TW201141696A - Aluminum-bonded composite material and method of manufacturing the same - Google Patents

Abstract

To provide an aluminum-bonded composite material and a method of manufacturing the same wherein an aluminum form body and a metal or resin-bonded body are integrally bonded through an adhesive layer, and boundary surface adhesion strength between the aluminum form body and adhesive layer is very high, and excellent durability can be exhibited. The aluminum-bonded composite material includes the aluminum form body 1 having protruded and recessed parts on a part or the whole of a surface, the metal or resin-bonded body positioned on the surface side, and the adhesive layer 2 bonding the aluminum form body 1 to the bonded body. A plurality of recessed parts 3 (forms a-d) due to the protruded and recessed parts are formed on the surface of the aluminum form body 1, and a fit-in part of the adhesive layer 2 in which the adhesive enters and is solidified is formed in the recessed part, and the aluminum form body 1 and the adhesive layer 2 are fitted with each other by the recessed part 3 and the fit-in part.

Description

[Technical Field] The present invention relates to an aluminum-shaped composite material made of aluminum or an aluminum alloy integrally bonded to a coating layer made of metal or resin, and a method for producing the same, which can be used in a wide range of fields. Aluminium-adhesive composite material having a moderately different adhesive strength and a method for producing the same (previous art) Among various parts for automobiles, parts for building materials for home electric appliances, building materials parts, and the like, excellent in workability and corrosion resistance, and Lightweight aluminum material, but some parts require insulation and heat insulation. Thermal and thermal insulation must be part of the aluminum or integral or insulated components. Since the past, metal and metal, metal and resin Q adhesives have been proposed as a general technique. The surface roughness (Rmax) is about gold, and the organic resin or organic-inorganic composite resin is used. Laminated aluminum foil foil. Further, Patent Document 2 proposes a method of polymerizing, characterized in that a sheet is heated and melted after laminating a polyorganoamide sheet of 1 to 100 mg/m 2 of an epoxyorganophthalene coupling agent. Further, in Patent Document 3, a metal adhesive is proposed to be used for the adhesive bonding of the aluminum surface to obtain a superior component, various heat conductivity or electrical conductivity, and on the other hand, the aluminum material is bonded to the insulating member for imparting the spacer. Used. For example, the patent application of 18 μm of the inlaid or brocade-adhesive metal foil is applied to the surface of the aluminum plate of the special amine laminated aluminum plate to adhere the overlapping polyimide, and its characteristics are: in the case of a water-soluble reducing agent. The metal shape is impregnated into the aqueous solution. The metal shape lifted from the aqueous solution is washed with water and dried to be used as an adherend. Further, in Patent Document 4, an adhesive composite containing a metal alloy is proposed, which is characterized in that it has a coarse degree of sugar formed by chemical contact, and its surface is an irregular period of 5 to 5 〇〇 11111. a shape covered by a minute uneven shape, and a metal part whose surface is a metal oxide or a metal phosphorus oxide thin layer; an adhesive material adhered to the metal part; and an adhesion to the metal part and the adhesive material The adhesive layer of the cured product of the one-component thermosetting resin adhesive to which the two are adhered is formed. However, when the adhesive is used, there is a case where the joint strength is insufficient, especially aluminum and metal. In the case of adhesion of aluminum and resin, the joint strength of the interface of the aluminum-adhesive layer when exposed to an excessively harsh environment may be insufficient. In the aluminum-adhesive composite using an adhesive, an aluminum-adhesive layer is developed. The interface bonding strength is excellent for aluminum bonded composites. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 09-169, No. [Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-061, No. 048 (Convention) -6-201141696 [Problems to be Solved by the Invention] Therefore, the present inventors directed the metal through the adhesive layer. The aluminum-adhesive composite material in which the surface of the aluminum-shaped body made of the aluminum or the aluminum alloy is integrally bonded to the bonded body made of a resin or the like, provides an interface bonding strength between the aluminum adhesive layer which can be produced, and exhibits excellent durability. As a result of further investigation of the aluminum-adhesive composite, it was found that a specific surface shape in which a concave portion is formed on the surface of the aluminum-shaped body by etching treatment can significantly improve the joint strength between the aluminum-shaped body and the adhesive layer 0. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide an aluminum-shaped body and an adhesive layer in which an aluminum-shaped body made of aluminum or aluminum alloy and an aluminum-adhesive composite material made of metal or resin are integrally bonded through an adhesive layer. An aluminum adhesive composite having excellent interfacial bonding strength and exhibiting excellent durability. Further, another object of the present invention is to provide an aluminum-shaped body made of aluminum or aluminum alloy integrally bonded to a metal or through an adhesive layer. In the adhesive-bonded aluminum-adhesive composite material, the interface between the aluminum-shaped body and the adhesive layer is extremely high, and the aluminum adhesive composition which exhibits excellent durability can be produced. In other words, the aluminum-adhesive composite material of the present invention comprises: a part of the surface or an aluminum-shaped aluminum or aluminum alloy having a concavo-convex portion; and a metal or resin layer on the surface side of the aluminum-shaped body; And an aluminum-adhesive composite comprising an adhesive layer between the aluminum-shaped body and the adherend and integrally bonded between the aluminum-shaped body and the adherend, characterized in that: 201141696 The surface of the aluminum-shaped body is formed with a plurality of concave portions due to the uneven portion, and an adhesive portion in which the adhesive enters the adhesive layer solidified in the concave portions is formed, by the concave portion The embedding portion engages the aluminum-shaped body and the adhesive layer with each other. Further, the in-situ composite material of the present invention comprises: a part of the surface or an aluminum-shaped aluminum or aluminum alloy having a concave-convex portion; a metal or resin adherend on the surface side of the aluminum shaped body; and an aluminum containing an adhesive layer between the aluminum shaped body and the adherend and integrally bonded between the aluminum shaped body and the adherend The adhesive composite material is characterized in that a plurality of concave portions due to the uneven portion are formed on a surface of the aluminum-shaped body, and each of the concave portions is perpendicular to the thickness direction in a thickness direction cross section of the aluminum-shaped body, and In the half line between the top line passing through the highest portion of the uneven portion and the bottom line passing through the deepest portion, the width of the opening measured by scanning electron microscopic observation is a size below 30 μm of Ο.ίμιη, and the depth is Ο.ίμηι The above-mentioned size of 30 μm or less is formed in the concave portion to form an embedding portion of the adhesive layer which is adhered to the post-curing adhesive layer, and the aluminum-shaped body and the concave portion are formed by the concave portion and the embedded portion. Engaged with each other with the adhesive layer. Further, the method for producing an aluminum-adhesive composite according to the present invention comprises: a part of the surface or an aluminum-shaped body made of aluminum or an aluminum alloy having a concavo-convex portion; a metal or resin made on the surface side of the aluminum-shaped body; And an aluminum-adhesive composite comprising an adhesive layer between the aluminum-shaped body and the adherend and integrally bonded between the aluminum-shaped body and the adherend, characterized in that: The aluminum alloy material is etched to form a part of the surface or a plurality of aluminum shapes which are caused by the plurality of concave portions of the uneven portion. The surface of the shape body is formed by adhesion through an adhesive. When the adhesive is adhered, the adhesive is inserted into each concave portion of the aluminum-shaped body to form an adhesive portion of the adhesive layer, and the concave portion of the aluminum-shaped body and the embedded portion of the adhesive layer are engaged with each other to form an aluminum shape. The aluminum-adhesive composite in which the body and the adhesive layer are integrally combined. In the present invention, the aluminum or aluminum alloy material for forming an aluminum-shaped body may, for example, be a rolled material, an extruded material, a die-cast material, a cast material or the like. Specifically, a pure A1 1000 system, an Al-Cu 2000 system, an Al-Mn 3000 system, an Al-Si 4000 system, an Al-M 5000 system, an ADC 5 and an ADC 6 can be exemplified. Al-Mg-Si 6000 system, Al-Zn-Mg system 7000 system, Al-Fe system 8000 system, Al-Si-Mg system ADC3, Al-Si-Cu system ADC10, ADC10Z, ADC12 and A material obtained by a material such as an ADC 12Z or an Al-Si-Cu-Mg-based ADC 14 is appropriately processed into a processed material obtained in a predetermined shape, and a composite material obtained by processing the materials is appropriately combined. Further, in the present invention, the plurality of concave portions formed on the surface of the aluminum body by the uneven portion on the surface of the aluminum body may be a hole or a hole having an open end edge portion having an end edge portion (having The concave portion of the end opening portion may have a slit shape or a groove shape (a concave portion having an end opening edge portion) having both end portions, and may be mixed with the endless opening edge A hole or a hole of a portion and a slit or groove having an edge of the end opening. Further, the plurality of concave portions of the aluminum-shaped body are formed with a projection portion that protrudes in a snow-like shape from a part or the whole of the opening edge portion of the concave portion toward the center in the opening width direction. Therefore, the width of the opening -9 - 201141696 of the concave portion is narrower than the width of the inner portion thereof, so that the fitting portion of the adhesive layer which has been solidified into the concave portion is formed to be inseparable from the concave portion. The structure is such that one or both of the fitting portions of the adhesive layer of the concave portion of the aluminum-shaped body are not broken, and the joint strength between the aluminum-shaped body and the adhesive layer can be further improved. In the present invention, a plurality of concave portions formed by the uneven portions on the surface of the aluminum-shaped body are described in the first view of the mode, and the thickness of the aluminum-shaped body 1 in the cross-section of the aluminum-shaped body 1 is described with reference to the first drawing. The direction is orthogonal, and the width of the opening (d) is observed by a scanning electron microscope through a half line (HL) between the top line (TL) of the highest portion of the uneven portion and the bottom line (BL) passing through the deepest portion. It is ι.ιμηι or more 3〇μπ1 or less, and is more preferably 05μηι or more and 20μιη or less. 'The best size is 1 ιηη or more, and the depth is Ο. ίμιη or more 30μιη or less, 〇.5μπι or more and 20μηι or less. It is better. When the opening width (d) of the concave portion is narrower than 〇·1 μηη, the adhesive is difficult to enter during the adhesion of the adhesive, and fine voids are formed at the interface between the aluminum-shaped body 1 and the adhesive layer to obtain excellent joint strength. On the contrary, when it is wider than 30 μm, the surface treatment (etching treatment) of the aluminum body 1 causes excessive dissolution reaction, which may cause the surface of the material to fall off or the thickness of the material to decrease. The problem 'causes a product with insufficient material strength to cause a decrease in productivity. When the depth is also shallower than 〇μιη, it is difficult to obtain a sufficient embedding layer of the adhesive layer. Conversely, when the depth is greater than 111, the surface treatment (etching treatment) of the inscription body 1 may cause excessive dissolution reaction. There is a problem of causing the surface of the material to fall off or the thickness of the material to decrease. -10- 201141696 In the present invention, the density of the plurality of concave portions formed by the uneven portions on the surface of the aluminum-shaped body is one in the range of 0.5 μm to 20 μm and a depth of 0.5 μm to 20 μm per 0.1 mm square opening width. Or two or more sizes may exist in the range of about 5 to 200. Further, in the aluminum-shaped body of the present invention, the snow-like projecting portion formed in the concave portion thereof is formed in the thickness direction cross section of the aluminum-adhesive composite material from the adhesive layer side toward the aluminum-shaped body side. When a plurality of observation lines extending in the thickness direction of 0 are drawn at intervals of 1 μm, at least one or more laminated portions formed of an adhesive-aluminum-adhesive agent are formed on the observation line, and the aluminum-shaped body portion of the laminated portion is formed. The thickness of the parts is preferably Ο. ίμιη or more in the range of 30 μηι or less, and one or more sleigh-like projections may be present in the range of the observation line of the aluminum adhesive. Further, in a part or all of the plurality of concave portions of the aluminum-shaped body, the inner wall surface may have a double concave portion structure forming at least one inner concave portion or may be formed on the inner wall surface. At least one of the inner concavo-convex structures of the inner protrusions on the Q may have the double recessed structure and the inner concavo-convex structure. In a part or all of the plurality of concave portions of the aluminum-shaped body, since the above double recessed structure and the internal uneven structure are present, the concave portion of the aluminum-shaped body and the embedded portion of the adhesive layer can be more mutually It is firmly bonded to give a more excellent joint strength between the aluminum body and the adhesive layer. In the present invention, when manufacturing the above aluminum-adhesive composite material, first, an aluminum-shaped body having the plurality of predetermined concave portions described above is formed on the surface, and the method may be, for example, a part of the surface of the aluminum alloy material which is subjected to an etching treatment. Part or full -11 - 201141696 A method of forming an uneven portion and forming an aluminum-shaped body having a plurality of concave portions due to the uneven portion. Further, examples of the etching liquid used for the etching treatment of the aluminum alloy material include hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, oxalic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, formic acid, lactic acid, isobutyric acid, malic acid, An etching solution made of a hydrogen-oxygen solution such as propionic acid or tartaric acid, but forming a plurality of concave portions having a predetermined width in order to form an opening width and a depth, or forming an orientation at a part or all of the opening edge portion of the concave portion a snow-like projection or the like protruding from the center in the width direction direction controls the concave portion formed on the surface to a predetermined shape and size, and uses a hydrogen-oxygen solution having a weak oxidizing power as a hydrogen-oxygen solution, and the oxidizing power is relatively high here. In the weak hydrogen-oxygen solution, an etching solution containing a predetermined concentration of halide ions must be used to dissolve the oxide film formed on the surface of the aluminum alloy material. That is, as the etching liquid, one or two kinds of chlorine ions (cr), fluorine ions (F_), and iodide ions (Γ) selected in a predetermined concentration range in a hydrogen-oxygen solution having a weak oxidizing power can be used. The above etching solution of halide ions. When the aluminum alloy material is immersed in the etching liquid using a hydrogen-oxygen solution having a weak oxidizing power containing a halogen ion, first, the halogen ion in the etching liquid dissolves the oxide film on the surface of the aluminum alloy material, and then dissolves the aluminum inside. The alloy is further immersed in the interior of the aluminum alloy material. However, at this time, the inner aluminum alloy is more likely to be etched (easy to dissolve) than the surface oxide film. Therefore, the composition of the etching liquid or the etching treatment conditions can be set, and the formation can be caused by the formation. The concave portion of the uneven portion on the surface is controlled to have a predetermined width or depth, or a portion of the opening portion of the surface is formed with a snow-like projection projecting toward the center in the opening width direction. -12- 201141696 The etching liquid used for this purpose is specifically, for example, an oxygen concentration of 0.1% by weight or more and 80% by weight. / ό ' 并 5 5% 5% by weight or more of 50% by weight or less of aqueous hydrochloric acid solution, phosphoric acid aqueous solution, dilute sulfuric acid aqueous solution, aqueous acetic acid solution, or oxygen concentration of 5% by weight or more and 30% by weight or less 'and 10% by weight The oxalic acid aqueous solution or the like of the above-mentioned 20% by weight or less is preferably used as the halide added for the introduction of the acidic aqueous solution of the halide ion, and examples thereof include chlorine such as sodium chloride, potassium chloride, magnesium chloride or aluminum chlorate. A fluoride such as a compound or calcium fluoride, or a bromide such as potassium bromide or the like is preferably a chloride in consideration of safety. Further, the concentration of the halide ion in the etching solution is usually 〇5 g/L (g/L) or more and 30 〇g/L or less, and preferably lg/L or more and 200 g/L or less, and less than 〇5 g/ In the case of L, the effect of the halide ion is small, and there is a problem in that the concave portion having the ferrule-like projection cannot be formed at the edge of the opening, and in the case of the surface treatment (etching treatment) of the aluminum-shaped body when the temperature exceeds 300 g/L The dissolution reaction proceeds abruptly, resulting in a problem that control of the concave portion is difficult. Further, in the present invention, an etching solution for forming a predetermined concave Q-shaped portion on the surface of the shape-shaped body, an aqueous acid solution having a relatively strong oxidizing power such as nitric acid or concentrated sulfuric acid having a concentration of more than 80% by weight, or sodium hydroxide or hydroxide An alkaline aqueous solution such as potassium is not suitable. The aqueous acid solution having a relatively strong oxidizing power has a film forming ability for the aluminum alloy, and conversely, a strong oxide film is formed on the surface of the aluminum body, which causes difficulty in dissolving the oxide film of the halide ion. Further, the dissolution mechanism of the aluminum alloy in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide is a fully soluble type, and does not change its tendency even when a halogen ion is added, and forms a concave portion having a predetermined shape or size. It is difficult. In the present invention, the processing conditions in the etching treatment of the surface of the aluminum alloy material-13-201141696 using the etching liquid described above are based on the type of the etching liquid to be used, the acid concentration, the halide ion concentration, or the like, or the plural required for the aluminum body. Although the number, size, and the like of the concave portions are different, in general, in the case of an aqueous hydrochloric acid solution, the immersion time is 1 to 30 minutes at a bath temperature of 20 to 80 ° C, and in the case of a phosphoric acid aqueous solution at a bath temperature of 30 to 80 ° C, the immersion time is 1 ~5 hours, sulfuric acid aqueous solution, bath temperature 40~80 ° C immersion time 2~8 minutes, oxalic acid aqueous solution, bath temperature 50~80 °C immersion time 1~3 minutes, acetic acid aqueous solution, bath temperature 50~80 °C immersion time can be 1~3 minutes. The higher the acid concentration or bath temperature of the etching solution used, the more remarkable the effect of the etching treatment, and the treatment can be performed in a short time. However, when the bath temperature is lower than 2 〇 ° C, the dissolution rate is gradually reduced to a sufficient size (opening width and The concave portion of the depth requires a long time, and when the bath temperature exceeds 8 〇 ° C, the dissolution reaction is sharply performed in the control of the opening width and depth of the concave portion, and the immersion time is less than 1 minute. The control of the opening width and depth of the portion is difficult, and conversely, the immersion time exceeding 30 minutes leads to a decrease in productivity. In the present invention, when the aluminum alloy material as described above is subjected to an etching treatment to form an aluminum-shaped body having a concave portion, the surface of the aluminum alloy material before the etching treatment may be degreased or surface-adjusted or surface-attached as needed. For the purpose of removing substances, contaminants, etc., the acid treatment is carried out by acid treatment and/or pretreatment by alkaline treatment with an alkaline aqueous solution. Here, as the aqueous acid solution used in the pretreatment, a preparation such as a commercially available acidic degreaser, a mineral acid such as sulfuric acid, nitric acid hydrofluoric acid or phosphoric acid, or an organic acid such as acetic acid or citric acid, or A mixture of an acid reagent such as a mixed acid obtained by mixing the acids, and the like, and, as an alkaline aqueous solution, a preparation such as a commercially available alkaline degreaser or an alkali reagent such as caustic soda can be used. The preparation or the mixture of the substances and the like. The operation method and processing conditions for pretreatment using the above aqueous acid solution and/or aqueous alkali solution are conventionally the same as the operation method and treatment conditions for pretreatment with an acid aqueous solution or an aqueous alkali solution of this kind, for example, a dipping method, It is carried out by a method such as a spraying method. Further, after the surface treatment of the aluminum alloy material is subjected to the above-described pretreatment, or after the etching treatment for forming the concave portion is performed, if necessary, a water washing treatment may be applied, which may use industrial water, ground water, or tap water. Ion exchange water or the like can be appropriately selected depending on the aluminum shape to be produced. In addition, the aluminum alloy material to which the pretreatment or the etching treatment is applied may be subjected to a drying treatment if necessary, but for the drying treatment, in addition to natural drying at room temperature, it may be forced by using a blower, a dryer, an oven, or the like. dry. The surface of the aluminum-shaped body obtained by the above-described etching treatment, or the previous treatment and etching treatment, is formed by etching treatment to form a concave-convex portion, and the surface of the surface is glossed at a 60-degree surface (the digital angle of the SUG A test machine company) The gloss meter measurement is preferably 60 or less. When the surface glossiness exceeds 60, the adhesive does not sufficiently enter the concave portion of the aluminum-shaped body at the time of the adhesion of the adhesive, and sufficient adhesion between the aluminum-shaped body and the adhesive layer cannot be obtained. Further, the surface of the aluminum-shaped body obtained by the above-described etching treatment, or the previous treatment and the etching treatment was observed by a SEM or an optical microscope at a magnification of 1 〇〇〇, and a photograph of the obtained cross-section was observed. The surface area of the body is preferably 1.2 times or more and 10 times or less of the area of the aluminum alloy material before the formation of the uneven portion by the engraving treatment. When the surface area increase rate is less than 1.2 times or more than 1 time, the adhesive does not sufficiently enter the concave portion of the aluminum-shaped body when the adhesive is applied, and sufficient adhesion between the aluminum-shaped body and the adhesive layer cannot be obtained. . Next, in order to obtain the aluminum adhesive composite of the present invention, a metal or resin adherend is bonded to the aluminum body obtained as described above through the adhesive layer, but the adherend may be bonded to the adherend. Prior to this aluminum body, the surface treatment of the aluminum body was performed in advance. For the surface treatment of the aluminum body, an acid solution containing an hydrazine compound and/or an alkaline aqueous solution or a commercially available chromium-free treatment agent may be used. By performing such surface treatment, it is expected that the adhesion between the surface of the aluminum-shaped body and the adhesive layer formed thereon is more effective. The acid solution and/or the alkali solution containing the ruthenium compound may, for example, be an acid solution containing phthalic acid gel or an alkali solution containing bismuth citrate or the like. An example of a commercially available chromium-free treatment agent is, for example, SURF registered trademark of Japan Paint Co., Ltd., SURFCOAT, and PALCOAT manufactured by Japan PARKERIZING. An adhesive layer is disposed between the aluminum-shaped body and the adherend, and the method of integrally bonding the aluminum-shaped body and the adherend is an aluminum-shaped body and/or an adhesive for adhering the adhesive, and the applied adhesive is sandwiched between In this case, it is preferable that the aluminum-shaped body and the adherend are adhered under pressure to cure the adhesive, but the adhesive is effectively introduced into the concave portion of the aluminum-shaped body to increase the aluminum-shaped body and the adhesive as much as possible. The bonding strength of the interface between the layers may be such that the aluminum-shaped body and the adherend are adhered to each other by applying an adhesive on both the aluminum-shaped body side or the aluminum-shaped body side and the adherend side. Moreover, in order to improve the bonding strength of the interface between the adherend and the adhesive layer, the type of the adhesive to be used may be selected depending on the material of the adhesive to be used, or the aluminum may be formed on the side of the adhesive. In the case of the shape body, the same concave portion is such that the concave portion and the insertion portion formed on the t occupying agent layer are locked. The coating method for the adhesive may be carried out by, for example, a latex coating method, a spray coating method, a dipping method, a brush coating method, a roll coating method, or the like, or a post-coating method. And after the adhesion of the adhesive, before the hardening, the intended metal or resin f) adherend is bonded. For the curing treatment of the adhesive after adhering to the adherend, a drying method depending on the type of the adhesive, for example, drying at a normal temperature or drying and drying using a blower, a dryer, an oven or the like may be employed. An adhesive layer is formed between the aluminum body and the adherend, thereby producing an intended aluminum adhesive composite. In the present invention, an aluminum-adhesive composite material which is particularly preferably bonded is an aluminum-adhesive composite material which is bonded to a part of the surface of the aluminum-shaped body through an adhesive layer. In the present invention, the adhesive for forming the adhesive layer formed between the aluminum body and the adherend is not particularly limited, and a preferred example thereof is a nitrile rubber type or a synthetic rubber. The epoxy resin is a cyanoacrylate, a vinyl chloride, a plastic, or a hot melt. In the present invention, the thickness of the adhesive layer formed between the aluminum-shaped body and the adherend may be appropriately selected depending on the purpose of use of the aluminum-adhesive composite, etc., but it is usually 5 μm or more and 5 mm or less, and is ΙΟμπι or more. 2000μηη or less is preferable, and when it is thinner than 5μηι, sufficient joint strength cannot be exerted. Conversely, when it is thicker than 5mm, only the effect is saturated and the durability is still unchanged. -17- 201141696 Also, the aluminum alloy shape is bonded to the adhesive layer. The metal adherend on the surface of the body is suitably selected depending on the application, but a preferred example is a metal such as aluminum, iron, copper, zinc or magnesium or an alloy thereof. In the case where the metal bonded through the adhesive layer is aluminum, the aluminum body having the concave portion may be subjected to the etching treatment of the present invention. When the bonding metal is made of aluminum other than the adhesive, the etching treatment of the acid or the alkali solution, the roughening of the blasting paper, the honing treatment, the cleaning treatment of the solvent, the surfactant, etc. may be performed. Adjust the surface. In addition, a resin such as a thermoplastic resin, a thermosetting resin, or a room temperature curing resin can be widely used as the resin-made adherend which is bonded to the aluminum-shaped body through the adhesive layer, and the thermoplastic resin may, for example, be a polypropylene resin or a polyethylene resin. , polyarylene sulfide resin such as acrylonitrile-butadiene-styrene copolymer (ABS), polycarbonate resin, polyimide resin, polyphenylene sulfide (PPS), polyacetal resin, liquid crystalline resin Polyester resins such as polyethylene terephthalate (P ET ) and polybutylene terephthalate (PBT ), polyoxymethylene, polyimide resin, syndiotactic polystyrene resin, etc. For example, a thermosetting resin may be, for example, an epoxy resin, and the room temperature curable resin may, for example, be a polyester resin. These resins may also be subjected to a cleaning treatment by alkali solution, a solvent, an surfactant, or the like, or by roughening or honing the surface by sandblasting, honing, or the like before the adhesion. [Effect of the Invention] The aluminum-adhesive composite of the present invention has an extremely high joint strength (aluminum/adhesive interface) between the aluminum-shaped body and the adhesive layer, and can be exposed even in an excessively harsh environment. Maintaining its excellent durability, it maintains high reliability for a long period of time. Therefore, the aluminum-adhesive composite material of the present invention can be suitably used, for example, for interior and exterior decoration of a building, various building members such as a high-rise building outer wall or interior decoration, road materials, various casings, refrigerated 'freezer container interior and exterior decoration, and freezing. Display cabinets, automotive parts, electrical and electronic parts, home appliances, various daily necessities, and other products in a wide range of fields. [Embodiment] Hereinafter, embodiments of the present invention will be specifically described based on examples and comparative examples. Further, the present invention is not limited to the examples described below. [Example 1] [Preparation of aluminum-shaped body] An aluminum sheet (aluminum alloy material) having a size of 50 mm x 50 mm was prepared from an aluminum alloy (JIS A 1 050-H24) plate having a thickness of 1.0 mm, and for these aluminum sheets, first, at 3 The Owt% aqueous solution of nitric acid was immersed at room temperature for 5 minutes and thoroughly washed with ion-exchanged water, followed by washing in a 5 wt% sodium hydroxide solution at 5 (TC for 1 minute, and after immersing for 3 minutes at room temperature for 30 minutes in a 30 wt% aqueous solution of nitric acid). Pre-treatment of the cleaning. Next, for the aluminum sheet after the pretreatment, 54 g/L of aluminum chloride hexahydrate (A1C13 · 6H20) was added to a 2.5 wt% aqueous hydrochloric acid solution to prepare an etching solution (chloride ion concentration: 48 g/L) was immersed at 66 ° C for 4 minutes and then subjected to a cleaning etching treatment. Further, it was washed with a 30 wt% aqueous solution of nitric acid at a temperature of -19 - 201141696 for 3 minutes, and dried with hot air at 120 ° C. 5 minutes, an aluminum-shaped body for the preparation of a boiling water test and a salt spray test. [A concave portion of the surface of the aluminum-shaped body is observed.] For the obtained aluminum-shaped body, a scanning electron microscope (FE) is used. -SEM, S-45 00 type) observe it In the cross section of the region in the thickness direction, the cross section in the thickness direction of the aluminum body is orthogonal to the thickness direction, and the top line (TL) passing through the highest portion of the uneven portion is determined, and then the same as the above-mentioned large 槪Crossing the thickness direction of the aluminum body, and determining the bottom line passing through the deepest portion of the uneven portion, and drawing a straight line from the top line (TL) toward the vertical direction of the bottom line (BL), passing through the middle portion of the line, and The distance between the gap between the aluminum-shaped body and the aluminum-shaped body on the half line (HL) in which the top line (TL) [or the bottom line (B1)] is drawn in parallel is taken as the opening width (d) of the concave portion, and the cause of observation is observed. The shape and size (opening width and depth) of the concave portion formed on the uneven portion on the surface of the aluminum-shaped body were measured, and the cross-section of a certain region of the aluminum-shaped body after observation was as shown in the cross-sectional view of Fig. 1 . A typical example of the shape of the concave portion as viewed from the first drawing is as shown in Fig. 2, and has a projection which protrudes from a portion of the opening edge toward the center in the width direction of the opening. Concave part (shape a: ginseng (Fig. 2(a))) has a concave portion (shape b: see Fig. 2(b)) from the entire opening edge portion toward the center of the opening width direction. -20-201141696 concave portion (shape C: see Fig. 2(c))' of the double concave portion structure of the concave portion and the concave portion having the inner concave and convex structure forming the inner protrusion portion (shape d: Referring to Fig. 2(d), the concave portions of all the shapes a to d in the first embodiment are observed, and the shape of the above concave portions is the same even if the observation position is changed. Here, the evaluation of the shape of the concave portion after observation is good if one of the shapes a to d has one or two or more, and the shape a to d does not exist. (X) ° Further, the shapes of the concave portions observed in Examples 2 to 17 and Comparative Examples 1 to 8 below 0 were also evaluated on the same basis. Further, the size (opening width and depth) of the concave portion observed in the cross section of a certain region of the measured aluminum-shaped body and the ratio thereof are the opening width per 0.1 mm square opening Ο. ίμιη~Ιμιη The number of concave portions of the opening width Ιμιη~ΙΟμηι is 1~1〇, and the concave width of the opening width Ιίμηι~30μιη is 1~3, and the depth is in the range of 〇·1μιη~30μπι . The size Q (opening width and depth) of the concave portion of the inner portion forming the double concave portion structure and the ratio thereof are also the same as the above-mentioned large opening. The opening width of each 0.11111 square opening is 0.; ^111~; The concave portion of 111 is 1〇~50, and the concave portion of the opening width Ιμιη~ΙΟμηι is 1 to 50' opening width Ιίμιη~30μιη concave portion is 1 to 2 'depth range Inside. With regard to the size of the concave portion, there is almost no change even if the observation place is changed. Here, the evaluation of the size of the concave portion after observation is good (〇) in the case of the opening width of 0.1 to 30 μm and the depth of 〇.1 to 30 μm. In the case of this, it is defective (X). Further, the sizes of the concave portions observed in the following Examples 2 to 17-21-201141696 and Comparative Examples 1 to 8 were also evaluated on the same basis. [Evaluation of Surface Gloss of Aluminum Shape Body] For the obtained aluminum body, a 60-degree gloss of the surface was measured using a digital variable angle gloss meter (manufactured by SUGA Test Machine Co., Ltd.). Further, in the following Examples 2 to 17 and Comparative Examples 1 to 8, the glossiness measurement was performed in the same manner [Evaluation of the surface area increase degree by the aluminum shape body] With respect to the obtained aluminum body, by SEM or optical microscope The cross-sectional observation was performed at a magnification of 1 〇〇〇, and the surface area of the surface of the aluminum-shaped body was measured using the image processing software (Image) for the obtained cross-sectional observation photograph. The ratio of the increase in the surface area of the aluminum shaped body obtained with respect to the untreated aluminum alloy material is defined as the surface increase rate. Further, the surface area increase rates of the concave portions observed in the following Examples 2 to 17 and Comparative Examples 1 to 8 were also measured on the same basis. [PosiTEST test of the test object for evaluation] 1. Evaluation of the evaluation of the test object for evaluation The preparation of the test test body for the aluminum adhesive composite of the present invention is prepared by bonding an aluminum-shaped body to an adhesive such as the following, or a joint made of metal or The resin was evaluated for the adhesion test piece, and the evaluation of the joint strength of the test body for evaluation was carried out using the posiTEST test. -22- 201141696 (1) Evaluation of the material of the bonded test piece to form an aluminum shape body ・Adhesive layer ・The metal adhesive body for the aluminum adhesive composite made of the metal adherend is aluminum and cl〇 using A1100. 2 无 oxygen-free copper. Further, a resin-made adherend for an aluminum-adhesive composite formed of an aluminum-shaped body, an adhesive layer, or a resin-made adherend is made of polyphenylene sulfide (manufactured by TORAY). 〇 (2) Fabrication of the adhesion test piece for evaluation The joint strength evaluation with the aluminum body and the metal or resin adherend was carried out using the posiTECT test. A1100 material made of a metal-adhered body made of an aluminum-shaped body, an adhesive layer, and an aluminum-adhesive material, is made of aluminum (JISA1100) attached to the posiTEST test (DeFelsko) Company system; size: 20mm φ, All 00 close to the test piece). Forming an aluminum-shaped body, an adhesive layer, a metal-bonded metal-bonded metal-bonded metal-bonded metal-clad C1 02 0 oxygen-free copper is processed into the same shape as the A1100-bonded test piece. . Further, polyphenylene sulfide (PPS) of a resin for forming an aluminum-adhesive composite formed of an aluminum-shaped body, an adhesive layer, or a resin-made adherend is also processed to be closely attached to the above-mentioned A 1 10000 test piece. The same shape. (3) Surface preparation of the adhesion test piece for evaluation The A 1 10000 adhesion test piece described above is treated with the same treatment as in the case of the above-described aluminum shape body. For C 1 020, it is #240-23-201141696

The SiC honing paper is subjected to degreasing treatment with ethanol after honing the surface to which the adhesive adheres. For the polyphenylene sulfide (PPS adhesion test piece), the surface to which the adhesive adhered was rubbed with #240 SiC honing paper, and then degreased with ethanol. The c 1 0 2 0-contact test piece and the P P S-bonded test piece produced as described above are used in the same manner as the A 1 1 0 0-contact test piece for P〇siTEST. (4) Preparation of the test body for evaluation (joining of the aluminum body and the adherend by the adhesive) As shown in Fig. 3, the aluminum body 1 obtained above and the evaluation shown in Tables 1 and 2 are closely attached. The test piece was bonded through a two-liquid mixing type epoxy-based rapid-hardening adhesive (trade name: Araldite rapid, manufactured by HUNT Advanced Materials Co., Ltd.) 2, and then pressurized at a pressing pressure of 0.1 MPa by a hot press (AH-2003 manufactured by ASONE). , maintaining the pressure bonding for 24 hours in its state. Then, after the adhesive is cured, the excess adhesive 2 exposed by the bonding surface between the aluminum body 1 and the adhesion measuring member 4 is separated and removed from the bonding surface by using a cutter. Adjust the bonding surface to form 3.4 cm2, make: aluminum shape body; adhesive layer • A 1 1 00 close-contact aluminum test piece; aluminum shape body • adhesive layer • C 1020 densely connected to the test piece Copper test piece; and aluminum shape body/adhesive layer • PPS-bonded test piece made of resin, and each test piece of aluminum-adhesive composite material (evaluation test body) was produced. 2. Evaluation of the tensile strength of the joint surface of the posiTEST tester The posiTEST tester (manufactured by DeFelsko Co., Ltd.) was used for the above-mentioned evaluation test body, and the test method was ASTMD 4 5 4 1 (IS Ο 4 6 2 4 ). - 201141696 According to the tensile strength of the aluminum/adhesive interface of the above-mentioned aluminum test piece, copper test piece and resin test piece (closed test piece size: 20 min φ, decomposition energy: soil O.OIMPa, accuracy: ± 1% and determination Range: 〇~2〇MPa). The posiTEST test is shown in Fig. 4. When the actuator 5 of the posiTEST tester passes through the fixture for fixing the specimen, and the portion of the specimen for evaluation of the test specimen is connected, the pressure is applied by the pump. The load (peeling load) of the measuring piece 4 from the aluminum body 1 was peeled off, and the peeling state of the joint portion of the aluminum body 1 after the stripping was examined. The peeling load at the aluminum/adhesive interface of the evaluation test piece was 6.3 MPA in the case of the aluminum test piece, 6.4 MPA in the case of the copper test piece, and 6.2 MPA in the case of the resin test piece. In the case of the peeling state after the observation, when the adhesive layer is entirely present on the joint surface of the aluminum-shaped body, it is good (〇), and when only one part remains on one side of the aluminum-shaped body, it is partially good ( △) ' When there is no residue on one side of the aluminum body (interfacial peeling), it is a defect (X), but it is good (〇). Further, the following Examples Q 2 to 17 and Comparative Examples 1 to 8 were evaluated on the same basis. [Aluminum shape body, adhesive, metal, aluminum shape body, observation evaluation of laminated body of adhesive and resin] Further, as shown in Fig. 5, 'three kinds of evaluation test bodies prepared for the above (aluminum test piece, copper) The test piece and the resin test piece are respectively cut by the thickness of the 纟S shape body 1 toward the thickness of the adhesive layer 2 laminated thereon. The thickness direction cross section is observed by a SEM or an optical microscope at a magnification of 1,000 times. The cross-sectional observation photograph is extended from the side of the adhesive layer 2 toward the side of the shape of the body 1 - 25, 2011. The majority of the observation lines (〇 L ) extending in the thickness direction are subtracted from each other by 1 pm, and 1 observation line (0) In the L), at least one or more laminated portions are formed in the adhesive layer-information-adhesive layer, and the thickness of the inscribed body portion of the laminated portion is in the range of 0.1 μηη or more and 30 μmη or less. When there is one or more ratios in the range of the observation line (〇L), it is good (〇), and when the above laminated portion does not exist in the range of 1000 observation lines (OL), it is defective (X). 'The results are arbitrary in any occasion. Billion). Further, the following Examples 2 to 17 and Comparative Examples 1 to 3 were also evaluated on the same basis. [Example 2] An aluminum-shaped body was produced in the same manner as in the above-described Example 1 except that the JIS Α1100-Η14 was used as the aluminum alloy plate for cutting the aluminum sheet, and the material for the evaluation of the material shown in Table 1 was evaluated. The test object for the evaluation evaluation was carried out in the same manner as in the above-described first embodiment, and the observation and evaluation of the posiTEST test and the test body laminated portion for evaluation were carried out in the same manner as in the case of the above-described first embodiment. The results are shown in Table 1 together with the results of Example 1. [Example 3] An aluminum-shaped body was produced in the same manner as in the above-described Example 1 except that JIS A5〇52-H34 was used as the aluminum alloy plate for cutting the aluminum sheet, and the adhesion measuring piece for evaluation was prepared by the material shown in Table 1. In the same manner as in the above-described Example 1, the test object for the evaluation evaluation was the same as in the above-described Example, and the observation and evaluation of the test body lamination portion for the p 〇si TE s T test and evaluation were carried out. -26- 201141696 The results are shown in Table 1 together with the results of Example 1. [Example 4] The etching treatment was carried out in the same manner as in Example 1 except that an etching liquid (chloride ion concentration: 30 g/L) was prepared by adding 50 g/L of sodium chloride to a 50 wt% phosphoric acid aqueous solution. The aluminum-shaped body was the same as the above-described first embodiment for the evaluation evaluation f) test piece except for the material preparation evaluation evaluation-attached sheet shown in Table 1, and the posiTEST test and evaluation were carried out in the same manner as in the case of the above-described first embodiment. Observation evaluation of the test body laminate. The results are shown in Table 1 together with the results of Example 1. [Example 5] The etching treatment was carried out in the same manner as in Example 1 except that an etching liquid (chloride ion concentration: 30 g/L) was prepared by adding 50 g/L of sodium chloride to a 1 wt% sulfuric acid aqueous solution. The aluminum-shaped body was adjusted to the material shown in Table 1 (the test piece for the same evaluation as in the above-described Example 1 except the J-measurement-bonded test piece, and the posiTEST test and evaluation were carried out in the same manner as in the case of the above-described Example 1. The evaluation of the test body laminate portion was carried out. The results are shown in Table 1 together with the results of Example 1. [Example 6] In the etching treatment, except that 5 〇g/L was added to a 30 wt% aqueous oxalic acid solution An aluminum-shaped body was produced in the same manner as in the above-described Example 1 except that the sodium chloride-containing etchant (chlorine ion concentration: 30 g/L) was used, and the material shown in Table 1 was adjusted except for the adhesion test piece. In the same manner as in the above-described first embodiment, the test object for the evaluation evaluation of the P〇siTEST test and the evaluation test layer was carried out in the same manner as in the above-described first embodiment. The results are shown together with the results of the first embodiment. In Table 1. [Examples 7 and 8] In the same etching liquid (chloride ion concentration: 48 g/L) as in Example 1, a brocade body was produced in the same manner as in the above-described Example 1 except that 5 (TC immersion for 1 Torr) was carried out, and the material preparation evaluation shown in Table 1 was carried out. In the same manner as in the above-described first embodiment, the P 0 si TEST test and the evaluation of the test body laminated portion for evaluation were carried out in the same manner as in the above-described first embodiment. The results of Example 1 are shown together in Table 1. [Examples 9 and 1] The same etching solution (chloride ion concentration: 48 g/L) as in Example 1 was used, and the mixture was immersed at 40 ° C for 15 minutes. In the same manner as in the above-described first embodiment, the first embodiment of the present invention is the same as that of the above-described first embodiment. In the same manner, the observation evaluation of the test body laminate portion for the posiTEST test and evaluation was carried out. The results are shown in Table 1 together with the results of Example 1. [Example 11] -28- 201141696 In addition to use in a 2.5 wt% hydrochloric acid aqueous solution Add 50§/1^ of sodium chloride (NaCl)-modified etching (Chlorine ion concentration: 54 g/L) A brocade body was produced in the same manner as in the above-described Example 1 except for the immersion liquid. The material was the same as the above-described Example 1 except for the material preparation evaluation adhesion test piece shown in Table 1. The evaluation evaluation test body was subjected to the observation evaluation of the posiTEST test and the evaluation test body lamination portion as in the case of the above-described Example 1. The results are shown in Table 1 together with the results of Example 1. [Example 1 2 An aluminum shape was produced in the same manner as in the above Example 1, except that an etching solution was used as an etching solution using a 2.5 wt% hydrochloric acid aqueous solution (chloride ion concentration: 24 g/L) and immersed at 76 ° C for 1 Torr. In the same manner as in the above-described first embodiment, the test body for the measurement evaluation is the same as the case of the first embodiment described above, and the test body lamination portion for the posiTEST test and evaluation is performed. Observational assessment. The results are shown together with the results of Example 1 in Table 1 » [Examples I3 to 16] Except that etching was carried out by adding 268 g/L of aluminum chloride hexahydrate (A1C13 · 6H20) in a 6 wt% aqueous hydrochloric acid solution. In the same manner as in the above Example 1, an aluminum-shaped body was prepared in the same manner as in the above Example 1 except that the liquid (chlorine ion concentration: I73 g/L) was immersed at 30 ° C for 〇 minutes and then washed with water. In the same manner as in the above-described Example 1, the test object for the evaluation evaluation was used in the same manner as in the above-described Example 1, except for the adhesion test piece, and the observation evaluation of the test body lamination portion for the -29-201141696 posiTEST test and evaluation was carried out. The results are shown in Table 1 together with the results of Example 1. [Example 17] An aluminum-shaped body was produced in the same manner as in Example 1 except that the same etching liquid (chloride ion concentration: 48 g/L) as in Example 1 was used and immersed at 40 ° C for 20 minutes. In addition to the adhesion measuring piece for material preparation evaluation shown in Fig. 1, the test object for modulation evaluation is the same as that of the above-described first embodiment, and the observation of the P〇siTEST test and the test body laminated portion for evaluation is performed in the same manner as in the case of the above-described first embodiment. Evaluation. The results are shown in Table 1 together with the results of Example 1. -30- 201141696 TJ 1Λ 111c

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Al -31 - 201141696 [Comparative Example 1] As an aluminum alloy plate, except for using JIS A1050-H24, only the pretreatment of Example 1 was carried out without etching treatment to prepare an aluminum body, and the material shown in Table 2 was prepared. In addition to the adhesion test piece, the evaluation test object was prepared in the same manner as in the above-described first embodiment, and the observation and evaluation of the posiTEST test and the evaluation test piece lamination unit were carried out in the same manner as in the case of the above-described first embodiment. The results are shown in Table 2. [Comparative Example 2] As an aluminum alloy sheet, in addition to JIS A5052-H34, after performing the pretreatment of Example 1, it was immersed in a 2.5 wt% aqueous hydrochloric acid solution at 6 6 ° C for 4 minutes, washed with water, and immersed at 50 ° C. The 5 wt% sodium hydroxide solution was washed with water for 5 minutes, and further immersed in a normal temperature of 3 Owt% nitric acid for 3 minutes, then washed with water. Then, it was dried by hot air at 120 ° C for 5 minutes, and then an aluminum body was prepared, and the material shown in Table 2 was used. In the same manner as in the above-described first embodiment, the evaluation test object was prepared in the same manner as in the above-described first embodiment, and the observation and evaluation of the posiTEST test and the evaluation test body laminated portion were carried out in the same manner as in the above-described first embodiment. The results are shown in Table 2. [Comparative Example 3] As an aluminum alloy plate, in addition to JIS A1 100-H14, after performing the pretreatment of Example 1, it was immersed in a 50 wt% phosphoric acid aqueous solution at 66 ° C for 4 minutes, followed by water washing, followed by 1 2 0 r After the hot air was dried for 5 minutes, the aluminum body was prepared, and the evaluation test piece was prepared in the same manner as in the above-mentioned Example No. 32-201141696, except that the adhesion measuring piece was prepared by the material shown in Table 2, and the above-described Example 1 was prepared. In the same manner, the observation evaluation of the test body lamination unit for the posiTEST test and evaluation was carried out. The results are shown in Table 2. [Comparative Example 4] As an aluminum alloy plate, in addition to JIS A 1 050-H24, after performing the pretreatment of Example 1 1, it was immersed in a 1 Owt% sulfuric acid aqueous solution at 66 ° C for 4 minutes, followed by water washing, followed by 120 °. The hot-air drying of C was carried out for 5 minutes, and an aluminum-shaped body was prepared. The evaluation test object was prepared in the same manner as in the above-described first embodiment except that the evaluation-bonded test piece was prepared by the material shown in Table 2, and the same as in the case of the first embodiment. The observation and evaluation of the test body lamination section for the posiTEST test and evaluation were carried out. The results are shown in Table 2.比较 [Comparative Example 5] As an aluminum alloy plate, in addition to the use of JIS A1 050-H24, after the pretreatment of Example 1, the immersion in a 3 Owt% aqueous solution of oxalic acid at 66 ° C for 4 minutes was followed by water washing, followed by 1 2 ( In the same manner as in the above-described first embodiment, the evaluation test object was prepared in the same manner as in the above-described first embodiment, except that the aluminum-shaped body of the TC was dried for 5 minutes, and the material for the evaluation shown in Table 2 was used to prepare the evaluation-bonded test piece. The observation evaluation of the test body lamination section of the posiTEST test and evaluation was carried out. The results are shown in Table 2. -33- 201141696 [Comparative Example 6] As an aluminum alloy plate, first, it was immersed at 2 ° C in addition to JIS A1050-H24. An etchant (aqueous solution) containing 26 g/L of hydrogen peroxide and 90 g/L of sulfuric acid. The rust preventive film was removed after 1 minute, and then immersed in a hydrogen peroxide containing 8 〇g/L of sulfuric acid at a temperature of 25 ° C. 9〇g/L Etching solution of benzotriazole 5g/L and sodium chloride 〇2g/L (aqueous solution; chloride ion concentration: 0.1 g/L) After 5 minutes, it was washed with ion-exchanged water, and then dried by hot air at 120 °C. After 5 minutes, the aluminum body was modulated, and the material shown in Table 2 was used to modulate the evaluation. In the same manner as in the case of the above-described Example 1, the evaluation of the posiTEST test and the test sample laminate portion was carried out in the same manner as in the first embodiment, and the results are shown in Table 2. [Comparative Example 7] As aluminum In addition to the use of JIS A 1 050-H24, the alloy plate was subjected to the pretreatment of Example 1, and immersed in an etching solution of a 30 wt% aqueous solution of nitric acid at 66 ° C for 4 minutes, followed by water washing, followed by drying at 120 ° C with hot air. The aluminum-shaped body was prepared after 5 minutes, and the evaluation test object was prepared in the same manner as in the above-described first embodiment except that the adhesion-measuring test piece was prepared in the material shown in Table 2, and the posiTEST test was carried out in the same manner as in the above-described first embodiment. And the observation evaluation of the test body laminated portion. The results are shown in Table 2. -34- 201141696 [Comparative Example 8] As an aluminum alloy plate, an alumina having an average particle diameter of 3 ΟΟμη was used in addition to JIS A105 0-H24. Then, only the pretreatment of the first embodiment was carried out to prepare an aluminum-shaped body, and the evaluation test object was prepared in the same manner as in the above-described first embodiment except that the evaluation-attached probe was prepared by the material shown in Table 2. The above-described embodiment the case in Example 1 was used, and evaluated by the test embodiment posiTEST Specimen Observation _ laminate portion assessed. The results are shown in Zhi 2.

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Claims (1)

201141696 VII. Patent application scope: 1. An aluminum adhesive composite comprising: a part of the surface or an aluminum shape made of aluminum or aluminum alloy having a concave-convex portion; a metal or a side of the surface of the aluminum body; a resin-made adherend; and an aluminum-adhesive composite comprising an adhesive layer between the aluminum-shaped body and the adherend and integrally bonded between the aluminum-shaped body and the adherend, wherein: The surface of the inscribed body is formed with a plurality of concave portions which are caused by the uneven portion, and each of the concave portions is perpendicular to the thickness direction in the thickness direction of the aluminum body and passes through the highest portion of the uneven portion. The width of the opening measured by scanning electron microscopy in the half line between the top line and the bottom line passing through the deepest part is 〇·1 μm or more and 30 μm or less, and the depth is Ο.ίμιη or more and 30 μΓη or less. The concave portion is formed with an embedding portion of the adhesive layer which is adhered to the post-curing adhesive layer, and the aluminum-shaped body and the adhesive are placed on each other by the concave portion and the embedded portion. The aluminum-adhesive composite material according to the invention of claim 1, wherein the aluminum-shaped body is formed with a part of or all of the plurality of concave portions from the opening edge of the concave portion. a portion or a whole portion protruding toward the center of the opening width direction in a snow-like shape, whereby the protruding portion forms a locking structure of the concave portion of the aluminum formed body and the embedded portion of the adhesive layer that cannot be separated from each other. The aluminum-adhesive composite material according to claim 2, wherein -39-201141696, in the thickness direction cross section of the aluminum-adhesive composite material, a plurality of observation lines extending from the adhesive layer side toward the aluminum-shaped body side in the thickness direction When the interval of 0.1 μm is subtracted from each other, the snow-like protruding portion is formed by forming at least one laminated portion of the adhesive-aluminum-adhesive agent on the observation line and making the aluminum-shaped body portion of the laminated portion. The thickness is in the range of 0. Wm or more and 3 Mm or less, and the snow-like protruding portion has one or more in the range of 1000 observation lines. The aluminum-adhesive composite material according to any one of claims 1 to 3, wherein the plurality of concave portions of the aluminum-shaped body have at least one wall portion having a part or all of the inner wall surface. A double concave portion structure of more than one inner concave portion. The aluminum-adhesive composite material according to any one of claims 1 to 3, wherein the plurality of concave portions of the aluminum-shaped body have at least one wall portion having a part or all of the inner wall surface. The internal concavo-convex structure of one or more internal protrusions. 6. The aluminum-adhesive composite material according to any one of claims 1 to 5, wherein the 60-degree specular gloss of the aluminum-shaped body is 6 〇 or less 〇7. The aluminum-adhesive composite material according to any one of the above-mentioned, wherein the surface area of the aluminum-shaped body is 1.2 times or more and 10 times or less of the surface area of the aluminum alloy material before the uneven portion is formed. (8) A method for producing an aluminum-adhesive composite, comprising: a part of a surface or an aluminum-shaped aluminum or aluminum alloy having a concave-convex portion; a metal or resin layer on the surface side of the shape-shaped body An adherend; and a method for producing an aluminum-adhesive composite comprising the adhesive layer between the aluminum-shaped body and the adherend and integrally bonded between the aluminum-shaped body and the adherend, The method is characterized in that: the uranium engraving treatment of the aluminum alloy material is performed on a part of the surface or an aluminum body having a plurality of concave portions due to the uneven portion, and the surface of the aluminum body is formed with an adhesive. The adhesive portion of the adhesive layer 0 which is cured by adhering the adhesive to the concave portions of the aluminum-shaped body when the adhesive is adhered, and the concave portion of the aluminum-shaped body and the embedded portion of the adhesive layer are engaged with each other. An aluminum-adhesive composite in which an aluminum body and an adhesive layer are integrally combined. 9. The method for producing an aluminum-adhesive composite material as described in claim 8 of the patent application, wherein the uranium engraving treatment of the aluminum alloy material is carried out using a halide ion concentration of 0.5 g/L or more and 300 g/L or less. An aqueous acid solution of 1% by weight or more and 8% by weight or less is used as an etching solution. 10. The method for producing an aluminum-adhesive composite according to claim 9, wherein the etching liquid is prepared by adding a water-soluble inorganic halogenated Q compound to an aqueous acid solution. The method for producing an aluminum-adhesive composite according to any one of claims 8 to 10, wherein the 'aluminum-shaped body' is formed in part or all of a plurality of concave portions There is a projection which protrudes from a part or the whole of the opening edge portion of the concave portion toward the center in the opening width direction, whereby the projection portion forms the concave portion of the molded body and the embedded portion of the adhesive layer with each other The locking structure that cannot be detached. 12. The method for producing an aluminum-adhesive composite according to claim 11, wherein in the thickness direction cross section of the aluminum-adhesive composite, the adhesive layer side of -41 - 201141696 extends toward the thickness of the aluminum body side. When a plurality of observation lines in the direction are subtracted from each other by a distance of 0·1 μm, the 'snow-like projection is an adhesive layer formed on the 1 observation line—at least one or more laminated portions formed by the aluminum-adhesive layer' and The thickness of the aluminum-shaped body portion of the laminated portion is in the range of μ. 1 μηα or more and 30 μm or less, and the snow-like protruding portion has one or more in the range of the observation line of one string. The aluminum-adhesive composite material according to any one of claims 8 to 2, wherein a plurality of concave portions formed on the surface of the aluminum-shaped body due to the uneven portion are in an aluminum shape. The thickness direction cross section of the body is orthogonal to the thickness direction and the width of the opening measured by scanning electron microscopy is in the half line between the top line passing through the highest portion of the concavo-convex portion and the bottom line passing through the deepest portion. Ίμη! Above 30μηι, the depth is Ο.ίμιη above 3 0 μιη below. The method for producing an aluminum-adhesive composite according to any one of claims 8 to 3, wherein the aluminum-shaped body has a 6-degree specular gloss of 60 or less. The method for producing an adhesive-bonding composite according to any one of the first to eighth aspects of the present invention, wherein the surface area of the aluminum-shaped body is 1.2 of the surface area of the aluminum alloy material on which the uneven portion is formed. More than 1 times the time. -42-