JP2021123035A - Adhesive integrated body containing heterogeneous construction materials and manufacturing method thereof - Google Patents

Abstract

To provide an adhesive construction body of high-strength construction materials that is resistant to a severe thousands-cycle test of temperature impacts.SOLUTION: An adhesive integrated body containing two heterogeneous materials such as an (A) material and a (B) material selected from FRP materials and a metal material group for construction, at both ends, in which a difference between linear expansion coefficients of the (A) material and the (B) material is 0.3×10-5K-1 or more. A (D) material which is a tabular body made of pure-aluminum-based aluminum alloy having a thickness of 1.5-5.0 mm or a construction material made of the pure-aluminum-based aluminum alloy is laminated between the (A) material and the (B) material, and bonded using an adhesive to obtain the adhesive integrated body.SELECTED DRAWING: Figure 4

Description

The present invention relates to a bonded integrated product containing different structural materials in which different materials of high-strength materials such as various metal materials, FRP materials, and FRTP materials are bonded to each other with high strength, and a method for producing the same. More specifically, various different materials such as fiber reinforced plastics such as various metal materials, GFRP materials, and CFRTP materials, which have greatly different differences in linear expansion coefficient, are bonded and laminated with high strength, and the joints include dissimilar structural materials. Regarding the product and its manufacturing method.

The inventor of the present invention has an adhesive structure for joining various metal materials such as aluminum alloy member, magnesium alloy member, stainless steel material, copper alloy material, titanium alloy material, steel material, and aluminum-plated steel plate with various FRP materials with an adhesive. A bonding method and the like have been proposed (Patent Documents 1 to 9). In addition, a one-component epoxy adhesive and an adhesive method used for this have also been proposed (Patent Documents 10 and 11). The bonding technology using these adhesives is basically a chemical conversion treatment that differs depending on the various metal materials, and is an assembly (laminate) of the bonding technology using the adhesive between the various metal materials that have undergone the chemical conversion treatment and FRP and FRTP. Is.

(Advanced adhesive technology: NAT)
The present inventors have developed and proposed an advanced adhesion technology called NAT (abbreviation of Nano adhesion technology) for increasing the adhesive strength. This is not a technique for improving the performance of an adhesive, but a technique related to a surface treatment method for a metal piece to be adhered, that is, a metal piece as an adherend. That is, NAT is a joining technique using an adhesive for all metal species, and NAT defines the following five points as prerequisites for its establishment. Of these, the following three points ((1) to (3)) are necessary conditions for the metal pieces to be used, and a surface treatment method that chemically treats the metal pieces so as to satisfy these three points is called "NAT treatment". bottom.

The requirements for NAT are:
(1) Making the metal surface an uneven rough surface with a period of 0.8 to 10 μm,
(2) Make sure that the rough surface has ultrafine irregularities with a period of 5 to 300 nm.
(3) The surface forming the double uneven surface of (1) and (2) above is made of a thin layer of hard ceramic such as metal oxide and metal phosphor oxide.
It is a processing method that satisfies the above three conditions. Furthermore, the following two conditions regarding the type of adhesive used in NAT and the bonding operation are required.
(4) Priority should be given to the use of a one-component adhesive as the adhesive, and if the one-component adhesive does not exist, the slow-acting curing agent should be selected and adopted.
(5) Including the process of "soaking treatment" in the bonding operation,
There are two conditions.

The above condition (4) requires that the adhesive adhere to the surface of the metal material as uncured low molecular weight molecules, and the condition (5) is that the low molecular weight molecules are the ultrafine irregularities described in the condition (2). This is a process for intruding into the deep bottom of the ultrafine recess on the surface. That is, to put it simply, what NAT aims at is that the surface shape of the metal as an adherend is preferably an ultrafine uneven surface with a period of 5 to 300 nm, and a rough surface with a molecular order period. What it has is that the presence density of the ultrafine concavo-convex surface is high, and that the adhesive is applied in a low molecular weight state (with low viscosity) and up to the bottom of the recess of the ultrafine concavo-convex surface. The simple reason why the strongest adhesive force is produced by invading and then promoting polymerization and hardening is summarized.

This NAT theory has been demonstrated in various metal materials (Patent Documents 1 to 7). Further, although one-component adhesive is preferable in the condition (4), the present inventors have determined that the most effective adhesive for NAT is an epoxy adhesive at the current technical level from the viewpoint of adhesive strength. However, most of the verification tests were based on a one-component epoxy adhesive. In fact, the strong adhesive force exhibited by NAT shocked many engineers and others skilled in the art. Speaking from an example, for example, using the general-purpose one-component epoxy adhesive "EP106NL (manufactured by Cemedine Co., Ltd. (Headquarters: Tokyo, Japan)", almost all metal species are the same kind of metal treated with NAT as described above. This is because the shear bonding strength of the bonding pair between the pieces was about 70 MPa at 23 ° C., which was almost double the shear bonding strength of the conventional bonding method.

(One-component epoxy adhesive and its heat resistance)
In the test described in Patent Document 1, NAT-treated Japanese Industrial Standards A7075 aluminum alloy (hereinafter, only referred to as "Japanese Industrial Standards" and "aluminum alloy" is also referred to as "Al") were joined to each other. The shear bond strength obtained by pulling and breaking the bond pair (test piece shown in FIG. 1) using the above "EP106NL" was as high as 70 MPa and stable. From this, it is possible to evaluate the adhesive strength of the adhesive by obtaining a one-component epoxy adhesive that is widely available on the market and measuring the shear adhesive strength with the same A7075Al piece adhesive pair described above. Thought. Therefore, more than a dozen types of one-component epoxy adhesives commercially available in Japan and overseas were purchased, and the shear adhesive strength was measured for each. Furthermore, the shear adhesive strength of the A7075Al test pair using these adhesives was measured in an environment of 150 ° C. to obtain the heat resistance performance of each adhesive. As a result, it was determined that "EW2040 (3M Japan Ltd. (Headquarters: Tokyo, Japan))" is the most suitable for the above NAT among the current commercially available one-component epoxy adhesives. That is, in the above test, the shear adhesion strength was about 60 MPa at 23 ° C. and 30 MPa at 150 ° C. However, after this, the present inventor made efforts to develop a heat-resistant one-component epoxy adhesive, and the shear adhesive strength at 150 ° C. of the adhesive pair (test piece) using the same A7075Al became 35 MPa or more. A one-component epoxy adhesive has been developed and proposed (Patent Document 9).

(Measuring method of adhesive strength)
Patent Documents 1 to 7 disclose the shear adhesive strength and the tensile adhesive strength of a one-component epoxy adhesive subjected to NAT treatment and NAT operation with respect to various metal materials. However, the adhesive used in the experiments and the like of the present invention was changed from the above "EP106NL" to the above "EW2040". The reason is that even CFRP materials, which had begun mass production as ultra-lightweight high-strength structural materials, can be completed as an adhesive technology with metal materials and used as the main element of mobile machines such as aircraft and automobiles. It is because it was judged that the heat resistance of was indispensable. In Patent Document 8, after the above-mentioned "EW2040" having excellent heat resistance is used as the above-mentioned standard adhesive for NAT, the improvement result of this NAT treatment method is disclosed, and in an adhesive pair of various metal materials at 23 ° C. It was disclosed that the shear adhesive strength became more stable and the tensile adhesive strength became higher.

The adhesive strength measuring methods adopted in Patent Documents 1 to 9 and the present invention described later are different from general adhesive strength measuring methods. That is, the shear adhesive strength and the tensile adhesive strength described in these patent documents are not measured by the measuring method specified in JIS (Japanese Industrial Standards) K6849, K6850 and the like. It was judged that these standardized measurement methods have strong adhesive strength and cannot measure accurate shear lap-shear strength. Regarding this tensile strength measurement, it is difficult to obtain a metal piece having a shape determined by a standardized method, and it is particularly commercially available as a plate material having a thickness of 0.5 to 3.0 mm. This is because for many metal materials, accurate values cannot be measured. That is, in each of the patents related to NAT disclosed by the present inventors and the present invention, the shear adhesion strength was measured using the test piece shown in FIG. 1 described later. Further, the shape of the adhesive pair for measuring the tensile adhesive strength is such that the 4 mm × 3 mm end faces of two metal pieces having a thickness of 18 mm × 4 mm × 3 mm are bonded to each other at the time of inventing the invention described in Patent Document 1. Measured with an adhesive pair. After that, there was a transition, and the present invention was described in a form in which two 18 mm × 1.5 mm thick end faces of two metal pieces having a thickness of 45 mm × 18 mm × 1.5 mm, which will be described later, were bonded to each other, that is, FIG. 2 of the present invention. It has the shape shown.

(Shear adhesion strength of CFRP pieces)
The ultimate goal of the present inventor regarding the bonding technique was to completely bond the CFRP material and A7075Al to be useful for manufacturing the basic structure of an aircraft or the like, which requires the ultimate weight reduction. On the other hand, NMT (abbreviation of Nano molding technology) proposed by the inventors of the present invention is a joining technology for joining and integrating a metal material and a highly crystalline thermoplastic resin with high strength by injection molding. .. The inventor of the present invention has determined that if the metal surface treatment technology used in this NMT is diverted, it will lead to a high-strength bonding technology between metal materials even when bonding different materials with an adhesive, and completes the above-mentioned NAT. I let you. Then, it was thought that if the CFRP material and the CFRP material and A7075Al were successfully adhered to each other by partially utilizing this NAT, the target would be considerably close. However, the shear bond strength of the bond pair, which is a test piece having the shape shown in FIG. 1 according to the above "EW2040" between CFRP pieces, was an unexpected value.

As a result of joint research with a carbon fiber (hereinafter referred to as "CF") manufacturer, the latest CF used in CFRP materials for aircraft is a high-strength fiber having a tensile strength of about 6 GPa. The electron micrograph has a nearly perfect circular cross section, no vertical streaks on the sides, and is smooth. A CFRP piece is cut out from a CFRP thick plate obtained by laminating prepregs using this CF, surface processing such as roughening the surface end portion thereof is performed, and then using the above "EW2040", FIG. 1 When the adhesive pair has the shape shown in (1) and its shear adhesive strength is measured, it is about 40 MPa. On the other hand, if CF manufacturers have manufactured CF before the industrialization of this latest CF, and if this is an old CF, this is a high-strength fiber with a tensile strength of about 3 GPa, and its electron micrograph is There are various types such as those having an oval cross-sectional shape and a gourd-shaped cross section. On the side surface of this CF, there are always one or two vertical stripes, and small protrusions and recesses can be seen in some places. Similarly, from the CFRP thick plate using this CF, the above-mentioned "EW2040" is used to form an adhesive pair having the shape shown in FIG. 1, and the shear adhesive strength is measured to be about 60 MPa. In short, when the adhesive pair of CFRP pieces with a one-component epoxy adhesive is forcibly shear-broken, the fracture start point is not the surface layer part where the adhesive and CF are adhered, but the matrix resin separated from this. It was a layer.

The true adhesive force between the CF and the cured matrix resin is estimated to be about 40 MPa, and the value is the shear adhesive strength in the CFRP piece using the new CF, but the surface area is large in the CFRP piece using the old CF. It is shown that. That is, the new CF is a fiber with a cross section close to a perfect circle, but the old CF is not a perfect circle, so the actual surface area is larger than the nominal surface area, and the shear adhesion strength is about 60 MPa. (Patent Document 9). In short, how can the strong adhesive structure between the CFRP material and A7075Al, which the present inventor aimed at, be brought close to the maximum strength of the material? Since the present invention presupposes the use of a high-strength CFRP material for aircraft, the highest strength between the adhesive and the CFRP material is achieved even when the above-mentioned "EW2040", which is a heat-resistant one-component epoxy adhesive and has high strength, is used. It means that the adhesive strength of the above is assumed to be about 40 MPa, which is less than the strength of the adhesive, which is slightly lower than expected.

WO2008 / 114669 WO2008 / 133096 WO2008 / 133296 WO2008 / 126812 WO2008 / 133030 WO2008 / 146833 WO2009 / 084648 JP 2016-210942 Japanese Patent Application Laid-Open No. 2011-073191 JP 2011-006544 JP 2011-206457 JP 2016-60051

It has been more than 10 years since CFRP material has been used in earnest as a main structural material for passenger aircraft as an ultra-lightweight and high-strength material. It is well known that aircraft manufacturers struggled when constructing an assembly structure (fixed structure) between multiple CFRP members and an assembly structure (connecting structure) between CFRP members and extra super duralumin (A7075Al of Japanese Industrial Standards). ing. The rigidity of CFRP is higher than that of high-strength metal, but it is actually plastic, and various problems occur when it is used as a structure to form a fastening structure. For example, when a through hole is made in a CFRP material and a bolt to be inserted into the through hole is fastened to another structural material, if the nut is tightened too much, the CFRP material is destroyed.

Even if the CFRP material and the metal material such as A7075Al material can be strongly adhered, in order to adopt the adhesive structure as a moving machine such as an automobile or an aircraft, the temperature changes received from the usage environment, when moving, or There is an effect of the temperature shock cycle due to the heat of the engine received when stopped. Furthermore, there are temperature changes due to seasons and climate, and in the case of aircraft, the cryogenic temperature of -50 to -60 ° C in the stratosphere, the high temperature of + 50 ° C in tropical desert airports, and +80 on the surface of the aircraft. It must withstand temperature changes that reciprocate to and from high temperature environments above ° C. In addition, automobiles used in extremely cold weather such as Alaska and Siberia need to support the current test method of 3,000 ° C temperature shock 3,000 cycle test, and in the engine room, light emitter, etc. In the vicinity, it must withstand a temperature impact of 3,000 cycles of -50 ° C / + 150 ° C.

At the beginning of the development of the chemical conversion treatment in the above-mentioned adhesive technology, the present inventors thought that such a temperature change could be easily solved by significantly improving the adhesive force. However, it was not always possible to solve the problem when the durability test for practical use was started. Since the linear expansion coefficient of CFRP material is ( ^{0.1 to 0.2) × 10 -5} K ^-1, and A7075Al called extra super duralumin is 2.3 × 10 ^-5 K ^-1 . The difference in linear expansion coefficient between the two is as large as 2.2 × ^10-5 K ^-1 . If the temperature drops (or rises) by 200 ° C in a temperature impact of -50 ° C / + 150 ° C in a 3000 cycle test, the product is 4.4 × 10 ^-3 , or 0.44% between the two materials. The length of is changed.

In short, if the adhesive strength is weak, it cannot withstand such deformation due to temperature impact and breaks immediately, and if the adhesive strength is high, the shape of the two materials is deformed small without breaking due to temperature changes, and the deformation due to temperature changes. The cycle will be repeated. If the temperature change cycle is repeated thousands of times, it is estimated that the temperature suddenly breaks at a low temperature with a breaking noise such as "snap". Even if the adhesive strength is very high, the cured adhesive has durability such as moisture and heat resistance, and the metal material is a type that does not easily rust, the deformation due to temperature change will occur. It lasts semi-permanently. However, if the thickness of both materials is, for example, 10 mm or more, if the joints are made of rigid materials, both materials have high rigidity and are difficult to bend and deform. In this case, a large internal stress is generated inside the material. Even if the adhesive strength is strong, the adhesive portion will break if there is a large temperature change.

The present inventors have proposed to increase the adhesive strength between various metals and CFRP materials. However, it was confirmed that when these proposed test pieces with the maximum adhesive strength were subjected to a severe temperature impact thousands of cycles, the larger the test pieces with the wider adhesive area, the more they were destroyed. That is, there is a limit to the development of an improvement in the adhesive method for pushing through the difference in the coefficient of linear expansion depending on the usage environment. In particular, there is a limit to the adhesion between various metals having a large difference in linear expansion coefficient and non-metal materials such as CFRP materials.

The present invention solves the above problems and achieves the following objects.
An object of the present invention is to obtain a dissimilar structural material in which two types of high-strength materials having a large difference in linear expansion coefficient selected from various structural metal materials, CFRP materials, and CFRTP materials are joined and laminated by joining with an adhesive. It is to provide a joint integral body including and a method for manufacturing the same.
Another object of the present invention is to join and laminate two or more kinds of high-strength structural materials having a large difference in linear expansion coefficient selected from various structural metal materials, CFRP materials, and CFRTP materials by a joining method using an adhesive. It is an object of the present invention to provide a bonded integrated product containing dissimilar structural materials and a method for producing the same, which is resistant to temperature changes.
Still another object of the present invention is to join two or more kinds of high-strength structural materials having a large difference in linear expansion ratio selected from various structural metal materials, FRP materials, and FRTP materials with an adhesive or clad joint. Including a heterogeneous structural material including a heterogeneous structural material including, etc., which can be bonded and laminated using a commercially available one-component epoxy adhesive and a two-component epoxy adhesive in the manufacturing method thereof. It is an object of the present invention to provide a bonded integrated product and a method for producing the same.

The present invention adopts the following means in order to achieve the above object.
The joint integrated product (for example, 3 layers and 3 materials in FIG. 4) containing different structural materials of the present invention 1 is
Two different types of FRP material, "A" material and "B" material selected from the structural metal material group are used at both ends.
It is an integrated product in which members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^-1 or more are joined with an adhesive.
The integrated product is
Between the "A" material and the "B" material, a plate-like product of a pure aluminum-based aluminum alloy having a thickness of 1.5 to 5.0 mm, which is a "D" material, or a structure of the pure aluminum-based aluminum alloy. It is a stack of things,
It is characterized in that it is composed of three materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "D" material, and the "B" material.

The joint integrated product (for example, 4 layers and 4 materials in FIG. 6) containing different structural materials of the present invention 2 is
Two different types of FRP material, "A" material and "B" material selected from the structural metal material group are used at both ends.
It is an integrated product in which members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^-1 or more are joined with an adhesive.
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
It is characterized in that it is composed of four materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, and the "B" material.

The joint integrated product (for example, 5 layers and 5 materials in FIG. 5) containing different structural materials of the present invention 3 is
Two different types of FRP material, "A" material and "B" material selected from the structural metal material group are used at both ends.
It is an integrated product in which members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^-1 or more are joined with an adhesive.
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to It is a plate-like product of 5.0 mm pure aluminum-based aluminum alloy.
It is characterized in that it is composed of five materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, the "C" material, and the "B" material.

The joint integrated product containing the dissimilar structural materials of the present invention 4 (for example, the deformation of the four layers and four materials in FIGS. 6 and 4) is
The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
It is composed of four materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, and the "B" material.
The method of joining the FRTP material and the "C" material is to join the "C" material with a resin of the same type as the matrix resin of the FRTP material by an injection joining method, and then join the FRTP material. The resin is joined by heat fusion, and is
The joint surface of the joint other than the heat fusion is characterized in that it is joined by an adhesive.

The joint integrated product containing the dissimilar structural material of the present invention 5 is
The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
It is composed of 5 materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, the "C" material, and the "B" material.
In the method of joining the FRTP material and the "C" material, a resin of the same type as the matrix resin of the FRTP material is joined to the "C" material by insert molding, and then the FRTP material and the resin are heat-sealed. It is joined and
The joint surface of the joint other than the heat fusion is characterized in that it is joined by an adhesive.

The joint integrated product containing different structural materials of the present invention 6 is a joint integrated product containing different structural materials of the present inventions 1 to 5, and the "D" material is a pure aluminum-based aluminum alloy, and Japanese Industrial Standards A1080 and A1085. , And one selected from A1050.

The joint integrated product containing different structural materials of the present invention 7 is a joint integrated product containing different structural materials of the present inventions 2 to 5, and the "C" material is a Japanese industrial standard A5052 aluminum alloy, A5083 aluminum alloy, A6061 aluminum. It is characterized in that it is one selected from an alloy and SUS304 stainless steel.

The joint integrated product containing different structural materials of the present invention 8 is the joint integrated product containing different structural materials of the present inventions 1 to 5, and the joint surface is one or more surfaces selected from a flat surface, a curved surface, and a cylindrical surface. It is characterized by including.

The joint integrated product containing the dissimilar structural materials of the present invention 9 is the joint integrated product containing the dissimilar structural materials of the present inventions 1 to 8, and the lower surface of the "D" material is a flat surface or a curved surface, and the cross-sectional area is 0 on the upper surface. It is characterized in that it is a plate-like body in which a large number of circular or square columnar objects of .05 to 0.25 cm ^{2 stand side by side.}

The joint integrated product containing the different structural materials of the present invention 10 is the joint integrated product containing the different structural materials of the present inventions 1 to 8, and the lower surface of the "D" material is a flat surface or a curved surface, and the upper surface has a thickness of 3. A large number of wall-shaped protrusions with a width of 2 to 3 mm and a large number of forests with a width of 2 to 3 mm, or a plate-like wall with a thickness of 3 to 5 mm having concentric wall-like protrusions with a width of 2 to 3 mm. It is characterized by being a body.

Integrally bonded containing a heterologous structural material of the present invention 11 is the integrally bonded containing heterologous material of the present invention 10, the center of the concentric of the wall-like projection, the portion of 1 to 5 cm ² the thickness 1 It is characterized by having a circular thick plate shape of 5 mm.

The joint integrated product containing the different structural materials of the present invention 12 is the joint integrated product containing the different structural materials of the present inventions 2 to 5, the "A" material, the "B" material, the "C" material, and the "C" material. In the bonding between the five materials of the "D" material, the adhesive curing layers existing at the joints joined by the adhesive are all the cured layer of the one-component epoxy adhesive or the cured layer of the two-component epoxy adhesive. It is characterized in that it contains.

The joint integrated product containing the different structural materials of the present invention 13 is the joint integrated product containing the different structural materials of the present inventions 2 to 5, the "A" material, the "B" material, the "C" material, and the "C" material. It is characterized in that four or more lumbers of the "D" material are joined, and a part of the joint is a clad joint instead of the joint joined by an adhesive.

The bonded integrated product containing the dissimilar structural material of the present invention 14 is the bonded integrated product containing the dissimilar structural material of the present invention 12 or 13, and the one-component epoxy adhesive has a shear adhesive strength of 23 in the tensile break test. It is a heat-resistant one-component epoxy adhesive that exhibits 50 MPa or more at ° C. and 25 MPa or more at 150 ° C.

The bonded integrated product containing the dissimilar structural materials of the present invention 15 is a bonded integrated product containing the dissimilar structural materials of the present inventions 1 to 14.
The "A" material and the "B" material are CFRP material and titanium alloy material, CFRP material and general steel material, CFRP material and stainless steel material, CFRP material and high-strength aluminum alloy material, GFRP material and high-strength aluminum alloy material. , CFRTP material and titanium alloy material, CFRTP material and general steel material, CFRTP material and stainless steel material, CFRTP material and high-strength aluminum alloy material, titanium material and general steel material, titanium material and stainless steel material, titanium material and high-strength aluminum alloy material, It is characterized in that it is one selected from general steel material and stainless steel material, general steel material and high-strength aluminum alloy material, ferrite-based stainless steel material and austenite-based stainless steel material, and stainless steel material and high-strength aluminum alloy material.

The joint integrated product containing the dissimilar structural materials of the present invention 16 is the joint integrated product containing the dissimilar structural materials according to the present inventions 4 to 13.
The FRTP of the "A" material is CFRTP, and
The resin is a highly crystalline thermoplastic synthetic resin composition having a thickness of 0.5 mm or more, and the total thickness of the "C" material and the resin is a composite plate having a thickness of 2 mm or less.
The bonding between the "A" material and the "C" material is obtained by fixing the CFRTP matrix resin and the highly crystalline thermoplastic synthetic resin composition by heat fusion.
The "B" material is one selected from a titanium alloy material, a general steel material, a stainless steel material, and a high-strength aluminum alloy material.

The joint integrated product containing the dissimilar structural materials of the present invention 17 is the joint integrated product containing the dissimilar structural materials according to the present inventions 1 to 16.
The high-strength aluminum alloy material is duralumin selected from Japanese Industrial Standards A2014, A2017, A2024, and A7075, or one type of aluminum alloy selected from Japanese Industrial Standards A5052, A5083, A6061, and A6063. It is characterized by being.

The method for producing a bonded integrated product containing different structural materials of the present invention 1 is
The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
It is a method for manufacturing a joint integrated product containing dissimilar structural materials consisting of four materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, and the "B" material. hand,
In order to bond a resin of the same type as the matrix resin of the FRTP material to the "C" material, the "C" material is inserted into a mold, and then the resin is injected to bond the FRTP material and the "C" material. Injection joining process to join and
After the injection joining, a heat fusion step of joining the FRTP material and the resin by heat fusion,
The other joint is characterized in that it comprises a joining process method using an adhesive.

The method for producing a bonded integrated product containing different structural materials of the present invention 2 is
The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
A joint integrated product containing five different structural materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, the "C" material, and the "B" material. It is a manufacturing method of
In order to bond a resin of the same type as the matrix resin of the FRTP material to the "C" material, the "C" material is inserted into a mold, and then the resin is injected to bond the FRTP material and the "C" material. Injection joining process to join and
After the injection joining, a heat fusion step of joining the FRTP material and the resin by heat fusion,
The other joints are characterized by consisting of an adhesive joining process.

Hereinafter, each element constituting the present invention will be described.
[Overview of "A" material, "B" material, "C" material, and "D" material of the present invention]
The "A" material and the "B" material in the present invention mean the members at both ends of the bonded integrated product containing the different structural materials of the present invention, which are laminated bodies. The "C" material and the "D" material mean members that are fixed and laminated between the "A" material and the "B" material. The "A" material, "B" material, and "C" material of the present invention are selected from the following "(1) FRP material, FRTP material", and "(2) Structural metal material". Point to. The "D" material of the present invention] means "(3)" D "material" described later.

(1) FRP material, FRTP material The FRP material referred to in the present invention is general fiber reinforced plastic (Fiber Reinforced Plastics), and is a matrix resin, a thermosetting resin, an epoxy resin, etc., and glass fibers, carbon fibers, etc. It is a molding material or a molded product in which the fibers of the above are composited to improve the strength. The FRP using carbon fiber is CFRP, and the FRP using glass fiber is GFRP. On the other hand, the FRTP material (Fiber Reinforced Thermo-plastics) is a matrix of polyamide resin, polyphenylene sulfide resin (hereinafter referred to as PPS), polyetheretherketone resin (hereinafter referred to as PEEK), etc., which are thermoplastic resins having crystallinity and the like. It is a molding material that is made of resin and reinforced and improved by adding fibers such as glass fiber and carbon fiber, or a general-purpose material such as a molded product, a pipe material, and a plate material. FRTP using carbon fiber is called CFRTP, and FRTP using glass fiber is called GFRTP. The molded products of these FRP materials and FRTP materials include standardized general-purpose materials such as plate materials, pipe materials, bar materials, and sheets, and individually designed molded products.

(2) Structural metal materials The structural metal materials referred to in the present invention are standardized by Japanese Industrial Standards, etc., or special Ti alloy materials, various structural steel materials, various stainless steels, various aluminum alloys, etc. Means the structural metal material of. Aluminum alloys include Al-Cu series (Japanese Industrial Standard 2000 series), Al-Mn series (Japanese Industrial Standard 3000 series), Al-Si series (Japanese Industrial Standard 4000 series), and Al-Mg series (Japan). Industrial Standard 5000 series), Al-Mg-Si series (Japanese Industrial Standard 6000 series), Al-Zn-Mg series (Japanese Industrial Standard 7000 series), and Pure Aluminum (Japanese Industrial Standard 1000 series) And so on. Further, the aluminum alloy used in the present invention includes 1000 to 8000 series aluminum alloys for extension defined by Japanese Industrial Standards, and aluminum alloys for casting such as ADC12. Therefore, the structural aluminum alloy material of the present invention includes both an aluminum alloy for extension and an aluminum alloy for casting.

(3) "D" material of the present invention The "D" material referred to in the present invention is responsible for important functions and actions among the constituent elements constituting the present invention. That is, the "D" material of the present invention is a soft metal having extensible property as a mechanical property and has high bondability, for example, with respect to the above-mentioned one-component epoxy adhesive "EW2040". , A member having a sufficiently strong adhesive force (shear adhesive strength). In addition to this, as a basic characteristic, it is sandwiched between the above-mentioned "A" material and "B" material and adhered with a sufficiently high adhesive force, and the "A" material, "D" material, Three or four materials, "B" material and "C" material, form a bonded integrated product. The integrated product is required to have the property of not being destroyed even when subjected to a temperature shock of 3,000 cycle test at -50 ° C / + 150 ° C. In the present invention, there is a large difference in the coefficient of linear expansion between the "A" material and the "B" material. Therefore, the lengths of the "A" material and the "B" material change due to a drastic temperature change. As a result, in the case of three layers and three materials, the length elongation or contraction is different on both the upper and lower surfaces of the "A" material and the "D" material that is strongly adhered to the "B" material. The material is stressed by deformation. However, since the "D" material is a malleable and flexible member, it deforms by itself, absorbs and suppresses the stress due to its thermal shrinkage, and maintains an adhesive state even when it is subjected to a temperature impact of several thousand cycle tests. be able to. As the "D" material, the most suitable metal material is a pure aluminum-based aluminum alloy, and preferably pure aluminum-based aluminum alloys such as A1085, A1080, and A1050 as defined in Japanese Industrial Standards can be used.

(4) "C" material of the present invention The "C" material referred to in the present invention has a special role different from that of the "D" material. That is, the joint integrated product containing the different types of high-strength structural materials of the present invention is required to have high strength and light weight, and the most suitable ones for realizing this are CFRP materials, CFRTP materials and the like. However, when CFRP pieces are bonded to each other with, for example, the above-mentioned one-component epoxy adhesive "EW2040" and tested with the bonding pair of the test pieces shown in FIG. 1, the shear bonding strength is about 40 MPa. The reason is as described above, but therefore, for example, when a CFRP piece is used for the "A" material, it is preferable to use the above-mentioned "D" material utilizing its malleability as described above. When the "D" material is subjected to a surface chemical conversion treatment that is optimal for adhesion, the adhesive force between the metal "D" material and the cured adhesive is about 60 MPa. However, when a CFRP piece is used for the "A" material, even if the strongest adhesive force is obtained with the direct adhesive between the "A" material and the "D" material, the CF and the matrix resin are used for the reasons described above. Since the true adhesive force between the cured products is considered to be about 40 MPa, it is dragged by the lower adhesive force, and the adhesive force which is the shear adhesive strength of the laminated body which is a bonded integrated product becomes about 40 MPa or less.

Further, when the CFRTP material is used for the "A" material, the bonding method cannot be used for joining the CFRTP and the "D" material. The reason is that the surface of the CFRTP material is a thermoplastic resin which is the matrix resin thereof, and there is no general technique for directly and strongly bonding the thermoplastic resin and the metal material. Therefore, in the bonding method proposed by the inventor of the present invention, the matrix resin used in the CFRTP material, for example, PEEK (polyetheretherketone) resin, is bonded in the following steps. That is, after applying surface treatment for injection bonding (NMT treatment, new NMT treatment, etc. described above) to the thin metal plate material, this is inserted into an injection molding die, and PEEK resin prepared for injection bonding is injected. A composite plate-like material in which a thin plate-like material of PEEK-based resin is surface-bonded to the metal thin plate that has been joined and inserted is temporarily prepared. Then, the composite plate and the CFRTP thick plate made of PEEK resin are heat-press fused to prepare a CFRTP thick plate with a metal thin plate (see Patent Document 12).

In short, as a method for producing a bonded integrated product of a CFRTP material and a metal material, for example, there is a bonding method proposed in Patent Document 12. In the case of this joining method, when the CFRTP material is used, the bonding force (shear bonding strength) between the CFRTP material and the metal thin plate material of the joint integrated product of the present invention is PEEK used for injection bonding with the surface-treated metal material. It becomes the same value as the injection bonding force between the based resins. At present, when a soft "D" material, for example, A1050Al, is used as the metal material, the shear breaking strength of the injection-bonded PEEK-based resin for injection bonding is about 45 MPa. This value of 45 MPa is lower than the expected value of 60 MPa when the "A" material and the "D" material are directly bonded with an adhesive in a bonded integrated product using a metal material for the "A" material. Furthermore, when the matrix resin of the CFRTP material is a PPS-based resin, the above value is about 40 MPa, and when the matrix resin of the CFRTP material is a semi-aromatic polyamide resin, the above value is 45 to 50 MPa. It is also lower than 60 MPa.

In short, when a CFRP material, a CFRTP material, or the like is used as the "A" material and the "B" material, the adhesive strength remains at about 40 to 50 MPa. Further, when a new alloy appears, if the chemical conversion treatment on the surface thereof is not optimal, the adhesive force with the metal material may remain at about 40 to 50 MPa. Therefore, when the basic adhesive force of the joint surface of the "A" material and the "B" material is about 40 MPa or less, the joint portion is weak, so that the joint integrated product has mechanical strength. Becomes weak. Therefore, as a result, the adhesive strength between the "A" material and the "D" material, the adhesive force between the "B" material and the "D" material, etc. of this joint integrated product is at the same level as the other joint portions. It is necessary to construct a fully bonded structure so as to reach a strength of around 60 MPa. This is the reason why the "C" material, which is a thin metal plate material, is further sandwiched between the "A" material and the "D" material, and between the "B" material and the "D" material.

(Role and function of "C" material)
As can be understood from the above description, in conclusion, the "C" material of the present invention is preferably a malleable thin metal having properties different from those of "D". Even if the structural materials have significantly different linear expansion rates, if the adhesive strength of both materials to the epoxy adhesive is sufficiently high, if one is a thin plate material, it will follow the other and adhere strongly as it is, and it will be severe. Can withstand changes in environmental temperature. In short, if a thin "C" material, which is more rigid than the "D" material, is sandwiched between the "A" material and the "D" material and bonded with an adhesive, a large temperature can be obtained in the integrated product in which these three materials are integrated. Even if there is a change or temperature impact, the "C" material, which is a thin plate and has more rigidity than the "D" material, first follows the expansion and contraction of the "A" material, which is more rigid than this, and then follows the expansion and contraction of the "A" material. The expansion and contraction of the "C" material is directly transmitted to the soft material "D" material.

Similarly, if a thin plate "C" material different from the above is sandwiched between the "B" material and the "D" material and joined with an adhesive, the temperature change and temperature of the adhesive in which these three are integrated can be obtained. Even if there is an impact, this "C" material first follows the expansion and contraction of the "B" material, and the expansion and contraction of this "C" material that follows the expansion and contraction of the "B" material becomes the "D" material as it is. It is transmitted. With this thinking pattern, a five-layer laminated structure consisting of "A" material, "C" material, "D" material, "C" material, and "B" material is bonded and integrated (for example, the laminated body of FIG. 5). Assuming the fully bonded structure, both the expansion and contraction of the "A" material and the expansion and contraction of the "B" material are transmitted to the upper and lower surfaces of the "D" material in the central portion. At this time, since the "D" material is a soft metal which is a pure aluminum-based aluminum alloy, all the forces absorb the deformation without drawing a break into the adhesive surface. In other words, the "C" material has a cushioning function for deformation between the "A" material and the "D" material, and between the "B" material and the "D" material. However, the "C" material does not have only a buffer function that absorbs the expansion and contraction of the "A" material and the expansion and contraction of the "B" material.

More specifically, in the bonded integrated product of the present invention, the adhesive strength between the "A" material such as CFRP material and CFRTP material and the cured adhesive is only about 30 MPa, and the other "B" When the adhesive strength between the material, "C" material, "D" material, etc. and the cured adhesive has a shear breaking strength of, for example, about 60 MPa, the adhesive area between the "A" material and the "C" material is In order to maintain the same shear breaking strength, it is necessary to double the bonding area of the "C" material and the "D" material in terms of structural design. In short, since the actual adhesive force is the product of the shear adhesive strength and the adhesive area, the treatment for amplifying the adhesive force can be performed in this way, which is the reason for using the "C" material. In order for this amplification action to actually occur, the "C" material also needs to have a high yield strength (or allowable stress in design), and even if it is a thin plate, it is within the range of its elastic deformation. Therefore, it is necessary to follow the expansion and contraction of the "A" material and the "B" material. Moreover, in order to fulfill the role of amplification that increases the bonding strength, the condition that does not cause the tearing phenomenon (fracture fracture) is related to the magnitude of the yield strength. In the present invention, the "C" material is used when four materials have four or more layers and strength is required. The "D" material made of malleable soft metal has a weak mechanical strength, and even if it is directly adhered to the "A" material or the "B" material, the adhesive strength does not reach the desired size.

Therefore, as described above, in order to give the "C" material a role as an adhesive strength amplifying material, even if it becomes a thin plate, it must not cause a tearing phenomenon by itself, and it should be about the general adhesive strength. The material must have a proof stress (allowable stress) to withstand, and at the same time, tensile strength is required. This point is based on the results of the test experiment (see Table 6) described in the experimental example (test piece shown in FIG. 1) described later, but it is desirable that the proof stress is about 150 MPa or more (for the “C” material). In the experiments described later, a metal material with a higher yield strength is practically preferable to the A5052Al alloy), and since a thin plate with a thickness of 0.28 mm could be used with SUS304, the product of Young's modulus ≈190 GPa and thickness of 0.28 mm. 53 GPa · mm can be used as a standard. In short, "Young's modulus x thickness = 53 GPa · mm" was set as the upper limit standard for the "C" material.

According to the above equation, all of the aluminum alloys have a Young's modulus of about 70 GPa, so that the preferable thickness of the “C” material is 0.75 mm or less (see Table 6 described later). The development of NAT treatment method is well advanced, and it is aluminum alloy and stainless steel that show high adhesive strength, are practical and resistant to rust. From this formula, the thickness of "C" material is 1 mm or less. It becomes a thin plate. There is an example of the "C" material that can be demonstrated in the examples described later, but in the example that has been verified, A5052, A6061 aluminum alloy, SUS304 stainless steel, and the like. Therefore, preferably usable metals include aluminum alloys of A5052, A5083 and A6061, and austenitic stainless steels of SUS304 and SUS316.

[Means and Members for Fixing and Laminating Joint Surfaces of the Present Invention]
The method of fixing and laminating the joint surfaces of the present invention is an adhesive and a clad joint.
(1) Adhesive The adhesive that fixes and laminates the joint surfaces of the present invention is an adhesive that uses various FRP materials and FRTP materials used in the present invention and various structural metal materials used in the present invention under the required environment. Any type may be used as long as it can be bonded with the strength of the design value. However, one of the high-strength structural materials important in the present invention is a CFRP material, and since the matrix resin of this CFRP material is generally an epoxy resin, an epoxy adhesive is preferable as the adhesive. Moreover, the epoxy adhesive is also preferable for adhering various metal materials, and is also preferable in this respect. This epoxy adhesive can be used as either a one-component or two-component epoxy adhesive. The two-component epoxy adhesive is an adhesive that copolymerizes and cures by chemically reacting a liquid epoxy resin as a main component and a curing agent called polyamines at room temperature. The one-component epoxy adhesive contains a curing agent and is polymerized by reacting by heating. Since some of them have excellent heat resistance and strength, they are used for bonded integrated products that require heat resistance. ..

(2) Clad joining The clad joining referred to in the present invention means that various dissimilar alloys are superposed and joined by a method (explosion welding) based on the explosive force of explosives, hot rolling, temperature heating rolling, or the like. The member used for clad bonding is a temperature rise and pressure treatment method as described above, and this treatment method strongly joins as if welded, and generally has a higher bonding force than bonding with an adhesive. However, some surface treatment is often performed in advance, which is necessary especially when an aluminum alloy such as temperature-temperature rolling is used. In short, if you want to clad two kinds of materials, which method should be selected for that method, and if you select the simplest temperature-heating rolling method, each two materials to ensure successful joining. It is necessary to first develop the optimum surface treatment method for.

[Difference in linear expansion coefficient of the present invention (0.3 × ^10-5 K ^-1 or more)]
The difference in linear expansion coefficient between the "A" material and the "B" material used in the "joint integrated product containing dissimilar structural materials" of the present invention means that the maximum difference is 0.3 × 10 ^-5 K ^-1 or more. The reason is as follows. The linear expansion coefficient of the FRP material constituting the present invention, for example, the CFRP material is (0.1 to 0.2) × ^10-5 K ^-1 . On the other hand, the coefficient of linear expansion of various structural metal materials constituting the present invention is about 2.3 × ^10-5 K- ¹ for the A7075 aluminum alloy called extra super duralumin. Among various structural metal materials that are widely used, the one having the lowest coefficient of linear expansion is Ti alloy material, which is about 0.8 × ^10-5 K- ¹ . Generally steel and ferritic stainless steel of about 1.1 × ¹⁰ -5 ^{K -1,} austenitic stainless steel of about 1.7 × ¹⁰ -5 ^{K -1,} duralumin, aluminum alloy of about 2.3 × ^{10 -5} It is K- ^1. Furthermore, although it is hard to say that it is a structural material ^{, among other metal materials, copper material is about 1.8 × 10-5} K ^-1 , silver material is about 1.9 × ^10-5 K ^-1 , and tin material is about 2. .3 × 10 ^-5 K ^-1 , magnesium material is about 2.5 × 10 ^-5 K ^-1 , and lead material is about 2.9 × 10 ^-5 K ^-1 . It differs by about 0.1 × 10 ^-5 K ^-1).

Among these various structural metal materials, the coefficient of linear expansion is closest between the Ti alloy material, the general steel material, and the ferritic stainless steel, and these metal members are the laminated body which is the joint integrated product of the present invention. , May be used in combination. The difference in coefficient of linear expansion between these various structural metal materials is about 0.3 × ^10-5 K ^-1 , and if the difference in coefficient of linear expansion is less than this, the load on the adhesive surface is substantially small, so consider it. There is no need. Therefore, in the bonded integrated product containing the dissimilar structural materials of the present invention, the linear expansion coefficient when the closest dissimilar structural materials are combined is set to about 0.3 × ^10-5 K ^-1 or more. Further, in the temperature impact test (3,000 cycles) by the experiment in the present invention, the test was carried out in a low temperature chamber of −50 ° C. and a high temperature chamber of 150 ° C. That is, the CFRP material and the A2017 aluminum alloy (duralumin), which have the largest difference in linear expansion coefficient, are used as the "A" material in a temperature change (-50 ° C to 150 ° C) of about 200 ° C, which is the environmental temperature required for automobile parts and the like. , "B" material, and the temperature impact 3,000 cycle test was carried out with the four-layer type adhesive integral body of "A" material, "C" material, "D" material, and "B" material of the present invention. As a result, the shear adhesive strength between the "C" material and the "D" material, which had the most possibility of breaking the adhesive structure, was within the permissible value without any problem. By the way, in the temperature shock cycle test, the temperature change of about 200 ° C. (-50 ° C to 150 ° C) was repeated and applied between the "A" material and the "B" material, but between the "A" material and the "B" material. Has a linear thermal expansion rate difference of 2.1 × ^10-5 K- ¹ , and this temperature change of 200 ° C. caused a length difference of 0.42%, so the “A” and “B” materials were directly bonded. If so, this would definitely have been broken.

As described in detail above, the method for producing a bonded integrated product containing dissimilar structural materials of the present invention is to indirectly bond two or more types of high-strength materials having a large difference in linear expansion coefficient, rather than directly. Even if there is a large temperature impact, there is an effect that the adhesive laminated structure can be maintained. Therefore, basically, the basic structure does not change even if it is installed in a place where the environmental temperature changes drastically, or in a place where not only the environmental temperature changes drastically but also the temperature change is repeated thousands of times. Therefore, it can be very preferably used as a component for outdoor installation machines and equipment, and for automobiles, aircraft, and other mobile machines. In particular, the product of the present invention in which the CFRP material and the duralumin material are the "A" material and the "B" material is ultra-lightweight and is most preferable as a component member for mobile machinery.

FIG. 1 is a test piece between metal pieces, and is a perspective view showing a test piece for measuring the shear adhesion strength between metals. FIG. 1 (a) is a single test piece, and FIG. 1 (b) is a single test piece. ) Is a test piece made of laminated test pieces in the case of a thin test piece. FIG. 2 is a test piece of metal pieces, and is a perspective view showing a test piece for measuring the tensile adhesive strength between metal end faces. FIG. 3 shows five 0.3 mm-thick A5052 aluminum alloy thin plates and a 0.3 mm-thick CFRP prepreg bonded and laminated with a one-component epoxy adhesive having excellent heat resistance. It is an end photograph of a compound. FIG. 4 shows three materials and three layers in which high-strength structural materials "A" and "B", which have different linear expansion rates, are used at both ends, and a pure aluminum-based A1050 aluminum alloy plate, which is a "D" material, is sandwiched between them. This is an example of a laminated body having an adhesive structure of a mold. In FIG. 5, high-strength structural materials "A" and "B", which have different linear expansion rates, are used at both ends, and A5052Al alloy thin plate, which is "C", and pure aluminum-based A1050 aluminum alloy, which is "D". This is an example of a laminated body having a five-layer, five-layer adhesive structure of "A" material, "C" material, "D" material, "C" material, and "B" material sandwiching a plate. FIG. 6 shows a thin plate of A5052 aluminum alloy, which is a “C” material, and a pure aluminum-based A1050, which is a “D” material, with high-strength structural materials “A” and “B” having different linear expansion rates at both ends. This is an example of a laminated body having a four-layer, four-layer adhesive structure of four materials, "A" material, "C" material, "D" material, and "B" material, sandwiching an aluminum alloy plate. FIG. 7 is a five-layer type stacking example similar to that shown in FIG. 5, and is a stacking example for measuring the shear adhesion strength at a stress-concentrated portion (shear surface). FIG. 8 is a four-layer type lamination example similar to that shown in FIG. 6, and is an example of lamination for measuring the shear adhesion strength at a place (shear surface) where stress is strongly concentrated.

FIG. 9 is a five-layer type lamination example similar to that shown in FIG. 5, which is laminated and adhered in a form close to a practical product, and is prepared for being put into a temperature impact several thousand cycle test. be. FIG. 10 is an example of the same 4-layer type lamination as that shown in FIG. 6, but is an example in which a CFRP thick plate is used for the “A” material and a duralumin material is used for the “B” material, and the temperature is severe. It was created to be put into a shock thousands cycle test. FIG. 11 shows a manufacturing process in the case of a composite material using CFRTP material for the “A” material. FIG. 12 shows a manufacturing process in the case of a composite material using CFRTP material for the “A” material. FIG. 13 shows an example of a plate material in which the pure aluminum alloy as the “D” material does not have a flat plate material shape but has a large number of thin columns on the surface. FIG. 14 is an example of a plate material in which the pure aluminum alloy which is the “D” material does not have a plate material shape but has concentric walls. FIG. 15 shows a method for measuring shear strength when a thick plate of 64Ti alloy is used as a high-strength structural material and a thin plate of aluminum alloy or SUS304 stainless steel is bonded to the thick plate with a one-component epoxy adhesive. It is a process diagram. FIG. 16 is a process chart showing a work procedure for measuring the “tensile adhesive strength” of the plate surface of the metal piece. FIG. 17 is a process diagram following FIG. 16 and showing a procedure of work for measuring the “tensile adhesive strength” of the plate surface of the metal piece.

FIG. 18 is a process diagram following FIG. 17, showing a procedure of work for measuring the “tensile adhesive strength” of the plate surface of the metal piece. FIG. 19 shows an example of a four-layer structure in which an A7075 aluminum alloy thick plate is bonded to the end of the CFRP material, and a structural example in which the CFRP material can be bolted / nut-fastened to another material via the A7075 aluminum alloy thick plate. Is shown. FIG. 20 shows an example of a four-layer structure in which an A7075 aluminum alloy thick plate is bonded to the end of the CFRP material, and a structural example in which the CFRP material can be bolted / nut-fastened to another material via the A7075 aluminum alloy thick plate. Is shown. FIG. 21 shows an example of a four-layer structure in which an A7075 aluminum alloy thick plate is bonded to the end of the CFRP material, and a structural example in which the CFRP material can be bolted / nut-fastened to another material via the A7075 aluminum alloy thick plate. Is shown. FIG. 22 shows an example of a three-layer type structure in which an aluminum alloy machined product is bonded to the end of the CFRP material, and the CFRP material can be bolted / nut-fastened to another material via an A7075 aluminum alloy thick plate. Is shown. FIG. 23 shows an example of a three-layer structure in which an aluminum alloy thick plate having a bolt fastening hole is bonded to the end of the CFRP material of the pipe material, and the CFRP pipe material is bolted to another material via an A7075 aluminum alloy work piece.・ It shows that nuts can be fastened.

Regarding the surface treatment method of various materials according to the present invention, the bonding method after the treatment, the method for measuring the physical properties of the adhesive, and the shear adhesion strength, shear adhesion stickiness, etc. of the bonded integral including the dissimilar structural materials of the present invention. , The following description and examples will be specifically described.

Hereinafter, the description will be described in detail with experimental examples instead of the examples of the present invention.
(A) Observation with an electron microscope An electron microscope was used for observing the surface of the base material used in this example. This electron microscope was observed at 1 to 2 kV using a scanning (SEM) electron microscope "SSM-7000F (product name)" (manufactured by JEOL Ltd. (Headquarters: Tokyo, Japan)).

(B) Measurement of Adhesive Strength Using a tensile tester "AG-500N / 1kN" (Shimadzu Seisakusho Co., Ltd. (Headquarters: Tokyo, Japan)), the adhesive joint (for example, the test piece shown in FIG. 1) is pulled. The breaking force at the time of breaking was defined as "shear adhesive strength" (x-y plane). Further, the test piece (see FIG. 2) bonded at the end face was pulled by a tensile tester, and the breaking force at the time of breaking by this pull was defined as "tensile adhesive strength" (yz plane). The tensile tester used was measured at a tensile speed of 10 mm / min.

(C) Measurement of Shear Adhesive Stickiness "Shear Adhesive Stickiness" in this experimental example means the result obtained by the following experimental method. When measuring the shear adhesion stickiness, the "shear adhesion strength" is measured in advance with a test piece (Fig. 1) using a tensile tester. Then, a test is started in which a tensile force of about 75% of this "shear adhesive strength" is continuously and repeatedly applied to this test piece only 300 times. The load method by the tensile tester according to this test method is set by the operation software of the control device of the tester. In this operation software, the maximum tensile force is about 75%, the minimum tensile force is about 2/3 of the maximum tensile force, and the tensile speed is ± 10 mm / min for one cycle. If shear failure does not occur with this repeated load, the maximum tensile load is increased by about 2 MPa, the minimum tensile force is corrected, and the same 300 times repeated load is applied. If it still does not break, the same operation is repeated by further adding about 2 MPa, and this repetition is continued until the test piece shown in FIG. 1 breaks. After fracture, the maximum tensile force before fracture was displayed in MPa, and this was used as the "shear adhesion stickiness" value in this experiment.

(D) Non-destructive inspection of the adhesive surface Judgment and observation of whether or not peeling occurred on the adhesive surface were performed by the following methods. Simply, it can be confirmed by a test method in which a colored aqueous penetrant is applied to the appearance portion of the adhesive layer and wiped off, and whether or not the colored portion can be wiped off is inspected. If you want to check in detail to what extent the peeling has spread to the adhesive area, you can observe the adhesive surface by irradiating ultrasonic waves with the non-destructive inspection machine "MS Line (Hitachi Power Solutions Company (Headquarters: Japan)). Country Ibaraki Prefecture)) ”was used.

(E) Temperature shock cycle test For the temperature shock cycle test, a temperature shock cycle tester "Small cold shock shock device TSE-12-A" (Espec Co., Ltd. (Headquarters: Osaka, Japan)) was used. The conditions of the standard temperature shock cycle test were a low temperature chamber temperature of −50 ° C. and a high temperature chamber temperature of + 150 ° C., and the staying time of each chamber was 25 minutes and the traveling time was about 5 minutes. The room temperature in which this testing machine is installed is a room where the temperature is constantly controlled to 27 ° C., and the cold room temperature is periodically raised to room temperature to automatically melt the frozen part of the testing machine. Set to drive.

[Experimental Example A] Surface Treatment of Each Material An experimental example of chemical conversion treatment for treating the surface of a structural metal material constituting the present invention will be described below. That is, the experimental chemical conversion treatment described below is for searching for the optimum chemical conversion treatment method for each of various structural metal materials.

[Experimental Example A1-1] Surface treatment (NAT treatment) of A1050 aluminum alloy (hereinafter referred to as "A1050Al alloy")
A plate material of pure aluminum-based A1050Al alloy having a thickness of 0.5 to 3.0 mm was obtained, and this was machined into a rectangular piece, and a hole was formed at this end to obtain an alloy piece as a test piece. A wire with a horticultural PVC cover was passed through the hole of this alloy piece and hung so that it could be immersed in each liquid treatment. A water tank with an ultrasonic oscillation end was filled with an aqueous solution containing 10% of a degreasing agent for aluminum "NA-6" (Meltex Inc. (Headquarters: Tokyo, Japan)) at 60 ° C., and the alloy piece was immersed for 5 minutes. After that, it was washed with water. Next, a 1% aqueous hydrochloric acid solution at 40 ° C. was prepared in another tank, immersed for 1 minute, and then washed with water. Next, a caustic soda aqueous solution having a concentration of 1.5% at 40 ° C. was prepared in another tank, and the alloy piece was immersed in this sodium hydroxide aqueous solution for 4 minutes and then washed with water. Next, a nitric acid aqueous solution having a concentration of 3% at 40 ° C. was prepared in another tank, and the Al alloy piece was immersed in the nitric acid aqueous solution for 3 minutes and then washed with water.

Next, a 3.5% hydrated hydrazine aqueous solution at 60 ° C. was prepared in another tank, the A1050Al alloy piece was immersed for 2 minutes, and then in another tank, 0.5% at 33 ° C. After immersing in a concentrated aqueous hydrazine solution for 0.5 minutes, the mixture was washed with water. Then, a 5% concentration hydrogen peroxide solution was prepared in another tank, and the A1050Al alloy piece was immersed for 5 minutes and then washed thoroughly with water. After these treatments, they were placed in a warm air dryer set at 67 ° C. for 15 minutes to dry.

[Experimental Example A1-2] Surface treatment of A1050Al alloy (NAT7 treatment: Reference example)
Similar to Experimental Example A1-1, an A1050Al alloy piece capable of being immersed was prepared. A water tank with an ultrasonic oscillation end was filled with an aqueous solution containing 10% of a degreasing agent for aluminum "NA-6" at 60 ° C., and the A1050Al alloy piece was immersed for 5 minutes and then washed with water. Next, a caustic soda aqueous solution having a concentration of 10% at 40 ° C. was prepared in another tank, immersed for 1 minute, and then washed with water. Next, in another tank, an aqueous solution containing 1% aluminum chloride hydrate at 40 ° C. and 5% hydrochloric acid was prepared, and the Al alloy piece was immersed in the aqueous solution for 10 minutes and then washed with water. .. Next, an aqueous solution containing 2% deuterium difluorinated ammon at 40 ° C. and 10% sulfuric acid was prepared in another tank, and an A1050Al alloy piece was immersed in the aqueous solution for 1 minute and then washed with water. Next, a 1.5% caustic soda aqueous solution at 40 ° C. was prepared in another tank, and the A1050Al alloy piece was immersed in the caustic soda aqueous solution for 2 minutes and then washed with water. Next, a 3% aqueous nitric acid solution at 40 ° C. was prepared in another tank, and the A1050Al alloy piece was immersed in the aqueous solution for 2 minutes and then washed with water.

Next, a 3.5% hydrated hydrazine aqueous solution at 60 ° C. was prepared in another tank, the A1050 alloy piece was immersed for 2 minutes, and then in another tank, 0.5% at 33 ° C. After immersing in a concentrated aqueous hydrazine solution for 0.5 minutes, this was washed with water. Then, a 5% concentration hydrogen peroxide solution was prepared in another tank, and the A1050Al alloy piece was immersed for 5 minutes and then washed thoroughly with water. This was placed in a warm air dryer set at 67 ° C. for 15 minutes to dry.

[Experimental Example A1-3] Surface treatment of A1050Al alloy (NAT5 treatment)
Similar to Experimental Example A1-1, an A1050Al alloy piece capable of being immersed was prepared. A water tank with an ultrasonic oscillation end was filled with an aqueous solution containing 10% of a degreasing agent for aluminum "NA-6" at 60 ° C., and the A1050Al alloy piece was immersed for 5 minutes and then washed with water. Next, a caustic soda aqueous solution having a concentration of 10% at 40 ° C. was prepared in another tank, immersed in this solution for 1 minute, and then washed with water. Next, an aqueous solution containing 1% hydrated aluminum chloride at 40 ° C. and 5% hydrochloric acid was prepared in another tank, and the A1050 alloy piece was immersed in the aqueous solution for 3 minutes and then washed with water. Next, a caustic soda aqueous solution having a concentration of 1.5% at 40 ° C. was prepared in another tank, and the A1050 alloy piece was immersed in the aqueous solution for 4 minutes and then washed with water. Next, a 3% aqueous nitric acid solution at 40 ° C. was prepared in another tank, and the A1050Al alloy piece was immersed in the aqueous solution for 1.5 minutes and then washed with water.

Next, a 3.5% hydrated hydrazine aqueous solution at 60 ° C. was prepared in another tank, the A1050 alloy piece was immersed for 2 minutes, and then in another tank, 0.5% at 33 ° C. After immersing in a concentrated aqueous hydrazine solution for 0.5 minutes, this was washed with water. Then, a 5% concentration hydrogen peroxide solution was prepared in another tank, the A1050 alloy piece was immersed for 5 minutes, and then washed thoroughly with water. This was placed in a warm air dryer set at 67 ° C. for 15 minutes to dry.

[Experimental Example A1-4] Surface treatment of A1050Al alloy (NAT (20 minutes) treatment)
The same treatment as in Experimental Example A1-1 was carried out in all the treatment steps, and the final reaction step, that is, a hydrogen peroxide solution having a concentration of 5% was prepared, and the A1050Al alloy piece was immersed in the hydrogen peroxide solution for 5 minutes. The only difference is that you change only the part you want to do and extend it to 20 minutes.

[Experimental Example A1-5] Surface treatment of A1050Al alloy (NAT5 (20 minutes))
The same treatment as in Experimental Example A1-3 was carried out in all steps, and the final reaction step, that is, a hydrogen peroxide solution having a concentration of 5% was prepared, and only the portion where the A1050Al alloy piece was immersed for 5 minutes was changed. Only the time change was changed to 20 minutes.

[Experimental Example A1-6] Surface treatment of A1050Al alloy (NAT-Ano (anodizing) treatment)
The same treatment step as in [Experimental Example A1-1] is carried out, a 3% aqueous nitric acid solution at 40 ° C. is prepared, the Al alloy piece is immersed therein for 3 minutes, and then washed with water. Next, in another tank, a 10% concentration phosphoric acid aqueous solution at 25 ° C. was prepared, the Al alloy piece was connected to the Ti anode, the carbon rod cathode was inserted into the end of the immersion tank, and DC was applied. It was anodized at 20 V for 15 minutes. The anodized aluminum alloy piece was washed with water for 30 minutes, then placed in a warm air dryer set at 67 ° C. for 15 minutes to dry, and further placed in a warm air dryer set at 100 ° C. for 30 minutes to dry. ..

[Experimental Example A1-7] Surface treatment of A1050Al alloy (NAT5-Ano (anodizing) treatment)
The process was carried out in the same manner as in [Experimental Example A1-3], a 3% aqueous nitric acid solution at 40 ° C. was prepared, the A1050Al alloy piece was immersed in the aqueous solution for 1.5 minutes, and then washed with water. Performed the same process. After this treatment, the treatment method of NAT5 was changed, then a 10% concentration phosphoric acid aqueous solution at 25 ° C. was prepared in another tank, and the A1050Al alloy piece was connected to a Ti anode to make a carbon rod. The cathode was inserted into the end of the immersion tank and anodized for 15 minutes by applying 20 V DC. The anodized A1050Al alloy piece is washed with water for 30 minutes, then placed in a warm air dryer set at 67 ° C. for 15 minutes to dry, and further placed in a warm air dryer set at 100 ° C. for 30 minutes to dry. rice field.

[Experimental Example A2-1] Surface treatment of A5052Al alloy (NAT7 treatment method)
An A5052Al alloy plate with a thickness of 0.5 to 3.0 mm was obtained, machined into rectangular pieces of various sizes, and perforated at the ends. A wire with a vinyl chloride cover for horticulture was passed through the hole of the A5052Al alloy piece and hung so that it could be immersed in each liquid. An aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was heated to 60 ° C. in the immersion tank, and the A5052Al alloy piece was immersed for 5 minutes and then washed with water. Next, a caustic soda aqueous solution having a concentration of 10% at 40 ° C. was prepared in another tank, and the A5052Al alloy piece was immersed in the caustic soda aqueous solution for 1 minute and then washed with water. Next, an aqueous solution containing 1% aluminum chloride hydrate at 40 ° C. and 5% hydrochloric acid was prepared in another tank, and the A5052Al alloy piece was immersed in the aqueous solution for 6 minutes and then washed with water. .. Next, in another tank, an aqueous solution containing 2% concentration of 1 hydrogen difluorinated ammon at 40 ° C. and 10% concentration of sulfuric acid was prepared, and the A5052Al alloy piece was immersed in the aqueous solution for 4 minutes and then washed with water. .. Next, a 1.5% caustic soda aqueous solution at 40 ° C. was prepared in another tank, and the A5052Al alloy piece was immersed in the caustic soda aqueous solution for 1 minute and then washed with water. Next, a 3% aqueous nitric acid solution at 40 ° C. was prepared in another tank, and the A5052Al alloy piece was immersed in the aqueous solution for 1.5 minutes and then washed with water. Next, a 3.5% hydrated hydrazine aqueous solution at 60 ° C. was prepared in another tank and immersed in it for 2 minutes, and then in another tank at a concentration of 0.5% at 33 ° C. After immersing in a hydrated hydrazine aqueous solution for 0.5 minutes, this was washed with water. Then, this was immersed in a hydrogen peroxide solution having a concentration of 5% for 5 minutes, washed well with water, and then placed in a warm air dryer set at 67 ° C. for 15 minutes to dry.

[Experimental Example A2-2] Surface treatment of A5052Al alloy (NAT treatment: Reference example)
Similar to Experimental Example A2-1, an A5052Al alloy piece capable of being immersed was prepared. An aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was heated to 60 ° C. in the immersion tank, and the A5052Al alloy piece was immersed for 5 minutes and then washed with water. Next, a 1% aqueous hydrochloric acid solution at 40 ° C. was prepared in another tank, and the A5052Al alloy piece was immersed in the aqueous solution for 1 minute and then washed with water. Next, a 1.5% caustic soda aqueous solution at 40 ° C. was prepared in another tank, and the A5052Al alloy piece was immersed in the caustic soda aqueous solution for 4 minutes and then washed with water. Next, a 3% aqueous nitric acid solution at 40 ° C. was prepared in another tank, and the A5052Al alloy piece was immersed in the aqueous nitric acid solution for 3 minutes and then washed with water. Next, a 3.5% hydrated hydrazine aqueous solution at 60 ° C. was prepared in another tank and immersed in it for 2 minutes, and then in another tank at a concentration of 0.5% at 33 ° C. After immersing in a hydrated hydrazine aqueous solution for 0.5 minutes, this was washed with water. Then, after immersing it in a 5% concentration hydrogen peroxide solution for 5 minutes, washing it thoroughly with water, and then putting it in a warm air dryer set at 67 ° C. for 15 minutes, the A5052Al alloy piece after the treatment was completed. It was dried, wrapped in clean aluminum foil and stored.

[Experimental Example A3] Surface treatment of A6061Al alloy (NAT treatment)
An A6061 Al alloy plate having a thickness of 0.5 to 3.0 mm was obtained, machined into rectangular pieces of various sizes, and holes were drilled at the ends. A wire with a vinyl chloride cover for horticulture was passed through the hole of the A6061 Al alloy piece and hung so that each liquid could be immersed. The subsequent surface treatment method is exactly the same as the NAT treatment method shown in Experimental Example A1-1.

[Experimental Example A4-1] Surface treatment of A2017Al alloy (NAT7 treatment method)
A2017Al alloy plates with a thickness of 0.5 to 3.0 mm were obtained, machined into rectangular pieces of various sizes, and holes were drilled at the ends. A wire with a vinyl chloride cover for horticulture was passed through the hole of the A2017Al alloy piece and hung so that it could be immersed in each liquid. The aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was heated to 60 ° C., and the A2017Al alloy piece was immersed for 5 minutes and washed with water. Next, a caustic soda aqueous solution having a concentration of 10% at 40 ° C. was prepared in another tank, and the A2017Al alloy piece was immersed in the caustic soda aqueous solution for 1 minute and then washed with water. Next, an aqueous solution containing 1% aluminum chloride hydrate at 40 ° C. and 5% hydrochloric acid was prepared in another tank, and the A2017 alloy piece was immersed therein for 1 minute and washed with water. Next, in another tank, an aqueous solution containing 2% concentration of 1 hydrogen difluorinated ammon at 40 ° C. and 10% concentration of sulfuric acid was prepared, and the A2017Al alloy piece was immersed in the aqueous solution for 3 minutes and then washed with water. ..

Next, a 1.5% caustic soda aqueous solution at 40 ° C. was prepared in another tank, and the A2017 alloy piece was immersed in the caustic soda aqueous solution for 2 minutes and then washed with water. Next, a 3% aqueous nitric acid solution at 40 ° C. was prepared in another tank, and the A2017Al alloy piece was immersed in the aqueous solution for 2.5 minutes and then washed with water. Next, a 3.5% hydrated hydrazine aqueous solution at 60 ° C. was prepared in another tank, the A2017Al alloy piece was immersed in the aqueous solution for 2 minutes, and then the temperature was 33 ° C. in another tank. After immersing in a 0.5% hydrated hydrazine aqueous solution for 0.5 minutes, this was washed with water. Then, it was immersed in a 5% concentration hydrogen peroxide solution for 5 minutes, washed with water, and then placed in a warm air dryer set at 67 ° C. for 15 minutes to dry.

[Experimental Example A4-2] Surface treatment of A2017Al alloy (NAT treatment: Reference example)
A2017Al alloy plates with a thickness of 0.5 to 3.0 mm were obtained, machined into rectangular pieces of various sizes, and holes were drilled at the ends. A wire with a vinyl chloride cover for horticulture was passed through the hole of the A2017Al metal piece and hung so that it could be immersed in each liquid. The subsequent surface treatment method is exactly the same as the NAT treatment method shown in Experimental Example A1-1.

[Experimental Example A5] Surface treatment of A7075Al alloy (NAT treatment)
A7075 Al alloy plates with a thickness of 1.5-3.0 mm were obtained, machined into rectangular pieces of various sizes, and perforated at the ends. A wire with a vinyl chloride cover for horticulture was passed through the hole of the A7075Al alloy piece and hung so that it could be immersed in each liquid. The subsequent surface treatment method is exactly the same as the NAT treatment method shown in Experimental Example A1.

[Experimental Example A6] Surface treatment of ADC12Al alloy (NAT7 treatment)
Obtained the above-mentioned ADC12Al alloy piece, which was cast using Japanese Industrial Standards ADC12Al alloy, which is an aluminum die-cast material, and has a small piece shape of 45 mm × 18 mm × thickness 1.5 mm and a hole at the end. Liquid treatment was performed. An aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was heated to 60 ° C. in the immersion tank, and the ADC12Al alloy piece was immersed for 5 minutes and then washed with water. Next, a caustic soda aqueous solution having a concentration of 10% at 40 ° C. was prepared in another tank, and the ADC12Al alloy piece was immersed in the aqueous solution of caustic soda at 40 ° C. for 1 minute, and then washed with water. Next, an aqueous solution containing 1% aluminum chloride hydrate at 40 ° C. and 5% hydrochloric acid was prepared in another tank, and the ADC12Al alloy piece was immersed in the aqueous solution for 4 minutes and then washed with water. .. Next, in another tank, an aqueous solution containing 2% concentration of 1 hydrogen difluorinated ammon at 40 ° C. and 10% concentration of sulfuric acid was prepared, and the ADC12Al alloy piece was immersed in the aqueous solution for 1 minute and then washed with water. .. Next, a caustic soda aqueous solution having a concentration of 1.5% at 40 ° C. was prepared in another tank, and the ADC12Al alloy piece was immersed in the aqueous solution of caustic soda at 40 ° C. for 4 minutes, and then washed with water. Next, an aqueous nitric acid solution having a concentration of 3% at 40 ° C. was prepared in another tank, and the ADC12Al alloy piece was immersed in the aqueous solution for 2 minutes and then immersed in a water tank with an ultrasonic transmitting end for 5 minutes. Next, the mixture was returned to the immersion tank containing the 3% aqueous nitric acid solution at 40 ° C., the ADC12Al alloy piece was immersed for 0.5 minutes, and then washed with water.

Next, a 3.5% hydrated hydrazine aqueous solution at 60 ° C. was prepared in another tank, and the ADC12Al alloy piece was immersed therein for 2 minutes, and then the temperature was adjusted to 33 ° C. in another tank. After immersing in a 0.5% hydrated hydrazine aqueous solution for 0.5 minutes, this was washed with water. Then, after immersing it in a 5% concentration hydrogen peroxide solution for 5 minutes, it was washed with water. This was placed in a warm air dryer set at 67 ° C for 15 minutes, further placed in a warm air dryer set at 100 ° C for 15 minutes to dry, and then immersed again in a water tank with an ultrasonic transmitting end for 5 minutes. , This was placed in a warm air dryer set at 67 ° C. for 15 minutes to dry.

[Experimental Example A7] Surface treatment of SUS304 stainless steel (latest NAT treatment)
SUS304-2B steel sheets with a thickness of 0.3 to 3.0 mm were obtained, machined into rectangular pieces of various sizes, and holes were drilled at the ends. A wire with a vinyl chloride cover for horticulture was passed through the hole of the metal piece and hung so that it could be immersed in each liquid. An aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was heated to 60 ° C. in a dipping tank, and a steel piece was immersed in the aqueous solution for 5 minutes and then washed with water. Next, in another tank, an aqueous solution containing 10% sulfuric acid at 65 ° C. and 1 hydrogen difluorinated ammon at 1% concentration was prepared, and the SUS304 stainless steel piece was immersed in the aqueous solution for 10 minutes, and then this was added. Washed with water. Next, it was immersed in a water tank with an ultrasonic oscillation end for 5 minutes to separate the smut adhering to the SUS304 stainless steel piece. Next, in another immersion tank, an aqueous solution containing 5% sulfuric acid at 60 ° C. and 0.5% concentration of 1 hydrogen difluorinated ammon was prepared, and the SUS304 stainless steel piece was immersed in the aqueous solution for 20 minutes. , This was washed with water. Next, the smut adhering to the SUS304 stainless steel piece was separated by immersing it in a water tank with an ultrasonic oscillation end for 5 minutes. Next, a 3% aqueous nitric acid solution at 40 ° C. was prepared, and the SUS304 stainless steel piece was immersed therein for 3 minutes and washed with water. Next, in another immersion tank, the mixture was immersed in an aqueous solution containing 10% caustic soda at 55 ° C. and 5% sodium chlorate for 6 minutes, and then washed with water. Then, it was put in a warm air dryer set at 80 ° C. for 15 minutes to dry.

[Experimental Example A8-1] SPCC surface treatment (new NAT treatment: reference example)
Commercially available SPCCs (cold-rolled steel sheets) having a thickness of 1.6 mm and 3.2 mm were purchased, and the steel pieces cut into various desired shapes were used as test pieces. This SPCC test piece was blasted with white alumina powder (WAF100) using a shot blasting machine to roughen the portion to be the adhesive surface. An aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was prepared at 60 ° C. in a dipping tank with an ultrasonic transmitting end, and the SPCC test piece was immersed for 5 minutes and then washed with water. .. Next, in another immersion tank, an aqueous solution containing 1% hydrogen difluorinated ammon at 65 ° C. and 10% sulfuric acid was prepared, and the SPCC test piece was immersed in the aqueous solution for 1 minute and then washed with water. bottom. Next, 1% concentration of ammonia water was prepared in another immersion tank, and the SPCC test piece was immersed in this for 1 minute and then washed with water. Next, in another immersion tank, an aqueous solution containing 2% potassium permanganate at 45 ° C., 1% acetic acid and 0.5% sodium hydrated sodium acetate was prepared, and the SPCC test piece was prepared. Was soaked for 5 minutes and then washed with water. Then, it was immersed in a water tank with an ultrasonic oscillation end for 7 minutes to remove the smut and washed with water. The SPCC test piece washed with water was placed in a warm air dryer set at 80 ° C. for 15 minutes to dry.

[Experimental Example A8-2] SPCC surface treatment (latest NAT treatment)
Commercially available SPCCs with a thickness of 1.6 mm and 3.2 mm were purchased and cut into various desired shapes by machining to obtain SPCC steel pieces as test pieces. An aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was heated to 60 ° C. in the immersion tank, the SPCC test piece was immersed for 5 minutes, and then washed with water. Next, an aqueous solution of 1 hydrogen difluorinated Ammon having a concentration of 5% at 65 ° C. was prepared in another tank, and the SPCC test piece was immersed in the aqueous solution for 25 minutes and then washed with water. Next, 1% concentration of ammonia water was prepared in another tank, the test piece was immersed in the aqueous solution for 1 minute, and then washed with water. Next, in another tank, an aqueous solution containing 2% potassium permanganate at 45 ° C., 1% acetic acid, and 0.5% sodium hydrated sodium acetate was prepared, and the SPCC test was performed on the aqueous solution. The pieces were soaked for 5 minutes and then washed with water. Then, it was immersed in a water tank with an ultrasonic oscillation end for 7 minutes to remove the smut and washed with water. Next, an aqueous solution containing 0.2% concentration triethanolamine at 40 ° C. was prepared in another tank, and the SPCC test piece was immersed in the aqueous solution for 30 minutes and then washed with water. Then, this was put in a warm air dryer set at 80 ° C. for 15 minutes to dry.

[Experimental Example A9-1] Surface treatment of 64Ti alloy (new NAT treatment)
64Ti alloy pieces such as 150 mm x 50 x 3 mm, 45 mm x 18 mm x 3 mm, 45 mm x 18 mm x 1.5 mm, etc. created by requesting a metal processing manufacturer [Original material is "KS6-4" (Kobe Steel Co., Ltd.) (Headquarters: Made in Hyogo, Japan)] was prepared. The surface treatment method is a treatment method called new NAT described in Patent Document 8 and the like, and the surface texture is applied as it is, and since it is a known technique, the treatment method is omitted. After this surface treatment, it was wrapped in clean aluminum foil and stored.

[Experimental Example A9-2] Surface treatment of 64Ti alloy (latest NAT treatment)
Similar to the above experimental example, a 64Ti alloy piece was obtained and used as a test piece. An aqueous solution containing 10% of the aluminum degreasing agent "NA-6" was heated to 60 ° C. in the immersion tank, and the 64Ti alloy piece was immersed for 5 minutes and then washed with water. Next, an aqueous solution of 1 hydrogen difluorinated Ammon having a concentration of 5% at 65 ° C. was prepared in another tank, and the 64Ti alloy piece was immersed in the aqueous solution for 5 minutes and then washed with water. Next, a 3% aqueous nitric acid solution was prepared in another tank, and the test piece, which was the 64Ti alloy piece, was immersed in the test piece for 3 minutes and then washed with water. Next, an aqueous solution containing 2% potassium permanganate and 3% potassium caustic at 70 ° C. was prepared in another tank, and the 64Ti alloy piece was immersed in the aqueous solution for 30 minutes and then washed with water. Then, it was immersed in an aqueous solution containing 15% of the newly developed adjusting agent at 55 ° C. for 20 minutes, and then washed with water. Then, it was put in a warm air dryer set at 80 ° C. for 15 minutes to dry.

[Experimental Example A10] Surface treatment of Ti alloy "KSTi-9" (new NAT treatment)
A 1 mm thick "KSTi-9" (manufactured by Kobe Steel, Ltd. (Headquarters: Hyogo Prefecture, Japan)) plate, which is a heat-resistant titanium alloy, was obtained and cut to the required size. The surface treatment is exactly the same as that of Experimental Example A9 described above. The above is the surface treatment method for various metal pieces used in this experimental example. Next, a method of surface treatment of the CFRP material when adhering to these metal pieces will be described.

[Experimental Example A11] Surface treatment of CFRP material There are two types of CFRP material used in this experiment. One is a CF (commercially available product) with a tensile strength of about 3 GPa, which is a unidirectional type. It is a product having a thickness of 45 mm × 15 mm × 3 mm, which is obtained by stacking and curing prepregs in the same direction.

The other type is a 0.2 mm thick CFRP unidirectional prepreg "P225S-25" (manufactured by Toray Industries, Inc. (Headquarters: Tokyo, Japan)), which is outsourced to a specialized processing company to align the CF directions. We requested the production of a CFRP thick plate material with a thickness of 3 mm and a thickness of 500 mm × 500 mm, and produced a thick plate. A part of this plank was cut into CFRP pieces having CF parallel to the long side of 45 mm × 15 mm. The CF used was "T800SC" (manufactured by Toray Industries, Inc. (Headquarters: Tokyo, Japan)), and the tensile strength of the CF yarn was about 6 GPa. In both cases, heat-resistant matrix resin is used.

The surface pretreatment of the CFRP material for adhesive bonding is strongly polished with # 600 sandpaper to the extent that some CF is exposed. The polished CFRP piece was immersed in a degreasing tank with ultrasonic waves (a water tank containing a degreasing material for aluminum materials at 60 ° C.) to separate the adhering stains, and then washed thoroughly with water. After that, it was put in a hot air dryer at 100 ° C. for about 15 minutes to dry, and then wrapped in clean aluminum foil and stored.

[Experimental Example A12] Preparation of Adhesive Integration of CFRP Material and Al Alloy Thin Plate A method of preparing an adhesive integration of CFRP piece and Al alloy thin plate from CFRP prepreg at once was also carried out. That is, a 0.75 mm thick A5052Al alloy thin plate was cut into 98 mm × 98 mm in advance, and the same treatment as in Experimental Example A3 was performed. A one-component epoxy adhesive "EW2040 (manufactured by 3M Japan Ltd. (Headquarters: Tokyo, Japan)" was thinly applied to one side of the adhesive, and a Teflon sheet was pressed onto it for storage as an adhesive preparation. Using both this adhesive preparation and CFRP prepreg "P225S-25" (manufactured by Toray Industries, Inc. (Headquarters: Tokyo, Japan)), a CFRP thick plate shape with a thickness of 3.5 mm with a 100 mm x 100 mm A5052Al alloy thin plate is made. Created. This preparation is a method of heating and adhering in an autoclave under reduced pressure, and the maximum heating condition is 150 ° C. × 40 minutes. The obtained CFRP thick plate with an A5052Al alloy thin plate was cut so that the CF was parallel to the long side of 45 mm × 15 mm.

[Experimental Example B] Adhesive strength confirmation test [Experimental Example B1] Measurement of adhesive strength (shear adhesive strength, tensile adhesive strength) 45 mm × which was the same treatment as that of the above-mentioned [Experimental Examples A1 to A12] group Various test pieces having a thickness of 18 mm × (3 to 6) mm were used to prepare an adhesive pair having the shapes shown in FIGS. 1 and 2. More specifically, in the shape of the test piece shown in FIG. 1A, the shape of the test piece is 45 mm × 18 mm × (4.5 to 6.0) mm thick in order to apply a tensile load. ing. However, when the Al alloy material is soft, especially when a thin pure aluminum-based Al alloy is used, the thickness is 6.0 mm, and the thickness of the others is 4.5 mm. For this reason, we often used products with a thickness of 4.5 mm or 6.0 mm by adhering 1.5 mm thick products in 3 or 4 layers, but this is the shape shown in FIG. 1 (b). It is shown as. Regarding the CFRP pieces described in Experimental Example A11 and later, the CFRP piece shape was 45 mm × 15 mm × 3 mm thick. These were directly used as the laminated structure shown in FIG. 1 (a).

[Procedure for making test pieces]
Hereinafter, a specific bonding method for producing the test pieces shown in FIGS. 1 and 2 will be described. The basic shapes of various metal pieces used by the present inventor are often 45 mm × 18 mm × 1.5 mm thick, and CFRP pieces and CFRTP pieces are 45 mm × 15 mm × 3 mm thick. When the base material is a rolled plate with a metal piece, the rolling direction is 45 mm on the long side of the rectangle, the perpendicular direction is the width direction of 18 mm, and the thickness is the thickness direction of the rolled plate of the base material. bottom. Therefore, only the SPCC piece has a thickness of 1.6 mm, 3.2 mm, or the like, which is an integral multiple of 1.6 mm. This is because only products of this thickness are produced. With A6063 aluminum alloys and 64 titanium alloys, the base material of which is supplied as a plank or ingot, such a decision cannot be made, and it depends on the processing accuracy of metal processing. Further, the CFRP material is a product using a prepreg containing bundled CF, and for CFRP in which all the CF bundles are arranged in the same direction, the bundle arrangement direction line is 45 mm long. In the case of the shape shown in FIG. 1 (b), since a large number of metal pieces are laminated, all the individual metal pieces described above are surface-treated by a predetermined treatment method and then bonded.

As a pretreatment before bonding, take a very small amount of one-component epoxy adhesive "EW2040" in an adhesive container, add MIBK (methylisobutylketone), which is a solvent, to make a very thin solution, and leave it as a wooden stick. An adhesive from a container is attached to the tip of the material, and this is applied to a portion of the metal piece, which is a chemical-treated test piece, to be adhered. Then, the test piece is placed in a hot air dryer set at 50 ° C. for 20 minutes to volatilize the solvent. Then, the above-mentioned adhesive "EW2040" is applied to the undercoat portion. The laminated adhesive surface, which is not related to the shear failure test, does not require such a primer coating operation, and the adhesive is directly applied to the entire surface of the test piece, and the laminated adhesive surface is laminated as shown in FIG. 1 (b). , This is pressure-fixed with a jig (stationery clip) to form a laminated body.

During the bonding operation, a large desiccator is placed in a hot air dryer set at 50 ° C. to preheat it. This desiccator is taken out, and the jig-fixed laminate created in the above operation is put into the desiccator as it is. Then, the air inside the desiccator is evacuated with a vacuum pump, and after about 5 minutes, air is added. The depressurization / pressurization operation is repeated two or more times to remove the air from the desiccator, and then put it in a hot air dryer and heat it at 170 ° C for 20 minutes. Then, after the curing process is completed, remove the fixing jig. The hardened test piece has many hardened parts where the adhesive overflows from the adhesive surface, and these are scraped off with a router. This machining was performed the day after the curing treatment to reduce the influence of machining, and the respective values of "shear bond strength" and "shear bond stickiness" were measured by a tensile tester. The method of preparing the test piece shown in FIG. 2 for measuring the "tensile strength" is the same as the above method.

Table 1 shows the main parts of the data of the results of the measured shear bond strength of the same type of test pieces bonded by the above chemical conversion treatment and bonding method. As can be seen in Table 1, the shear bond strength between metal pieces of the same type was approximately 60 MPa, and the one with the lowest value was only about 54 MPa of the A1050Al alloy, which is a pure aluminum alloy that is a soft metal. .. On the other hand, in the test piece of CFRP pieces prepared in Experimental Example A11, about 60 MPa was obtained in the test piece of CFRP pieces prepared by using a material having a tensile strength of about 3 GPa as CF. However, even with the same test pieces of CFRP pieces, the pressure was about 40 MPa for the test pieces of CFRP pieces prepared by using a CF with a tensile strength of about 6 GPa. The data in Table 1 show that the treatment of the adhesive surface is not a mechanical surface treatment such as polishing, but the adhesive method by various chemical conversion treatments proposed by the present inventors is effective for the adhesive strength. Further, it was found that the tensile adhesive strength (test piece of FIG. 2 described later) was stronger than the shear adhesive strength. It is understood that the reason for this is that the rolling direction of the metal, that is, the direction of the metal fibers described later, affects the adhesive strength.

[Experimental Example B2] Measurement of Tension Adhesive Strength of Various Surface-treated Metal Materials Using various metal pieces of 45 mm × 18 mm × 1.5 mm that have been subjected to the same treatment as Experimental Examples A1 to A9 described above, the shape shown in FIG. It was used as a test piece. That is, in the shape of the test piece shown in FIG. 2, since the end shape of the metal piece is 18 mm × 1.5 mm, various metal pieces for measuring the shear joint strength in ISO19095 are manufactured by a company that produces the test piece and are commercially available. Has been done. Therefore, the test piece was diverted as it was.

Table 1 also shows the measurement results of the tensile adhesive strength using the test piece shown in FIG. As described above, the tensile adhesive strength for the yz plane of the supplied metal plate is measured. According to the experimental result of the tensile adhesive strength, only the A1050Al alloy, which is a pure aluminum-based aluminum alloy, protrudes and records about 95 MPa. In the actual measurement, some test pairs showed about 100 MPa, and about 95 MPa is an average value of several pieces, which is not an abnormal value due to the variation of the experiment. It is speculated that the metal crystal system shape of the Al alloy formed by stretching processing such as rolling roll processing when forming the metal is related. The crystal-based shape becomes elongated and fiber-like, so that the tensile strength in the x direction is high, which is considered to be related to the tensile adhesive strength. According to this inference, for rolled products, even if a treatment method that produces a high tensile adhesive strength value using the test piece shown in FIG. 2 is developed, the adhesive method that does not consider the direction of the metal fiber is The shear bond strength of the treated product does not increase. On the contrary, if the metal ingot that was once made into a metal ingot by forging is machined into a plate-shaped small piece, there seems to be a proportional relationship between the tensile adhesive strength value and the shear adhesive strength value. Presumed.

[Experimental Example B3] Measurement experiment of "tensile adhesive strength" of metal plate surfaces (xy surface) As shown in Table 1, for example, the "tensile adhesive strength" of the yz surface of Experimental Example A1 is It is abnormally high at about 95 MPa. It is presumed that the reason is that the direction of the metal fiber is different from that of the adhesive surface of the xy surface as described above. The numerical values of A1050, which is a pure aluminum-based aluminum alloy recorded in Table 1, were analyzed, and the "tensile adhesive strength" on the plate surface (plate surface: xy surface) was measured with the test piece shown in FIG. It is predicted that it is different from the "tensile adhesive strength" based on the plate cross section (yz plane). Since there is no standardized test method for measuring the "tensile adhesive strength" based on the plate cross section (xy plane) in the rolling direction, a test piece was prepared and measured by the method described below.

(1) Method for measuring "tensile adhesive strength" on the plate surface (plate surface: xy surface) FIGS. 16 to 18 show "tensile adhesive strength" on the plate surface (xy surface (FIG. 2)). It is a schematic diagram which shows the outline of the procedure for making the test piece in order to measure "sa". First, six plates of A5052Al alloy having a length of 45 mm, a width of 18 mm, and a thickness of 1.5 mm were bonded and laminated with a one-component epoxy adhesive. After heat-curing this, as shown in FIG. 16 (lower stage), it was cut with a saw blade in the plate thickness direction, and further machined to a thickness of 18 mm width × 9 mm length × 1.5 mm thickness by end milling. As shown in FIG. 17, on the end face of this machined piece and two plates (45 mm length × 18 mm width × 1.5 mm thickness) of the above A5052Al alloy which are the same material in wall thickness and width, the above It was bonded with the same adhesive, and the excess part was cut after curing (lower part of FIG. 17).

In this bonded state, it is not possible to determine which bonded surface will break even if a tensile load is applied, which is not preferable as a test method. Therefore, as shown in the lower part of FIG. 18, the central portion was excised by cutting in a circular shape with an end mill. Then, among the above-mentioned laminated test pieces, the width direction of the adhesive surface was made the narrowest (9 mm width × 1.5 mm thickness) so as to break from the adhesive surface at the center. The load when the adhesive surface was broken was defined as the tensile adhesive strength of the xy surface. As a result, the tensile adhesive strength of the xy plane is 46.0 MPa for the same pure aluminum alloy-based A1050Al alloy with the same adhesive and the same chemical conversion treatment (NAT) product, which is 46.0 MPa for the yz plane. It is lower than 95.0 MPa (see Table 1). Similarly, the A5052Al alloy is 51.3 MPa, which is lower than 76.4 MPa on the yz plane, and the 64Ti alloy is 47.0 MPa, which is lower than 75.2 MPa on the yz plane.

In the present invention, the physical characteristics of the plate surface of the metal piece produced by rolling are important for the bonding operation. In the NAT treatment, how to improve the shear adhesion strength using the shape of the test piece shown in FIG. 1 has become a concrete improvement study of the NAT treatment method, and the present invention also has the present invention at 60 MPa and 150 ° C. at room temperature. The present invention has been successfully developed based on the securing of a strong adhesive force showing 30 MPa. However, research on improving surface treatment methods for various metal alloys reaches a limit and stagnates when the shear adhesive strength approaches about 60 MPa. This is because it definitely approaches the upper limit. Therefore, there is no clear indicator to use after approaching this high. Theoretically speaking, the shear adhesive strength is measured on the plate surface of many metal pieces, so if the tensile adhesive strength on the plate surface can be measured, "the higher the value, the better. It has the structure of the adhesive surface. " Therefore, when the shear adhesive strength reaches 60 MPa, it was decided that the surface treatment method should be tried and errored while measuring the tensile adhesive strength of this portion. This is the reason for implementing the above-mentioned "Experimental Example B3". However, since the test method is too difficult and experimental mistakes are likely to occur, it was determined that the test method is not suitable as an improvement degree evaluation method for advancing the improvement while performing trial and error in the surface treatment in the present invention.

[Experimental Example B4] Measurement of Adhesive Strength (Shear Adhesive Stickiness Value) of Various Metal Materials From the above-mentioned background, the adhesive strength can be easily measured instead of a simple tensile load, and when used in an actual device. We searched for an adhesive strength evaluation method that is close to the load. This is the conclusion drawn by the present inventor and the proposed measurement of "shear adhesive stickiness". Table 2 shows the measurement results of the above-mentioned "shear adhesion stickiness" in the test piece shown in FIG. 1 when metal materials of the same material are bonded to each other. That is, as described above, with reference to the shear adhesive strength value measured earlier, the force of about 75% is applied 300 times, and if it does not break, the force is increased by about 2 MPa and added 300 times as it is, but it still breaks. If not, this will be repeated. As can be seen from the results shown in Table 2, all the target metals were measured in the NAT-treated product, and the "shear adhesive stickiness" value was also measured in the NAT5 and NAT7-treated products. As a practical judgment, the "shear adhesive stickiness" is preferably 50 MPa or more.

[Experimental Example B5] Measurement of Adhesive Strength (Shear Adhesive Strength) of One-Liquid Epoxy Adhesives Between Dissimilar Metal Materials 45 mm × 18 mm × (4) subjected to the same chemical conversion treatment as shown in Experimental Example A above. Using a one-component epoxy adhesive "EW2040" to cure a metal piece of .5-6.0) mm, a test piece of dissimilar metal pieces (the shape shown in FIG. 1) was cured at 170 ° C. for 20 minutes. Created with conditions. The results are shown in Table 3. As mentioned above, the one-component epoxy adhesive usually cures at 150-180 ° C. for 15-30 minutes. In the experiment of the present invention, when "EW2040" was used, the curing conditions were all 170 ° C. × 20 minutes. Therefore, when it is taken out of the hot air dryer after curing, it is immediately allowed to cool and returns to room temperature completely if left for 1 hour. That is, the adhesive surface was fixed at 170 ° C., and after returning to room temperature, the environmental temperature was lowered by about 150 ° C. If the shape of the test piece shown in FIG. 1 is an adhesive pair of dissimilar metal materials and there is a large difference in linear expansion coefficient between the dissimilar materials, will part or all of the adhesive hardening layer be damaged? Or, although the bonding condition does not change, it should be slightly deformed even if it is not visible visually. Internal stress commensurate with the deformation of the test piece should be generated, and the adhesive strength should be reduced by that amount. In any case, if the shear bond strength is measured with a tensile tester as it is, the value will surely decrease. It was estimated that if the cured adhesive pair was subjected to a temperature impact test at -50 ° C / + 150 ° C, the deterioration situation would be more clearly understood.

Four pairs were prepared as the adhesive pairs for measurement, the adhesive strength of these two pairs was measured the day after the bonding operation, and the remaining two pairs were measured after a temperature impact 100 cycle test at −50 ° C./+ 150 ° C. However, since there was no clear difference between the former 2 pairs and the latter 2 pairs, Table 3 shows the average value of 4 pairs. As a result, in the adhesive pair of different materials bonded to the A1050Al alloy and the A7075Al alloy on one side, the shear adhesion strength was 55 to 57 MPa, and there was almost no difference in the coefficient of linear expansion, so that the adhesive strength was naturally high. Also, when bonded to a different material whose linear expansion coefficient is significantly different from that of A1050 aluminum alloy, which is a pure aluminum-based aluminum alloy, it is strange that it is about 55 MPa or more, but both before and after the temperature impact test have strong adhesive strength. You can see that it has been obtained. This data has an important meaning in the present invention and is the origin of the present invention.

On the other hand, as shown in the lower column of Table 3, the shear adhesive strength of the adhesive made of the one-component epoxy adhesive between the high-strength materials whose linear expansion coefficient difference is clearly significantly reduced. It is presumed that a part of the adhesive curing layer was damaged by allowing to cool after curing. The adhesive area of the test piece, which is the shape shown in FIG. 1, is about ^{0.7 cm 2.} It can be seen that even with such a small area, the difference in linear expansion coefficient has a large effect. In short, in the data in Table 3, the clear fact that the shear bond strength does not decrease is a phenomenon caused by the physical properties of the soft metal due to the pure aluminum-based aluminum alloys A1050 and A1085 aluminum alloys.

[Experimental Example B6] Measurement of Adhesive Force (Shear Adhesive Strength) Between Test Pieces in Multilayer Metal Adhesive A bonded integrated product in which the material is used as both end members, and the above-mentioned "C" material and "D" material are sandwiched between the "A" material and the "B" material, and the four or five layers are laminated with an adhesive. be. This joint integrated product has three or four adhesive surfaces. Therefore, it was decided to actually measure how the actual adhesive force (shear adhesive strength) on each of these adhesive surfaces is. Examples of laminating the four-layer or five-layer adhesive are shown in FIGS. 5 (5 layers) and 6 (4 layers). However, the shear adhesion strength and the temperature impact strength cannot be measured with the laminates shown in FIGS. 5 (5 layers) and 6 (4 layers). Table 4 shows the measurement results obtained by the test piece shown in FIG. 7 as a 5-layer laminate and the test piece of FIG. 8 as a 4-layer laminate.

Table 4 shows nine measurement examples. Here, as the "A" material and the "B" material, 64Ti alloy, A2017Al alloy (duralumin), A7075Al alloy (super duralumin), SUS304 steel, CFRP piece, Etc. were used. Further, as the C material, an A5052Al alloy 0.75 mm thin plate, an A6061 Al alloy 0.5 mm thick thin plate, and a SUS304 0.28 mm thin plate were used, and as the "D" material, an A1050 Al alloy 1.5 mm plate was used. The shear adhesive strength of each adhesive part (// part in Table 4) is as high as 55 to 58 MPa, and the shear adhesive strength after the same test piece is put into a temperature impact 1000 cycle test at -50 ° C / + 150 ° C. The difference was small, and even after the temperature impact test, there was no problem in the adhesive strength of the bonded portion. As can be understood from the bonding examples of FIGS. 7 and 8, this data shows that the bonding portion to be bonded to the A1050Al alloy, which is a pure aluminum-based aluminum alloy, has a narrow bonding area and is the weakest. Therefore, by this test, data of at least the shear adhesion strength and the temperature impact strength of the portion to be bonded to the member to be bonded to the A1050Al alloy were obtained.

[Experimental Example B7] Experiment of Moisture and Heat Resistance Test of Test Piece of One-Liquid Epoxy Adhesive with Shape Shown in FIG. 1 The data in Table 4 described above is not the test data in a high temperature and high humidity environment. The present invention is a three-layer, four-layer, or five-layer laminated adhesive in which a "C" material and a "D" material are sandwiched between an "A" material and a "B" material. The first thing that is required for this adhesive is whether or not both the "C" material and the "D" material can withstand the adhesive strength of the adhesive surface in a harsh environment when used as structural materials for automobiles and the like. Is it? Specifically, even if there is no problem in the above-mentioned temperature impact test, a test in a high humidity environment is also necessary. In a general high humidity test, a humidity test with a temperature of 50 ° C and a humidity of 95% is performed, but in this experiment, this is accelerated and exposed to a high temperature and high humidity tester with a temperature of 85 ° C and a humidity of 85% for 1000 hours. The test was carried out. However, aluminum alloys are rusted when thin hydroxides (rust) are generated on the surface and the color tone changes, and when water droplets adhere when opening and closing the tester door during the test. Therefore, before the test piece was put into the testing machine, engine oil (10W-30), which is generally commercially available in this experiment, was applied and then put into the testing machine. As shown in Table 5, the samples are A1085Al alloy, A1050Al alloy, A6061Al alloy, and SUS304 used for "C" material and "D" material, but they are used as "A" material and "B" material for reference. A 64 titanium alloy, which is likely to be used, was also tested. The adhesive is the aforementioned "EW2040". The results are shown in Table 5. The data shown in Table 5 show that the pure aluminum-based aluminum alloy did not decrease in shear adhesion strength even when subjected to the heat resistance test, but other materials decreased.

That is, as seen from the results in Table 5, the adhesive strength of the product excluding pure aluminum-based aluminum alloys (Japanese Industrial Standards 1000 series) is subject to the process of being placed under high temperature and high humidity of 85 ° C. and 85% humidity for 1000 hours. As a result, the shear adhesion strength decreased to around 45 MPa. From the results, it was judged that the reason for this was that the cured adhesive (cured epoxy resin) absorbed water molecules under high temperature and high humidity for a long period of time and was slightly softened. It was understood that the reason why the decrease in adhesive strength was slightly suppressed in the pure aluminum-based aluminum alloy was that the hardness of the cured adhesive that had absorbed and softened and the hardness of the pure aluminum-based aluminum alloy approached and the stress was dispersed. That is, in the case of A6061Al alloy, SUS304, etc., which have a large hardness difference with the adhesive, it was understood that the hardness difference between the metal and the adhesive became large, and the material was easily broken due to stress concentration.

Therefore, it was determined that the hygroscopic adhesive pair was heated at a temperature of 80 ° C. for 92 hours and then dried with hot air at 170 ° C. for 1 hour to expel the water molecules that had settled in the narrow adhesive curing layer. This 1000-hour high-temperature and high-humidity test at 85 ° C and 85% humidity is an accelerated test under harsh conditions that cannot be achieved in an actual environment. It was to know. Therefore, the drying step as described above was carried out. First, when it was heated at 80 ° C for a long time and placed at a high temperature of 150 ° C or higher from the beginning, it prevented steam from ejecting from the sufficiently absorbed adhesive cured product and damaging the adhesive cured product structure. It is. Then, after removing the majority of water molecules, it was considered that the hygroscopic material was almost completely expelled by heating at 150 ° C. or higher.

As can be seen from the results in Table 5, the adhesive pairs between the same metal pieces by the cured product of the one-component epoxy adhesive "EW2040" that has undergone severe moisture absorption conditions are all 53 to 55 MPa except for the NAT-treated 64Ti. The present inventor has determined that the result is good. In short, the environmental humidity conditions on the earth to which mobile machines moving on the ground such as automobiles are exposed are 100% humidity at a maximum of about 40 ° C, and the temperature is 25 to 30 even in the world's heaviest northeastern India. ℃. Therefore, in the 64 titanium alloy shown in Table 5, the decrease in shear adhesive strength is slightly large and is 43 MPa. However, since the titanium material is used for the "A" material and the "B" material referred to in the present invention, when the adhesive force of the thin plate material used as the "C" material to the titanium material is weak, the adhesive area should be increased. Can be covered with. Conversely, if the adhesive performance of the "C" material and the "D" material does not show an irreversible decrease in the adhesive strength in this accelerated test in a high humidity environment, the present invention is practically troublesome. You don't have to have a big problem. In that sense, regarding A6061 aluminum alloy and SUS304 stainless steel that can be used as "C" material, and A1050 and A1085 aluminum alloy that can be used as "D" material, the same metal types are bonded to each other, but they are strong under high temperature and high humidity. It was found that adhesive strength was obtained.

[Experimental Example B8] 64Ti / Pure Aluminum-based Al Alloy Surface Adhesive (Preliminary Test 1)
From the consideration of the above experiments, in order to confirm the effectiveness of the pure aluminum-based aluminum alloy as the "D" material as a laminate, the Ti alloy and the pure aluminum-based aluminum alloy with the one-component epoxy heat-curable adhesive were used. The adhesive strength of the aluminum was measured. The new NAT-treated product described in [Experimental Example A9-1] of a 64Ti alloy having a thickness of 45 mm × 18 mm × 3 mm and the NAT described in [Experimental Example A1-1] of an A1080Al alloy plate having a thickness of 45 mm × 18 mm × 1.5 mm. The treated product was surface-bonded by a NAT bonding method with "EW2040", which is a one-component epoxy heat-curable adhesive. Next, a surface-treated product of a 64 Ti alloy having a thickness of 45 mm × 18 mm × 3 mm and a NAT-treated product of an A1050 Al alloy plate having a thickness of 45 mm × 18 mm × 1.5 mm were subjected to the above-mentioned “EW2040” by the NMT bonding method. Surface-bonded.

Further, the same surface-treated product of the above-mentioned 64Ti alloy having a thickness of 45 mm × 18 mm × 3 mm and the NAT-treated product of the A1100Al alloy plate having a thickness of 45 mm × 18 mm × 1.5 mm were subjected to the above-mentioned “EW2040” by the NMT bonding method. Surface-bonded. In short, Al alloy plates A1080, A1050, and A1100 were surface-bonded to a 64Ti thick plate in the same manner with an adhesion area of 45 mm × 18 mm and 8.1 cm ² . A total of 9 pieces were prepared in units of 3 pieces each, and these adhesives were put into a temperature shock cycle tester at −50 ° C./+ 150 ° C. and loaded with 1000 cycles. By this load test, all three of the 64Ti / A1100Al alloy adhesives were surface-broken, and no abnormality was found in the other six. Therefore, when the temperature impact test was continued and taken out after 2,000 cycles, the 64Ti / A1050Al alloy adhesive had two small peeling-like appearances in one or two of its four corners with a non-destructive inspection machine. Observed, no peeling was observed in all three of the 64Ti / A1080Al alloy test pieces.

In this experiment, aside from the softest A1080, even if it is a soft Al alloy, the A1050 Al alloy caused a slight but clear problem in terms of adhesion to the Ti material. According to Table 2 described above, the "shear adhesive stickiness" value in the test piece of A1050 (NAT-treated product) of Experimental Example A1 is 50.5 MPa, which is the limit level as the value of the allowable shear stickiness assumed in this experiment. The "shear adhesive stickiness" value of 64Ti (new NAT-treated product) of [Experimental Example A9-1] is clearly low at 45.8 MPa. At the start of this experiment, the 64Ti alloy (latest NAT-treated product) of [Experimental Example A9-1] had not yet been found. Therefore, in response to this result, a new NAT-treated product of the above-mentioned "KSTi-9", which is a Ti alloy of [Experimental Example A10], was made, and three 45 mm × 18 mm × 1 mm thick plates were laminated and bonded to each other. A new NAT-treated product of the alloy "KSTi-9" and a NAT-treated product of an A1050Al alloy plate having a thickness of 45 mm x 18 mm x 1.5 mm were NAT-bonded with the above-mentioned "EW2040" to prepare two sheets. As recorded in Table 2, the "KSTi-9" used had a very high "shear adhesive stickiness" value of 56.5 MPa, and the temperature impact was 2,000 due to insufficient adhesive force between 64Ti and A1050Al alloy. This is because, if the end peeling occurs in the vicinity of the cycle, it is considered that the Ti material having the weaker adhesive force should be replaced. As a result of subjecting to a temperature shock 3,000 cycle test, there was no problem at all and no end peeling occurred.

[Experimental Example B9] Test piece of Al alloy and Ti alloy sandwiched between A1050 plates (preliminary test 2)
A three-layer adhesive having the shape shown in FIG. 4 was prepared. A new NAT-treated product of 64Ti alloy with a thickness of 45 mm x 18 mm x 3 mm, a NAT-treated product with an A1050 Al alloy with a thickness of 45 mm x 18 mm x 1.5 mm, and a NAT-treated product with an A7075 Al alloy with a thickness of 45 mm x 18 mm x 3 mm are used in "EW2040". , The surface was bonded by the NAT bonding method. Although it is said to be a three-layer type, to be precise, in this experiment, all metal pieces with a thickness of 1.5 mm were used, two 64Ti alloys were laminated, and the A7075Al alloy was also a two-layer laminated adhesive. It became a layered surface adhesive. Two identical products were prepared and subjected to a temperature shock 3,000 cycle test at -50 ° C / + 150 ° C.

The adhesive taken out from the testing machine did not cause any trouble by visual observation. From the above experimental results, there is a sufficient possibility that there is peeling at the four corners between the 64Ti alloy part and the A1050Al alloy plate, and this point was investigated by a non-destructive inspection machine. As a result, a peeling signal was obtained at one of the four corners. And no signal of peeling could be detected in other parts. As a result, this test result was only the same as that of Experiment B8.

[Experimental Example B10] A test piece in which an A5052Al alloy thin plate and an A1050Al alloy plate are sandwiched between an Al alloy and a Ti alloy (main test 1).
The joint integrated product shown in FIG. 5 is a laminated body composed of 5 materials and 5 layers. The joint integrated product shown in FIG. 6 is a laminated body composed of four materials and four layers. The bonded integrated product shown in FIG. 5 is the latest NAT-treated product of 64Ti alloy (A material) having a thickness of 45 mm × 18 mm × 3 mm, and the NAT7-treated product of A5052Al alloy thin plate (C material) having a thickness of 45 mm × 18 mm × 0.75 mm. 45 mm x 18 mm x 1.5 mm thick A1050 Al alloy (D material) NAT treated product, 45 mm x 18 mm x 0.75 mm thick A5052 Al alloy (C material) thin plate NAT7 treated product, and 45 mm x 18 mm x 3 mm thick A NAT7-treated product of A2017Al alloy (B material) was laminated with the above-mentioned adhesive "EW2040" to prepare a five-layer type adhesive.

The bonded integrated product shown in FIG. 6 is a simplified form of the laminated body shown in FIG. 5, and is a laminated body composed of four materials and four layers. This laminate is the latest NAT-treated product of 64Ti alloy (A material) with a thickness of 45 mm x 18 mm x 3 mm, the surface-treated product of A5052Al (C material) alloy thin plate with a thickness of 45 mm x 18 mm x 0.75 mm, 45 mm x 18 mm x It is a laminate of a 1.5 mm thick A1050 Al alloy (D material) surface-treated product and a 45 mm × 18 mm × 3 mm thick A2017 All alloy (B material) surface-treated product. It is a layered adhesive.

The results of the temperature impact test in the preliminary experimental example were examined, and with these laminated composites, there is no problem even if an A5052Al alloy thin plate is inserted (intervened) between the 64Ti alloy and the A1050Al alloy in this experimental example. It was confirmed. When the 64Ti alloy and the A5052Al alloy thin plate are adhered, the A5052Al alloy thin plate of the "C" material is heated or cooled from the temperature impact test, and the 64Ti alloy thick plate is thick and has high rigidity. The plank expands and contracts following the expansion and contraction. Therefore, shear fracture internal stress occurs between the A1050Al alloy of the "D" material, which follows the thin plate of the A5052Al alloy of the "C" material due to its low rigidity and softness as it expands and contracts. be. If the internal stress here exceeds the adhesive force between A5052 and A1050, fracture will occur, but theoretically both have strong shear adhesive stickiness in their own test pieces, and the internal stress is elasticity in the A1050Al alloy. It is reduced by both physical deformation and plastic deformation (figurative). At the time of this experiment, A1050 uses a NAT-treated product, and A5052Al alloy thin plate uses a NAT7-treated product, so the adhesive force between the two should be sufficiently high.

[Experimental Example B11] Measuring the adhesive strength between the high-strength lumber thick plate and the thin plate material Next, the shear adhesive strength between the structural metal thin plate material and the titanium alloy material was measured. This is because the linear expansion rate of the titanium alloy material is 0.8 × 10 ^-5 K ^-1 , which is the smallest among the metals, and the other structural metal materials are ^{about 1.7 × 10 -5} K ^-1 even in SUS304, duralumin. Since all the aluminum alloys contained are ^{about 2.3 × 10 -5} K- ¹ , when these metal pieces and titanium material pieces are bonded with a one-component epoxy adhesive, usually high shear bonding strength cannot be obtained. This is because the curing conditions of the one-component epoxy adhesive are as high as 150 to 180 ° C. This is because a part of the adhesive curing layer is broken when the temperature is lowered to room temperature by allowing to cool after curing. The only way to obtain and maintain a strong adhesive state without destroying the cured adhesive is to make the metal material that adheres to the titanium material a thin plate to reduce its rigidity. However, in order to know how much thin plate can be used and how much metal material with proof stress and Young's modulus can be used, actually create an adhesive pair and measure its shear adhesion strength. Should be decided. FIG. 15 is an explanatory diagram showing how to make a test piece for this test. Since the thin plate material has no rigidity, it bends and deforms even when subjected to a shear test, so a member of the thick plate material is adhered to reinforce this (lower part of FIG. 15). In general, if the thickness of the metal piece is not set to 4 to 6 mm, the thin plate material side is deformed before shear fracture, and peeling occurs due to stress concentration due to the deformation, resulting in early fracture. Alternatively, the thin plate is torn and broken. Table 6 shows the measurement results of the shear bond strength and the shear bond stickiness when the titanium alloy material and the SUS or aluminum alloy are bonded.

Judging from the shear adhesive strength and shear adhesive tenacity values shown in Table 6, it is judged that the 0.28 mm thick SUS304 steel thin plate can be used as the "C" material. Further, the A5052 aluminum alloy can be used as long as it has a thickness of 0.75 mm or less, but if it is thinner and has a thickness of 0.5 mm, it will break when an external force in a strong shearing direction is applied, resulting in a structural material or an amplification material. It shows that the role of may not be fulfilled. Next, it is judged that the 0.5 mm thick A6061 aluminum alloy has no problem as a "C" material. What can be further said in this experiment is that when CFRP material or CFRTP material is used for "A" material, the difference in linear expansion coefficient between "A" material and "C" material becomes even larger than in this experimental series. That is. When the "C" material is an aluminum alloy, the linear expansion coefficient difference when the "A" material is a titanium material is 1.5 x ^10-5 K- ^1, whereas when the "A" material is a CFRP material, for example. Is 2.2 × 10 ^-5 K ^-1 , and the difference is increased by 50%. According to the data shown in Table 6, in the adhesion between the titanium alloy of the "A" material and the high-strength Al alloy of the "B" material, the "C" material that can most obediently follow the "A" material is 0. It turned out that a 75 mm thick Al alloy was preferable.

However, it is doubtful that a 0.75 mm thick Al alloy can be used for the "C" material in the bonded integral body that uses the CFRP material as the "A" material and the high-strength Al alloy as the "B" material. Become. That is, if the difference in linear expansion coefficient increases by 50%, it means that the thickness of the "C" material should be 0.5 mm, which is 1 / 1.5. According to this idea, what can be used as the "C" material is an aluminum alloy having a yield strength that does not cause the tearing phenomenon even at a thickness of 0.5 mm, which is not A5052 but at least A5083 or A6061Al alloy or higher. It is an aluminum alloy with proof stress. That is, according to the data shown in Table 6, it is judged that the A6061Al alloy having a thickness of 0.5 mm can withstand this performance requirement. Based on the same idea, if we infer the SUS304 steel thin plate, we can first use a thin plate with a thickness of 0.28 mm for the Ti alloy, but if this is used for adhesion to the CFRP material, the thickness will be 1 / 1.5. It should be 8 to 1.9 mm thick. However, it is a little difficult to obtain a SUS304 thin sheet of this thickness in the market, and the NAT type treatment, which is a chemical conversion treatment with SUS304 steel, reduces the thickness by about 0.02 mm on both sides, so the steel material itself. The chemical stability of the steel is also required to be particularly reliable. From these experimental results, it is considered that the present inventor should select an A6061Al alloy having a thickness of 0.5 mm as a standard use of the "C" material.

[Experimental Example B12] Preparation of all-adhesive structure containing A6061 thin plate and A1050 soft metal material between CFRP piece and duralumin material and temperature impact test (main test 2)
As can be seen from the data in Table 6 above, it was found that 0.5 mm thick A6061 aluminum alloy seems to be the most compatible as the "C" material. As the "D" material to be adhered to the "C" material, it seems that an A1050 aluminum alloy having a thickness of at least 1.5 mm can be used. In order to confirm this consideration with an actual bonded integrated product, CFRP (material A), aluminum alloy (material C), pure aluminum-based aluminum alloy (material D), and aluminum alloy (material B) as shown in FIG. ) Was laminated to create a bonded integrated product. Therefore, a fully bonded structure using a CFRP thick plate as the "A" material and an A2017 aluminum alloy thick plate as the "B" material was prepared, and this laminated bonded integrated product was subjected to a temperature impact of -50 ° C / + 150 ° C. Tested in a 3,000 cycle test.

However, in order to prevent an adhesion error from occurring in the adhesion between the CFRP material which is the "A" material and the "C" material, the method for producing the entire adhesive structure is as follows. That is, a CFRP piece (“A” material) having a thickness of 90 mm × 18 mm × 3 mm is bonded to an A6061 Al alloy thin plate (“C” material) having a thickness of 45 mm × 18 mm × 0.5 mm with an epoxy adhesive to form a composite plate material. A joint integrated product of CFRP material and A6061 Al alloy thin plate was prepared. In the manufacturing method, a 0.5 mm thick A6061 alloy thin plate was cut into the above rectangular shape in advance, treated with NAT7, and then thinly coated with the above-mentioned one-component epoxy adhesive "EW2040" on one side thereof. A Teflon sheet was pressed onto the coated surface, further placed in a polyethylene bag, sealed, and placed in a refrigerator at 5 ° C. for storage as an adhesive preparation. Using both this adhesive preparation and the CFRP prepreg "P225S-25" (manufactured by Toray Industries, Inc. (Headquarters: Tokyo, Japan)), a 45 mm x 18 mm A5052Al alloy thin plate with a thickness of 90 mm x 18 mm x 3 mm We outsourced the production to a processing specialist company so that CFRP thick plate shapes can be produced. This preparation was performed by an autoclave method, and heating was performed by designating the heating conditions to be 150 ° C. × 40 minutes.

The CFRP thick plate with the A6061 aluminum alloy thin plate thus obtained may have the exposed part of the A6061 alloy thin plate dirty due to these operations. Therefore, after polishing with # 600 sandpaper to obtain a metallic luster, With the CFRP plate adhered, the surface to which the CFRP was not adhered was subjected to NAT treatment. After this liquid treatment, a CFRP thick plate material with an A6061 alloy thin plate was prepared for the next process. In addition, a NAT7-treated 45 mm x 15 mm x 1.5 mm thick A1050 Al alloy and a NAT7 treated 45 mm x 18 mm x 3 mm thick A2017 Al alloy are prepared, and a one-component epoxy adhesive "EW2040" is used together with these. The three materials were surface-bonded by the NAT bonding (adhesion operation with soaking treatment is referred to in this way) method, and finally the shape shown in FIG. 10 was obtained. The joint integrated product shown in FIG. 10 was put into a temperature impact of 3,000 cycle test at −50 ° C./+ 150 ° C. As a result, no abnormality occurred on any of the adhesive surfaces.

[Experimental Example B13] Preparation of a large-sized all-adhesive structure The pure aluminum-based aluminum alloy, which is the "D" material in the present invention described above, was a member of a flat plate material. However, this "D" material is not a flat plate, but as shown in FIG. 13, the lower surface is a flat surface or a curved surface, and the upper surface is a plate-like body in which a large number of circular or square columnar objects are lined up in parallel. There may be. In the plate-like body of this example, the cross-sectional area of the circular or square columnar object is 0.05 to 0.25 cm ² . In this method of manufacturing a plate-like body, a thick plate of A1050Al alloy, which is a pure aluminum-based aluminum alloy, was machined and manufactured by machining with a tool such as a cutting saw so as to have the dimensions and shape shown in FIG. This plate-like body was subjected to NAT treatment according to Experimental Example A1 described above.

Further, a 200 mm × 100 mm × 0.75 mm A5052Al alloy thin plate piece was subjected to NAT7 treatment by the method described in [Experimental Example A2-1]. Further, using the above-mentioned CFRP prepreg "P225S-25" and the above-mentioned surface-treated A5052Al alloy piece with the one-component epoxy adhesive "EW2040", a CFRP thick plate piece having a thickness of 300 mm x 100 mm x 5 mm. On top of this, a CFRP plate with a metal plate in which 200 mm × 100 mm × 0.75 mm Al alloy thin plates match on one end face was produced by an autoclave method. Since the A5052Al alloy plate on the CFRP was dirty, the entire surface was polished with # 1000 sandpaper, and then the surface treatment of Experimental Example A2 was performed again while adhering to the CFRP plate.

Further, a 64Ti alloy thick plate piece having a thickness of 300 mm × 100 mm × 3 mm was obtained and prepared by surface treatment as described in Experimental Example A9. Then, all were completely bonded using the adhesive "EW2040". That is, an A5052Al alloy thin plate is adhered onto a 64Ti alloy plate, a three-dimensional product of the first obtained A1050Al alloy is adhered onto the A5052Al alloy thin plate, and a CFRP plate with an A5052Al alloy thin plate is further attached to the metal portion. It was glued so that it was on the bottom. With this, a large fully bonded structure having an area covered by the A1050Al alloy piece, that is, an apparent bonding area of 200 mm × 100 mm = 200 cm ^{2, was completed.}

This adhesive is similar to that shown in FIG. 5, except that the A1050Al alloy portion is not a simple plate material but a three-dimensional product with voids. Regarding the area ratio occupied by this gap, the actual adhesive area is 200 mm × 100 mm × (9/25) = 72 ^{cm 2 with} respect to the adhesive surface of 200 mm × 100 mm = 200 ^{cm 2,} which is 64%. This was applied to a temperature impact tester at −50 ° C./+ 150 ° C. for 3,000 cycles, and the surface where the upper part of the column was adhered was observed with a non-destructive inspection machine, but no peeling was observed.

[Experimental Example B14] Preparation of a large-sized all-adhesive structure An A1050Al alloy plate having a thickness of 3 mm was obtained and machined to obtain the shape shown in FIG. That is, a 200 mm × 100 mm thick plate is created by cutting a groove with a width of 2 mm and a depth of 2 mm into a circle while leaving the central part with a diameter of 10 mm as it is, and a lot of 3 mm wide circumferential walls are overlapped at intervals of 2 mm. bottom. Then, a large number of A1050Al alloy pieces with linear walls were surface-treated according to the same chemical conversion treatment as in [Experimental Example A1] described above.

On the other hand, instead of the CFRP material and A5052Al alloy thin plate used in Experimental Example B12, a surface-treated product of SUS304 stainless steel having a thickness of 300 mm × 100 mm × 3 mm (the same treatment method as in Experimental Example A7) and a surface-treated A5052Al alloy thin plate. A 0.75 mm thickness was prepared. ^{Using these, the three-dimensional shape of the 200 cm 2} large all-adhesive structure using the Fig. 10 shape shown in Experimental Example B11 and the A1050 Al alloy part, and the shape in which SUS304 steel is used instead of CFRP material are the same. I made an appearance thing. This was subjected to a 3,000 cycle test on a temperature impact tester at −50 ° C./+ 150 ° C., and the surface where the upper part of the column was adhered was observed with a non-destructive inspection machine, but no peeling was observed.

[Experimental Example C] Experiments and tests for additional adhesive strength improvement [Experimental Example C1] Practicing a new idea for improving the adhesive strength of A1050Al alloy Table 5 obtained in the above-mentioned [Experimental Example B7], and [Experimental Example] From the results in Table 6 obtained in [B11], it was found that the adhesive performance between the "A" material or the "B" material and the "C" material is the most important in the actual bonded integrated product of the present invention. The bonded integrated product of the present invention has been changed from the evaluation method based only on the shear adhesive strength to the evaluation method of the "shear adhesive tenacity" value, and the durability performance such as moisture and heat resistance has also been confirmed. However, when viewed as a bonded integrated product, the adhesive performance between the "A" material or the "B" material and the "C" material is not sufficient, but the basic performance required for the "D" material, that is, its softness and its softness. We thought that the adhesive performance of the epidermis should be reexamined.

In short, the data on the shear adhesion strength of the pure aluminum-based aluminum alloys A1085 and A1050 shown in Table 5 did not change significantly before and after the high-temperature and high-humidity test. In A1085, there was no change between 55 MPa, and in A1050, it decreased to 54 MPa before the test and 50 MPa after the test, but returned to the original at 54 MPa when dried. It is the moisture absorption of the cured adhesive, not the metal, that changes most with the application of high temperature and high humidity, indicating that the cured adhesive has softened slightly. Therefore, the fact that the adhesive strength did not change much in A1085 and A1050 means that the change in hardness of the cured adhesive was close to the hardness level of A1085 and A1050, so that when a tensile breaking force was applied, for example, the ground (metal side). ) And the nail (hardened adhesive) are close in hardness, so it is estimated that both the metal side and the hardened adhesive are deformed, which has the effect of delaying breakage. For hard metals, SUS304 and 64 titanium alloys in Table 5, the initial shear adhesion strength was around 60 MPa, but it dropped sharply to 43 to 45 MPa due to softening due to moisture absorption of the resin part. Then, in SUS304, the resin portion was dried to recover to 53 MPa. The present inventor understood that if the metal side was hard and the surface shape of the metal side did not change with high humidity, the shear bond strength fluctuated as in the case of SUS304. In short, the pure aluminum-based aluminum alloys A1085 and A1050 followed a different course from SUS304 and the like because of their softness.

Therefore, I expected what would happen if the final process of the surface treatment method of A1050 or A1085 was slightly changed to make only the epidermis harder. The outer skin of pure aluminum-based aluminum alloy, which is a soft metal, is hard, and the inside is soft. The epidermis should be harder and slightly thicker to leave the outer skin hard and the inside soft and soft. At least the same test as in Table 6 was carried out, and it was estimated that the state where the shear adhesive strength was 54 to 55 MPa, which was clearly lower than that of other materials, could be escaped. As a result, a test experiment was started on a new surface treatment method for A1050 aluminum alloy. The five items [Experimental Example A1-3] to [Experimental Example A1-7] in [Experimental Example A] are as described above after all the items of [Experimental Example A] and [Experimental Example B] are completed. After analyzing the data in Tables 5 and 6, an experiment different from the above-mentioned surface treatment method was performed. The experimental results are shown in Table 7. That is, the data shown in Table 7 is a chemical conversion treatment in which only the surface of the pure aluminum-based aluminum alloy is further cured.

Looking at the upper part of the data shown in Table 7, the final immersion time in the 5% concentration hydrogen peroxide solution for the NAT-treated product and NAT5-treated product was 5 minutes, but if it is set to 20 minutes, the NAT-treated product The shear bond strength increased from 57.5 MPa to 60 MPa, and the shear bond stickiness value did not change at around 50.5 MPa. On the other hand, in the NMT5 treated product, when the immersion in the hydrogen peroxide solution was changed from 5 minutes to 20 minutes, the shear adhesion strength increased from 55.5 MPa to 57 MPa, and the shear adhesion stickiness value increased from 51 MPa to 53.4 MPa. .. The largest change is in the anodized product, and the NAT-Ano treated product has a high shear adhesive strength of 68 MPa, and the shear adhesive tenacity value is also high, 57.5 MPa, and NAT5-Ano. The treated product has a shear adhesive strength of 63 MPa and a shear adhesive tenacity value of 54 MPa.

There is no doubt that the aluminum oxide thin layer on the surface was strengthened by long-term hydrogen peroxide treatment, and it was confirmed that it is effective to harden the outer skin and soften the inside of the "D" material. It was also confirmed that the surface layer of the A1050 alloy became an unsealed alumite by anodizing, and the structure had a harder surface layer, and exhibited surprisingly high shear adhesion strength and shear adhesion tenacity. In the case of other A6061 and A2024 aluminum alloys that are not pure aluminum-based aluminum alloys, there are many cases where there is no difference in shear adhesion stickiness between the reinforced product of hydrogen peroxide solution treatment and the anodized product. It is presumed to be a characteristic of soft aluminum alloy. In short, it was confirmed that in a soft metal such as A1050 aluminum alloy, the adhesive strength can be improved by undoubtedly increasing the hardness of the surface layer, and that it can be more reliably achieved by an anodizing method or the like.

Joined integrated products containing different types of structural materials can be applied to structures such as mobile machines such as aircraft and automobiles, and industrial machines such as machine tools.

Claims (19)

Two different types of FRP material, "A" material and "B" material selected from the structural metal material group are used at both ends.
It is an integrated product in which members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^-1 or more are joined with an adhesive.
The integrated product is
Between the "A" material and the "B" material, a plate-like product of a pure aluminum-based aluminum alloy having a thickness of 1.5 to 5.0 mm, which is a "D" material, or a structure of the pure aluminum-based aluminum alloy. It is a stack of things,
A joint integrated product containing dissimilar structural materials, which comprises three materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "D" material, and the "B" material. Two different types of FRP material, "A" material and "B" material selected from the structural metal material group are used at both ends.
It is an integrated product in which members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^-1 or more are joined with an adhesive.
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
A joint integrated product containing dissimilar structural materials, which comprises four materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, and the "B" material. Two different types of FRP material, "A" material and "B" material selected from the structural metal material group are used at both ends.
It is an integrated product in which members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^-1 or more are joined with an adhesive.
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to It is a plate-like product of 5.0 mm pure aluminum-based aluminum alloy.
A heterogeneous structural material characterized in that the joint surface is fixed and laminated in the order of the "A" material, the "C" material, the "D" material, the "C" material, and the "B" material. Joining integration including. The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
It is composed of four materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, and the "B" material.
The method of joining the FRTP material and the "C" material is to join the "C" material with a resin of the same type as the matrix resin of the FRTP material by an injection joining method, and then join the FRTP material. The resin is joined by heat fusion, and is
A joint integrated product containing a dissimilar structural material, wherein the joint surface of a joint other than the heat fusion is one that is joined by an adhesive. The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
It is composed of 5 materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, the "C" material, and the "B" material.
In the method of joining the FRTP material and the "C" material, a resin of the same type as the matrix resin of the FRTP material is joined to the "C" material by insert molding, and then the FRTP material and the resin are heat-sealed. It is joined and
A joint integrated product containing a dissimilar structural material, wherein the joint surface of a joint portion other than the heat fusion is one that is joined by an adhesive. In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 1 to 5.
The "D" material is a pure aluminum-based aluminum alloy, and is a bonded integrated product containing a dissimilar structural material, which is one selected from Japanese Industrial Standards A1080, A1085, and A1050. In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 2 to 5.
The "C" material is a bonded integrated product containing a dissimilar structural material selected from A5052 aluminum alloy, A5083 aluminum alloy, A6061 aluminum alloy, and SUS304 stainless steel of Japanese Industrial Standards. In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 1 to 5.
The joint surface is a joint integrated product containing dissimilar structural materials, which comprises one or more surfaces selected from a flat surface, a curved surface, and a cylindrical surface. In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 1 to 8.
The "D" material is a plate-like body having a flat surface or a curved surface on the lower surface and a large number of circular or square columnar objects having a ^{cross-sectional area of 0.05 to 0.25 cm 2 standing side by side on the upper surface.} A joint integrated product containing dissimilar structural materials. In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 1 to 8.
The lower surface of the "D" material is a flat surface or a curved surface, and a large number of walls having a thickness of 3 to 5 mm are standing on the upper surface at intervals of 2 to 3 mm, or wall-shaped protrusions having a thickness of 3 to 5 mm. A joint integrated product containing dissimilar structural materials, characterized in that the walls of the above are plate-like bodies having concentric wall-shaped protrusions at intervals of 2 to 3 mm in width. In the joint integrated product containing dissimilar structural materials according to claim 10.
The center of the concentric wall-shaped protrusion is a joint integrated product containing a different type of structural material, characterized in that a portion of 1 to 5 ^{cm 2 is a circular thick plate having a thickness of 1 to 5 mm.} In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 2 to 5.
In the bonding between the five materials of the "A" material, the "B" material, the "C" material, and the "D" material, all the adhesive hardening layers existing in the joint portion joined by the adhesive are all. A bonded integrated product containing a dissimilar structural material, which comprises a cured layer of a one-component epoxy adhesive or a cured layer of a two-component epoxy adhesive. In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 2 to 5.
In the case where four or more materials of the "A" material, the "B" material, the "C" material, and the "D" material are joined, a part is clad instead of the joint portion joined by the adhesive. A joint integrated product containing dissimilar structural materials characterized by being a joint. In the joint integrated product containing the dissimilar structural material according to claim 12 or 13.
The one-component epoxy adhesive is a heat-resistant one-component epoxy adhesive having a shear adhesion strength of 50 MPa or more at 23 ° C. and 25 MPa or more at 150 ° C. in a tensile break test. A joint integrated product containing different types of structural materials. A bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 1 to 14.
The "A" material and the "B" material are CFRP material and titanium alloy material, CFRP material and general steel material, CFRP material and stainless steel material, CFRP material and high-strength aluminum alloy material, GFRP material and high-strength aluminum alloy material. , CFRTP material and titanium alloy material, CFRTP material and general steel material, CFRTP material and stainless steel material, CFRTP material and high strength aluminum alloy material, titanium material and general steel material, titanium material and stainless steel material, titanium material and high strength aluminum alloy material, A heterogeneous structure characterized by being one selected from general steel and stainless steel, general steel and high-strength aluminum alloy, ferrite-based stainless steel and austenite-based stainless steel, and stainless steel and high-strength aluminum alloy. Joined alloy containing material. In the bonded integrated product containing the dissimilar structural material according to claim 1, which is selected from claims 4 to 13.
The FRTP of the "A" material is CFRTP, and
The resin is a highly crystalline thermoplastic synthetic resin composition having a thickness of 0.5 mm or more, and the total thickness of the "C" material and the resin is a composite plate having a thickness of 2 mm or less.
The bonding between the "A" material and the "C" material is obtained by fixing the CFRTP matrix resin and the highly crystalline thermoplastic synthetic resin composition by heat fusion.
The "B" material is a bonded integrated product containing a dissimilar structural material, which is one selected from a titanium alloy material, a general steel material, a stainless steel material, and a high-strength aluminum alloy material. In the bonded integrated product containing different structural materials according to claim 15.
The high-strength aluminum alloy material is duralumins selected from Japanese industrial standards A2014, A2017, A2024, and A7075, or one type of aluminum alloy selected from Japanese industrial standards A5052, A5083, A6061, and A6063. A bonded integrated product containing dissimilar structural materials. The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
It is a method for manufacturing a joint integrated product containing dissimilar structural materials consisting of four materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, and the "B" material. hand,
In order to bond a resin of the same type as the matrix resin of the FRTP material to the "C" material, the "C" material is inserted into a mold, and then the resin is injected to bond the FRTP material and the "C" material. Injection joining process to join and
After the injection joining, a heat fusion step of joining the FRTP material and the resin by heat fusion,
The other joint is a method for manufacturing a joint integrated product containing dissimilar structural materials, which comprises a joining process method using an adhesive. The FRTP material is "A" material, and two different types of "B" material selected from the structural metal material group are used at both ends.
It is an integrated product obtained by joining members having a difference in linear expansion coefficient between the "A" material and the "B" material of 0.3 × ^10-5 K ^{-1 or more.}
The integrated product is
Between the "A" material and the "B" material, a thin plate of a metal material having a proof stress of more than 150 MPa, which is a "C" material, and a thickness of 1.0 mm or less, and a "D" material having a thickness of 1.5 to A 5.0 mm pure aluminum-based aluminum alloy plate-like material or a structure in which the above-mentioned "C" material is laminated.
A joint integrated product containing five different structural materials in which the joint surfaces are fixed and laminated in the order of the "A" material, the "C" material, the "D" material, the "C" material, and the "B" material. It is a manufacturing method of
In order to bond a resin of the same type as the matrix resin of the FRTP material to the "C" material, the "C" material is inserted into a mold, and then the resin is injected to bond the FRTP material and the "C" material. Injection joining process to join and
After the injection joining, a heat fusion step of joining the FRTP material and the resin by heat fusion,
The other joint is a method for manufacturing a joint integrated product containing dissimilar structural materials, which comprises a joining process method using an adhesive.

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