KR20170097337A - 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 adhesion between an aluminum alloy and a resin, and a method for producing the same. The aluminum alloy-resin composite may comprise: an aluminum alloy; an adhesive layer formed on at least part of the surface of the aluminum alloy by coupling of a boehmite film and a triazine thiol-based derivative; and a resin adhering to the adhesive layer.

Description

[0001] ALUMINUM ALLOY-RESIN COMPOSITE AND METHOD FOR PRODUCING THE SAME [0002]

The present invention relates to an aluminum alloy-resin composite and a method of manufacturing the same, and more particularly, to an aluminum alloy-resin composite having an improved structure for improving bonding strength between an aluminum alloy and a resin and a method of manufacturing the same.

Electronic products require constant innovation in design and function. As an example of electronic products, in the case of mobile products, metal materials are attracting attention as a means of implementing sophisticated designs. 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 has been considered. In the case of using a metal material-resin composite, it is possible to realize a differentiated design and to solve the problem of the function of the product of electromagnetic wave shielding. In the metal material-resin composite, the bonding force between the metal material and the resin is one of important factors determining the quality of the product. Accordingly, various attempts have been made to improve the bonding force between the metal material and the resin.

An aspect of the present invention provides an aluminum alloy-resin composite having an improved structure capable of realizing tight bonding between an aluminum alloy and a resin, and a method of manufacturing the same.

Another aspect of the present invention provides an aluminum alloy-resin composite having an improved structure for securing waterproof performance and a method of manufacturing the same.

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

Another aspect of the present invention provides an aluminum alloy-resin composite which can be produced through a simple manufacturing process and a method of manufacturing the same.

The aluminum alloy-resin composite according to the present invention may include an adhesive layer formed on at least a part of the surface of the aluminum alloy by bonding of an aluminum alloy, a boehmite coating and a triazine thiol-based derivative, and a resin adhered to the adhesive layer have.

The adhesive layer may be formed by bonding of the boehmite coating and the triazine thiol derivative while forming the boehmite coating on at least a part of the surface of the aluminum alloy.

The triazine thiol derivative may be represented by the following general formula (1).

[Chemical Formula 1]

Here, R is _{SM 3, OR 1, SR 1} , NHR 1 or N (R ₁₎ represents a _2, R ₁ represents an alkyl group, an alkenyl group, a phenyl group, a phenyl group, an alkylphenyl 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 may be 1,3,5-triazine-2,4,6-trithiol (TT), 1,3,5-triazine-2,4,6-trithiol monosodium (TTM) Triazine-2,4,6-trithiol triethanolamine (F-TEA), 6-anilino-1,3,5-triazine-2,4-dithiol (AF), 6-anylino-1,3,5-triazine 2,4-dithiol monosodium (AFN), 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB), 6-dibutylamino-1,3,5-triazine- (DBN), 6-diallylamino-1,3,5-triazine-2,4-dithiol (DA), 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium , 6-dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt (DBA), 6-dithioctylamino- Triazine-2,4-dithiol (DO), 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium (DON), 6-dilaurylamino- , 4-dithiol (DL), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN), 6-stearylamino- , 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK), 6-oleylamino-1,3,5-triazine-2,4-dithiol 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium (OLK).

The adhesive layer may be formed under an electroless process.

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

The adhesive layer may be formed by immersing the aluminum alloy in an aqueous solution containing the triazine thiol derivative for not less than 30 seconds but not longer than 1200 seconds.

The resin may comprise 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 can do.

The method of manufacturing an aluminum alloy-resin composite according to the present invention is characterized in that an aluminum alloy is dipped in an aqueous solution containing a thiazine-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 And forming the aluminum alloy-resin composite, wherein the adhesive layer is formed by bonding a boehmite film to at least a part of the surface of the aluminum alloy and bonding the boehmite film and the triazine thiol-based derivative .

The triazine thiol derivative may be represented by the following general formula (1).

[Chemical Formula 1]

Here, R is _{SM 3, OR 1, SR 1} , NHR 1 or N (R ₁₎ represents a _2, R ₁ represents an alkyl group, an alkenyl group, a phenyl group, a phenyl group, an alkylphenyl 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 adhesive layer may be formed under an electroless process.

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

The adhesive layer may be formed by immersing the aluminum alloy in an aqueous solution containing the triazine thiol derivative for not less than 30 seconds but not longer than 1200 seconds.

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

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

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

Since the use of harmful substances such as strong acids is not required in the process of forming the adhesive layer, the manufacturing process of the aluminum alloy-resin composite is relatively safe and environmentally friendly.

Since the adhesive layer can be formed under the electroless process, it is unnecessary to use electrical equipments and the like, and 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
3 is a view schematically showing a process of forming an aluminum alloy-resin composite according to an embodiment of the present invention;
4 is a block diagram illustrating a method of manufacturing an aluminum alloy-resin composite according to an embodiment of the present invention.
5 is a graph showing the tensile strength of an aluminum alloy-resin composite according to an embodiment of the present invention
6 is a SEM photograph showing an adhesive layer of an aluminum alloy-resin composite according to an embodiment of the present invention
7 is a SEM photograph showing the adhesive layer of the first comparative example of Fig. 5
8 is a SEM photograph showing the adhesive layer of the third comparative example in Fig. 5
9 is a graph showing tensile strength of an aluminum alloy-resin composite according to an embodiment of the present invention,
10 is a graph showing the waterproof performance of an aluminum alloy-resin composite according to an embodiment of the present invention
11 is a view showing a test aluminum alloy-resin composite for measuring the bonding strength of the aluminum alloy-resin composite according to an embodiment of the present invention

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The term "front end", "rear end", "upper", "lower", "upper" and "lower end" used in the following description are defined with reference to the drawings, And the position is not limited. Hereinafter, the aluminum alloy 10 may be used to mean a combination of aluminum and an aluminum alloy. Hereinafter, the unit um in the SEM photograph means μm. Hereinafter, the reference numeral "2" in Fig. 11 means an aluminum alloy-resin composite for testing.

FIG. 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. FIG. 2 is a cross-sectional view of an electronic product to which an aluminum alloy- Fig. 8 is a view showing another example.

As shown in Fig. 1, the aluminum alloy-resin composite 1 can be applied to the appearance of the cellular phone 100 for sophisticated design constructions.

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

The electronic product to which the aluminum alloy-resin composite 1 can be applied is not limited to the cellular phone 100 and the display device 200 but may be any electronic product such as a refrigerator or an air conditioner, .

FIG. 3 is a view schematically showing 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 can be used to mean aluminum and an aluminum alloy. Specifically, the aluminum alloy can be used in all alloys such as aluminum alloy for A1000 to 7000 (anti-corrosion aluminum alloy, high-strength aluminum alloy, heat-resistant aluminum alloy, etc.) and ADC 1 to 12 kinds of aluminum alloys prescribed in Japanese Industrial Standard (JIS) An aluminum alloy for die-casting) may be used. As the shape, it is possible to use a part shaped by a die-casting method such as a casting alloy, or a part shaped by further machining and shaping it. As the wrought alloys, it is also possible to use plate materials as intermediate materials, and parts formed by subjecting them to mechanical processing such as heat press processing.

The resin 20 may include a thermoplastic resin.

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

As one example, the resin 20 may include at least one selected from a polyalkylene terephthalate, a copolymer mainly composed of a polyalkylene terephthalate, and a thermoplastic resin containing a polyalkylene terephthalate as a single 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 part of the surface of the aluminum alloy 10.

The adhesive layer 30 may be formed on at least a part of the surface of the aluminum alloy 10 by bonding of a boehmite coating (AlO (OH)) 31 and a triazine thiol derivative 32. The adhesive layer 30 may be formed on at least a part of the surface of the aluminum alloy 10 by bonding of the aluminum hydroxide coating (Al (OH) ₃ ) and the triazine thiol derivative 32. Specifically, the adhesive layer 30 is formed by chemical bonding of the boehmite film 31 and the triazine thiol derivative 32 or chemical bonding of the aluminum hydroxide film and the triazine thiol derivative 32 to the surface of the aluminum alloy 10 As shown in FIG. More specifically, the adhesive layer 30 may be formed on at least a part 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 have. Hereinafter, the case where the adhesive layer 30 is formed by bonding of the boehmite film 31 and the triazine thiol derivative 32 will be mainly described.

The triazine thiol derivative may be represented by the following formula (1).

[Chemical 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 phenylalkyl group, an alkylphenyl 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 a derivative of 1,3,5-triazine-2,4,6-trithiol (TT), 1,3,5-triazine-2,4,6-trithiol monosodium ), 1,3,5-triazine-2,4,6-trithiol triethanolamine (F-TEA), 6-anilino-1,3,5-triazine- , 3,5-triazine-2,4-dithiol monosodium (AFN), 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB), 6-dibutylamino- 2,4-dithiol monosodium (DBN), 6-diallylamino-1,3,5-triazine-2,4-dithiol (DA), 6-diallylamino-1,3,5-triazine- DAN), 1,3,5-triazine-2,4,6-trithiol di (tetrabutylammonium salt) (F2A), 6-dibutylamino-1,3,5-triazine- 6-dithioctylamino-1,3,5-triazine-2,4-dithiol (DO), 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium , 5-triazine-2,4-dithiol (DL), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN), 6-stearylamino- 4-dithiol (ST), 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK), 6-oleylamino-1,3,5-triazine- hyal (DL) and 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium (OLK). However, the type of the triazine thiol derivative (32) is not limited to the above example.

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

The resin 20 can be adhered to the adhesive layer 30. [ Specifically, the resin 20 can bond with the triazine thiol-based derivative 32 of the adhesive layer 30. The boehmite film (31) or the aluminum hydroxide film can serve to improve the bonding strength between the resin (20) and the triazine thiol derivative (32).

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

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

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. The method of manufacturing the aluminum alloy-resin composite 1 may further include a pre-processing step (P2) of the aluminum alloy 10. The method for producing the aluminum alloy-resin composite 1 may further include an adhesive layer forming step (P3) for forming the adhesive layer 30 on at least a part of the surface of the aluminum alloy 10. The manufacturing method of the aluminum alloy-resin composite 1 may further include a drying step (P4). The method for producing the aluminum alloy-resin composite 1 may further include a molding step (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 step for mechanically processing the shape of the aluminum alloy 10. As an example, the processing step P1 of the aluminum alloy 10 may include a pressing step, a CNC step, a die-cast step, and the like.

When the processing step P1 of the aluminum alloy 10 is completed, the pre-processing step P2 of the aluminum alloy 10 can be performed.

The pre-processing 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, oil or dust may be present on the surface of the aluminum alloy 10. The surface of the machined aluminum alloy 10 may be adhered with cooling liquid, debris, etc. used in machining. A degreasing step (S1) of the aluminum alloy 10 is required to remove the foreign substances as described above from the surface of the aluminum alloy 10. The degreasing step (S1) of the aluminum alloy (10) is preferably carried out at a temperature of from 40 to 60 deg. It is preferable that the degreasing step (S1) of the aluminum alloy (10) is performed for not less than 2 minutes and not more than 5 minutes. The material constituting the degreasing liquid may be an aluminum alloy cleaning article whose main component is a surfactant. The degreasing step S1 of the aluminum alloy 10 may include an acid degreasing process using an acidic substance and a surfactant together.

The pre-treatment step (P2) may further include an alkali etching step (S2). The alkali etching step S2 removes the aluminum oxide film naturally formed on the surface of the aluminum alloy 10, so that the adhesive layer 30 can be smoothly formed on the surface of the aluminum alloy 10. The alkali etching step S2 is preferably performed at a temperature of 30 DEG C or more and 50 DEG C or less. Further, it is preferable that the alkali etching step (S2) is performed for a period of from 1 minute to 2 minutes or less. The material constituting the degreasing liquid may include a basic material capable of etching the aluminum alloy 10. Specifically, the material constituting the degreasing liquid may include hydroxides of alkali metal hydroxides such as sodium hydroxide (NaOH), potassium hydroxide (KOH) and the like.

The preprocessing step P2 may further include a desmut process (desmut) S3. The foreign substance present on the surface of the aluminum alloy 10 can be removed through the desmutting step S3. Specifically, after the alkali etching step (S2), the metal dissolved in the aluminum alloy (10) such as sodium hydroxide and magnesium, copper, silicon and the like is not completely dissolved in the alkali etching (S2) Or other composition. Dismount S3 is a process for removing such foreign matter. The desmut S3 is preferably performed at a temperature of 20 ° C or more and 40 ° C or less. It is also preferable that the desmut S3 is performed for a time of not less than 1 minute and not more than 3 minutes. In the dismant (S3) process, an aqueous acid solution can be used as the 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 pre-processing step P2 of the aluminum alloy 10 is completed, an adhesive layer forming step P3 for forming the adhesive layer 30 on at least a part of the surface of the aluminum alloy 10 may be performed. The adhesive layer forming step (P3) is preferably carried out at a temperature of 60 DEG C or more and 100 DEG C or less. It is preferable that the adhesive layer forming step (P3) is performed for 30 seconds to 1200 seconds. Specifically, the adhesive layer 30 is obtained by immersing the aluminum alloy 10, which has undergone the pre-processing step (P2) of the aluminum alloy 10, in an aqueous solution containing a thiazine thiol derivative for 30 seconds to 1200 seconds have.

When the aluminum alloy 10 is immersed in an aqueous solution containing a thiazine thiol derivative, the boehmite film 31 may be formed on at least a part of the surface of the aluminum alloy 10. The triazine thiol derivative (32) may be chemically bonded to the boehmite film (31) to form the adhesive layer (30). Specifically, the adhesive layer 30 can be formed on at least a part 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 adhesive layer 30 by the chemical bond between 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 boehmite film 31 and the triazine thiol derivative 32 is simultaneously carried out . 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 thiazine thiol derivative. As described above, the present invention is advantageous in that the step of forming the adhesive layer 30, which bonds the aluminum alloy 10 and the resin 20, is simple and the time required for forming the adhesive layer 30 can be shortened.

The adhesive layer 30 can be formed under the 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 thiazine thiol-based derivative in order to form the adhesive layer 30, and it is not necessary to undergo a separate process of electrochemical polymerization.

Therefore, since the present invention does not require an electric facility for the electric polymerization, it is possible to save the facility investment cost and the maintenance cost. In addition, a strong acid such as sulfuric acid is used in the electropolymerization process, and sulfuric acid may be scattered by the gas at a temperature of 60 DEG C or more at which the adhesive layer formation step (P3) is performed, which may cause safety problems. As a result, since the adhesive layer 30 of the present invention can be formed under the electroless process, it can be expected that the process is eco-friendly, the manufacturing process is simplified, and the manufacturing cost is reduced.

When the adhesive layer forming step P3 is completed, a drying step P4 for drying the aluminum alloy 10 on which the adhesive layer 30 is formed can be performed.

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

When the drying step P4 is completed, a molding step P5 for injection molding the resin 20 into the adhesive layer 30 can be performed.

In the molding step (P5), the higher the mold temperature or injection temperature is, the more it is not necessary to increase the temperature forcibly. The molding step (P5) can be carried out under the same conditions as the ordinary injection molding process using a thermoplastic resin.

In the molding step (P5), the resin (20) is adhered to the adhesive layer (30) to form the aluminum alloy-resin composite (1) having a firm bonding force.

A method of forming an aluminum alloy-resin composite 1 by using an adhesive layer 30 as an alternative to the method of bonding the aluminum alloy 10 and the resin 20 as in the present invention, There is a method of bonding the alloy 10 and the resin 20. This is because the surface of the aluminum alloy 10 is roughened and then the resin 20 is penetrated to the surface of the roughened aluminum alloy 10 to form the aluminum alloy-resin composite 1. That is, the aluminum alloy-resin composite 1 is formed using physical bonding between the aluminum alloy 10 and the resin 20. However, in order to form the aluminum alloy-resin composite 1 by using the physical bonding between the aluminum alloy 10 and the resin 20, it is inevitable to use a large amount of strong acid, . Further, the resin 20 is hardly densely packed on the rough surface of the aluminum alloy 10, so that 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 it is unnecessary to use harmful substances such as strong acid in the process of forming the adhesive layer 30, it is eco-friendly. Since the chemical bonding between the aluminum alloy 10 and the resin 20 can be achieved through the adhesive layer 30, the bonding strength between the aluminum alloy 10 and the resin 20 is relatively strong.

[Example]

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

(a) Electron microscopic observation

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

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

A universal material 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 into a plurality of rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in an experimental tank, and a commercially available degreasing agent for aluminum alloy "Al Clean paste (Burim Aya)" and nitric acid (70%) was added thereto to prepare an aqueous solution having a concentration of 5% at a temperature of 50 ° C. The rectangular aluminum alloy piece was immersed in this for 3 minutes and washed well. Subsequently, NaOH (98%) was added to another experimental tank at 40 DEG C to prepare an aqueous solution having a concentration of 5% at a temperature of 40 DEG C, and the aluminum alloy piece was dipped in the aluminum alloy piece for 90 seconds. Next, nitric acid (70%) was added to another experimental tank to prepare an aqueous solution having a temperature of 25 ° C and a concentration of 7%, and the aluminum alloy piece was immersed for two minutes to wash well. Next, an aqueous solution containing 0.36 g / L of 1,3,5-triazine-2,4-dithiol-6-sodium thiolate at 80 ° C. is prepared in another experimental tank, and the aluminum alloy piece is immersed in the solution for 3 minutes. Then, in another experimental tank, water (60 ° C) was taken out with water and dried with an air blower. When one of the pieces was observed with an electron microscope, a disordered network-like film was formed and its shape was more rounded than that of the aluminum hydroxide film, so that the triazine thiol derivative was covered with the aluminum hydroxide film I could confirm that it was gone. This is shown in the SEM photograph of Fig. The five surface-treated aluminum alloy pieces were taken out and extruded into a 140-ton horizontal sodick in the same shape as the test aluminum alloy-resin composite shown in Fig. 11 with a PBT / GF 40% resin, and then subjected to a tensile fracture test As a result, the average tensile strength was very strong, as shown in FIG. 5, at 32 MPa.

≪ Comparative Example 1 > (Adhesion with Al 6013 Aluminum Alloy-Aluminum hydroxide surface)

A commercially available Al 6013 extruded material was obtained and cut into a plurality of rectangular pieces of 40 mm x 12 mm x 3 mm. Water was prepared in an experimental tank, and a commercially available degreasing agent for aluminum alloy "Al Clean paste (Burim Aya)" and nitric acid (70%) was added thereto to prepare an aqueous solution having a concentration of 5% at a temperature of 50 ° C. The rectangular aluminum alloy piece was immersed in this for 3 minutes and washed well. Subsequently, NaOH (98%) was added to another experimental tank at 40 DEG C to prepare an aqueous solution having a concentration of 5% at a temperature of 40 DEG C, and the aluminum alloy piece was dipped in the aluminum alloy piece for 90 seconds. Next, nitric acid (70%) was added to another experimental tank to prepare an aqueous solution having a temperature of 25 ° C and a concentration of 7%, and the aluminum alloy piece was immersed for several minutes to wash well. Subsequently, an aqueous solution at a temperature of 80 ° C was prepared in another experimental tank, and the aluminum alloy piece was immersed in the solution for 3 minutes and dried with an air blower. Thereafter, one of the pieces was observed with an electron microscope to reveal that a disorderly network-like film was formed, and that this was an aluminum hydroxide film. This is shown in the SEM photograph of Fig. Five aluminum alloy pieces subjected to the surface treatment described above were taken out and extruded under the same conditions as in Experimental Example 1, and then subjected to a tensile fracture test.

≪ Comparative Example 2 > (Adhesion with Al 6013 Aluminum Alloy - Utilizing an anchor effect)

A commercially available Al 6013 extruded material was obtained and cut into a plurality of rectangular pieces of 40 mm ㅧ 12 mm ㅧ 3 mm. Water was prepared in an experimental tank, and a degreasing agent "Al Clean paste (Burim Aya)" for aluminum alloy, which was commercially available, and nitric acid were added thereto to prepare an aqueous solution having a concentration of 5% at 50 ° C. The rectangular aluminum alloy piece was immersed in this for 5 minutes and washed well. Subsequently, the surface treatment solution was prepared at 25 캜 in another test tank, and the aluminum alloy piece was immersed for one minute and washed well. Here, the surface treatment liquid may be an aqueous solution containing an alkaline source and a positive metal ion. Next, a 7% strength hydrochloric acid solution and a 45% strength aqueous solution of aluminum chloride hexahydrate at 30 占 폚 were prepared in another experimental tank, and the aluminum alloy piece was immersed for two minutes and washed well. Subsequently, a 15% nitric acid aqueous solution at 25 캜 was prepared in another experimental tank, and the aluminum alloy piece was immersed in water for 2 minutes and then washed with water. Subsequently, an ultrasonic wave water bath at room temperature was prepared in another experimental tank, and ultrasonic cleaning was performed for 3 minutes. The resultant was placed in a warm air dryer at 70 ° C for 15 minutes and then dried. Five aluminum alloy pieces subjected to the surface treatment described above were taken out and extruded 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 shown in FIG.

≪ Comparative Example 3 > (Electropolymerization Surface Treatment Containing Al 6013 Aluminum Alloy and Bonding-Triazine Thiol Derivative)

A commercially available Al 6013 extruded material was obtained and cut into a plurality of rectangular pieces of 40 mm ㅧ 12 mm ㅧ 3 mm. Water was prepared in an experimental tank, and a commercially available degreasing agent for aluminum alloy "Al Clean paste (Burim Aya)" and nitric acid (70%) was added thereto to prepare an aqueous solution having a concentration of 5% at a temperature of 50 ° C. The rectangular aluminum alloy piece was immersed in this for 3 minutes and washed well. Subsequently, NaOH (98%) was added to another experimental tank at 40 DEG C to prepare an aqueous solution having a concentration of 5% at a temperature of 40 DEG C. The aluminum alloy piece was immersed in the solution for 60 seconds and washed well. Next, sulfuric acid (98%) was added to another experimental tank to prepare an aqueous solution having a concentration of 2% at a temperature of 30 DEG C, and the aluminum alloy piece was immersed for two minutes to wash well. Next, an aqueous solution having a sulfuric acid (98%) concentration of 5% and a DBN (98%) concentration of 0.18 g / L at a temperature of 60 ° C was prepared in another experiment vessel. A carbon rod was attached to the anode and an aluminum alloy piece was connected to the anode. ² , immersed in the prepared solution for 15 minutes, and washed well. The treated aluminum alloy piece was dried with an air blower, and one of the pieces was observed with an electron microscope. As a result, it was confirmed that a triazine thiol-based derivative bonding layer was formed on the surface of the aluminum alloy as the electric polymerization was performed on the aluminum alloy surface . This is shown in the SEM photograph of Fig. As a result of 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 32 MPa as shown in FIG.

≪ Comparative Example 4 > (Surface treatment using a triazine thiol-based derivative containing an Al 6013 aluminum alloy and an adhesive alkoxysilane)

A commercially available Al 6013 extruded material was obtained and cut into a plurality of rectangular pieces of 40 mm ㅧ 12 mm ㅧ 3 mm. The rectangular aluminum alloy piece was immersed in an aqueous solution having a temperature of 40 ° C and an alkali component of 30 g / L (the proportion of condensed phosphate in the mixture was 50 to 60%) at about pH 9.5 for 5 minutes for washing treatment. After the washing treatment, the aluminum alloy piece of the rectangular piece was washed with pure water for 1 minute. Then, a triethanolamine aqueous solution having a concentration of 3 g / L and a pH of 8.0 was used as the boehmite treatment liquid. The temperature of the triethanolamine aqueous solution was adjusted to 95 占 폚, and the aluminum alloy piece of the rectangular piece was immersed in a triethanolamine aqueous solution for 15 minutes. As a result, a metal compound coating film containing boehmite as a main component, which is a hydrated oxide of aluminum, was obtained. Thereafter, the aluminum alloy piece of the rectangular piece was immersed in the alkoxysilane-containing triazine thiol derivative solution. The trialkoxysilyl-containing triazinethiol derivative containing triethoxysilylpropylamino triazine dithiol monosodium was dissolved in a solvent of ethanol 95: water 5 (volume ratio) so as to have a concentration of 0.7 g / L To obtain a solution of an alkoxysilane-containing triazine thiol derivative. An aluminum alloy piece of a rectangular piece was immersed in this solution for 30 minutes at room temperature. Subsequently, the aluminum alloy piece of the rectangular piece was heat-treated in an oven at 160 DEG C for 10 minutes, and the reaction was completed and dried at the same time. Then, to a solution of acetone having a concentration of 1.0 g / L of N, N'-m-phenylene dimaleimide (N, N'-1,3-phenylene dimaleimide) and a concentration of 2 g / L of dicumyl peroxide Immersed at room temperature for 10 minutes, and then heat-treated in an oven at 150 DEG C for 10 minutes. Thereafter, an ethanol solution of dicumyl peroxide having a concentration of 2 g / L was sprayed to the entire surface of the rectangular aluminum alloy piece at room temperature and dried with an air blower. As a result of tensile fracture test after the above-mentioned 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 shown in FIG.

≪ Experimental Example 2 > (Al 6013 Aluminum Alloy and Adhesion _ Experiment by Temperature)

A commercially available Al 6013 extruded material was obtained and cut into a plurality of rectangular pieces of 40 mm ㅧ 12 mm ㅧ 3 mm. Water was prepared in an experimental tank, and a commercially available degreasing agent for aluminum alloy "Al Clean paste (Burim Aya)" and nitric acid (70%) was added thereto to prepare an aqueous solution having a concentration of 5% at a temperature of 50 ° C. The rectangular aluminum alloy piece was immersed in this for 3 minutes and washed well. Subsequently, NaOH (98%) was added to another experimental tank at 40 DEG C to prepare an aqueous solution having a concentration of 5% at a temperature of 40 DEG C, and the aluminum alloy piece was dipped in the aluminum alloy piece for 90 seconds. Next, nitric acid (70%) was added to another experimental tank to prepare an aqueous solution having a temperature of 25 ° C and a concentration of 7%, and the aluminum alloy piece was immersed for several minutes to wash well. Next, 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 increased from 60 ° C to 10 ° C, The alloy pieces were immersed for 5 minutes in each of the five pieces. Then, in another experimental tank, water (60 ° C) was taken out with water and dried with an air blower. A total of twenty-five aluminum alloy pieces subjected to the above-mentioned surface treatment were taken out and extruded into a 140-ton horizontal sodick in the same shape as the test aluminum alloy-resin composite shown in FIG. 11 with PBT / GF 40% Test. The test results are shown in Fig.

EXPERIMENTAL EXAMPLE 3 (Experiment with Al 6013 Aluminum Alloy-Time-Bond Test)

A commercially available Al 6013 extruded material was obtained and cut into a plurality of rectangular pieces of 40 mm ㅧ 12 mm ㅧ 3 mm. Water was prepared in an experimental tank, and a commercially available degreasing agent for aluminum alloy "Al Clean paste (Burim Aya)" and nitric acid (70%) was added thereto to prepare an aqueous solution having a concentration of 5% at a temperature of 50 ° C. The rectangular aluminum alloy piece was immersed in this for 3 minutes and washed well. Subsequently, NaOH (98%) was added to another experimental tank at 40 DEG C to prepare an aqueous solution having a concentration of 5% at a temperature of 40 DEG C, and the aluminum alloy piece was dipped in the aluminum alloy piece for 90 seconds. Next, nitric acid (70%) was added to another experimental tank to prepare an aqueous solution having a temperature of 25 ° C and a concentration of 7%, and the aluminum alloy piece was immersed for two minutes to wash 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 immersed for 30, 60, 120, 180, 300 , 600, and 1200 seconds, respectively. Then, in another experimental tank, water (60 ° C) was taken out with water and dried with an air blower. A total of 35 aluminum alloy pieces subjected to the surface treatment described above were taken out and extruded into a 140-ton horizontal sodick in the same shape as the test aluminum alloy-resin composite shown in Fig. 11 with PBT / GF40% resin, Test. The test results are shown in Fig.

≪ Experimental Example 4 > (Waterproof performance test)

The waterproof performance of the aluminum alloy-resin composite produced was replaced by a more severe condition, the air leak test. The air leak test conditions were such that inner and outer portions of a plate-shaped aluminum alloy of about 100 mm, 80 mm and 7 mm were processed and surface-treated in the same manner as in Experimental Example 1, Comparative Example 2, and Comparative Example 3. And then injected with a resin containing PBT / GF 40% to prepare an aluminum alloy-resin composite. A jig capable of sealing the manufactured aluminum alloy-resin composite is manufactured, and the jig is placed on the press machine. The aluminum alloy-resin composite was placed on the jig, the press machine was operated, and the jig was closely adhered to the upper and lower sides to create an airtight space, and air of 10 kPa was blown into the airtight space. When the air pressure injected for 10 seconds was less than 1%, it was judged that the waterproof performance failed and 10 pieces were measured for each condition. The waterproof performance test results are shown in Fig. 10 shows that the aluminum alloy-resin composite produced by Experimental Example 1 has superior waterproof performance to the aluminum alloy-resin composite produced by Comparative Example 2 and Comparative Example 3 Can be confirmed.

The foregoing has shown and described specific embodiments. However, it should be understood that the present invention is not limited to the above-described embodiment, and various changes and modifications may be made without departing from the technical idea of the present invention described in the following claims .

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

Claims (15)

Aluminum alloy;
An adhesive layer formed on at least a part of the surface of the aluminum alloy by bonding of a boehmite film and a triazine thiol derivative; And
And a resin adhered to the adhesive layer. The method according to claim 1,
Wherein the adhesive layer is formed by bonding the boehmite coating film and the triazine thiol-based derivative with the boehmite film formed on at least a part of the surface of the aluminum alloy. The method according to claim 1,
The triazine thiol derivative is represented by the following formula (1).
[Chemical Formula 1]

Wherein 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 phenylalkyl group, an alkylphenyl 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 method according to claim 1,
The triazine thiol derivative may be 1,3,5-triazine-2,4,6-trithiol (TT), 1,3,5-triazine-2,4,6-trithiol monosodium (TTM) Triazine-2,4,6-trithiol triethanolamine (F-TEA), 6-anilino-1,3,5-triazine-2,4-dithiol (AF), 6-anylino-1,3,5-triazine 2,4-dithiol monosodium (AFN), 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB), 6-dibutylamino-1,3,5-triazine- (DBN), 6-diallylamino-1,3,5-triazine-2,4-dithiol (DA), 6-diallylamino-1,3,5-triazine-2,4-dithiol monosodium , 6-dibutylamino-1,3,5-triazine-2,4-dithiol tetrabutylammonium salt (DBA), 6-dithioctylamino- Triazine-2,4-dithiol (DO), 6-dithioctylamino-1,3,5-triazine-2,4-dithiol monosodium (DON), 6-dilaurylamino- , 4-dithiol (DL), 6-dilaurylamino-1,3,5-triazine-2,4-dithiol monosodium (DLN), 6-stearylamino- , 6-stearylamino-1,3,5-triazine-2,4-dithiol monopotassium (STK), 6-oleylamino-1,3,5-triazine-2,4-dithiol 6-oleylamino-1,3,5-triazine-2,4-dithiol monopotassium (OLK). The method according to claim 1,
Wherein the adhesive layer is formed under an electroless process. The method according to claim 1,
Wherein the adhesive layer is formed at a temperature of 60 占 폚 or more and 100 占 폚 or less. The method according to claim 1,
Wherein the adhesive layer is formed by immersing the aluminum alloy in an aqueous solution containing the triazine thiol derivative for 30 seconds to 1200 seconds. The method according to claim 1,
Wherein the resin comprises a thermoplastic resin. 9. The method of 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 Aluminum alloy-resin composite. An aluminum alloy is immersed in an aqueous solution containing a thiazine thiol derivative to form an adhesive layer on at least a part of the surface of the aluminum alloy,
And forming an aluminum alloy-resin composite by injection molding a thermoplastic resin into the adhesive layer,
Wherein the adhesive layer is formed by forming a boehmite film on at least a part of the surface of the aluminum alloy and by bonding the boehmite film and the triazine thiol-based derivative. 11. The method of claim 10,
Wherein the triazine thiol derivative is represented by the following formula (1).
[Chemical Formula 1]

Wherein 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 phenylalkyl group, an alkylphenyl 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. 11. The method of claim 10,
Wherein the adhesive layer is formed under an electroless process. 11. The method of claim 10,
Wherein the adhesive layer is formed at a temperature of 60 ° C or more and 100 ° C or less. 11. The method of claim 10,
Wherein the adhesive layer is formed by immersing the aluminum alloy in an aqueous solution containing the triazine thiol derivative for not less than 30 seconds but not longer than 1200 seconds. 11. The method of 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 Wherein the aluminum alloy-resin composite is produced by a method comprising the steps of:

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