa with a shear breaking force or tensile breaking force at the maximum. It is. In short, the contents of NAT should have the same surface structure as that shown in Patent Documents 3 to 8 on the metal alloy side, and the adhesive should be in a liquid state of about 10 Pa seconds or less at the time of application or after application. For example, an operation of adding a pressure reducing pressure operation to infiltrate the liquid adhesive into the fine recesses on the metal alloy is performed. Details thereof are described in Patent Documents 9 to 16.

  For example, an experimental example of an aluminum alloy will be briefly described as an example of NAT. That is, A7075 aluminum alloy pieces are surface-treated according to the requirements of NAT. Next, a one-component epoxy adhesive is applied to the necessary part of the surface treated. This is put into a desiccator which has been heated to 50 to 70 ° C. to lower the viscosity of the adhesive, and then the pressure fluctuation operation of decompression / return to normal pressure is repeated several times to soak the adhesive on the aluminum alloy surface.

  When the metal alloys are bonded to each other, the adhesive-coated surfaces are combined and then fixed with a clip or a clamp, and cured with a hot air dryer at 120 to 180 ° C. to obtain an adhesive. When the metal alloy piece is bonded to the CFRP, the metal alloy piece with adhesive and the CFRP prepreg are attached and fixed, and similarly subjected to high temperature curing treatment. Normally, NAT performs the above operations continuously. In practice, however, a one-component epoxy adhesive applied to a metal alloy piece and soaked and treated is put in a plastic bag, etc. If it is stored in a refrigerator or the like without being exposed, it can be used anytime.

JP 2004-216425 A WO2004-055248 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. 2008-67313 Japanese Patent Application No. 2007-62736 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. 2008-11551 Japanese Patent Application No. 2008-308019

  If the molded product and the metal alloy piece inserted in advance can be strongly bonded and integrated by injection molding of a thermosetting resin, it can be said that it greatly contributes to streamlining processes, facilitating assembly, and mass production. From such a point of view, past information was gathered, but metal parts were inserted into an injection mold for thermosetting resin injection, and thermosetting resin was injected to obtain a molded product. We could not find a technique to strongly bond and integrate with metal alloy parts. There was an example of manufacturing an integrated part by inserting a metal part with rough surfaces in anticipation of joining, and injecting a thermosetting resin. It was not adhered microscopically and was different from the intention of the present inventors.

  If a metal alloy piece can be inserted into an injection mold and a thermosetting resin can be injected and joined to integrate the metal alloy piece and the thermosetting resin, an injection molding machine with excellent mass productivity can be used. The resulting composite has a thermosetting resin, is excellent in heat resistance and weather resistance, etc., and the application of the metal / resin composite is expected to enter a new wide field. Further, a thermosetting resin composition for a BMC molding machine is also excellent in heat resistance and weather resistance by forming a composite integrated with a metal alloy piece, and is expected to be applied to a new wide field.

  Therefore, an adhesive composition is applied and soaked into a NAT-treated metal alloy piece, this is inserted into an injection mold, a thermosetting resin is injected, and an integrated product of the resin molded product and the metal alloy part is formed. We decided to develop a technology that could be obtained all at once, that is, an injection joining technology using a thermosetting resin. Theoretically, this should be possible by the above-mentioned basic technology addition that has been acquired by the present inventors for a long time. A commercially available thermosetting resin composition for injection or BMC is injected and cured in the mold, and the curing timing of the adhesive composition on the metal alloy piece previously inserted in the injection mold is good. The key is to match. Various types of thermosetting resin compositions for injection are commercially available from chemical companies at a relatively low cost. In practical terms, such commercial products should be used. Therefore, the point is whether the timing can be adjusted by adjusting the curing speed on the adhesive side.

  Prepared a commercially available injection molding machine for thermosetting resin, and obtained and commercialized unsaturated polyester resin, phenolic resin, and epoxy thermosetting resin compositions for injection molding that are commercially available as general-purpose molds. Went. Fortunately, for all three types of unsaturated polyester resin adhesives, phenol resin adhesives, and epoxy adhesives, the adhesive composition ratio, mold temperature, and holding time until injection from the insert are varied within the range of fine adjustment. It was confirmed that a strong injection joining force was obtained.

  The present invention has been made to solve the above-mentioned problems, and the adhesive composite of a metal alloy and a thermosetting resin according to claim 1 of the present invention has a surface roughness of micron order by chemical etching. The surface is covered with a fine irregular shape with an irregular period of 5 to 500 nm, and the surface is a metal oxide or metal phosphor oxide thin layer, and obtained by injection molding. The molded product made of the resulting epoxy resin thermosetting resin composition is integrated with a cured product layer of an epoxy adhesive in between.

  The adhesive composite of the metal alloy and the thermosetting resin according to claim 2 of the present invention has a micron-order roughness by chemical etching on the surface, and the surface is covered with fine irregularities having an irregular period of 5 to 500 nm. A metal shape that has a cracked shape and the surface is a thin layer of a metal oxide or a metal phosphate, and a molded product made of a phenol resin thermosetting resin composition obtained by injection molding, Is formed by interposing a cured product layer of a phenolic resin adhesive in between.

  The adhesive composite of the metal alloy and thermosetting resin according to claim 3 of the present invention has a micron-order roughness by chemical etching on the surface, and the surface is covered with fine irregularities with an irregular period of 5 to 500 nm. And a molded product made of an unsaturated polyester resin-based thermosetting resin composition obtained by injection molding, and a molded product made of a thin layer of metal oxide or metal phosphate Is a thermosetting resin composition comprising 1) an unsaturated polyester resin and / or vinyl ester resin, 2) a styrene monomer, 3) an inorganic filler, and 4) an organic peroxide. It is formed by interposing a cured product layer of a saturated polyester resin adhesive between them.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 4 of the present invention which refers to any one of claims 1 to 3 is characterized in that the metal shape has a surface roughness of micron order by chemical etching. In addition, the surface has a shape covered with an ultrafine uneven surface that is a concave or convex portion 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 made of an aluminum alloy having a thin aluminum oxide layer.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 5 of the present invention quoting any one of claims 1 to 3, wherein the metal shape has a surface roughness of micron order by chemical etching. In addition, the surface has a shape in which a rod-shaped object having a diameter of 5 to 20 nm and a length of 20 to 200 nm is covered with an infinite number of complex fine uneven surfaces, and the surface has a thin layer of manganese oxide. It is made of a magnesium alloy.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 6 of the present invention quoting any one of claims 1 to 3 is characterized in that the metal shape has a surface roughness of micron order by chemical etching. In addition, the surface is covered with an ultra-fine irregular surface of a shape in which spherical objects having a diameter of 5 to 20 nm and a rod-shaped convex part having a length of 10 to 30 nm and having an infinite number of diameters of 80 to 100 nm are randomly stacked, And the surface is made of a magnesium alloy having a thin layer of manganese oxide.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 7 of the present invention quoting any one of claims 1 to 3, wherein the metal shape has a surface roughness of micron order by chemical etching. In addition, the surface has a shape covered with a super fine uneven surface in a shape in which a particle size of 20 to 40 nm or an indefinite polygonal shape is stacked, and the surface has a thin layer of manganese oxide. It is made of a magnesium alloy.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 8 of the present invention which refers to any one of claims 1 to 3 is characterized in that the metal shape has a surface roughness of micron order by chemical etching. And the surface is almost entirely covered with an ultra fine uneven shape in which hole openings or recesses having an average diameter or major axis and minor axis of 10 to 150 nm are present on the entire surface at irregular intervals of 30 to 300 nm, And the surface is made of a copper alloy whose thin layer is mainly cupric oxide.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 9 of the present invention quoting any one of claims 1 to 3, wherein the metal shaped product has a surface roughness of micron order by chemical etching. In addition, the surface has an ultra-fine uneven 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 the surface is mainly a thin layer of cupric oxide. It is made of copper alloy.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 10 of the present invention quoting any one of claims 1 to 3, wherein the metal shaped article has a surface roughness of micron order by chemical etching. And the surface is almost entirely covered with an ultrafine concavo-convex shape of a shape in which a particle diameter or an indefinite polygonal shape having an average diameter or major axis and minor axis of 10 to 150 nm is continuous and partly melted and stacked, And the surface is made of a copper alloy whose thin layer is mainly cupric oxide.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 11 of the present invention, which refers to any one of claims 1 to 3, is characterized in that the metal shape has a surface roughness of micron order by chemical etching. And the surface is almost entirely covered with a super fine uneven shape of a shape in which a particle having a diameter of 10 to 20 nm and an indefinite polygon having a diameter of 50 to 150 nm are mixed and stacked, and the surface is mainly It is made of a copper alloy that is a thin layer of cupric oxide.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 12 of the present invention which refers to any one of claims 1 to 3 is characterized in that the metal shape has a surface roughness of micron order by chemical etching. In addition, the surface has an extremely fine concavo-convex shape having a height or width of 10 to 350 nm, and a mountain-shaped or continuous mountain-shaped convex portion having a length of 10 nm or more in a period of 10 to 350 nm, and the surface is mainly The titanium oxide is a thin layer of titanium oxide.

  The bonded composite of a metal alloy and a thermosetting resin according to claim 13 of the present invention quoting any one of claims 1 to 3, wherein the metal shaped object has an average interval between peaks and valleys (RSm) by chemical etching. Has a roughness of 1 to 10 μm and a maximum roughness height (Rz) of 1 to 5 μm, and the surface has a fine concavo-convex shape in which both a smooth dome shape and a dead leaf shape are mixed within an area of 10 μm square And the surface is of an α-β type titanium alloy which is a metal oxide thin layer mainly containing titanium and aluminum.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 14 of the present invention which refers to any one of claims 1 to 3 is characterized in that the metal shape has a surface roughness of micron order by chemical etching. In addition, the surface is almost entirely covered with a super fine uneven shape in which a particle having a diameter of 20 to 70 nm or an indefinite polygonal shape is stacked, and the surface is a thin layer of metal oxide. It is for steel parts.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 15 of the present invention which refers to any one of claims 1 to 3 is characterized in that the metal shape has a surface roughness of micron order by chemical etching. And the surface is almost entirely covered with an ultra-fine uneven shape having a height of 80 to 150 nm, a depth of 80 to 200 nm, and a width of several hundred to several thousand nm that is infinite, and the surface Is made of a steel material which is a thin layer of manganese oxide, chromium oxide, zinc phosphorous oxide or zinc and calcium phosphorous oxide.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 16 of the present invention quoting any one of claims 1 to 3, wherein the metal shape has a surface roughness of micron order by chemical etching. And the surface is almost entirely covered with an ultra-fine concavo-convex shape having a height of 80 to 150 nm, a depth of 80 to 500 nm, and a width of several hundred to several thousand nm, which is infinitely long, and The surface is made of a steel material which is a thin layer of manganese oxide, chromium oxide, zinc phosphorous oxide or zinc and calcium phosphorous oxide.

  The adhesive composite of a metal alloy and a thermosetting resin according to claim 17 of the present invention which refers to any one of claims 1 to 3 is characterized in that the metal shape has a surface roughness of micron order by chemical etching. And the entire surface is almost entirely covered with an ultra-fine irregular shape having a height of 50 to 100 nm, a depth of 80 to 200 nm, and a width of several hundred to several thousand nm, which is infinite. The surface is made of a steel material which is a thin layer of manganese oxide, chromium oxide, zinc phosphorous oxide or zinc and calcium phosphorous oxide.

  A method for producing a bonded composite of a metal alloy and a thermosetting resin according to claim 18 of the present invention includes a step of forming a metal alloy material into a predetermined shape by mechanical processing, and a step of forming the formed metal alloy material. The surface is covered with fine irregularities having an irregular period of 5 to 500 nm, and the average interval (RSm) of large irregularities constituted by the fine irregularities is 1 to 10 μm and the maximum roughness height (Rz) is 0. A surface treatment step of performing various liquid treatments including chemical etching that gives a roughness of 2 to 5 μm, a step of applying a one-component epoxy adhesive to the metal alloy material, and a metal alloy material coated with the adhesive Inserting into an injection mold and injection molding machine loaded with the injection mold to inject an epoxy thermosetting resin and open the mold to form a metal alloy material and a thermosetting resin molding The process of releasing the integrated product , Including.

  According to a nineteenth aspect of the present invention, there is provided a method for producing a bonded composite of a metal alloy and a thermosetting resin, the step of forming a metal alloy material into a predetermined shape by mechanical processing; The surface is covered with fine irregularities having an irregular period of 5 to 500 nm, and the average interval (RSm) of large irregularities constituted by the fine irregularities is 1 to 10 μm and the maximum roughness height (Rz) is 0. .Surface treatment process for performing various liquid treatments including chemical etching that gives a roughness of 2 to 5 μm; a process for applying a phenol resin adhesive to the metal alloy material; and an injection-coated metal alloy material for injection molding A step of inserting into a mold; injection of a phenol resin thermosetting resin with an injection molding machine loaded with the injection mold, the mold is opened, and the metal alloy material and the thermosetting resin molding are integrated. Process of releasing the chemical product And including;

  A method for producing a bonded composite of a metal alloy and a thermosetting resin according to claim 20 of the present invention includes a step of forming a metal alloy material into a predetermined shape by mechanical processing; and The surface is covered with fine irregularities having an irregular period of 5 to 500 nm, and the average interval (RSm) of large irregularities constituted by the fine irregularities is 1 to 10 μm and the maximum roughness height (Rz) is 0. A surface treatment step for performing various liquid treatments including chemical etching that gives a roughness of 2 to 5 μm; 1) an unsaturated polyester resin and / or vinyl ester resin, 2) a styrene monomer, 3) an inorganic filler, 4) a step of producing an unsaturated polyester resin adhesive comprising an organic peroxide; a step of applying the unsaturated polyester resin adhesive to the metal alloy material; and the unsaturated polyester resin A step of inserting a metal alloy material coated with an adhesive into a mold for injection molding; an unsaturated polyester thermosetting resin or a block molding compound in an injection molding machine or a block molding compound molding machine loaded with the mold And releasing the mold to release the integrated product of the metal alloy material and the thermosetting resin molded product.

  A method for producing an adhesive composite of a metal alloy and a thermosetting resin according to claim 21 of the present invention, which refers to any one of claims 18 to 20, is a method of producing an adhesive composite of a metal alloy and a thermosetting resin. In the above, after the step of applying the adhesive to the metal alloy material, the resin is applied to the surface of the metal alloy, which is air-dried and then stored in a sealed container after air-drying, and the container is decompressed and then pressurized. A composition is impregnated and a process is added.

  The method for producing a bonded composite of a metal alloy and a thermosetting resin according to claim 22 of the present invention which refers to claim 19 is air-dried after the step of applying an adhesive to the metal alloy material, and further 80 The phenol resin adhesive is precured by placing it in a hot air drier at ˜100 ° C. for 5-15 minutes.

  A method for producing a bonded composite of a metal alloy and a thermosetting resin according to claim 23 of the present invention which refers to claim 20 uses a sand grind mill in the step of preparing the unsaturated polyester resin adhesive. And a step of forcibly dispersing an inorganic filler or the like in the unsaturated polyester resin main liquid.

  The composite of a metal alloy and a thermosetting resin of the present invention and a method for producing the same are as follows: an epoxy adhesive is applied to a metal alloy that has been subjected to a specific treatment, and then inserted into an injection mold, and then an epoxy resin thermosetting The mold resin composition is injected and the adhesive component and the injection resin component are simultaneously heat-cured and strongly integrated. Similarly, a phenolic resin thermosetting resin composition can be injected and joined by inserting a metal alloy piece coated with a phenolic resin adhesive. In addition, an unsaturated polyester resin-based adhesive is prepared, and a metal alloy piece coated with the unsaturated polyester resin-based adhesive is inserted into an injection mold, and an unsaturated polyester resin-based thermosetting resin composition or BMC can be injection-bonded.

  Since injection molding of thermosetting resin and adhesion of the molded product and metal alloy pieces can be performed at once, it helps to rationalize the process, and the obtained integrated product is excellent in dimensional stability and heat resistance. GFRP member shape that can be screwed, bolted, and welded if a metal alloy is made of stainless steel or titanium alloy, and this is used at the end of the component, and the central important part is made of a thermosetting resin part with a filler. Thus, it becomes a member that can be easily assembled, and at the same time, it can be made into a standard part. That is, inexpensive mass production is possible. The present invention shows that injection joining is possible also for thermosetting resins.

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 is a 100,000 times electron micrograph of two parts 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 with a sulfuric acid aqueous solution. FIG. 11 is a 10,000 times and 100,000 times electron micrograph of what was obtained by etching the cold rolled steel SPCC with a sulfuric acid aqueous solution and chemical conversion treatment with a potassium permanganate aqueous solution. FIG. 12 is an electron micrograph of 10,000 times and 100,000 times that obtained by etching the cold rolled steel SPHC with a sulfuric acid aqueous solution and chemical conversion treatment with a potassium permanganate aqueous solution. FIG. 13 is a view showing the shape of an adhesive complex in which a metal piece and a thermosetting resin molded product by injection molding are integrated. FIG. 14 is a schematic partial cross-sectional view showing a metal alloy surface structure in the new NMT theory and NAT theory.

Hereinafter, [1] the concept of the present invention, [2] the characteristics of the bonded composite containing the metal alloy and the method for producing the same will be described, and further examples will be described.
[1] Idea in the present invention The present inventors have explained the injection molding of the metal alloy piece with an adhesive obtained in the intermediate process of the adhesive bonding between the metal alloy piece and the resin or the metal alloy pieces by NAT, as explained in the background art. I came up with the idea of inserting into a mold and injecting a thermosetting resin material developed for injection molding. We expected that if both the adhesive and the injection material were cured simultaneously in a timely manner, they would always join. In short, it has been determined that injection joining of thermosetting resins that have failed in the past can be made possible by sandwiching an adhesive in the middle. It has already been found that a strong bonding force of 60 to 70 MPa can be obtained by heating between the metal alloy part and the adhesive. On the other hand, the injection resin composition is extruded into a mold at 150 to 180 ° C., and reaches an appropriate degree of hardening in about 30 seconds to 1 minute. It seemed to be successful if the adhesive was not cured too quickly.

  In other words, it is only necessary to match the curing timing of the adhesive with the curing timing of the injection resin. If the curing timing of the adhesive is slow, insert and seal the mold and wait for a while (take idle time). Then just inject. On the contrary, the adhesive cures quickly, and even if the injection is closed as soon as possible after inserting and closing the mold, the adhesive side may already be completely cured when the injection resin is cured. In such cases, the mold temperature should be adjusted slightly lower. If the curing speed on the adhesive side is still too fast, the adhesive itself may be adjusted. That is, even if it became the range which cannot be adjusted by use of a commercially available adhesive, it was thought that it could respond if there was an ability to make the adhesive itself.

  From the above, the present inventors prepared an unsaturated polyester resin resin composition, an epoxy resin resin composition, and a phenol resin resin composition as the injection resin. All of these are commercial products from domestic material manufacturers. Moreover, as an adhesive, in addition to the one-component epoxy adhesive and phenol resin adhesive which can be obtained as a commercial product, the unsaturated polyester resin adhesive by the above-mentioned inventors' invention technology (Patent Document 17) is prepared. Prepared.

  The metal alloy piece used first was a NAT-processed “A7075 aluminum alloy piece, but the expected strong injection joining was observed in all three systems of epoxy resin system, phenol resin system and unsaturated polyester resin system. A mold that can be molded into an integrated product that can measure the shear breaking force of injection-bonded products, metal alloy types are expanded to all types, and this injection-bonding technology is a basic technology that can be organized in general terms. Since this technology is in the form of diverting the NAT technology generalized by the present inventors to injection molding, the present inventors have referred to as “new NAT”.

  Since the present inventors have an inexpensive unsaturated polyester resin-based thermosetting resin for injection molding at hand, it was decided to immediately confirm whether or not the above-mentioned idea is established by a simple test. That is, it was a commercially available general-purpose one-component epoxy adhesive that was used as an injection material and applied onto a NAT-treated A7075 aluminum alloy piece inserted into one mold.

  In this experiment, the time axis of the epoxy adhesive placed under high temperature is cured (tens of seconds, minutes, tens of minutes, etc.). It is for actually seeing how many incidents occur when the injection resin containing the inorganic filler flows. I thought injection joining wouldn't work. This is because the injection resin is radical polymerization, and the adhesive is addition polymerization. If the gels are mixed at a good timing, there is a possibility that they will warp and interfere with each other and join together, but there is also a possibility that both will interfere and the polymerization rate will decrease, resulting in a bad result. Because it was thought.

  The result of the injection joining experiment using a commercially available one-component epoxy adhesive as the adhesive and the unsaturated polyester resin thermosetting resin composition as the injection resin was not injection joining. However, as expected, the following could be confirmed. In the experiment, an A7075 aluminum alloy piece, which was coated with an epoxy adhesive “EP106NL (made by Cemedine)”, soaked and processed, was inserted into a mold set at 180 ° C., and the mold was closed. The thermosetting resin was injected at idle times such as 15 seconds, 45 seconds, 75 seconds, 135, and 195 seconds.

  When the mold was opened and the molded product was taken out, the aluminum alloy pieces and the cured resin appeared to be bonded, but when struck with a hammer, they were peeled off in all cases. When the surface of the peeled metal alloy piece was observed, the adhesive that had been applied was washed away in the product with an idle time of 15 seconds, and the metal surface was clean. On the other hand, in the 195 second product, the layer of the cured adhesive was firmly attached on the metal. In these intermediate 75-second and 135-second products, the layer of the cured adhesive was firmly adhered on the metal, but the surface was cut away.

  The one-component epoxy adhesive “EP106NL (manufactured by Cemedine)” used is a dicyandiamide curing type, and the curing conditions specified by the manufacturer are 120 ° C. and 40 minutes + 150 ° C. and 20 minutes. When this was 180 minutes at 3 minutes, it was considered that almost complete curing was achieved. Then, during 1 to 2 minutes after being heated to 180 ° C., the gelation progresses at a high speed and the components near the surface of the metal alloy harden relatively firmly, while the adhesive component of the upper layer in contact with the outside air also gels. Progress. If a similar injection resin was charged with kinetic energy as it progressed to gelation, it could be expected that this would surely create a strong mix.

  In particular, in the above experiment, when the idle time is 15 seconds, there is no adhesive piece on the aluminum alloy, but when it is 75 seconds or 135 seconds, the hardened adhesive is firmly attached to the aluminum alloy. This is because the entire surface of the adhesive phase that has been adhered and hardened thereon was clearly roughened by being scraped off. It is preferable that both the resin components of the adhesive resin and the injection resin are mixed and strongly interfere with each other because it leads to strong adhesion, but it is difficult to remove the anchor portion of the adhesive in this step. The experimental results show that there was no problem in the generation of the adhesive force between the aluminum alloy and the adhesive when the idle holding time was 75 and 135 seconds.

[2] Features of Adhesive Composite Containing Metal Alloy and Manufacturing Method Thereof The adhesive composite containing metal alloy and the manufacturing method thereof will be described separately.
(A) Metal alloy part The metal alloy part as used in the present invention, that is, the metal alloy used as the 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 related to the present invention, and soft metal species such as lead are 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.

  The present inventors consider an alloy type mainly composed of magnesium, aluminum, copper, titanium, and iron as a metal alloy type that is useful for NAT. Hereinafter, these will be described. However, the NAT theory does not limit the metal species, and moreover, it does not limit the metal itself. It is not easy to simultaneously provide the non-metal with the three conditions of roughness, ultra-fine uneven surface, and high hardness surface layer, which are required by NAT. 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 7 describes aluminum alloy, Patent Document 8 describes magnesium alloy, Patent Document 9 describes copper alloy, Patent Document 10 describes titanium alloy, Patent Document 11 describes stainless steel, Patent Document 12 general The description about steel materials is given respectively. Regarding these metal alloy types arranged from aluminum alloys to general steel materials, the section of [Metal Alloy Parts] in each of these patent documents is also applied to the present invention, and therefore, detailed description thereof is omitted. The individual contents are exactly the same in the present invention.

(B) 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 a wide variety of elements in order to obtain characteristic physical properties. There are few pure metal materials, and they 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 the case of an alloy, the target chemical etching is often not possible even when using acid bases or specific chemical substances applied with reference to the literature as described above. In short, the use of the acid-bases and specific chemicals described above is fundamental, and in practice, the concentration of the acid-base aqueous solution to be used, the liquid temperature, the immersion time, and in some cases, appropriate by trial and error while devising the additive Chemical etching is performed.

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

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

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

(C) Surface hardening treatment, fine etching Depending on the type of metal alloy, fine etching on the nano-order is also 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 and hardened. Processing 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 the surface obtained by reacting an oxidant or the like with a metal alloy after chemical etching or chemical conversion treatment for the purpose of surface hardening treatment or surface stabilization treatment 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 5 to 10 nm diameter rod-like crystals that can finally be distinguished 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, in the magnesium alloy, the chemical conversion treatment also served as a fine etching operation. The same is true for copper alloys. 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 hole opening with a circular shape or a distorted circle. 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 micro unevenness occur simultaneously.

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

  Although there is a possibility that these can be prevented by chemical conversion treatment, there are no precedents, so there are tests to apply the adhesive to the temperature shock test, tests to leave in a general environment, tests to apply the coated material 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 formation of ultra-fine irregularities are performed to improve 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 is reduced. I know that there are many. A strong adhesive force is observed when the thin layer is such that a diffraction line is not detected by XRD, such as the thin layer of manganese oxide adhered to the magnesium alloy. When the chemical conversion layer is 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 our experience, the bonding force between a thick film (chemical conversion film) prepared 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 adhesive 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.

(D) Epoxy adhesive First, an epoxy adhesive will be described. Epoxy adhesives are usually composed of 1) an epoxy resin, 2) a curing agent or a curing agent and a curing aid, and 3) an inorganic filler, but in the present invention using NAT, in addition to this, 4) an ultrafine inorganic material The mixing and dispersion of the filler is effective for improving the heat resistance, and 5) mixing of the elastomer component is also effective depending on the physical properties of the thermosetting resin composition to be joined by injection.

  Commercially available epoxy adhesives include 1), 2), 3), and 5) depending on the type. It is 1) and 2) that are related to the cured and temperature properties as an adhesive, and 3) and 5) do not lead to total destruction when a strong breaking force is applied to the adhesive phase. Is the role. In the present invention, a combination of 1), 2) and 3) and a commercially available one-part epoxy adhesive based on a combination of 1), 2), 3) and 5) can be used. An adhesive that is well dispersed by adding a material can also be preferably used.

  Each of the above components will be described in some detail. First, the epoxy resin of 1) is commercially available, such as bisphenol type epoxy resin, polyfunctional polyphenol type epoxy resin, alicyclic epoxy resin, etc., and the epoxy group is a polyfunctional compound such as a plurality of hydroxyl groups or Various polyfunctional epoxy resins bonded with polyfunctional compounds having amino groups, oligomers, and the like are also commercially available.

  In order to use it as an adhesive, it is necessary that the final product is at least a paste. Therefore, the majority of all epoxy resins are liquid and low-viscosity bisphenol-type epoxy resin monomer types. preferable. Most of the epoxy resin components in commercially available general-purpose one-component epoxy adhesives are short-form types of this bisphenol A type epoxy resin, and the content of other epoxy resin components is small. Normally, it is common to add a multimeric form of bisphenol-type epoxy resin to ensure the quickness of the cured adhesive, and to add a compound with a polyfunctional epoxy group to further secure the toughness of the cured product. It is also a feature of the epoxy adhesive that it can exert a strong adhesive force at room temperature without reaching that point.

  Next, it is the curing agent component of 2), but the curing ability of the epoxy resin is in an amine compound, a phenol resin, an acid anhydride or the like. In the present invention, a one-component epoxy adhesive is preferred, but the meaning is that gelation should not proceed at least during the application, soaking, and operation (described later). In NAT, the unevenness of the metal alloy surface of the adherend is on the order of microns, and the diameter of the recesses of the ultrafine unevenness on the inner wall surface of the recesses on the order of microns is on the order of several tens of nm. Therefore, in the polymer solution in which gelation has started, the polymer component does not easily enter the ultrafine recess even if there is some pressure.

  For example, it is an aliphatic amine among amine compounds, but when this is used as a curing agent, gelation starts immediately after mixing with an epoxy resin. This property is important as a two-component epoxy adhesive, but is not preferred in the present invention. In the case of such an adhesive, if the application and soaking after mixing with the curing agent is performed at high speed and skillfully, the decrease in the adhesive force can be suppressed small, but the adhesive force varies depending on the skill. In short, a product using an aliphatic amine as a curing agent is not preferable as a mass production method or a basic production method.

  In conclusion, dicyandiamide, imidazoles and acid anhydrides are preferred as the curing agent. Most of the curing agents used in commercially available one-component epoxy adhesives use dicyandiamide and imidazoles. In addition, there are no commercially available epoxy adhesives that use acid anhydrides as curing agents, but they are very easy to produce. Even if the injection resin is an epoxy resin-based thermosetting resin, if the curing system is an acid anhydride, it is preferable that the adhesive side also uses an acid anhydride as a curing agent.

  The filler of 3) plays an important role. In other words, according to the current fracture theory, a minute 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 microfractures expands and the size of the fractured part is not microscopic and becomes a large crack, which eventually leads to complete fracture and peeling of the adherends in the adhesive system. Actually, the strength of the cured adhesive is not uniform at all, and it is always strong and weak in the micro. Therefore, if destruction is easy to chain, microfracture almost reaches complete destruction, and complete destruction is determined by a 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 next local breakage occurs in the weakest minute part, and the adhesive force is improved as a result.

  The current fracture theory is that even if local fracture occurs, the presence of the inorganic filler is effective in stopping it locally. A commercially available one-component epoxy adhesive always contains an inorganic filler. Specifically, powder of silica, clay (clay, kaolin), talc, alumina or the like having a particle size of several μm to several tens of μm is usually contained in an amount of several percent or more as an inorganic filler. The details of the inorganic filler to be added is an important trade secret of the adhesive manufacturer only because it affects the adhesive performance, but it depends on whether the inorganic powder is added or not.

  The present invention relates to NAT. However, as described above, commercially available one-component epoxy adhesives include 1) an epoxy resin, 2) a curing agent component, 3) an inorganic filler, or 1) an epoxy resin, 2) a curing agent component, and 3). Inorganic filler, 5) It contains an elastomer component, and of course these do not give NAT at all. The present inventors have confirmed the usefulness of 4) an ultrafine inorganic filler as an adhesive for NAT (Patent Document 18). That is, 4) If the ultrafine inorganic filler can be well dispersed in the epoxy adhesive and added, the adhesive force at a high temperature with the NAT-treated metal alloy piece can be increased. That is, this addition hardly helps to improve the adhesive strength at room temperature, but has an effect of suppressing a sudden decrease in adhesive strength at high temperatures.

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

  Specifically, it utilizes the fact that the resol resin is thermosetting and dissolves in an organic solvent such as ketone or alcohol, and these solvents are added to the resole resin to lower the viscosity and are used as an adhesive. Some commercially available products further improve the adhesive properties by mixing a little epoxy adhesive, and many have increased the epoxy adhesive content to almost half of the adhesive component. It can be said that these are epoxy adhesives with a phenol resin as a curing agent, but these are also treated as phenol resin adhesives in the market and named as phenol resin adhesives, thermosetting phenol resin adhesives, phenol resin adhesives. It is said to be adhesive. The inventors of the present invention have included phenolic resin adhesives in all.

  The common feature is that the adhesive itself is a low-viscosity liquid containing a large amount of solvent, and that a dehydration condensation reaction is included in the reaction of gelation or curing and solidification. The properties described later, that is, the generation of water vapor during gelation and solidification is a property that is not preferable as an adhesive, and is also the reason why a phenol resin adhesive is not used as a general-purpose adhesive. On the other hand, when the bonding method can be devised reliably, the adhesive layer is a phenol resin itself and has excellent heat resistance and water resistance. The present inventors used “110 (manufactured by Cemedine)” which is widely used in Japan. This is a resol type phenolic resin product in which some epoxy adhesive is mixed, and 40 to 50% methyl ethyl ketone (hereinafter referred to as “MEK”) is used as a solvent. The present inventors considered "110" as a standard phenolic resin adhesive, and proceeded with the experiment using this.

  It was considered desirable and necessary to add and disperse an inorganic filler, an elastomer component, etc. in the adhesive component from the viewpoint of the past development of various adhesives conducted by the present inventors. It has been found that the above-mentioned concept does not necessarily become clear as experience with resin-based adhesives is accumulated. That is, it has been found that the phenol resin adhesive has little or no effect of adding an inorganic / organic filler depending on the use environment, or may be counterproductive in some cases. These are peculiar to phenol resin adhesives, and the destruction theory of phenol resin adhesives will be different from that of epoxy adhesives.

  That is, when the phenolic resin adhesive is firmly cured and the phenolic resin on the injection side is also cured at substantially the same timing, the two will adhere very strongly. However, the phenol resin on the adhesive side is a resol resin, and it is assumed that gelling curing is in progress and discharging water vapor even when the injection resin is approaching. On the other hand, in the injection resin, a novolak resin and a curing agent hexamethylenetetraamine (hereinafter referred to as “hexamine”) are resin components, and this compound does not discharge water vapor during polymerization. The curing mechanism is said to start from the start of thermal decomposition of hexamine at 140 to 150 ° C., and it is said that the decomposition product of hexamine advances the addition polymerization of the novolak resin.

  In short, since it is not dehydration condensation, it does not generate water vapor unlike gelling solidification of resole resin. Although they have two different polymerization mechanisms, when they are mixed, the decomposition product of hexamine will bind to each other with the reaction of the resole resin. The problem seems to be the film thickness on the resol resin side. That is, when the film thickness is thick, the amount of water vapor generated due to dehydration condensation is large, and when the amount of water vapor generated is large, these eventually become voids and do not produce good results. Then, what is better is an adhesive coating layer with very little adhesive coating and almost no thickness? Probably not so simple. That is, if the adhesive layer is too thin, the dehydration condensation reaction seems to get away quickly. If the curing speed of the adhesive phase is too fast, it is difficult to perform injection joining.

  In conclusion from the experimental results, the adhesive coating layer can be quite thin. More specifically, it is about a single brush painting. If the solvent contained in about 50% is volatilized, it seems that the film thickness will be very thin. As a result, the solvent is volatilized, and the majority of the dehydration condensation of the resole resin proceeds by preheating, and the adhesive layer becomes a thin one having a thickness of 0.1 mm or less. In the case of a phenol resin adhesive that does not contain a filler, it did not feel that there was a difference in adhesive strength between a thin application amount (thickness) part and a thick part (parts applied twice).

  However, when a phenol resin adhesive containing a filler and containing a filler is used even though it is well dispersed by use of a wet pulverizer, the adhesive strength clearly decreases at the thickened portion of the coating. It was. I don't know the chemical reason, but it may be contradictory to the fact that the thinner the adhesive layer is, the better it is to add various fillers to complicate the adhesive layer. If we dare to predict, if a small amount of water molecules generated are covered in a large amount of injection resin and disappear from the resol resin part, it becomes an adhesive cured layer with no voids and little variation in strength (no need to add filler), This may be close to ideal.

(F) Unsaturated polyester resin adhesive Basically, it has the same composition as the matrix resin for glass fiber reinforced plastic (hereinafter referred to as “GFRP”). 1) Unsaturated polyester resin and / Or vinyl ester resin, 2) styrenic monomer, 3) inorganic filler, and 4) organic peroxide. The main liquid for GFRP matrix resin marketed for GFRP manufacture is a mixed liquid of 1) and 2). Since most of the unsaturated polyester resins and vinyl ester resins of 1) are high-viscosity liquids, they are dissolved in styrene and α-methylstyrene of 2), which are low-viscosity liquids, to make medium viscosity liquids that are easy to handle. GFRP is a glass fiber added to 1), 2) and 4) organic peroxide (curing agent). There is also GFRP in which 1), 2), 4) and glass fiber are further added with 3) inorganic filler. On the other hand, the unsaturated polyester resin adhesive used in the present invention does not require glass fiber as described above, and 1), 2), 3) and 4) are essential components.

  There are no commercial products of unsaturated polyester resin adhesives. This type of adhesive that exhibits its ability when applied to a NAT-treated metal alloy material is the inventors' invention (Patent Document 17). The main points of the contents are 1), 2) 3) Add the inorganic filler to the mixture, then pass it through the latest wet pulverizer 3) Disperse the inorganic filler in the main liquid 1), 2) well That is. If fine particles of talc or clay with a particle size distribution center of about 10 to 15 μm are used for the inorganic filler and forcedly dispersed using a bead mill (a kind of sand grind mill) of the latest wet pulverizer, the fine powder Despite the content, it becomes a transparent liquid which can be a transparent liquid. When 100 parts by weight of this liquid is mixed with about 1 part by weight of a low decomposition rate type 4) organic peroxide, it can be used up within 1 hour in summer and within several hours in other seasons. It can be used as an adhesive for NAT.

  Organic peroxides that can be used as described above are those having a high kick-off temperature (starting temperature for thermal decomposition), such as bis (1-hydroxycyclohexyl) peroxide, hydroxyheptyl peroxide, t-butyl hydroperoxide, cumene. Hydroperoxide, t-butyl perbenzoate, t-butyl peracenate, di-t-butyl peroxide, dicumyl peroxide, t-butyl-peroxyisopropyl monocarbonate, t-hexyl-peroxyisopropyl monocarbonate, t-Butyl peroxybenzoate can be used. Among these, t-butyl-peroxyisopropyl monocarbonate, t-hexyl-peroxyisopropyl monocarbonate, t-butyl peroxybenzoate, or the like that is often blended in BMC as a curing agent is also particularly preferable in the present invention.

(G) Adhesive application and subsequent treatment The various adhesives obtained above are applied to the necessary portions of the NAT-treated metal alloy pieces. Brush painting or spatula painting may be used. Epoxy adhesives often have high viscosity. In this case, the coated material is put in a vacuum vessel or a pressure vessel preheated to 50 to 70 ° C., and after a few minutes, the pressure is reduced to about several tens of mmHg for several seconds, and then air is added to return to normal pressure. It is preferable to set the pressure under several atmospheres or several tens of atmospheres. The reason for keeping the container warm is to make the viscosity of the adhesive 10 or less Pa seconds or less. The cycle of pressure reduction and pressure increase is preferably repeated instead of once. 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 the case of a phenol resin adhesive, after application, leave it for more than ten minutes. The solvent ketone (mostly MEK is used) volatilizes. The subsequent treatment is the same as that of the above-mentioned epoxy adhesive part way through. That is, it is preferable to put in a decompression vessel or the like that has been preheated to 50 to 70 ° C. and repeat the decompression / normal pressure return operation several times. When the temperature reaches 60 to 70 ° C., the solvent is completely evaporated, and at the same time, the resol is changed from a solid to a paste and the viscosity is lowered.

  Metal alloy pieces are taken out from a decompression vessel or the like, and then placed in a hot air dryer set at 90 to 100 ° C. for 10 to 15 minutes. Although this heating is called preheating treatment, it is a process necessary only for the phenol resin adhesive. The preheating step is a step intended to advance the gelation by causing the dehydration condensation reaction to proceed by setting the resol resin to about 90 ° C. When the temperature of the adhesive layer on the metal alloy is raised to nearly 90 ° C., the adhesive layer dissolves and becomes liquid, and a dehydration reaction occurs and foams violently like the Bessho hot spring mud hell.

  However, this also grows up in about 10 minutes. It is preferable to take out from the hot air dryer at that timing. Although this operation is somewhat craftsman, according to the results, a slight time shift has little effect on the adhesive force, and a high adhesive force was obtained even if it was fairly rough. When it is taken out from the hot air dryer and allowed to cool, the applied adhesive returns to solid again. What is not sticky is the difference from the epoxy adhesive coating.

  In the case of an unsaturated polyester resin adhesive, the coating operation is performed by adding and dispersing 3) inorganic filler powder in the main liquid containing 1) and 2), and 4) adding organic peroxide to the liquid and mixing. It starts from the moment you do it, and you have to do it well. It becomes an adhesive from the moment of mixing, but at the same time gelation begins. Of course, when a preferred organic peroxide is used, gelation is not so fast, so it can be used for half a day if it is placed in a refrigerator and stored at 5 ° C. or lower and divided only during use.

  The treatment after applying to the metal alloy may be similar to the epoxy adhesive. That is, the coating material is put in a decompression container that has been heated to about 50 ° C. in advance, and the decompression / normal pressure return operation is performed several times. The adhesive soaking process on the metal alloy surface is different from the epoxy adhesive in that styrene and the like are discharged from the vacuum pump to be used, and an odor is generated. A part of the styrenic monomer in the adhesive volatilizes due to the reduced pressure. At the same time, gelation slightly proceeds at a slightly warm temperature near 50 ° C., and the adhesive layer changes to a viscous liquid. Therefore, the appearance at the end of this treatment is similar to that of an epoxy adhesive, and the applied portion is solid.

(H) Storage of adhesive applied product With regard to those subjected to the adhesive application and the treatment after application, those coated with an epoxy adhesive and a phenol resin adhesive can be stored for a long time. If an epoxy adhesive product can be sealed by placing a polyethylene film on the adhesive application site as it is and putting the whole in a large plastic bag, it can be sealed and stored in the refrigerator for more than a month. it can. The phenolic resin adhesive can be used for several weeks as long as dust does not adhere to the coated surface. If the whole can be sealed in a plastic bag, it can be stored in the refrigerator for months without any problems. Can be used.

  What is difficult to store is a piece of metal alloy that has been coated with an unsaturated polyester resin adhesive and processed after application, and this should proceed directly to the injection joining process within a few hours. In short, it is necessary to proceed from the moment when the adhesive is created (the moment when the organic peroxide is added) to the injection joining process without any interruption. In this case, the thermosetting resin composition for molding is injected.

(I) Thermosetting resin composition for injection There are basically three types of commercially available thermosetting resin compositions for injection molding, one of unsaturated polyester resin type, one of phenol resin type. One is an epoxy resin type. These can be injection-molded using an injection molding machine for thermosetting resins marketed by each machine manufacturer. The basic structure of these injection molding machines is that the temperature control of the injection cylinder is 40 to 90 ° C, and both water cooling and electric heating are provided. The somewhat difficult temperature control is performed such that the temperature is not raised to the temperature range where gelation is promoted by increasing the temperature. On the other hand, even if the mold temperature is low, the resin composition is cured and solidified in the mold at about 150 ° C., most of which is 160 to 180 ° C.

  Such temperature conditions are normal, and conversely, resin manufacturers adjust the resin composition so that molding can be performed within such temperature conditions. In addition, there are grades that place importance on heat resistance depending on product use, place importance on precision (fluidity) during molding, and increase the number of inorganic fillers and place importance on dimensional stability. However, various thermosetting resin compositions for injection molding are not greatly different in molding conditions, and can all be used in the present invention.

  On the other hand, there is a resin material called BMC, although it is close to an unsaturated polyester resin-based resin composition for injection molding. The outline of BMC is described above in the background art, but the composition is a mixture of unsaturated polyester resin, styrene monomer, short glass fiber, inorganic filler, and organic peroxide. In short, it is almost the same as an unsaturated polyester resin-based injection molding material, except that short glass fibers are included. Since it contains glass fiber, the cured product becomes GFRP. The BMC molding depends on the BMC molding machine, but the basic structure of the BMC molding machine is exactly the same as the injection molding machine. As described above, the difference is that a BMC compulsory supply device is installed in the BMC molding machine. In short, BMC can also be used in the present invention.

(J) Operation of injection joining The above-mentioned adhesive-coated metal alloy part is inserted into an injection mold set in a thermosetting resin injection molding machine or a BMC molding machine, and the above injection molding resin or BMC Inject. The injection molding conditions for various resins may be the same as those specified by the injection resin manufacturer. When a standard commercially available resin is used, the injection cylinder temperature is often set to 70 to 90 ° C. and the mold temperature is set to 150 to 180 ° C., but this is not particularly problematic.

  A procedure of an operation of using a metal alloy piece coated with a one-component epoxy adhesive as an insert and using an epoxy thermosetting resin composition as an injection resin for successful injection joining will be described. First, a metal alloy piece is inserted into the mold, and the mold is once closed. Since the mold is heated to 150 to 180 ° C., the gelation of the adhesive proceeds in the mold. Even if the mold is closed, the injection operation is not performed, and the mold is once opened 30 seconds after the mold is closed. At that time, the state of the adhesive on the metal alloy is observed. You may poke with a needle. Suppose the gelation of the adhesive is obvious and the softness remains a little. In this case, the insert metal alloy is replaced with a new one, and the resin is injected 30 seconds after the mold is closed. The pressure holding operation is continued, and after a few minutes, the mold is opened to release the molded product.

  The molded thermosetting resin and the inserted metal alloy piece are integrated through an adhesive. When the two are forcibly peeled off and the adhesive surface on the metal alloy side is somehow exposed, the state of bonding can be seen. If there is a hardened adhesive layer on the metal alloy surface that is easily peeled off, this indicates that the adhesive has hardened too early and the idle time after insertion should be shortened next. is there. On the other hand, it is judged that the state of adhesion is very good when a thin, resin-like material adheres to the entire surface of the metal piece. Also, if the idle time after insertion is too short and the gelation of the adhesive has not progressed during resin injection, the uncured adhesive on the metal surface will be washed away by the injection resin flow and cleaned cleanly. As a result, the metal alloy pieces are cleaned as if they were polished. Of course, it does not adhere at all.

  Therefore, after finding an idle time that is likely to be injection-bonded, insert several pieces of metal alloy pieces that have been infused and treated with adhesive after that, and the time from injection to injection is shorter than the initial time. Change it and do the injection joining test. Determine the optimum idle time by measuring the breaking strength of the monolith. Although it can be seen from actual tests, the time width of idle time which is not so sensitive and is an optimum condition is close to 30 seconds. The phenol resin adhesive is exactly the same as the one-pack epoxy adhesive case described above. Inserting metal alloy pieces that have been soaked and treated with about 5 adhesives, and performing an injection joining test while changing the time from injection to injection, the optimum idle time becomes clear.

  In the case of an unsaturated polyester resin adhesive, the idle time is usually none. However, even if the metal alloy piece is inserted into the injection mold and injected as soon as possible, it takes 10 to 15 seconds from the closing of the mold to the injection. This is because in the injection molding of thermosetting resin, the injection cylinder nozzle is not brought into contact with the mold except during the injection and until several tens of seconds after the injection. Therefore, even if the mold closing and the mold approaching of the injection cylinder are switched on, it usually takes 10 seconds or more for the injection cylinder nozzle to contact the mold. If you feel that the curing of the adhesive is too fast, the first action you should take is to lower the mold temperature by 5-10 ° C.

  Although the curing time will be slightly lower than the mold temperature specified by the manufacturer of the injection molding resin used, it will extend from 1 minute to several minutes, but the gel curing speed of the adhesive on the metal alloy will also be slower and idle time will also be Since it stretches, it becomes easy to match both timings of curing. When injection joining is performed but it is felt that the injection resin itself does not have sufficient strength, there is a hand that the integrated product obtained by injection joining is placed in a hot air dryer at 120 to 150 ° C. for about 1 hour and then cured.

  Hereinafter, embodiments of the present invention will be described by way of examples. FIG. 13 shows a bonded integrated product of a metal alloy piece and a thermosetting resin shaped product obtained by injection joining, and 60 shows a metal alloy piece and an injection-molded piece of a thermosetting resin composition. An integrated installation combination composite, 61 is a metal alloy piece, 62 is an injection-molded piece of a cured thermosetting resin composition, and 63 is an adhesive layer.

(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.

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 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% 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 was made to dry.

  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. The electron micrographs of 10,000 times and 100,000 times are shown in FIG. Another piece was subjected to a scanning probe microscope to obtain roughness data. According to this, the peak-valley average interval (RSm) was 3-4 μm, and the maximum height (Rz) was 1-2 μm.

[Experimental example 2] (Surface treatment of aluminum alloy)
A commercially available 1.6 mm thick A5052 plate was obtained and cut into a large number of 45 mm × 18 mm rectangular pieces. A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co.)” was poured into water to form an aqueous solution at 60 ° C. and a concentration of 7.5%. The aluminum alloy sheet was immersed in this for 7 minutes and washed thoroughly with water. Subsequently, a 1% 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 was made to dry. After drying, the aluminum alloy sheets were wrapped together with aluminum foil, which was then stored in a plastic bag. An A5052 piece treated in the same way was observed with an electron microscope and found to be covered with a recess having a diameter of 30 to 100 nm. An electron micrograph of 10,000 times and 100,000 times is shown in FIG. Another piece was subjected to a scanning probe microscope to obtain roughness data. According to this, the mean valley interval (RSm) was 1.8 to 2.6 μm, and the maximum height (Rz) was 0.3 to 0.5 μm.

[Experiment 3] (Surface treatment of magnesium alloy)
A commercially available 1 mm thick AZ31B plate was obtained and cut into a large number of 45 mm × 18 mm rectangular pieces. A commercially available magnesium alloy degreasing agent “Cleaner 160 (manufactured by Meltex Co., Ltd.)” was poured into water to form an aqueous solution at 65 ° C. and a concentration of 7.5%. The magnesium alloy sheet was immersed in this for 5 minutes and washed thoroughly with water. Subsequently, a 1% 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. Poured and dried. After drying, the magnesium alloy sheet was wrapped together with aluminum foil, which was then sealed in a plastic bag.

  Observation of an AZ31B piece treated in the same manner with an electron microscope revealed that 5-10 nm diameter rod-like crystals were intricately entangled and their lumps were gathered together with a diameter of about 100 nm, and the gathering formed ultra fine irregularities. There was a part covered with the shape. The 100,000 times electron micrographs of these two places are shown in FIG. In addition, when another one was scanned with a scanning probe microscope and the roughness was observed, the mean interval between peaks 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 to 1.5 μm.

[Experimental Example 4] (Surface treatment of copper alloy)
A commercially available tough pitch copper (C1100) plate material, which is a pure copper-based copper alloy with a thickness of 1 mm, was obtained and cut into a large number of 45 mm × 18 mm rectangular pieces. An aqueous solution containing 7.5% of a commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex)” was immersed in water at 60 ° C. for 5 minutes and then washed with water, and then 1.5% caustic soda at 40 ° C. It was immersed in an aqueous solution for 1 minute, washed with water, and washed with a preliminary base. Next, an aqueous solution containing 20% 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. Next, it was dried for 15 minutes in a warm air dryer set at 90 ° C. 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. Moreover, when observed with an electron microscope of 100,000 times, almost the entire surface is an extremely fine uneven shape in which hole openings or recesses having an average diameter or major axis and minor axis of 10 to 150 nm are present 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 dried in a hot air dryer set at 90 ° C. for 15 minutes. Wrapped in aluminum foil and stored.

  FIG. 5 shows a C5191 piece having the same treatment at a magnification of 10,000 times and a magnification of 100,000 times. In the observation 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. The shape of the ultra-fine irregularities present on the entire surface was completely different from the microstructure of tough pitch copper, which is pure copper. One piece was applied to a scanning probe microscope. As a result, the mean valley interval (RSm) in JIS was 1 to 3 μm, and the maximum roughness height (Rz) was 0.3 to 0.4 μm.

[Experimental Example 6] (Surface treatment of copper alloy)
A commercially available 1 mm thick iron-containing copper alloy “KFC (manufactured by Kobe Steel)” plate 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. Next, it was dried for 15 minutes in a warm air dryer set at 90 ° C. 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 ultrafine 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. Next, it was dried for 15 minutes in a warm air dryer set at 90 ° C. 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.

  Subsequently, an aqueous solution containing 2% of a universal etching material “KA-3 (manufactured by Metalworking Technology Laboratories)” containing 40% of ammonium monofluoride at 60 ° C. prepared in another tank was prepared. The alloy piece was immersed for 3 minutes and washed thoroughly with ion exchange water. Subsequently, it was immersed in a 3% nitric acid aqueous solution for 1 minute and washed with water. It put into the warm air dryer which was 90 degreeC for 15 minutes, and was 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. The 10,000 times and 100,000 times electron micrographs are 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 mainly composed of titanium oxide, and because it was dark, it was presumed 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, in another tank, an aqueous solution in which 2% by mass of a commercially available general-purpose etching reagent “KA-3 (manufactured by Metalworking Technology Laboratories)” is dissolved is prepared at 60 ° C., and the titanium alloy piece is 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. Next, it was dried for 15 minutes in a warm air dryer set at 90 ° C. 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)
Commercially available stainless steel SUS304 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 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 was dried. After drying, the stainless steel plate material was wrapped together with aluminum foil, which was then stored in a plastic bag.

  The SUS304 pieces subjected to the same treatment were observed with an electron microscope and a scanning probe microscope. 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. The 10,000 times and 100,000 times electron micrographs are 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 warm 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. The 10,000 times and 100,000 times electron micrographs are 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 warm 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. The 10,000 times and 100,000 times electron micrographs are 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] (From application of one-component epoxy adhesive to injection bonding of epoxy resin)
A one-component epoxy adhesive “EP160 (manufactured by Cemedine Co., Ltd.)” having a curing agent as an imidazole was applied to an end portion of an A7075 aluminum alloy having a thickness of 45 mm × 18 mm × 3 mm treated in the same manner as Experimental Example 1. The aluminum alloy piece was placed in a desiccator that had been heated to 60 ° C. in advance, and the pressure was reduced with a vacuum pump. After 3 minutes, the pressure was returned to normal pressure. The vacuum was again applied and the pressure was returned to normal pressure after a few minutes, and the same process was repeated. Eventually, the decompression / normal pressure return operation was repeated three times. This is the adhesive soaking process referred to by the present inventors. The product was taken out from the desiccator, and a polyethylene film was placed on the adhesive-coated surface to prevent the adhesion of dust and stored as it was.

  An injection mold for obtaining an injection molded product having the shape shown in FIG. 13 was used. The A7075 aluminum alloy with the epoxy adhesive application surface obtained above was inserted into the mold. The mold temperature was 180 ° C., the nozzle temperature of the injection cylinder was 90 ° C., and the resin used was an epoxy thermosetting resin composition “KE-4200 (manufactured by Kyocera Chemical Co.)”. Immediately after insertion, the mold was closed, and at the same time, the injection cylinder approached. The injection nozzle contacted the mold and the resin was injected 15 seconds after the mold was closed. The injection molding machine for the thermosetting resin used was “PN40-2AK (manufactured by Nissei Plastic Industry Co., Ltd.)”.

  One minute after injection, the injection cylinder nozzle was released from the mold, and after 1.5 minutes, the mold was opened to release the molded product. Although the molded product was integrated, it was annealed in a hot air dryer set at 150 ° C. for 1 hour for further stabilization. It stood to cool and when the shear breaking force was measured with the tensile tester the next day, it was 50 MPa.

[Experimental Example 14] (From application of one-component epoxy adhesive to injection bonding of epoxy thermosetting resin composition)
A one-component epoxy adhesive “EP106NL (manufactured by Cemedine)” having a curing agent of dicyandiamide was applied to an end portion of an A7075 aluminum alloy having a thickness of 45 mm × 18 mm × 3 mm treated in the same manner as in Experimental Example 1. The aluminum alloy piece was placed in a desiccator that had been heated to 60 ° C. in advance, and the pressure was reduced with a vacuum pump. After 3 minutes, the pressure was returned to normal pressure. The vacuum was again applied and the pressure was returned to normal pressure after a few minutes, and the same process was repeated. Eventually, the decompression / normal pressure return operation was repeated three times. This is the adhesive soaking process referred to by the present inventors. The product was taken out from the desiccator, and a polyethylene film was placed on the adhesive-coated surface to prevent the adhesion of dust, and stored as it was.

  An injection mold for obtaining an injection molded product having the shape shown in FIG. 13 was used. The A7075 aluminum alloy with the epoxy adhesive application surface obtained above was inserted into the mold. The mold temperature was 180 ° C., the nozzle temperature of the injection cylinder was 90 ° C., and the resin used was an epoxy thermosetting resin composition “KE-4200 (manufactured by Kyocera Chemical Co.)”. Immediately after the insertion, the mold was closed, and after waiting for one minute, the injection cylinder approached. Therefore, the injection nozzle contacted the mold and the resin was injected 75 seconds after the mold was closed.

  One minute after injection, the injection cylinder nozzle was released from the mold, and after 1.5 minutes, the mold was opened to release the molded product. Although the molded product was integrated, it was annealed in a hot air dryer set at 150 ° C. for 1 hour for further stabilization. It stood to cool, and when the shear breaking force was measured with the tensile tester the next day, it was 53 MPa.

[Experimental Example 15] (From application of phenol resin adhesive to injection joining of phenol resin thermosetting resin composition)
A resol resin type phenol resin adhesive “110 (manufactured by Cemedine)” containing nearly 50% of the solvent MEK was applied to the end of a 45 mm × 18 mm × 3 mm thick A7075 aluminum alloy treated in the same manner as in Experimental Example 1. After air drying and volatilizing MEK, the adhesive “110” was painted again. The aluminum alloy piece was placed in a desiccator that had been allowed to stand at room temperature for 10 minutes and then preheated to 60 ° C., and the pressure was reduced with a vacuum pump. After 3 minutes, the pressure was returned to normal pressure. The vacuum was again applied and the pressure was returned to normal pressure after a few minutes, and the same process was repeated. Eventually, the decompression / normal pressure return operation was repeated three times.

  After taking out from the desiccator, next, the adhesive coating layer was reacted in a hot air dryer at 90 ° C. for 10 minutes. That is, the resol resin melted at this temperature, and gelation progressed due to a dehydration condensation reaction. However, the number of crater-like products produced by the generation of water vapor was reduced by about 10 minutes. When it was taken out from the hot air dryer and allowed to cool, the adhesive-coated surface became a solidified resin surface. Just wrapped in aluminum foil and stored as it is.

  An injection mold for obtaining an injection molded product having the shape shown in FIG. 13 was used. The A7075 aluminum alloy with the phenol resin adhesive-coated surface obtained above was inserted into the mold. The mold temperature was 180 ° C., the nozzle temperature of the injection cylinder was 80 ° C., and the resin used was a phenol resin thermosetting resin composition “CY3312 (manufactured by Panasonic Electric Works)”. Immediately after the insertion, the mold was closed, and after waiting for one minute, the injection cylinder approached. Therefore, the injection nozzle contacted the mold and the resin was injected 75 seconds after the mold was closed.

  One minute after injection, the injection cylinder nozzle was released from the mold, and after 1.5 minutes, the mold was opened to release the molded product. Although the molded product was integrated, it was annealed in a hot air dryer set at 150 ° C. for 1 hour for further stabilization. It stood to cool, and when the shear breaking force was measured with the tensile tester the next day, it was 58 MPa.

[Experimental Example 16] (Preparation of unsaturated polyester resin adhesive)
Filled with 400g of the main liquid "Lipoxy R802 (made by Showa Polymer Co., Ltd.)" for FRP matrix resin consisting of vinyl ester resin and styrene monomer into the sand grind mill "Minitsu Air (made by Ashizawa Finetech Co., Ltd.)" did. In the mill grinding chamber, 80% by volume of 0.3 mmφ spherical zirconia beads were placed.

  Wet grinding operation was started at a peripheral speed of 11-12 m / sec, and 12 g of fine talc “Hi-micron HE5 (manufactured by Takehara Chemical Co., Ltd.)” and 2 g of fumed silica “Aerosil R805 (Nippon Aerosil Co., Ltd.)” were added to the system. The pulverization operation was continued for 30 minutes, and the liquid was extracted into a plastic bottle. This liquid originally seemed to be a suspension, but the liquid appeared to be transparent because the dispersion was greatly improved by the wet pulverizer. And although it was in the refrigerator set to 5 degreeC, even if it stored for 3 weeks, the deposit was not able to be confirmed.

  On the other hand, t-butyl peroxybenzoate “Perbutyl Z (manufactured by NOF Corporation)” which is an organic peroxide was obtained. 0.1 g of “Perbutyl Z” was added to 10 g of the main liquid containing the inorganic filler, and the mixture was stirred well to obtain an adhesive. This curing agent (polymerization initiator) is added immediately before use. Unlike the experimental examples 14 and 15, the unsaturated polyester resin adhesive is clearly two-component.

[Experimental Example 17] (From application of unsaturated polyester resin adhesive to injection joining of unsaturated polyester resin thermosetting resin composition)
The unsaturated polyester resin adhesive prepared in Experimental Example 16 was applied by brushing to the end of a 45 mm × 18 mm × 3 mm thick A7075 aluminum alloy that had been treated in the same manner as in Experimental Example 1. It was air-dried for about 10 minutes, an aluminum alloy piece was put in a desiccator, the pressure was reduced with a vacuum pump, and after 3 minutes, the pressure was returned to normal pressure. The vacuum was again applied and the pressure was returned to normal pressure after a few minutes, and the same process was repeated. Eventually, the decompression / normal pressure return operation was repeated three times. And it stored in the desiccator under normal pressure.

  In parallel with the adhesive application operation and the like, an injection mold for obtaining an injection molded product having the shape shown in FIG. 13 was attached to an injection molding machine for thermosetting resin, and the mold temperature was set to 150 ° C. The A7075 aluminum alloy with unsaturated polyester resin adhesive applied surface obtained above was inserted, and the mold was closed immediately. The nozzle temperature of the injection cylinder is 80 ° C., and the resin used is an unsaturated polyester resin thermosetting resin composition “Premix AP-700 (manufactured by Kyocera Chemical Co.)”. Started. Therefore, the injection nozzle contacted the mold and the resin was injected 15 seconds after the mold was closed.

  One minute after injection, the injection cylinder nozzle was released from the mold, and after 1.5 minutes, the mold was opened to release the molded product. Although the molded product was integrated, it was annealed in a hot air dryer set at 150 ° C. for 1 hour for further stabilization. It stood to cool, and when the shear fracture strength was measured with the tensile tester the next day, it was 49 MPa.

[Experimental Example 18] (From application of one-component epoxy adhesive to injection bonding test of phenol resin thermosetting resin composition: comparative example)
In exactly the same manner as in Experimental Example 14, a one-component epoxy adhesive “EP106NL” was applied to the end of an A7075 aluminum alloy having a thickness of 45 mm × 18 mm × 3 mm, and was soaked and treated.

  An injection mold that provides an injection-molded article having the shape shown in FIG. 13 was used, and the above-mentioned A7075 aluminum alloy with an epoxy adhesive application surface was inserted into the mold. The mold temperature is set to 180 ° C., the nozzle temperature of the injection cylinder is set to 80 ° C., and the injection resin is not an epoxy thermosetting resin composition “KE-4200 (manufactured by Kyocera Chemical Co.)” but a phenol resin-based heat. The curable resin composition “CY3221 (manufactured by Panasonic Electric Works Co., Ltd.)” was used. Immediately after the insertion, the mold was closed, and after waiting for one minute, the injection cylinder started to approach. Therefore, the injection nozzle contacted the mold and the resin was injected 75 seconds after the mold was closed.

  One minute after injection, the injection cylinder nozzle was released from the mold, and after 1.5 minutes, the mold was opened to release the molded product. The molded product was integrated and annealed in a hot air dryer set at 150 ° C. for 1 hour for further stabilization. When this was allowed to cool and the shear breaking strength was measured with a tensile tester the next day, it broke during handling. The cured adhesive layer remained thick on the aluminum alloy side, and both the adhesive and the injection resin were cured, but it seemed that they were not mixed and cured while being joined together.

[Experimental Examples 19 to 29] (Injection joining of phenol resin thermosetting resin to various metal alloys coated with phenol resin adhesive)
The experiment was carried out in exactly the same way as in Experimental Example 15, but the difference was the metal alloy type. In Experimental Example 15, A7075 aluminum alloy of the same method as that obtained in Experimental Example 1 was used, but in Experimental Examples 19 to 30, the aluminum alloy, magnesium alloy, copper alloy, titanium alloy, stainless steel shown in Experimental Examples 2 to 12 were used. General steel materials were used. When the insert was thin, the spacer was placed outside and the thickness of the metal alloy part was 3 mm. Table 1 shows the shear breaking force of the integrated product obtained in these experiments.

<Table 1> A phenol resin adhesive “110 (Cemedine)” coated metal alloy piece is inserted into an injection mold, and a phenol resin thermosetting resin composition “CY3221 (Panasonic Electric Works)” is used. Shear breaking force of injection bonded

DESCRIPTION OF SYMBOLS 61 ... Metal alloy piece 62 ... Injection-molded piece of the cured thermosetting resin composition 63 ... Adhesive layer 71 ... Metal alloy part 72 ... Super fine uneven part 73 ... Resin composition

Claims (23)

The surface has a roughness on the order of microns by chemical etching, and the surface is covered with a fine irregular shape having an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal layer that is a thin layer;
Molded product made of epoxy resin thermosetting resin composition obtained by injection molding,
Is an adhesive composite of a metal alloy and a thermosetting resin, which is formed by integrating a cured product layer of an epoxy adhesive. The surface has a roughness on the order of microns by chemical etching, and the surface is covered with a fine irregular shape having an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal layer that is a thin layer;
Molded product made of phenol resin thermosetting resin composition obtained by injection molding,
Is an adhesive composite of a metal alloy and a thermosetting resin, characterized by being integrated with a cured layer of a phenol resin adhesive in between. The surface has a roughness on the order of microns by chemical etching, and the surface is covered with a fine irregular shape having an irregular period of 5 to 500 nm, and the surface is made of metal oxide or metal phosphorous oxide. A metal layer that is a thin layer;
Molded product made of unsaturated polyester resin thermosetting resin composition obtained by injection molding,
Is a thermosetting resin composition comprising 1) an unsaturated polyester resin and / or vinyl ester resin, 2) a styrene monomer, 3) an inorganic filler, and 4) an organic peroxide. An adhesive composite of a metal alloy and a thermosetting resin, which is integrated with a cured product layer of a resin adhesive interposed therebetween.   4. The bonded composite body of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shape has a surface having a roughness on the order of microns by chemical etching and a surface of 10 to 10. It has a shape covered with an ultra-fine irregular surface that is a concave or convex portion with a diameter of 100 nm and an equivalent depth or height, and the surface has a thin aluminum oxide layer with a thickness of 2 nm or more that does not contain sodium ions. An adhesive composite of a metal alloy and a thermosetting resin, characterized by being made of an aluminum alloy.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shaped product has a surface roughness of 5 microns by chemical etching and a surface of 5 to 5. Made of a magnesium alloy having a 20 nm diameter and 20 to 200 nm long rod-shaped material covered with an infinite number of complex ultra-fine irregular surfaces, and the surface having a thin layer of manganese oxide An adhesive composite of a metal alloy and a thermosetting resin, characterized in that   4. The bonded composite body of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shape has a surface roughness of 5 microns by chemical etching and a surface of 5 to 5. It is a shape covered with an ultrafine irregular surface of an irregularly stacked spherical object with a diameter of 80 to 100 nm, which has an infinite number of rod-shaped convex portions with a diameter of 20 nm and a length of 10 to 30 nm, and the surface is oxidized with manganese An adhesive composite of a metal alloy and a thermosetting resin, characterized by being made of a magnesium alloy having a thin layer of material.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shaped product has a surface having a roughness of micron order by chemical etching and a surface of 20˜ It is made of a magnesium alloy having a shape covered with an ultrafine irregular surface of 40 nm particle size and indefinite polygonal shape, and the surface of which has a thin layer of manganese oxide. An adhesive composite of a metal alloy and a thermosetting resin.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shape has a surface having a roughness of a micron order by chemical etching and a surface having a diameter or Hole openings or recesses having an average of a major axis and a minor axis of 10 to 150 nm are almost entirely covered with ultra-fine irregularities existing on the entire surface at irregular intervals of 30 to 300 nm, and the surface is mainly oxidized. An adhesive composite of a metal alloy and a thermosetting resin, which is made of a copper alloy that is a thin layer of cupric copper.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shape has a surface having a roughness of a micron order by chemical etching and a surface having a diameter or It is made of a copper alloy in which convex portions having an average major axis and minor axis of 10 to 200 nm are mixed and present on the entire surface, and the surface is mainly a thin layer of cupric oxide. An adhesive composite of a metal alloy and a thermosetting resin.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shape has a surface having a roughness of a micron order by chemical etching and a surface having a diameter or The entire surface is covered with an ultra-fine irregular shape of a shape in which particles having an average major axis and minor axis of 10 to 150 nm or an indefinite polygonal shape are continuously fused and stacked, and the surface is mainly oxidized. An adhesive composite of a metal alloy and a thermosetting resin, which is made of a copper alloy that is a thin layer of cupric copper.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the surface of the metal shape has a roughness of a micron order by chemical etching and the surface has a diameter of 10 The entire surface is covered with an ultra-fine irregular shape of a shape in which particles having a particle diameter of ˜20 nm and indefinite polygons having a diameter of 50 to 150 nm are mixed and the surface is mainly a thin layer of cupric oxide An adhesive composite of a metal alloy and a thermosetting resin, characterized by being made of a copper alloy.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the surface of the metal shape has a roughness of a micron order by chemical etching and a height of the surface. And a ridge-like or ridge-like convex part having a width of 10 to 350 nm and a length of 10 nm or more is present on the entire surface with a period of 10 to 350 nm, and the surface is a thin layer mainly of titanium oxide. An adhesive composite of a metal alloy and a thermosetting resin, characterized by being made of a titanium alloy.   4. The bonded composite body of a metal alloy and a thermosetting resin according to claim 1, wherein the metal shape has a surface having a peak-to-valley average interval (RSm) of 1 to 10 μm by chemical etching and a maximum roughness. The surface has a roughness with a height (Rz) of 1 to 5 μm, and the surface has a fine concavo-convex shape in which both a smooth dome shape and a dead leaf shape are mixed within an area of 10 μm square, and the surface Is an α-β type titanium alloy which is a metal oxide thin layer mainly containing titanium and aluminum, and is an adhesive composite of a metal alloy and a thermosetting resin.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the surface of the metal shaped product has a micron-order roughness due to chemical etching, and the surface has a diameter of 20 mm. It is of a stainless steel part that is almost entirely covered with an ultrafine uneven shape of a shape in which particles having a particle diameter of ˜70 nm or indefinite polygonal shapes are stacked, and the surface is a thin layer of metal oxide. An adhesive composite of a metal alloy and a thermosetting resin.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the surface of the metal shape has a roughness of a micron order by chemical etching and a height of the surface. The entire surface is covered with an ultra-fine irregular shape of 80 to 150 nm, a depth of 80 to 200 nm, and a width of several hundred to several thousand nm, and the surface is covered with manganese oxide and chromium oxide. An adhesive composite of a metal alloy and a thermosetting resin, which is made of a steel material which is a thin layer of zinc phosphate or zinc phosphate and zinc phosphate.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the surface of the metal shape has a roughness of a micron order by chemical etching and a height of the surface. The entire surface is covered with an ultra-fine concavo-convex shape having a shape of 80 to 150 nm, a depth of 80 to 500 nm, and a width of several hundred to several thousand nm, and the surface is covered with manganese oxide and chromium. An adhesive composite of a metal alloy and a thermosetting resin, characterized by being made of a steel material that is a thin layer of oxide, zinc phosphate, or zinc and calcium phosphate.   4. The bonded composite of a metal alloy and a thermosetting resin according to claim 1, wherein the surface of the metal shape has a roughness of a micron order by chemical etching and a height of the surface. The entire surface is covered with an ultra-fine uneven shape of 50-100 nm, a depth of 80-200 nm, and a width of several hundred to several thousand nm, and the surface is covered with manganese oxide and chromium. An adhesive composite of a metal alloy and a thermosetting resin, characterized by being made of a steel material that is a thin layer of oxide, zinc phosphate, or zinc and calcium phosphate. Forming a metal alloy material into a predetermined shape by mechanical processing;
The surface of the shaped metal alloy material is covered with a fine irregular shape having an irregular period of 5 to 500 nm and has a large irregularity crest and valley mean interval (RSm) of 1 to 10 μm. A surface treatment step for performing various liquid treatments including chemical etching that gives a roughness with a maximum roughness height (Rz) of 0.2 to 5 μm;
Applying a one-component epoxy adhesive to the metal alloy material;
Inserting the adhesive-coated metal alloy material into an injection mold; and
A step of injecting an epoxy thermosetting resin in an injection molding machine loaded with the injection mold, opening the mold, and releasing an integrated product of the metal alloy material and the thermosetting resin molding;
A method for producing a bonded composite of a metal alloy and a thermosetting resin, comprising: Forming a metal alloy material into a predetermined shape by mechanical processing;
The surface of the shaped metal alloy material is covered with a fine irregular shape having an irregular period of 5 to 500 nm and has a large irregularity crest and valley mean interval (RSm) of 1 to 10 μm. A surface treatment step for performing various liquid treatments including chemical etching that gives a roughness having a maximum roughness height (Rz) of 0.2 to 5 μm;
Applying a phenolic resin adhesive to the metal alloy material;
Inserting the adhesive-coated metal alloy material into an injection mold; and
A step of injecting a phenolic resin thermosetting resin with an injection molding machine loaded with the injection mold, opening the mold, and releasing an integrated product of the metal alloy material and the thermosetting resin molding;
A method for producing a bonded composite of a metal alloy and a thermosetting resin, comprising: Forming a metal alloy material into a predetermined shape by mechanical processing;
The surface of the shaped metal alloy material is covered with a fine irregular shape having an irregular period of 5 to 500 nm and has a large irregularity crest and valley mean interval (RSm) of 1 to 10 μm. A surface treatment step for performing various liquid treatments including chemical etching that gives a roughness having a maximum roughness height (Rz) of 0.2 to 5 μm;
A step of producing an unsaturated polyester resin adhesive comprising 1) an unsaturated polyester resin and / or vinyl ester resin, 2) a styrene monomer, 3) an inorganic filler, and 4) an organic peroxide,
Applying the unsaturated polyester resin adhesive to the metal alloy material;
Inserting the unsaturated polyester resin adhesive-coated metal alloy material into an injection mold; and
Unsaturated polyester-based thermosetting resin or block molding compound is injected by an injection molding machine or block molding compound molding machine loaded with the mold, the mold is opened, and the metal alloy material and the thermosetting resin molding are integrated. A step of releasing the chemical product,
A method for producing a bonded composite of a metal alloy and a thermosetting resin, comprising:   21. The method for producing an adhesive composite of a metal alloy and a thermosetting resin according to any one of claims 18 to 20, wherein after the step of applying an adhesive to the metal alloy material, this is air-dried, and further air-dried. An adhesive composite of a metal alloy and a thermosetting resin, characterized in that a step of immersing the resin composition into the surface of the metal alloy is repeated, which is then housed in a sealed container, and the inside of the container is decompressed and then repeatedly pressurized. Body manufacturing method. In the manufacturing method of the adhesion complex of the metal alloy according to claim 19, and a thermosetting resin,
After the step of applying the adhesive to the metal alloy material, the metal is air-dried and further placed in a hot-air dryer at 80 to 100 ° C. for 5 to 15 minutes to pre-harden the phenol resin adhesive A method for producing an adhesive composite of an alloy and a thermosetting resin. In the manufacturing method of the adhesion composite_body | complex of the metal alloy of Claim 20, and a thermosetting resin,
The step of creating the unsaturated polyester resin adhesive includes a step of forcibly dispersing an inorganic filler or the like in the unsaturated polyester resin main liquid using a sand grind mill. A method for producing an adhesive composite of a curable resin.