KR102573784B1 - Aluminium alloy-resin composite and method for producing the same - Google Patents

Abstract

Disclosed are an aluminum alloy-resin composite having an improved structure to improve bonding strength between an aluminum alloy and a resin and a manufacturing method thereof. The aluminum alloy-resin composite may include an adhesive layer formed on at least a portion of the surface of the aluminum alloy by combining an aluminum alloy, a boehmite film, and a triazine thiol derivative, and a resin adhering to the adhesive layer.

Description

Aluminum alloy-resin composite and its manufacturing method

The present invention relates to an aluminum alloy-resin composite and a manufacturing method thereof, and more particularly, to an aluminum alloy-resin composite having an improved structure so as to improve bonding strength between an aluminum alloy and a resin and a manufacturing method thereof.

Electronic products require constant innovation in design and function. In the case of a mobile product as an example of an electronic product, a metal material is in the spotlight as a method for implementing a sophisticated design. However, the metal material may cause a problem of radio wave blocking. As a solution to this problem, the use of a metal material-resin composite was considered. When a metal material-resin composite is used, it is possible to realize a differentiated design and at the same time solve the product's functional problem of radio wave blocking. In the metal material-resin composite, the bonding strength between the metal material and the resin is one of the important factors determining the quality of the product. Therefore, various attempts have been made to improve the bonding force between the metal material and the resin.

One aspect of the present invention provides an aluminum alloy-resin composite having an improved structure and a manufacturing method thereof so as to realize a strong bond between the aluminum alloy and the resin.

Another aspect of the present invention provides an aluminum alloy-resin composite having an improved structure to ensure waterproof performance and a manufacturing method thereof.

Another aspect of the present invention provides an aluminum alloy-resin composite that can be manufactured using safe and environmentally friendly materials and a manufacturing method thereof.

Another aspect of the present invention provides an aluminum alloy-resin composite that can be manufactured through a simple manufacturing process and a manufacturing method thereof.

An aluminum alloy-resin composite according to the spirit of the present invention may include an adhesive layer formed on at least a part of the surface of the aluminum alloy by combining an aluminum alloy, a boehmite film, and a triazine thiol derivative, and a resin adhered to the adhesive layer. there is.

The adhesive layer may be formed by combining the boehmite film and the triazine thiol derivative at the same time as the boehmite film is formed on at least a portion of the surface of the aluminum alloy.

The triazine thiol-based derivative may be represented by Formula 1 below.

[Formula 1]

Here, R represents SM ₃ , OR ₁ , SR ₁ , NHR ₁ or N(R ₁ ) ₂ , R ₁ represents an alkyl group, an alkenyl group, a phenyl group, a phenyl alkyl group, an alkyl phenyl group or a cycloalkyl group, and M ₁ , M ₂ and M ₃ independently represent H, Na, Li, K, 1/2BA, 1/2CA, aliphatic primary to tertiary amine salts or aliphatic quaternary ammonium salts.

The triazine thiol derivative is 1,3,5-triazine-2,4,6-trithiol (TT, 1,3,5-triazine-2,4,6-trithiol), 1,3,5- triazine-2,4,6-trithiol monosodium (TTM, 1,3,5-triazine-2,4,6-trithiol monosodium), 1,3,5-triazine-2,4,6-trithiol triethanolamine (F-TEA, 1,3,5-triazine-2,4,6-trithiol triethanolamine), 6-anilino-1,3,5-triazine-2,4-dithiol (AF, 6-anilino -1,3,5-triazine-2,4-dithiol), 6-anylino-1,3,5-triazine-2,4-dithiol monosodium (AFN, -anilino-1,3,5-tri Azine-2,4-dithiol monosodium), 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB, 6-dibutylamino-1,3,5-triazine-2,4 -dithiol), 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium (DBN, 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium) , 6-diallylamino-1,3,5-triazine-2,4-dithiol (DA, 6-diallylamino-1,3,5-triazine-2,4-dithiol), 6-diallylamino-1, 3,5-triazine-2,4-dithiol monosodium (DAN, 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium), 1,3,5-triazine-2, 4,6-trithiol di(tetrabutylammonium salt) (F2A, 1,3,5-triazine-2,4,6-trithiol di(tetrabutylammonium salt)), 6-dibutylamino-1,3,5-triazine -2,4-dithiol tetrabutylammonium salt (DBA, 6-dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt), 6-dithioctylamino-1,3,5-triazine-2 ,4-dithiol (DO, 6-dithioctylamino-1,3,5-triazine-2,4-dithiol), 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium (DON , 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol (DL, 6-dilauryl amino-1,3,5-triazine-2,4-dithiol), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN, 6-dilaurylamino-1,3, 5-triazine-2,4-dithiol monosodium), 6-stearylamino-1,3,5-triazine-2,4-dithiol (ST, 6-stearylamino-1,3,5-triazine- 2,4-dithiol), 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK, 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium), 6-oleilamino-1,3,5-triazine-2,4-dithiol (DL, 6-oleylamino-1,3,5-triazine-2,4-dithiol) and 6-oleilamino -1,3,5-triazine-2,4-dithiol monopotassium (OLK, 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium) may contain at least one selected from there is.

The adhesive layer may be formed under an electroless process.

The adhesive layer may be formed at a temperature of 60° C. or more and 100° C. or less.

The adhesive layer may be formed by immersing the aluminum alloy in an aqueous solution containing the triazine thiol derivative for 30 seconds or more and 1200 seconds or less.

The resin may include a thermoplastic resin.

The thermoplastic resin includes at least one selected from polybutylene terephthalate (PBT), polyphthalamide (PPA), polyphenylene sulfide (PPS), acrylonitrile-butadiene-styrene (ABS), and polycarbonate (PC). can do.

In the method for producing an aluminum alloy-resin composite according to the spirit of the present invention, an aluminum alloy is immersed in an aqueous solution containing a triazine thiol derivative to form an adhesive layer on at least a part of the surface of the aluminum alloy, and a thermoplastic resin is injected into the adhesive layer. molding to form an aluminum alloy-resin composite, and the adhesive layer may be formed by forming a boehmite film on at least a portion of the surface of the aluminum alloy and combining the boehmite film and the triazine thiol-based derivative. .

The triazine thiol-based derivative may be represented by Formula 1 below.

[Formula 1]

Here, R represents SM ₃ , OR ₁ , SR ₁ , NHR ₁ or N(R ₁ ) ₂ , R ₁ represents an alkyl group, an alkenyl group, a phenyl group, a phenyl alkyl group, an alkyl phenyl group or a cycloalkyl group, and M ₁ , M ₂ and M ₃ independently represent H, Na, Li, K, 1/2BA, 1/2CA, aliphatic primary to tertiary amine salts or aliphatic quaternary ammonium salts.

The adhesive layer may be formed under an electroless process.

The adhesive layer may be formed at a temperature of 60° C. or more and 100° C. or less.

The adhesive layer may be formed by immersing the aluminum alloy in an aqueous solution containing the triazine thiol derivative for 30 seconds or more and 1200 seconds or less.

The thermoplastic resin includes at least one selected from polybutylene terephthalate (PBT), polyphthalamide (PPA), polyphenylene sulfide (PPS), acrylonitrile-butadiene-styrene (ABS), and polycarbonate (PC). can do.

The bonding strength between the aluminum alloy and the resin can be improved through the adhesive layer formed by the combination of the boehmite film and the triazine thiol derivative.

Through the adhesive layer formed by the chemical bonding of the boehmite film and the triazine thiol derivative, it is possible to realize an aluminum alloy-resin composite having excellent waterproof performance while improving the bonding strength between the aluminum alloy and the resin.

In the process of forming the adhesive layer, the use of harmful substances such as strong acids is unnecessary, so the manufacturing process of the aluminum alloy-resin composite is relatively safe and environmentally friendly.

Since the adhesive layer can be formed under an electroless process, electrical equipment and the like are unnecessary, and thus a simple manufacturing process and manufacturing cost reduction effect can be expected.

1 is a view showing an example of an electronic product to which an aluminum alloy-resin composite according to an embodiment of the present invention is applied;
2 is a view showing another example of an electronic product to which an aluminum alloy-resin composite according to an embodiment of the present invention is applied;
Figure 3 is a view schematically showing a process of forming an aluminum alloy-resin composite according to an embodiment of the present invention
Figure 4 is a block diagram showing a method for producing an aluminum alloy-resin composite according to an embodiment of the present invention
Figure 5 is a table showing the tensile strength of the aluminum alloy-resin composite according to an embodiment of the present invention
6 is an SEM photograph showing an adhesive layer of an aluminum alloy-resin composite according to an embodiment of the present invention
Figure 7 is a SEM picture showing the adhesive layer of the first comparative example of Figure 5
Figure 8 is a SEM picture showing the adhesive layer of the third comparative example of Figure 5
Figure 9 is a table showing the tensile strength of the aluminum alloy-resin composite according to an embodiment of the present invention according to the adhesive layer formation temperature or time
10 is a table showing the waterproof performance of an aluminum alloy-resin composite according to an embodiment of the present invention
11 is a view showing an aluminum alloy-resin composite for testing for measuring the bonding strength of the aluminum alloy-resin composite according to an embodiment of the present invention;

Hereinafter, a preferred embodiment according to the present invention will be described in detail with reference to the accompanying drawings. Meanwhile, the terms "front end", "rear end", "top", "bottom", "top", and "bottom" used in the following description are defined based on drawings, and by these terms, the shape of each component and location are not limited. Hereinafter, the aluminum alloy 10 may be used as a collective term for aluminum and aluminum alloys. Hereinafter, the unit um indicated in the SEM picture means μm. Hereinafter, reference number “2” described in FIG. 11 means an aluminum alloy-resin composite for testing.

1 is a view showing an example of an electronic product to which an aluminum alloy-resin composite according to an embodiment of the present invention is applied, and FIG. 2 is an electronic product to which an aluminum alloy-resin composite according to an embodiment of the present invention is applied. It is a drawing showing another example.

As shown in FIG. 1, the aluminum alloy-resin composite 1 may be applied to the exterior of the mobile phone 100 to build a sophisticated design.

As shown in FIG. 2 , the aluminum alloy-resin composite 1 may be applied to the exterior of the display device 200 to create a luxurious atmosphere using a metal material.

Electronic products to which the aluminum alloy-resin composite 1 can be applied include not only the mobile phone 100 and the display device 200, but also all electronic products that try to differentiate in design by using metal materials, such as refrigerators and air conditioners. can include

3 is a diagram schematically illustrating a process of forming an aluminum alloy-resin composite according to an embodiment of the present invention.

As shown in FIG. 3 , the aluminum alloy-resin composite 1 may include an aluminum alloy 10 and a resin 20 .

As described above, the aluminum alloy 10 may be used as a general term for aluminum and aluminum alloys. Specifically, aluminum alloys are all alloys and ADCs 1 to 12, such as A1000 series to 7000 series (corrosion-resistant aluminum alloy, high-strength aluminum alloy, heat-resistant aluminum alloy, etc.) An aluminum alloy for casting, such as an aluminum alloy for die-casting, can be used. As the shaped material, as long as it is an alloy for casting, it is possible to use a part shaped by a die-casting method or a part formed by further machining it to make the shape uniform. In addition, as the wrought alloy, it is possible to use plates and other intermediate materials, as well as parts formed by subjecting them to mechanical processing such as heat press processing.

The resin 20 may include a thermoplastic resin.

The thermoplastic resin may include at least one selected from polybutylene terephthalate (PBT), polyphthalamide (PPA), polyphenylene sulfide (PPS), acrylonitrile-butadiene-styrene (ABS), and polycarbonate (PC). can

As an example, the resin 20 may include at least one selected from polyalkylene terephthalate, a copolymer mainly composed of polyalkylene terephthalate, and a thermoplastic resin containing polyalkylene terephthalate as one component.

The aluminum alloy-resin composite 1 may further include an adhesive layer 30 .

The adhesive layer 30 may be formed on at least a portion of the surface of the aluminum alloy 10 .

The adhesive layer 30 may be formed on at least a portion of the surface of the aluminum alloy 10 by combining the boehmite film (AlO(OH)) 31 and the triazine thiol derivative 32 . In addition, the adhesive layer 30 may be formed on at least a portion of the surface of the aluminum alloy 10 by combining the aluminum hydroxide film (Al(OH) ₃ ) and the triazine thiol derivative 32 . Specifically, the adhesive layer 30 is formed on the surface of the aluminum alloy 10 by chemical bonding between the boehmite film 31 and the triazine thiol derivative 32 or chemical bonding between the aluminum hydroxide film and the triazine thiol derivative 32. It may be formed on at least a part of. More specifically, the adhesive layer 30 may be formed on at least a portion of the surface of the aluminum alloy 10 by chemically bonding the terminal thiol functional group of the triazine thiol derivative 32 to the boehmite film 31 or the aluminum hydroxide film. there is. Hereinafter, a case in which the adhesive layer 30 is formed by combining the boehmite film 31 and the triazine thiol-based derivative 32 will be mainly described.

A triazine thiol derivative may be represented by Formula 1 below.

[Formula 1]

Here, R represents SM ₃ , OR ₁ , SR ₁ , NHR ₁ or N(R ₁ ) ₂ . R ₁ represents an alkyl group, an alkenyl group, a phenyl group, a phenyl alkyl group, an alkyl phenyl group or a cycloalkyl group. M ₁ , M ₂ , and M ₃ independently represent H, Na, Li, K, 1/2BA, 1/2CA, aliphatic primary to tertiary amine salts or aliphatic quaternary ammonium salts.

The triazine thiol derivative (32) is 1,3,5-triazine-2,4,6-trithiol (TT, 1,3,5-triazine-2,4,6-trithiol), 1,3,5-triazine-2,4,6-trithiol monosodium (TTM, 1,3,5-triazine-2,4,6-trithiol monosodium), 1,3,5-triazine-2, 4,6-trithiol triethanolamine (F-TEA, 1,3,5-triazine-2,4,6-trithiol triethanolamine), 6-anilino-1,3,5-triazine-2,4-dithiol ( AF, 6-anilino-1,3,5-triazine-2,4-dithiol), 6-anylino-1,3,5-triazine-2,4-dithiol monosodium (AFN, -anilino-1 ,3,5-triazine-2,4-dithiol monosodium), 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB, 6-dibutylamino-1,3,5- triazine-2,4-dithiol), 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium (DBN, 6-dibutylamino-1,3,5-triazine-2,4 -dithiol monosodium), 6-diallylamino-1,3,5-triazine-2,4-dithiol (DA, 6-diallylamino-1,3,5-triazine-2,4-dithiol), 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium (DAN, 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium), 1,3, 5-triazine-2,4,6-trithiol di(tetrabutylammonium salt) (F2A, 1,3,5-triazine-2,4,6-trithiol di(tetrabutylammonium salt)), 6-dibutylamino-1 ,3,5-triazine-2,4-dithiol tetrabutylammonium salt (DBA, 6-dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt), 6-dithioctylamino-1,3 ,5-triazine-2,4-dithiol (DO, 6-dithioctylamino-1,3,5-triazine-2,4-dithiol), 6-dithioctylamino-1,3,5-triazine-2, 4-dithiol monosodium (DON, 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol ( DL, 6-dilaurylamino-1,3,5-triazine-2,4-dithiol), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN, 6-dilauryl Amino-1,3,5-triazine-2,4-dithiol monosodium), 6-stearylamino-1,3,5-triazine-2,4-dithiol (ST, 6-stearylamino-1,3 ,5-triazine-2,4-dithiol), 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK, 6-stearylamino-1,3,5-triazine- 2,4-dithiol monopotassium), 6-oleilamino-1,3,5-triazine-2,4-dithiol (DL, 6-oleylamino-1,3,5-triazine-2,4-dithiol Ol) and 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium (OLK, 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium) selected from may contain at least one. However, the type of triazine thiol-based derivative 32 is not limited to the above example.

The adhesive layer 30 may be formed by forming the boehmite film 31 on at least a portion of the surface of the aluminum alloy 10 and combining the boehmite film 31 and the triazine thiol derivative 32.

The resin 20 may adhere to the adhesive layer 30 . Specifically, the resin 20 may bind to the triazine thiol-based derivative 32 of the adhesive layer 30 . The boehmite film 31 or the aluminum hydroxide film may serve to improve the bonding strength between the resin 20 and the triazine thiol derivative 32 .

4 is a block diagram showing a method for manufacturing an aluminum alloy-resin composite according to an embodiment of the present invention. Hereinafter, reference numerals not shown refer to FIG. 3 .

The manufacturing method of the aluminum alloy-resin composite 1 may include an aluminum alloy surface treatment process. In addition, the method of manufacturing the aluminum alloy-resin composite 1 may further include a molding process.

In other words, the manufacturing method of the aluminum alloy-resin composite 1 may include a processing step (P1) of the aluminum alloy 10 for mechanically processing the shape of the aluminum alloy 10. In addition, the method of manufacturing the aluminum alloy-resin composite 1 may further include a pretreatment step (P2) of the aluminum alloy 10. In addition, the manufacturing method of the aluminum alloy-resin composite 1 may further include an adhesive layer forming step (P3) of forming the adhesive layer 30 on at least a portion of the surface of the aluminum alloy 10. In addition, the manufacturing method of the aluminum alloy-resin composite 1 may further include a drying step (P4). In addition, the method of manufacturing the aluminum alloy-resin composite 1 may further include a molding process (P5) of injection molding the resin 20 into the adhesive layer 30.

As shown in FIG. 4, the processing step (P1) of the aluminum alloy 10 is a process for mechanically processing the shape of the aluminum alloy 10. As an example, the processing process P1 of the aluminum alloy 10 may include a press process, a CNC process, a die casting process, and the like.

When the processing step (P1) of the aluminum alloy 10 is completed, the pretreatment step (P2) of the aluminum alloy 10 may be performed.

The pretreatment step (P2) of the aluminum alloy 10 may include a degreasing step (S1) of the aluminum alloy 10. Foreign substances may be present on the surface of the aluminum alloy 10 . As an example, fats and oils or dust may be present on the surface of the aluminum alloy 10 . The surface of the machined aluminum alloy 10 may have a coolant used during machining, debris, and the like adhered thereto. In order to remove the above foreign substances from the surface of the aluminum alloy 10, the degreasing step (S1) of the aluminum alloy 10 is required. The degreasing step (S1) of the aluminum alloy 10 is preferably performed at a temperature of 40° C. or more and 60° C. or less. In addition, the degreasing step (S1) of the aluminum alloy 10 is preferably performed for a time of 2 minutes or more and 5 minutes or less. A material constituting the degreasing solution may use a commercially available product for cleaning aluminum alloys, the main component of which is a surfactant. The degreasing process (S1) of the aluminum alloy 10 may include an acidic degreasing process using an acidic material and a surfactant together.

The pretreatment process (P2) may further include an alkali etching process (S2). The alkaline etching process (S2) allows the adhesive layer 30 to be smoothly formed on the surface of the aluminum alloy 10 by removing the aluminum oxide film naturally formed on the surface of the aluminum alloy 10. Alkaline etching process (S2) is preferably carried out at a temperature of 30 ℃ or more and 50 ℃ or less. In addition, the alkali etching process (S2) is preferably performed for a time of 1 minute or more and 2 minutes or less. A material constituting the degreasing solution may include a basic material capable of etching the aluminum alloy 10 . Specifically, the material constituting the degreasing solution may include an alkali metal hydroxide such as sodium hydroxide (NaOH) or potassium hydroxide (KOH).

The pretreatment process (P2) may further include a desmut process (S3). Foreign substances present on the surface of the aluminum alloy 10 may be removed through the desmut process (S3). Specifically, after the alkaline etching process (S2), metals dissolved in the aluminum alloy 10, such as sodium hydroxide, magnesium, copper, and silicon, are not completely dissolved in the alkaline etching (S2) process and form hydroxide on the surface of the aluminum alloy 10. to other compositions may be present. Desmut (S3) is a process for removing such foreign substances. Desmut (S3) is preferably performed at a temperature of 20°C or more and 40°C or less. In addition, desmutting (S3) is preferably performed for a time of 1 minute or more and 3 minutes or less. During the desmut (S3) process, an aqueous acid solution may be used as a material constituting the degreasing liquid. As an example, the aqueous acid solution may include nitric acid, sulfuric acid, dilute acetic acid, and the like.

When the pretreatment step (P2) of the aluminum alloy 10 is completed, an adhesive layer forming step (P3) of forming an adhesive layer 30 on at least a portion of the surface of the aluminum alloy 10 may be performed. The adhesive layer forming step (P3) is preferably performed at a temperature of 60° C. or more and 100° C. or less. In addition, the adhesive layer forming step (P3) is preferably performed for a time of 30 seconds or more and 1200 seconds or less. Specifically, the adhesive layer 30 can be obtained by immersing the aluminum alloy 10 that has undergone the pretreatment step (P2) of the aluminum alloy 10 in an aqueous solution containing a triazine thiol derivative for a time of 30 seconds or more and 1200 seconds or less. there is.

When the aluminum alloy 10 is immersed in an aqueous solution containing a triazine thiol derivative, a boehmite film 31 may be formed on at least a part of the surface of the aluminum alloy 10 . The triazine thiol-based derivative 32 may form the adhesive layer 30 by chemically bonding with the boehmite film 31 . Specifically, the adhesive layer 30 may be formed on at least a portion of the surface of the aluminum alloy 10 by chemically bonding the terminal thiol functional group of the triazine thiol derivative 32 to the boehmite film 31 . The formation of the boehmite film 31 on at least a part of the surface of the aluminum alloy 10 and the formation of the adhesive layer 30 by chemical bonding between the boehmite film 31 and the triazine thiol-based derivative 32 occur simultaneously. can That is, the adhesive layer 30 can be easily formed on at least a part of the surface of the aluminum alloy 10 simply by immersing the aluminum alloy 10 in an aqueous solution containing a triazine thiol derivative. As such, the present invention has the advantage that the process of forming the adhesive layer 30 in which the aluminum alloy 10 and the resin 20 are bonded is simple, and the time required to form the adhesive layer 30 can be shortened.

The adhesive layer 30 may be formed under an electroless process. That is, in the case of the present invention, it is sufficient to immerse the aluminum alloy 10 in an aqueous solution containing a triazine thiol derivative to form the adhesive layer 30, and there is no need to go through a separate process of electropolymerization.

Therefore, since the present invention does not require electrical equipment for electropolymerization, it is possible to save facility investment cost or maintenance cost. In addition, in the electropolymerization process, a strong acid such as sulfuric acid is used, and sulfuric acid may be scattered as a gas at a temperature of 60 ° C. or higher where the adhesive layer forming process (P3) is performed, which may cause safety problems. In conclusion, since the adhesive layer 30 of the present invention can be formed under an electroless process, an eco-friendly manufacturing process, simplification of the manufacturing process, and reduction of manufacturing costs can be expected.

When the adhesive layer forming process (P3) is completed, a drying process (P4) of drying the aluminum alloy 10 on which the adhesive layer 30 is formed may be performed.

The drying step (P4) is a step of removing water from the aluminum alloy 10 on which the adhesive layer 30 is formed. In other words, the drying process (P4) is a process of removing water from the adhesive layer 30. The drying step (P4) is preferably carried out at a temperature of 60 ° C or more and 70 ° C or less. In addition, the drying process (P4) is preferably performed for a time of 300 seconds or more and 900 seconds or less.

When the drying process (P4) is completed, a molding process (P5) of injection molding the resin 20 to the adhesive layer 30 may be performed.

In the molding process (P5), the higher the mold temperature or the injection temperature, the better, but there is no need to forcefully increase the temperature. The molding process (P5) may be performed under the same conditions as a conventional injection molding process using a thermoplastic resin.

During the molding process (P5), the resin 20 is bonded to the adhesive layer 30, thereby forming the aluminum alloy-resin composite 1 having a strong bonding strength.

As one of the methods for forming the aluminum alloy-resin composite 1, instead of combining the aluminum alloy 10 and the resin 20 using the adhesive layer 30 as in the present invention, aluminum through the anchor effect There is a way to combine the alloy 10 and the resin 20. This is to form the aluminum alloy-resin composite 1 by roughening the surface of the aluminum alloy 10 and then infiltrating the resin 20 into the roughened surface of the aluminum alloy 10 . That is, the aluminum alloy-resin composite 1 is formed by using a physical bond between the aluminum alloy 10 and the resin 20. However, the method of forming the aluminum alloy-resin composite 1 by using the physical bond between the aluminum alloy 10 and the resin 20 is dangerous in terms of possibility of burns and harm to the human body since the use of a large amount of strong acid is unavoidable. can In addition, it is difficult to densely fill the rough surface of the aluminum alloy 10 with the resin 20 , so the bonding force between the aluminum alloy 10 and the resin 20 may be relatively weak. However, in the case of the present invention, since the use of harmful substances such as strong acids is unnecessary in the process of forming the adhesive layer 30, it is environmentally friendly. In addition, since chemical bonding between the aluminum alloy 10 and the resin 20 can be promoted through the adhesive layer 30, the bonding force between the aluminum alloy 10 and the resin 20 is relatively strong.

[Example]

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following examples.

(a) electron microscope observation

It was observed at 10 kV or more and 15 kV or less using an HR-SEM (High Resolution Scanning Electron Microscope) type electron microscope S-4800 (manufactured by Hitachi).

(b) Measurement of bonding strength between aluminum alloy and resin

Universal testing machine TO-102 (Test One) was used.

<Experimental Example 1> (Adhesion with Al 6013 aluminum alloy)

A commercially available Al 6013 extruded material was obtained and cut to make many rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in the test tank, and commercially available aluminum alloy degreaser "Al Clean paste (Burim Yanghang)" and nitric acid (70%) were added to the mixture to form aqueous solutions at a temperature of 50°C and a concentration of 5%. The rectangular piece of aluminum alloy was immersed in this for 3 minutes and washed well with water. Next, NaOH (98%) was added to another test tank at 40 ° C to make an aqueous solution at a temperature of 40 ° C and a concentration of 5%, and the aluminum alloy piece was immersed in this for 90 seconds and washed well with water. Next, nitric acid (70%) was added to another test tank to make an aqueous solution at a temperature of 25 ° C. and a concentration of 7%, and the aluminum alloy piece was immersed for 2 minutes and washed well. Subsequently, an aqueous solution containing 0.36 g/L of 1,3,5-triazine-2,4-dithiol-6-sodium thiolate was prepared at 80°C in another experimental tank, and the aluminum alloy piece was immersed in this for 3 minutes. do. Subsequently, it was washed with water (60 ° C) in another experimental tank, taken out, and dried with an air blower. After that, when one of the pieces was observed with an electron microscope, a disordered net-shaped film was formed and the shape was more rounded at the end than the aluminum hydroxide film, so that the triazine thiol-based derivative was covered by the aluminum hydroxide film. was able to confirm that This is shown in the SEM picture of FIG. 6 . After taking out the five aluminum alloy pieces with the above-described surface treatment, and injecting them into the same shape as the test aluminum alloy-resin composite shown in FIG. As a result, the average tensile strength was very strong at 32Mpa, as can be seen in FIG.

<Comparative Example 1> (Al 6013 aluminum alloy and adhesion_aluminum hydroxide surface)

A commercially available Al 6013 extruded material was obtained and cut to make many rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in the test tank, and commercially available aluminum alloy degreaser "Al Clean paste (Burim Yanghang)" and nitric acid (70%) were added to the mixture to form aqueous solutions at a temperature of 50°C and a concentration of 5%. The rectangular piece of aluminum alloy was immersed in this for 3 minutes and washed well with water. Next, NaOH (98%) was added to another test tank at 40 ° C to make an aqueous solution at a temperature of 40 ° C and a concentration of 5%, and the aluminum alloy piece was immersed in this for 90 seconds and washed well with water. Next, nitric acid (70%) was added to another test tank to make an aqueous solution at a temperature of 25 ° C. and a concentration of 7%, and the aluminum alloy piece was immersed for 2 minutes and washed well. Subsequently, an aqueous solution at a temperature of 80 ° C was prepared in another test tank, and an aluminum alloy piece was immersed in this for 3 minutes and dried with an air blower. Thereafter, when one of the pieces was observed with an electron microscope, a disordered net-like film was formed, and it was confirmed that this was an aluminum hydroxide film. This is shown in the SEM photograph of FIG. 7 . Five aluminum alloy pieces subjected to the above-described surface treatment were taken out, injected under the same conditions as in <Experimental Example 1>, and then subjected to a tensile fracture test, and bonding with the resin was not achieved.

<Comparative Example 2> (Al 6013 aluminum alloy and adhesion_using anchor effect)

A commercially available Al 6013 extruded material was obtained and cut to make many rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in the test tank, and commercially available degreaser for aluminum alloys, "Al Clean paste (Burim Yanghang)" and nitric acid were added thereto to make aqueous solutions at 50 ° C., each having a concentration of 5%. The rectangular piece of aluminum alloy was immersed in this for 5 minutes and washed well with water. Subsequently, a surface treatment solution was prepared at 25° C. in another test tank, and the aluminum alloy piece was immersed in this for 1 minute and washed well with water. Here, the surface treatment liquid may be an aqueous solution containing an alkali source and positive metal ions. Next, in another test tank, 7% hydrochloric acid and 45% aluminum chloride hexahydrate solution at 30 ° C were prepared, and the aluminum alloy piece was immersed for 2 minutes and washed well with water. Next, a 15% aqueous solution of nitric acid at 25°C was prepared in another test tank, and the aluminum alloy piece was immersed in this for 2 minutes and then washed with water. Subsequently, an ultrasonic water cleaning tank at room temperature was prepared in another experimental tank, ultrasonic cleaning was performed for 3 minutes, and drying was put in a warm air dryer at 70 ° C for 15 minutes. Five aluminum alloy pieces subjected to the above-described surface treatment were taken out, injected under the same conditions as in <Experimental Example 1>, and then subjected to a tensile fracture test. As a result, the average tensile strength was 28 MPa, as can be seen in FIG.

<Comparative Example 3> (Al 6013 aluminum alloy and adhesion _ electropolymerization surface treatment containing triazine thiol derivative)

A commercially available Al 6013 extruded material was obtained and cut to make many rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in the test tank, and commercially available aluminum alloy degreaser "Al Clean paste (Burim Yanghang)" and nitric acid (70%) were added to the mixture to form aqueous solutions at a temperature of 50°C and a concentration of 5%. The rectangular piece of aluminum alloy was immersed in this for 3 minutes and washed well with water. Subsequently, NaOH (98%) was added to another test tank at 40 ° C to make an aqueous solution at a temperature of 40 ° C and a concentration of 5%, and the aluminum alloy piece was immersed in this for 60 seconds and washed well with water. Next, sulfuric acid (98%) was added to another test tank to make an aqueous solution at a temperature of 30 ° C and a concentration of 2%, and the aluminum alloy piece was immersed for 2 minutes and washed well with water. Subsequently, an aqueous solution of sulfuric acid (98%) concentration of 5% and DBN (98%) concentration of 0.18 g / L at a temperature of 60 ° C was prepared in another experimental tank, a carbon rod was connected to the cathode and an aluminum alloy piece was connected to the anode, and a direct current of 1 A / dm ² , immersed in the prepared solution for 15 minutes, and washed well. After drying the treated aluminum alloy piece with an air blower, one of the pieces was observed with an electron microscope. As a result, it was confirmed that an adhesive layer of a triazine thiol-based derivative was formed on the surface of the aluminum alloy as electropolymerization was performed on the surface of the aluminum alloy. . This is shown in the SEM photograph of FIG. 8 . As a result of the tensile fracture test after the above-described aluminum alloy piece was injected under the same conditions as in <Experimental Example 1>, the average tensile strength was found to be 32 MPa, as can be seen in FIG.

<Comparative Example 4> (Al 6013 aluminum alloy and adhesion_surface treatment using a triazine thiol derivative containing alkoxysilane)

A commercially available Al 6013 extruded material was obtained and cut to make many rectangular pieces of 40 mm x 12 mm x 3 mm. The rectangular aluminum alloy piece was washed by immersing it in an aqueous solution of about pH 9.5 at a temperature of 40° C. and containing 30 g/L of alkali component (condensed phosphate accounts for 50 to 60%) for 5 minutes. After the washing treatment, the aluminum alloy piece of the rectangular piece was washed with pure water for 1 minute. Subsequently, an aqueous solution of triethanolamine having a concentration of 3 g/L and pH 8.0 was used as a boehmite treatment solution. The temperature of the triethanolamine aqueous solution was set to 95°C, and the rectangular aluminum alloy piece was immersed in the triethanolamine aqueous solution for 15 minutes. As a result, a metal compound film containing boehmite, a hydrated oxide of aluminum, as a main component was obtained. Thereafter, the rectangular aluminum alloy piece was immersed in an alkoxysilane-containing triazine thiol derivative solution. The used alkoxysilane-containing triazine thiol derivative is Triethoxysilyl Propyl Amino Triazine dithiol monosodium, which is dissolved in a solvent of ethanol 95:water 5 (volume ratio) to a concentration of 0.7 g/L. An alkoxysilane-containing triazine thiol derivative solution was obtained. A rectangular aluminum alloy piece was immersed in this solution at room temperature for 30 minutes. Subsequently, the rectangular piece of aluminum alloy was subjected to heat treatment in an oven at 160° C. for 10 minutes, and upon completion of the reaction, it was dried. And, in an acetone solution containing N,N'-m-phenylenedimaleimide (N,N'-1,3-phenylenedimaleimide) at a concentration of 1.0 g/L and dicumyl peroxide at a concentration of 2 g/L It was immersed at room temperature for 10 minutes and heat treated at 150°C for 10 minutes in an oven. Thereafter, an ethanol solution of dicumyl peroxide having a concentration of 2 g/L was sprayed at room temperature over the entire surface of the rectangular piece of aluminum alloy piece, and dried with an air blower. As a result of the tensile fracture test after the above-described aluminum alloy piece was injected under the same conditions as in <Experimental Example 1>, the average tensile strength was found to be 7.9 MPa, as can be seen in FIG. 5.

<Experimental Example 2> (Al 6013 aluminum alloy and adhesion_test by temperature)

A commercially available Al 6013 extruded material was obtained and cut to make many rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in the test tank, and commercially available aluminum alloy degreaser "Al Clean paste (Burim Yanghang)" and nitric acid (70%) were added to the mixture to form aqueous solutions at a temperature of 50°C and a concentration of 5%. The rectangular piece of aluminum alloy was immersed in this for 3 minutes and washed well with water. Next, NaOH (98%) was added to another test tank at 40 ° C to make an aqueous solution at a temperature of 40 ° C and a concentration of 5%, and the aluminum alloy piece was immersed in this for 90 seconds and washed well with water. Next, nitric acid (70%) was added to another test tank to make an aqueous solution at a temperature of 25 ° C. and a concentration of 7%, and the aluminum alloy piece was immersed for 2 minutes and washed well. Subsequently, an aqueous solution containing 0.36 g/L of 1,3,5-triazine-2,4-dithiol-6-sodium thiolate was prepared in another experimental tank, and the temperature was raised to 100 °C by 10 °C from 60 °C. Five aluminum alloy pieces were immersed for 3 minutes to ° C. Subsequently, it was washed with water (60 ° C) in another test tank, taken out, and dried with an air blower. A total of 25 aluminum alloy pieces subjected to the above-described surface treatment were taken out, and PBT/GF40% resin was injected into a 140-ton horizontal injection machine (Sodick) in the same shape as the aluminum alloy-resin composite for testing shown in FIG. did the test The test results are shown in FIG. 9 .

<Experimental Example 3> (Al 6013 aluminum alloy and adhesion_test by time)

A commercially available Al 6013 extruded material was obtained and cut to make many rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in the test tank, and commercially available aluminum alloy degreaser "Al Clean paste (Burim Yanghang)" and nitric acid (70%) were added to the mixture to form aqueous solutions at a temperature of 50°C and a concentration of 5%. The rectangular piece of aluminum alloy was immersed in this for 3 minutes and washed well with water. Next, NaOH (98%) was added to another test tank at 40 ° C to make an aqueous solution at a temperature of 40 ° C and a concentration of 5%, and the aluminum alloy piece was immersed in this for 90 seconds and washed well with water. Next, nitric acid (70%) was added to another test tank to make an aqueous solution at a temperature of 25 ° C. and a concentration of 7%, and the aluminum alloy piece was immersed for 2 minutes and washed well. Subsequently, an aqueous solution containing 0.36 g/L of 1,3,5-triazine-2,4-dithiol-6-sodium thiolate was prepared at 80 ° C in another experimental tank, and the immersion time was 30, 60, 120, Five aluminum alloy pieces were immersed for 180, 300, 600, and 1200 seconds, respectively. Subsequently, it was washed with water (60 ° C) in another experimental tank, taken out, and dried with an air blower. A total of 35 aluminum alloy pieces subjected to the above-described surface treatment were taken out, injected into a 140-ton horizontal injection machine (Sodick) with PBT/GF40% resin in the same shape as the aluminum alloy-resin composite for testing shown in FIG. 11, and tensile fracture did the test The test results are shown in FIG. 9 .

<Experimental Example 4> (Waterproof performance test)

The waterproof performance of the manufactured aluminum alloy-resin composite was replaced by an air leak test under more severe conditions. The air leak test condition is about 100mm x 80mm x The inner and outer parts of the aluminum alloy in the form of a 7 mm plate were machined and surface treated in the same manner as in <Experimental Example 1>, <Comparative Example 2>, and <Comparative Example 3>. Then, an aluminum alloy-resin composite was produced by injection into a resin containing 40% PBT/GF. After making a jig capable of sealing the manufactured aluminum alloy-resin composite, the jig is seated in a press machine. An aluminum alloy-resin composite was placed on the jig, and a press machine was operated to press the jig up and down to create an airtight space, and 10 kPa air was blown into the airtight space to check for air leaks. If the injected air pressure fell by more than 1% for 10 seconds of measurement time, it was judged to be a failure in waterproof performance, and 10 pieces were measured for each condition. The waterproof performance test results are shown in FIG. 10 . 10, it can be seen that the aluminum alloy-resin composite prepared in <Experimental Example 1> has superior waterproof performance compared to the aluminum alloy-resin composites prepared in <Comparative Example 2> and <Comparative Example 3>. You can check.

In the above, specific embodiments have been illustrated and described. However, it is not limited to the above embodiments, and those skilled in the art will be able to make various changes without departing from the gist of the technical idea of the invention described in the claims below. .

1: aluminum alloy-resin composite 2: aluminum alloy-resin composite for testing
10: aluminum alloy 20: resin
30: adhesive layer 31: boehmite film
32: triazine thiol derivative 100: mobile phone
200: display device

Claims (15)

aluminum alloy;
an adhesive layer formed on at least a portion of the surface of the aluminum alloy by chemical bonding of a boehmite film and a triazine thiol derivative; and
Including; resin bonded under chemical bonding with the adhesive layer,
The adhesive layer is formed by combining the boehmite film and the triazine thiol derivative at the same time as the boehmite film is formed on at least a portion of the surface of the aluminum alloy,
The triazine thiol derivative is 1,3,5-triazine-2,4,6-trithiol (TT, 1,3,5-triazine-2,4,6-trithiol), 1,3,5- triazine-2,4,6-trithiol triethanolamine (F-TEA, 1,3,5-triazine-2,4,6-trithiol triethanolamine), 6-anilino-1,3,5-triazine-2, 4-dithiol (AF, 6-anilino-1,3,5-triazine-2,4-dithiol), 6-anylino-1,3,5-triazine-2,4-dithiol monosodium (AFN, - Anilino-1,3,5-triazine-2,4-dithiol monosodium), 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB, 6-dibutylamino-1, 3,5-triazine-2,4-dithiol), 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium (DBN, 6-dibutylamino-1,3,5-triazine -2,4-dithiol monosodium), 6-diallylamino-1,3,5-triazine-2,4-dithiol (DA, 6-diallylamino-1,3,5-triazine-2,4- dithiol), 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium (DAN, 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium), 1,3,5-triazine-2,4,6-trithiol di(tetrabutylammonium salt) (F2A, 1,3,5-triazine-2,4,6-trithiol di(tetrabutylammonium salt)), 6 -dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt (DBA, 6-dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt), 6-dithioctylamino -1,3,5-triazine-2,4-dithiol (DO, 6-dithioctylamino-1,3,5-triazine-2,4-dithiol), 6-dithioctylamino-1,3,5- triazine-2,4-dithiol monosodium (DON, 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium), 6-dilaurylamino-1,3,5-triazine-2, 4-dithiol (DL, 6-dilaurylamino-1,3,5-triazine-2,4-dithiol), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN, 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium), 6-stearylamino-1,3,5-triazine-2,4-dithiol (ST, 6-stearylamino -1,3,5-triazine-2,4-dithiol), 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK, 6-stearylamino-1,3,5 -triazine-2,4-dithiol monopotassium), 6-oleilamino-1,3,5-triazine-2,4-dithiol (DL, 6-oleylamino-1,3,5-triazine-2 ,4-dithiol) and 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium (OLK, 6-oleylamino-1,3,5-triazine-2,4-dithiol mono An aluminum alloy-resin composite containing at least one selected from potassium). delete delete delete According to claim 1,
The adhesive layer is an aluminum alloy-resin composite formed under an electroless process. According to claim 1,
The adhesive layer is an aluminum alloy-resin composite formed at a temperature of 60 ° C or more and 100 ° C or less. According to claim 1,
The adhesive layer is formed when the aluminum alloy is immersed in an aqueous solution containing the triazine thiol derivative for 30 seconds or more and 1200 seconds or less. According to claim 1,
The resin is an aluminum alloy-resin composite comprising a thermoplastic resin. According to claim 8,
The thermoplastic resin includes at least one selected from polybutylene terephthalate (PBT), polyphthalamide (PPA), polyphenylene sulfide (PPS), acrylonitrile-butadiene-styrene (ABS), and polycarbonate (PC). aluminum alloy-resin composite. Forming an adhesive layer on at least a part of the surface of the aluminum alloy by immersing the aluminum alloy in an aqueous solution containing a triazine thiol derivative,
Forming an aluminum alloy-resin composite by injection molding a thermoplastic resin on the adhesive layer,
The adhesive layer is formed by chemical bonding of the boehmite film and the triazine thiol-based derivative at the same time as the boehmite film is formed on at least a part of the surface of the aluminum alloy,
The triazine thiol derivative is 1,3,5-triazine-2,4,6-trithiol (TT, 1,3,5-triazine-2,4,6-trithiol), 1,3,5- triazine-2,4,6-trithiol triethanolamine (F-TEA, 1,3,5-triazine-2,4,6-trithiol triethanolamine), 6-anilino-1,3,5-triazine-2, 4-dithiol (AF, 6-anilino-1,3,5-triazine-2,4-dithiol), 6-anylino-1,3,5-triazine-2,4-dithiol monosodium (AFN, - Anilino-1,3,5-triazine-2,4-dithiol monosodium), 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB, 6-dibutylamino-1, 3,5-triazine-2,4-dithiol), 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium (DBN, 6-dibutylamino-1,3,5-triazine -2,4-dithiol monosodium), 6-diallylamino-1,3,5-triazine-2,4-dithiol (DA, 6-diallylamino-1,3,5-triazine-2,4- dithiol), 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium (DAN, 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium), 1,3,5-triazine-2,4,6-trithiol di(tetrabutylammonium salt) (F2A, 1,3,5-triazine-2,4,6-trithiol di(tetrabutylammonium salt)), 6 -dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt (DBA, 6-dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt), 6-dithioctylamino -1,3,5-triazine-2,4-dithiol (DO, 6-dithioctylamino-1,3,5-triazine-2,4-dithiol), 6-dithioctylamino-1,3,5- triazine-2,4-dithiol monosodium (DON, 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium), 6-dilaurylamino-1,3,5-triazine-2, 4-dithiol (DL, 6-dilaurylamino-1,3,5-triazine-2,4-dithiol), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN, 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium), 6-stearylamino-1,3,5-triazine-2,4-dithiol (ST, 6-stearylamino -1,3,5-triazine-2,4-dithiol), 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK, 6-stearylamino-1,3,5 -triazine-2,4-dithiol monopotassium), 6-oleilamino-1,3,5-triazine-2,4-dithiol (DL, 6-oleylamino-1,3,5-triazine-2 ,4-dithiol) and 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium (OLK, 6-oleylamino-1,3,5-triazine-2,4-dithiol mono including at least one selected from potassium);
The adhesive layer is a method for producing an aluminum alloy-resin composite formed under an electroless process. delete delete According to claim 10,
The adhesive layer is formed at a temperature of 60 ° C. or more and 100 ° C. or less. Method for producing an aluminum alloy-resin composite. According to claim 10,
The adhesive layer is formed by immersing the aluminum alloy in an aqueous solution containing the triazine thiol derivative for 30 seconds or more and 1200 seconds or less. According to claim 10,
The thermoplastic resin includes at least one selected from polybutylene terephthalate (PBT), polyphthalamide (PPA), polyphenylene sulfide (PPS), acrylonitrile-butadiene-styrene (ABS), and polycarbonate (PC). Method for producing an aluminum alloy-resin composite.

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