TWI475132B - Surface-treated metal, metal-resin composite and method for preparing the same - Google Patents

Description

Surface treated metal, metal resin composite and preparation method thereof

The present invention relates to the field of materials science, and in particular to a method of treating a metal surface and a surface treated metal, and a method of preparing a metal resin composite and a metal resin composite.

In the field of parts manufacturing of automobiles, household appliances, industrial machines, etc., an integral molding technique of metal and resin is required. At present, the technology that can be used to integrate metal and resin includes the use of adhesives, nano-processing technology, and chemical treatment of aluminum alloy surfaces under normal temperature or heating conditions to prepare metal-plastic integrated products. However, the obtained products have the disadvantages of poor bonding strength, high production cost, poor tensile strength and unfavorable safety production, poor environmental performance and the like.

Therefore, the current metal resin integration technology still needs further improvement.

The present invention is directed to solving at least some of the above technical problems or at least providing a useful commercial choice. Accordingly, it is an object of the present invention to provide a method for treating a surface and a surface-treated metal, wherein the surface-treated metal has a strong bonding force with a resin, and the process is simple and suitable for mass production; and at the same time, another object of the present invention It is to provide a method for preparing a metal resin composite and a metal resin composite, and the metal tree prepared by the method The resin layer of the lipid composite has good bonding strength with the metal layer substrate, has good tensile shear strength, and the process adopted by the invention has no pollution and meets environmental protection requirements.

In a first aspect of the invention, the present invention provides a method of treating a metal surface, comprising the steps of: anodizing a metal substrate to obtain a metal substrate having an anodized film on the surface, wherein The metal substrate is an aluminum alloy substrate or an aluminum substrate; the metal substrate having an anodized film on the surface is surface-treated with an etching solution to obtain a surface-treated metal substrate; wherein the etching The liquid contains at least one of a chloride ion and a phosphate ion, and the concentration of H+ in the etching solution is 0.55 to 5.5 mol/L. By treating the metal by the method of the invention, there is no obvious change in the appearance of the metal, the reaction heat is less, the temperature of the etching liquid is slow, the consumption is small, the corrosion to the device is small, and the method is more suitable for mass production.

In another aspect of the invention, the invention provides a surface treated metal obtained by the method described above. The surface-treated metal has a three-layered three-dimensional pore structure, and the pore structure has a unique structure of being small and large. Thereby, the surface-treated metal has a good bonding property, so that it can be firmly bonded with the resin to form a high-strength metal resin composite.

In yet another aspect of the invention, the invention provides a surface treated metal. The metal includes: a metal substrate which is an aluminum alloy substrate or an aluminum substrate; and an anodized film layer, the anodized layer is formed on a surface of the metal substrate; wherein the anode The oxide film layer includes: a barrier layer in contact with the metal substrate; and a loose layer formed on a surface of the barrier layer away from the metal substrate, an etching layer, the corrosion A layer is formed on the surface of the barrier layer adjacent to the metal substrate. The surface-treated metal has a three-layered three-dimensional pore structure, and the pore structure has a unique structure of being small and large. by Thus, the surface-treated metal has a good bonding property, so that it can be firmly bonded to the resin to form a high-strength metal resin composite.

In still another aspect of the present invention, the present invention provides a method of preparing a metal resin composite. The method comprises the steps of providing the surface-treated metal described above; and injection molding a resin composition onto the surface of the surface-treated metal to obtain the metal-resin composite. By preparing the metal resin composite by the method of the present invention, there is no requirement for the synthetic resin, the application range is wider, and the environmental pollution is small, and it is more suitable for large-scale production.

In still another aspect of the invention, the invention provides a metal resin composite. The metal resin composite is obtained by the above method. The metal and the resin in the metal-resin composite are firmly combined, high in strength, and meet environmental protection requirements due to the use of the metal provided by the present invention and having a three-layered three-dimensional pore structure with a unique structure on the surface.

In another aspect of the invention, the invention provides a metal resin composite. The metal resin composite includes: a metal layer which is the surface-treated metal, wherein the metal layer has an anodized film micropore, a barrier etching hole, and a metal etching hole; and a resin layer, A resin layer is bonded to the surface of the metal layer, wherein a resin composition forming the resin layer is filled in the anodized film micropores, the barrier layer etching holes, and the metal etching holes. The metal and the resin in the metal-resin composite are firmly combined, high in strength, and meet environmental protection requirements due to the use of the metal provided by the present invention and having a three-layered three-dimensional pore structure with a unique structure on the surface.

The additional aspects and advantages of the invention will be set forth in part in the description which follows.

The above and/or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the accompanying drawings in which <RTIgt; Fig. 2 is a temperature-time change diagram of the system when immersed according to Example 14 and Comparative Example 6 of the present invention; and Fig. 3 is an illustration of Comparative Example 21 and Comparative Example 9 according to the present invention. The temperature-time change diagram of the system when the etching solution is immersed.

The embodiments of the present invention are described in detail below, and the examples of the embodiments are illustrated in the drawings, wherein the same or similar reference numerals are used to refer to the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the drawings are intended to be illustrative of the invention and are not to be construed as limiting.

Moreover, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, features defining "first" and "second" may include one or more of the features either explicitly or implicitly. In the description of the present invention, the meaning of "a plurality" is two or more unless specifically and specifically defined otherwise.

In a first aspect of the invention, the present invention provides a method of treating a metal surface, comprising the steps of: anodizing a metal substrate to obtain a metal substrate having an anodized film on the surface, wherein The metal substrate is an aluminum alloy substrate or an aluminum substrate; the metal substrate having an anodized film on the surface is surface-treated with an etching solution to obtain a surface-treated metal substrate; wherein the etching Liquid contains chloride and phosphate At least one of the ions, the concentration of H+ in the etching solution is 0.55-5.5 mol/L. By treating the metal by the method of the invention, there is no obvious change in the appearance of the metal, the reaction heat is less, the temperature of the etching liquid is slow, the consumption is small, the corrosion to the device is small, and the method is more suitable for mass production.

According to an embodiment of the present invention, the metal substrate having the anodized film on the surface is surface-treated with an etching liquid, and the etching liquid is at least one selected from the group consisting of a hydrochloric acid solution and a phosphoric acid solution. According to an embodiment of the present invention, the composition of the etching liquid is not particularly limited. According to a specific embodiment of the present invention, the etching liquid may be a single acidic solution, and may be a composite solution. According to an embodiment of the present invention, the single acidic solution may be an aqueous solution of hydrochloric acid, a phosphoric acid solution or the like. According to an embodiment of the present invention, the composition of the composite solution is not particularly limited, and according to a specific example of the present invention, the composite solution may be a mixed solution of a soluble acid and a soluble salt such as hydrochloric acid and chloride. According to a specific example of the present invention, the content of hydrogen chloride may be 2% by weight to 20% by weight based on the total weight of the aqueous solution of hydrochloric acid and chloride, and the content of the chloride may be 1% by weight to 20% by weight. According to another specific example of the present invention, the composite solution may be an aqueous solution of phosphoric acid and phosphate, wherein the content of H3PO4 is 3 wt% to 30 wt%, and the content of phosphate is 1 wt% to 20 wt% based on the total weight of the phosphoric acid and phosphate aqueous solution. %. The inventors have found that by surface-treating a metal substrate having an anodized film on the surface by using the above etching liquid, the metal etching holes can be uniformly distributed on the surface of the metal substrate, and the pore diameter is uniform, and the resin layer and the metal substrate can be made. Better bonding performance and better tensile strength make the integrated combination of metal composites better.

According to an embodiment of the present invention, the metal substrate having an anodized film on the surface is surface-treated with a hydrochloric acid solution, and the content of hydrogen chloride is 2 wt% to 20 wt%, preferably 5 wt% to 18 wt%, based on the total weight of the hydrochloric acid solution. %, more preferably from 5 wt% to 15 wt%. The inventors have found that a metal substrate having an anodized film on its surface is carried out by using the above hydrochloric acid solution. The surface treatment can uniformly distribute the metal corrosion holes on the surface of the metal substrate, and has a uniform pore diameter, can better combine the resin layer and the metal substrate, and has better tensile strength, so that the metal composite is integrated. Better combination.

According to an embodiment of the present invention, the metal substrate having an anodized film on the surface is surface-treated with a phosphoric acid solution, and the content of H3PO4 is from 3 wt% to 40 wt%, preferably 5 wt%, based on the total weight of the phosphoric acid solution. ~30% by weight, more preferably 5% by weight to 20% by weight. The inventors have found that by surface-treating a metal substrate having an anodized film on the surface by using the above phosphoric acid solution, the metal etching hole can be uniformly distributed on the surface of the metal substrate, and the pore diameter is uniform, and the resin layer can be bonded to the metal substrate. Better performance, better tensile strength, and better integration of metal composites. According to some embodiments of the invention, the phosphoric acid solution further contains an inorganic halide, the inorganic halide being a soluble hydrochloride salt. According to an embodiment of the present invention, the soluble hydrochloride is not particularly limited as long as it does not react with H3PO4, produces precipitates and gases, and does not affect the performance of H3PO4, and may be various soluble hydrochlorides commonly used by those skilled in the art, according to the present invention. In a specific example of the invention, the soluble hydrochloride salt may be at least one selected from the group consisting of sodium chloride, potassium chloride, and aluminum chloride. According to a specific example of the present invention, the content of the soluble hydrochloride is 0.01% by weight to 10% by weight based on the total weight of the phosphoric acid solution. The inventors have surprisingly found that chloride ions tend to form pitting on the metal surface under acidic conditions, and it is easy to etch more holes on the metal surface, thereby further increasing the reaming speed of phosphoric acid corrosion, reducing the operation time, and optimizing. Hole structure.

According to some embodiments of the present invention, the metal substrate is pre-treated prior to anodizing the metal substrate, the pre-treatment comprising: grinding the metal substrate, and then de-oiling the metal substrate in sequence First wash, eclipse, second wash, neutralization and The third washing treatment. According to some embodiments of the present invention, the kind of the metal substrate to be pretreated is not particularly limited, and may be an aluminum alloy substrate or an aluminum substrate. According to a specific example of the present invention, the aluminum alloy substrate may be an industrial standard 1000. - A variety of aluminum alloys in the 7000 series or die cast grade. According to some embodiments of the present invention, the pattern of the aluminum alloy substrate is not particularly limited, and may be various forms and structures of aluminum alloy substrates commonly used by those skilled in the art. According to a specific example of the present invention, the aluminum alloy substrate Various shapes and structures can be obtained by machining. According to an embodiment of the present invention, the manner of sanding the metal substrate is not subject to any limitation, and those skilled in the art may employ various pre-treatment processes for pre-treating the metal substrate, according to an embodiment of the present invention, the metal The pretreatment process of the substrate may include mechanically grinding or grinding to remove foreign matter on the surface, and then degreasing and cleaning the surface of the metal substrate to remove the processing oil adhered to the surface of the metal substrate by polishing. According to a specific embodiment of the present invention, the pretreatment step of the metal substrate preferably includes grinding the surface of the metal substrate, for example, grinding with 100-400 mesh sandpaper or placing the metal substrate into the polishing machine. The surface of the metal substrate is ground to produce micron-sized pores, and then the steps of degreasing, first water washing, etching, second water washing, neutralization, and third water washing are sequentially performed. According to some embodiments of the present invention, the manner of degreasing and cleaning the polished metal substrate is not limited in any way, and those skilled in the art can degrease and clean the polished metal substrate in ultrasonic waves by using various commonly used solvents. According to a specific embodiment of the present invention, the polished metal substrate may be degreased and cleaned for 0.5 hour to 2 hours, and then the polished metal substrate is placed in an acid/alkaline aqueous solution in an ultrasonic wave. Further washing was carried out under the conditions. According to some embodiments of the present invention, the solvent for cleaning the ground metal substrate is not particularly limited, and according to a specific example of the present invention, the solvent for cleaning the ground metal substrate may be ethanol or acetone. According to this issue In other embodiments, the acid/alkaline aqueous solution for further washing the ground metal substrate is not particularly limited and may be various acid/alkaline aqueous solutions commonly used by those skilled in the art, according to some specific examples of the present invention. The acid/basic aqueous solution for further washing the polished metal substrate may be at least one selected from the group consisting of hydrochloric acid, sulfuric acid, sulfuric acid, sodium hydroxide, and potassium hydroxide. According to a preferred embodiment of the present invention, the surface of the metal substrate is degreased with anhydrous ethanol and then washed with water; after wiping off, the metal substrate is immersed in 30 g/L to 70 g/L, and the temperature is 40 to 80 degrees Celsius. The sodium aqueous solution is subjected to etch treatment for 1 minute to 5 minutes, and then taken out and rinsed with deionized water; then, the surface of the etched metal substrate is neutralized with 10 to 30% by weight of HNO3 solution to remove An alkaline solution remaining on the surface of the above-mentioned etched metal substrate; and the neutralized metal substrate is rinsed off with deionized water. The surface of the pretreated metal substrate according to an embodiment of the present invention forms micron-sized pores having a diameter of from 1 micrometer to 10 micrometers. Therefore, the pretreatment step can not only effectively remove foreign matter on the surface of the metal substrate, but also obtain a metal substrate having a uniform surface material, and can sufficiently expose the metal substrate and form micron-sized pores on the surface of the metal substrate, thereby The surface area of the metal substrate is enlarged to facilitate the next step of sufficiently contacting the etching liquid to anodize the metal substrate.

According to an embodiment of the present invention, anodizing the metal substrate before the surface treatment of the metal substrate having the anodized film on the surface by using the etching solution comprises: placing the metal substrate at a concentration of 10 wt%~ 30 wt% of sulfuric acid solution as an anode, and electrolysis at a temperature of 10 ° C to 30 ° C, at a voltage of 5 volts to 100 volts for 1 minute to 40 minutes to form an oxide film layer on the surface of the metal substrate, wherein The oxide film layer has a thickness of 1 micrometer to 20 micrometers. According to an embodiment of the present invention, an apparatus for anodizing a metal substrate is not particularly limited before the surface treatment of the metal substrate having the anodized film on the surface by using an etching solution The various anodizing devices commonly used by those skilled in the art can be used, for example, anodizing a pretreated metal substrate using an anodizing bath. Thereby, the metal substrate can be anodized under optimum temperature, voltage and time conditions to form an oxide film layer on the surface of the metal substrate.

According to an embodiment of the present invention, before the surface treatment of the metal substrate having the anodized film on the surface by using a hydrochloric acid solution, anodizing the metal substrate comprises: placing the metal substrate at a concentration of 10 wt% to 30 wt. The % sulfuric acid solution is used as an anode, and is electrolyzed at a voltage of 10 volts to 30 volts at a temperature of 10 volts to 30 degrees Celsius for 1 minute to 40 minutes to form an oxide film layer on the surface of the metal substrate. The thickness of the oxide film layer is from 1 micrometer to 20 micrometers. Preferably, the thickness of the oxide film layer is from 1 micrometer to 10 micrometers. According to the embodiment of the present invention, before the surface treatment of the metal substrate having the anodized film on the surface by the hydrochloric acid solution, the apparatus for anodizing the metal substrate is not particularly limited and may be variously used by those skilled in the art. An anodizing apparatus, for example, anodizing a pretreated metal substrate using an anodizing bath. Thereby, the metal substrate can be anodized under optimum temperature, voltage and time conditions to form an oxide film layer on the surface of the metal substrate.

According to an embodiment of the present invention, before the surface treatment of the metal substrate having the anodized film on the surface by using a phosphoric acid solution, anodizing the metal substrate comprises: placing the metal substrate at a concentration of 10 wt% to 30 wt. % of sulfuric acid solution or phosphoric acid solution as anode, and electrolysis at a temperature of 10 ° C ~ 30 ° C, 5 volts to 35 volts for 2 minutes to 15 minutes to form an oxide film on the surface of the metal substrate Wherein the thickness of the oxide film layer is from 1 micrometer to 20 micrometers, and preferably, the thickness of the oxide film layer is from 1 micrometer to 10 micrometers. According to an embodiment of the present invention, a metal substrate having an anodized film on the surface is made using a phosphoric acid solution. Before the surface treatment, the apparatus for anodizing the metal substrate is not particularly limited, and various anodizing apparatuses commonly used by those skilled in the art may be used, for example, anodizing the pretreated metal substrate by an anodizing bath. Thereby, the metal substrate can be anodized under optimum temperature, voltage and time conditions to form an oxide film layer on the surface of the metal substrate.

According to an embodiment of the present invention, after the metal substrate is anodized, the metal substrate having the anodized film on the surface is immersed in the etching solution a plurality of times, wherein each time is immersed for 1 minute to 10 minutes, and The metal substrate is washed with water after each completion of the immersion. According to an embodiment of the present invention, the metal substrate having the anodized film on the surface is immersed in the etching solution 2 to 10 times. According to an embodiment of the present invention, the metal substrate is washed with water after each completion of the immersion, and the metal substrate may be washed in a water bath containing deionized water for 1 minute to 5 minutes, or The metal substrate is placed in a water washing tank containing deionized water for 1 minute to 5 minutes. Therefore, the anodized metal substrate having an anodized film on the surface can be sufficiently contacted with the etching solution in advance before the surface treatment with the etching solution, thereby facilitating the subsequent surface. deal with.

According to the embodiment of the present invention, the condition for surface-treating the metal substrate having the anodized film on the surface by the etching liquid is not particularly limited, and those skilled in the art may employ various conventional immersion treatment methods according to the present invention. Some specific examples may be fully or partially immersed; in accordance with further specific examples of the invention, multiple sheets may be immersed or immersed in a single piece. According to some embodiments of the present invention, the surface treatment of the metal substrate having the anodized film on the surface by using the etching solution may include: the surface having an anodized film at a temperature of 18 degrees Celsius to 35 degrees Celsius The metal substrate is immersed in the etching solution for 1 minute to 60 minutes. According to a preferred example of the present invention, the metal substrate having an anodized film on the surface is formed by using an etching solution. The conditions for the surface treatment include: immersing the metal substrate having an anodized film on the surface in an etching solution at a temperature of 20 to 30 ° C for 1 minute to 30 minutes. Thereby, the metal substrate having an anodized film on the surface can be surface-treated in the etching liquid under optimal temperature and time conditions, further optimizing the thickness of the etching layer and the structure of the metal etching hole, thereby effectively obtaining the passing surface. Treated metal substrate. The invention uses an etching solution to etch a metal having an anodized film layer, and forms a large etching hole on the surface of the metal substrate under the anodized film layer, and re-forms the hole by the etching, in the subsequent molding process, the resin combination The material enters the metal corrosion hole on the surface of the metal substrate during the injection molding process, so that a good bond with the metal can be formed after the resin layer is formed.

According to an embodiment of the present invention, the condition of surface-treating the metal substrate having an anodized film on the surface by using a hydrochloric acid solution is not particularly limited, and those skilled in the art may employ various conventional immersion treatment methods, according to some aspects of the present invention. Specific examples may be fully or partially immersed; in accordance with further specific examples of the invention, multiple sheets may be immersed or immersed in a single piece. According to some embodiments of the present invention, the surface treatment of the metal substrate having the anodized film on the surface using a hydrochloric acid solution may include: a metal having an anodized film on the surface at a temperature of 18 degrees Celsius to 35 degrees Celsius The substrate is immersed in a hydrochloric acid solution for 1 minute to 60 minutes. According to a preferred example of the present invention, the surface treatment of the metal substrate having the anodized film on the surface by using a hydrochloric acid solution includes: a metal base having an anodized film on the surface at a temperature of 20 to 30 degrees Celsius The material is immersed in hydrochloric acid solution for 1 minute to 30 minutes. Thereby, the metal substrate having an anodized film on the surface can be surface-treated in a hydrochloric acid solution under optimal temperature and time conditions, further optimizing the thickness of the etching layer and the structure of the metal etching hole, thereby effectively obtaining the surface treatment. Metal substrate. The invention uses a hydrochloric acid solution to etch a metal having an anodized film layer, and forms a large corrosion hole on the surface of the metal substrate under the anodized film layer. By re-forming the pores by such etching, in the subsequent molding process, the resin composition enters the metal etching hole in the surface of the metal substrate during the injection molding process, so that a good bond with the metal can be formed after the resin layer is formed.

According to an embodiment of the present invention, the condition for surface-treating the metal substrate having an anodized film on the surface by using a phosphoric acid solution is not particularly limited, and according to some embodiments of the present invention, the surface is anodized with a phosphoric acid solution. The surface treatment of the metal substrate of the film may include: immersing the metal substrate having the anodized film on the surface in a phosphoric acid solution at a temperature of 20 to 30 ° C for 1 minute to 60 minutes. Thereby, the metal substrate having an anodized film on the surface can be surface-treated in a phosphoric acid solution under optimal temperature and time conditions, further optimizing the thickness of the etching layer and the structure of the metal etching hole, thereby effectively obtaining the surface treatment. Metal substrate. The present invention uses a phosphoric acid solution to etch a metal having an anodized film layer, and forms a large etching hole on the surface of the metal substrate under the anodized film layer, and re-forms the pore by such etching, in the subsequent molding process, the resin composition During the injection molding process, it enters the metal corrosion hole on the surface of the metal substrate, so that a good bond with the metal can be formed after the resin layer is formed.

In another aspect of the invention, the invention provides a surface treated metal obtained by the above method. The surface-treated metal has a three-layered three-dimensional pore structure, and the pore structure has a unique structure of being small and large. Thereby, the surface-treated metal has a good bonding property, so that it can be firmly bonded with the resin to form a high-strength metal resin composite.

In yet another aspect of the invention, the invention provides a surface treated metal. The metal includes: a metal substrate, the metal substrate is an aluminum alloy substrate or an aluminum substrate; and an anodized film layer, the anodized layer is formed on a surface of the metal substrate; wherein the anode The epitaxial oxide layer includes: a barrier layer in contact with the metal substrate; and a loose layer formed on the surface of the barrier layer away from the metal substrate, an etching layer, A corrosion layer is formed on the surface of the barrier layer adjacent to the metal substrate. The surface-treated metal has a three-layered three-dimensional pore structure, and the pore structure has a unique structure of being small and large. Thereby, the surface-treated metal has a good bonding property, so that it can be firmly bonded with the resin to form a high-strength metal resin composite.

According to an embodiment of the present invention, the surface treatment of the metal substrate having an anodized film on the surface is performed by using an etching solution, wherein the barrier layer has a thickness of 5 nm to 5 μm, and the barrier layer contains barrier layer corrosion. a hole having a pore diameter of 10 nm to 800 μm, preferably 10 nm to 500 μm, more preferably 10 nm to 200 μm; and the thickness of the loose layer is 100 nm to 100 μm, the looseness The layer contains an anodized film micropores, and the pores of the anodized film have a pore diameter of 10 nm to 800 μm, preferably 10 nm to 500 μm, more preferably 10 nm to 100 μm; and the thickness of the etching layer is 5 The nano-200 micrometers have a metal etching hole in the etching layer, and the metal etching hole has a pore diameter of 10 nm to 1 mm, preferably 10 nm to 800 μm, more preferably 10 nm to 600 μm. The surface-treated metal obtained by surface treatment with an etching solution has no obvious boundary between the etching layer and the metal substrate, and the anodized film layer has a higher bonding force with the metal substrate; and the surface-treated metal has an optimized property. Three-layered three-dimensional pore structure, which improves the bonding force between resin and metal without damaging the metal properties, optimizes the surface structure of the metal substrate, improves the filling degree of the molten resin on the surface of the metal substrate, and ensures the general injection molding process. The molten resin can penetrate the metal corrosion hole of this depth, not only does not reduce the bonding area of the resin and the metal substrate, and there is no gap in the metal corrosion hole, thereby further improving the bonding force between the resin and the metal.

According to an embodiment of the present invention, the surface treatment of the metal substrate having the anodized film on the surface is performed using a hydrochloric acid solution, wherein the barrier layer has a thickness of 5 nm to 5 μm, and the barrier layer contains a barrier a layer of etching holes, wherein the pores of the barrier layer have a pore diameter of 10 nm to 800 μm; the thickness of the porous layer is 100 nm to 100 μm, and the porous layer contains an anodized film micropores, and the anodized film micro The hole has a pore diameter of 10 nm to 800 μm; the corrosion layer has a thickness of 5 nm to 200 μm, the corrosion layer contains a metal corrosion hole, and the metal corrosion hole has a pore diameter of 10 nm to 1 mm. The surface-treated metal obtained by surface treatment with a hydrochloric acid solution has no obvious boundary between the corrosion layer and the metal substrate, the anodized film layer has a higher bonding force with the metal substrate; and the surface-treated metal has an optimized three Layered pore structure, which improves the bonding force between resin and metal without damaging the metal properties, optimizes the surface structure of the metal substrate, improves the filling degree of the molten resin on the surface of the metal substrate, and ensures the melting in the general injection molding process. The resin can penetrate the metal corrosion hole of this depth, not only does not reduce the bonding area of the resin and the metal substrate, and there is no gap in the metal corrosion hole, thereby further improving the bonding force between the resin and the metal.

According to an embodiment of the present invention, the surface treatment of the metal substrate having the anodized film on the surface is performed using a phosphoric acid solution, wherein the barrier layer has a thickness of 10 nm to 1 μm, and the barrier layer contains a barrier a layer of etching holes, wherein the pores of the barrier layer have a pore diameter of 10 nm to 500 μm; the thickness of the porous layer is 1 μm to 50 μm, and the porous layer contains an anodized film micropores, and the anodized film micro The hole has a pore diameter of 10 nm to 500 μm; the corrosion layer has a thickness of 10 nm to 200 μm, and the corrosion layer contains a metal corrosion hole, and the metal corrosion hole has a pore diameter of 10 nm to 1 mm. The surface-treated metal obtained by surface treatment with a phosphoric acid solution has no obvious boundary between the corrosion layer and the metal substrate, and the anodized film layer and the metal substrate It has a higher bonding force; and the surface-treated metal has an optimized three-layered three-dimensional pore structure, thereby improving the resin-metal bonding force without damaging the metal properties, optimizing the surface structure of the metal substrate, and improving the melting. The filling degree of the resin on the surface of the metal substrate ensures that the molten resin in the general injection molding process can penetrate the metal corrosion hole of this depth, not only does not reduce the bonding area of the resin and the metal substrate, and there is no gap in the metal corrosion hole. Further improve the bonding strength between the resin and the metal.

According to an embodiment of the present invention, the barrier etch hole, the anodic oxide film, and the metal etch hole are in communication with each other. Thereby, it is advantageous to further improve the permeability of the resin, and improve the bonding force between the resin and the metal substrate, thereby facilitating molding.

In still another aspect of the present invention, the present invention provides a method of preparing a metal resin composite. The method comprises the steps of providing the surface-treated metal described above; and injection molding a resin composition onto the surface of the surface-treated metal to obtain the metal-resin composite. By preparing the metal resin composite by the method of the present invention, there is no requirement for the synthetic resin, the application range is wider, and the environmental pollution is small, and it is more suitable for large-scale production.

According to an embodiment of the present invention, after the surface-treated metal is obtained, and before the resin composition is injection-molded to the surface of the surface-treated metal, the metal substrate may be modified, For example, a surface modification treatment, according to a preferred example of the present invention, the surface-treated metal substrate may be immersed in a solution containing a water-soluble polymer for immersion modification treatment. Thereby, the water-soluble polymer is adsorbed on the metal substrate, dried and then left on the metal substrate, and the metal substrate is modified, and at the same time, it is an organism, and has good compatibility with the resin, and is polymerized by water-soluble polymerization. The oleophilic modification of the metal substrate makes the resin more easily enter the pore structure of the metal substrate, accelerates the entry of the injection resin, and further improves the bonding force between the metal and the resin. Moreover, the process efficiency and the product yield are further improved, and the adsorption of the polymer into the micropores can effectively discharge the air in the micropores, and the resin is more likely to fill the entire hole during the injection molding.

According to an embodiment of the present invention, after the surface-treated metal is obtained, and the resin composition is injection-molded to the surface of the surface-treated metal, the surface-treated metal is immersed The conditions for performing the modification treatment in the solution containing the water-soluble polymer are not particularly limited, and according to some examples of the present invention, the surface-treated metal may be immersed in the water-containing solution at a temperature of from 15 ° C to 60 ° C. The solution of the polymer is immersed in the solution containing the water-soluble polymer at a temperature of from 20 ° C to 40 ° C for 1 minute to 30 minutes in accordance with other preferred examples of the present invention. 5 minutes to 20 minutes in the solution. Thereby, the surface-treated metal can be immersed in a solution containing a water-soluble polymer under optimum temperature and time conditions for modification treatment, thereby making the resin easier to enter the pore structure of the metal substrate, further improving the metal and the resin. The combination of strength and further improve process efficiency and product yield.

According to an embodiment of the present invention, the concentration of the solution containing the water-soluble polymer used for modifying the surface-treated metal is not particularly limited, and those skilled in the art may perform surface treatment treatment of the modification treatment as needed. The condition of the metal is adjusted. According to some embodiments of the present invention, the water-soluble polymer solution contains 1 wt% to 20 wt% of a water-soluble polymer based on the total weight of the water-soluble polymer solution. Thereby, the surface-treated metal can be immersed in a solution containing the water-soluble polymer having an optimum concentration for modification treatment, thereby making the resin more easy to enter the pore structure of the metal substrate, and further improving the bonding force between the metal and the resin. And further improve process efficiency and product yield.

Surface treated metal is modified according to an embodiment of the invention The water-soluble polymer to be used is not particularly limited, and various water-soluble polymers which are commonly used by those skilled in the art can be immersed in a water-soluble polymer solution through a metal substrate, and the water-soluble polymer can be adsorbed on the metal substrate. After drying, the water-soluble polymer remains on the metal substrate to achieve the purpose of modifying the metal substrate, and since the water-soluble polymer is an organism, the resin has good compatibility and can accelerate the injection molding. The entry of resin. According to some specific examples of the present invention, the water-soluble polymer is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylate, polymethacrylic acid, polymethacrylate, polyvinylsulfonic acid, poly At least one of a vinyl sulfonate, a polystyrene sulfonic acid or a polystyrene sulfonate. Thereby, the surface-treated metal can be immersed in the water-soluble polymer solution most suitable for the modification treatment, thereby making the resin easier to enter the pore structure of the metal substrate, further improving the bonding force between the metal and the resin. And further improve process efficiency and product yield.

The inventors have surprisingly found that the manner in which the above water-soluble polymer is formed on a metal substrate is not subject to any limitation. According to some embodiments of the present invention, the water-soluble polymer may be formed on the surface of the metal substrate or may be filled in In the holes of the metal substrate, for example, anodized film micropores and/or barrier etching holes and/or metal etching holes are used as long as the metal substrate can be modified. According to a preferred embodiment of the present invention, the water-soluble polymer may be filled in the pore structure of the surface-treated metal substrate, that is, in the anodized film micropores, in the barrier etching holes, and in the metal etching holes. Thereby, the water-soluble polymer can enter the unique pore structure of the surface-treated metal substrate, fill most of the pores, and discharge the air in the pores, thereby avoiding residual air which may exist in the pore structure when molding the resin. There is a gap between the metal and the resin, the problem of the bonding force is lowered, the modification property is optimized, and the performance of the metal substrate and the filling ability of the resin are ensured.

According to an embodiment of the present invention, after the modification treatment is completed, the metal substrate is subjected to a drying treatment to remove residual solvent. Thereby, the water-soluble polymer remaining on the modified metal substrate by the modified soaking treatment can be effectively removed, thereby facilitating the next step of the injection molding process with the resin composition.

According to the embodiment of the present invention, the resin composition is a resin composition which can be combined with a metal, and the present invention is not particularly limited and may be selected according to actual needs, and may be, for example, a thermoplastic resin composition. According to a preferred embodiment of the invention, the thermoplastic resin may be nylon. According to still other embodiments of the present invention, the thermoplastic resin composition contains a host resin and a polyolefin resin. According to some embodiments of the present invention, the inventors have found that it is preferred to use a non-crystalline host resin as the injection molding material, and the surface gloss and toughness thereof are all due to the high crystalline resin in the prior art, and the melting point is 65 degrees Celsius to 105 degrees Celsius. The polyolefin resin does not need to be injection molded at a specific mold temperature during molding, and the molding process is simplified, and at the same time, the obtained metal resin composite can have better mechanical strength and surface treatment characteristics, thereby solving the surface decoration problem of the plastic part. Meet the diverse needs of our customers.

According to some embodiments of the present invention, the host resin is a mixture of polyphenylene ether (PPO) and polyphenylene sulfide (PPS), wherein the weight ratio of polyphenylene ether to polyphenylene sulfide in the host resin is 3:1-1 :3, preferably 2:1-1:1. According to another embodiment of the present invention, the host resin is a mixture of polyphenylene ether and polyamine (PA), wherein the weight ratio of the polyphenylene ether to the polyamine in the host resin is from 3:1 to 1:3, preferably 2:1-1:1. According to other embodiments of the invention, the host resin is polycarbonate (PC), which may be selected from various linear polycarbonates and/or linear polycarbonates. Thereby, the resin composition having the best performance can be obtained to be integrated with the metal to form a metal resin composite. According to an embodiment of the present invention, the kind of the polyolefin resin is not particularly limited and may be in the field. Various polyolefin resins commonly used by the skilled person, according to a specific example of the present invention, the polyolefin resin is a polyolefin resin having a melting point of 65 degrees Celsius to 105 degrees Celsius, and the polyolefin resin may be a grafted polyethylene, preferably, the polyolefin resin Grafted polyethylene having a melting point of 100 degrees Celsius or 105 degrees Celsius can be used. The inventors have surprisingly found that by using a polyolefin resin having a melting point of 65 degrees Celsius to 105 degrees Celsius in a non-crystalline host resin to be used, in particular, a grafting polyethylene having a melting point of 100 degrees Celsius or 105 degrees Celsius can increase the resin. The ability to flow into the nano-scale micropores on the metal surface to ensure good adhesion and mechanical strength of the formed metal and plastic.

According to an embodiment of the present invention, the content of the host resin and the polyolefin resin is not particularly limited, and those skilled in the art may adjust according to circumstances, according to some specific embodiments of the present invention, based on 100 parts by weight of the thermoplastic resin, The amount of the host resin is 70 to 95 parts by weight, and the amount of the polyolefin resin is 5 to 30 parts by weight. Thereby, the resin composition having the best performance can be obtained to be integrated with the metal to form a metal resin composite.

As a further improvement of the present invention, the inventors of the present invention have also found that the use of a fluidity improver in a thermoplastic resin can also improve the flowability of the resin, further improve the adhesion of the metal to the resin and the injection molding property of the resin. According to an embodiment of the present invention, the content and kind of the flow agent are not particularly limited, and may be a flow agent commonly used by those skilled in the art, and the content thereof is adjusted according to a specific case, based on 100 parts by weight according to a preferred example of the present invention. The thermoplastic resin, the thermoplastic resin may further contain 1 to 5 parts by weight of the fluidity improver; and the fluidity improver may be a cyclic polyester.

The resin composition of the present invention may further contain other modifying additives and the like, and the present invention is not particularly limited, and those skilled in the art may be provided as needed, and for example, the resin composition may further contain a filler. The filler is various fillers commonly used by those skilled in the art, for example, Is at least one selected from the group consisting of a fibrous filler or a powdery filler, wherein the fibrous filler may be at least one selected from the group consisting of glass fibers, carbon fibers, and aromatic polyamide fibers; the powder type filler may be selected from the group consisting of calcium carbonate, magnesium carbonate, At least one of cerium oxide, heavy barium sulfate, talc, glass, and clay. More preferably, in order to make the plastic composition have a linear expansion coefficient similar to that of the metal substrate in the transverse direction and the longitudinal direction, according to some specific examples of the present invention, the content of the fibrous filler is 50-150 based on 100 parts by weight of the main resin. The powdery filler is contained in an amount of from 50 to 150 parts by weight. Thereby, a resin composition having better performance can be obtained, thereby integrating with a metal to form a metal resin composite.

According to a specific example of the present invention, the main resin and the polyolefin resin are uniformly mixed to prepare a resin composition. The preparation method of the resin composition is obtained by a physical blending method commonly used by those skilled in the art, that is, the main resin and the polyolefin resin are uniformly mixed, and are extruded and granulated by a twin-screw extruder, and are used. According to another specific example of the present invention, a filler, a fluidity improver may be further added to the main resin, and the mixture may be uniformly mixed to obtain a resin composition, so that the resin composition has a lateral direction and a longitudinal direction similar to the metal substrate. Linear expansion coefficient.

According to an embodiment of the present invention, the dried metal substrate is transferred into a mold, and the obtained resin composition is subjected to integration treatment, and the metal composite provided by the present invention can be obtained after molding. According to an embodiment of the present invention, the molding method is not particularly limited, and various molding methods commonly used in the art may be used as long as the molding method capable of integrating the metal resin can be used in the present invention, for example, but not limited to, injection molding. the way. According to a specific embodiment of the present invention, the injection molding conditions are: a mold temperature of 50 degrees Celsius to 300 degrees Celsius, a nozzle temperature of 200 degrees Celsius to 450 degrees Celsius, a dwell time of 1 second to 50 seconds, and an injection pressure of 50 MPa to 300 MPa. The injection time is from 1 second to 30 seconds, the delay time is from 1 second to 30 seconds, and the cooling time is from 1 second to 60 seconds.

The preparation method of the invention is simple, and the existing process using the adhesive simplifies the production process, shortens the production time, and the acid surface corrosion method of the existing surface nanopore injection molding also greatly reduces the corrosion time, and breaks through The limitation of the type of the resin can be achieved by direct injection molding after the treatment by the method of the present invention, and the bonding between the resin layer of the metal resin composite obtained by the preparation method of the invention and the metal substrate is good, and is preferable. Tensile shear strength.

The metal resin composite prepared by the present invention can be used as it is, or can be subjected to some post-treatment as needed, such as CNC (CNC machine tool processing), spray coating, and the like.

In still another aspect of the invention, the invention provides a metal resin composite. The metal resin composite is obtained by the above method. The metal and the resin in the metal-resin composite are firmly combined, high in strength, and meet environmental protection requirements due to the use of the metal provided by the present invention and having a three-layered three-dimensional pore structure with a unique structure on the surface.

In another aspect of the invention, the invention provides a metal resin composite. The metal resin composite includes: a metal layer which is the surface-treated metal, wherein the metal layer has an anodized film micropore, a barrier etching hole, and a metal etching hole; and a resin layer, A resin layer is bonded to the surface of the metal layer, wherein a resin composition forming the resin layer is filled in the anodized film micropores, the barrier layer etching holes, and the metal etching holes. The metal and the resin in the metal-resin composite are firmly combined, high in strength, and meet environmental protection requirements due to the use of the metal provided by the present invention and having a three-layered three-dimensional pore structure with a unique structure on the surface.

According to an embodiment of the present invention, the porous film of the anodized film, the corrosion hole of the barrier layer, the metal etching hole or the surface of the metal substrate further contains a water-soluble polymer. According to the invention In the embodiment, the water-soluble polymer contained in the micropores of the anodized film, the corrosion hole of the barrier layer, the metal corrosion hole or the surface of the metal substrate is not particularly limited, and various water-soluble polymers commonly used in the art may pass. The metal substrate is immersed in the water-soluble polymer solution, and the water-soluble polymer can be adsorbed on the metal substrate. After drying, the water-soluble polymer remains on the metal substrate, thereby achieving the purpose of modifying the metal substrate. At the same time, since the water-soluble polymer is an organism, it has good compatibility with the resin, and can accelerate the entry of the injection resin. According to some specific examples of the present invention, the water-soluble polymer is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylate, polymethacrylic acid, polymethacrylate, polyvinylsulfonic acid, poly At least one of a vinyl sulfonate, a polystyrene sulfonic acid or a polystyrene sulfonate. Thereby, the surface-treated metal can be immersed in the water-soluble polymer solution most suitable for the modification treatment, thereby making the resin easier to enter the pore structure of the metal substrate, further improving the bonding force between the metal and the resin. And further improve process efficiency and product yield. Thus, a metal resin composite having a resin layer thickness of 0.5 mm to 10 mm can be obtained.

The invention will now be further described in detail by way of specific examples.

Example 1

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. sheet;

2. Surface treatment 1: The above aluminum alloy sheet was placed as an anode in an H2SO4 anodizing bath containing a concentration of about 20 wt%, and electrolyzed at 15 V for 18 minutes at 80 °C, 80 shots. Dry for 20 minutes;

3. Surface treatment 2: 500 mL of 5 wt% hydrochloric acid and 10 wt% sodium chloride mixed solution was prepared in a beaker, and placed in a 25 ° C thermostat to raise the temperature to 25 ° C. The obtained aluminum alloy sheet 10PCS was immersed therein, 2 minutes later. Take it out and put it in a beaker containing water for 2 minutes, add a blisters to the etch bubble once as a loop, and then loop back 5 times. After the last water immersion, place the aluminum alloy piece in an oven at 80 degrees Celsius. Drying in.

The cross section of the aluminum alloy sheet subjected to surface treatment 2 was observed by a metallographic microscope, and a loose layer having a thickness of 6.5 μm to 7.5 μm was obtained on the surface of the aluminum alloy sheet, and a barrier layer having a thickness of 80 nm to 100 nm and a thickness of 20 nm were measured. - 35 micron corrosion layer.

The aperture of the anodized film micropores in the loose layer was measured by SEM field emission scanning electron microscope to be 15 nm-800 nm; the pore size of the barrier layer in the barrier layer was 15 nm-600 nm; the aluminum in the corrosion layer was observed. The pores of the alloy corrosion holes are from 40 nm to 80 microns. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

4. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and one batch of polyphenylene sulfide (PPS) resin composition containing 30wt% glass fiber is injected, and the other is The nylon resin was batch-molded, and both were released from the mold and cooled to obtain an aluminum alloy resin composite A1 group and B1 group of the aluminum alloy and the resin composition which were firmly bonded together.

Example 2

The aluminum alloy resin composites A2 and B2 were prepared in the same manner as in Example 1, except that the surface treatment 2 was to prepare 500 mL of a 5 wt% hydrochloric acid and a 10 wt% sodium chloride mixed solution in a beaker, and placed at 25 ° C. The temperature is raised to 25 degrees Celsius in the constant temperature bath, and the aluminum alloy obtained as described above is obtained. The sheet 10PCS was immersed therein, taken out after 10 minutes, and then immersed in a beaker containing water for 2 minutes, and then the aluminum alloy was placed in an oven at 80 degrees Celsius for drying. Using the same method as in Example 1, the surface of the aluminum alloy sheet after electrolysis was measured to obtain a loose layer having a thickness of 6 μm to 7 μm, a barrier layer having a thickness of 85 nm to 100 nm, and a thickness of 20 nm to 40 μm. Corrosion layer. The pore size of the anodized film micropores in the loose layer is 15 nm to 1 μm; the pore size of the barrier layer in the barrier layer is 16 nm to 800 nm; and the pore size of the aluminum alloy etching hole in the etching layer is 40 nm to 90 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 3

The aluminum alloy resin composites A3 and B3 were prepared in the same manner as in Example 1, except that the surface treatment 2 was to prepare 500 mL of a 10 wt% H3PO4 solution in a beaker, and the temperature was raised to 25 ° C in a 25 ° C thermostat. The above-mentioned aluminum alloy sheet 10PCS was immersed therein, and after 2 minutes, it was taken out, and it was immersed in a beaker containing water for 2 minutes, and an blister bubble was added once to form a loop, so that the loop was repeated twice, the last time. After soaking in water, the aluminum alloy pieces were placed in an oven at 80 degrees Celsius for drying. Using the same method as in Example 1, the surface of the aluminum alloy sheet after electrolysis was measured to obtain a loose layer having a thickness of 6 μm to 6.5 μm, a barrier layer having a thickness of 80 nm to 110 nm, and a thickness of 20 nm to 40 μm. Corrosion layer. The pore size of the anodized film micropores in the loose layer is about 20 nm to 1 μm; the pore size of the barrier layer in the barrier layer is about 18 nm to 800 nm; and the pore size of the aluminum alloy etching hole in the etching layer is 50 nm to 120 μm. about. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 4

The aluminum alloy resin composites A4 and B4 were prepared in the same manner as in Example 1, except that the surface treatment 2 was to prepare 10 mL of hydrochloric acid 500 mL in a beaker, and the temperature was raised to 25 ° C in a 25 ° C thermostat. The above-mentioned aluminum alloy sheet 10PCS was immersed therein, and after 2 minutes, it was taken out, and it was immersed in a beaker containing water for 2 minutes, and an blister bubble was added once to form a loop, so that the loop was 5 times, and the last time water After soaking, the aluminum alloy pieces were placed in an oven at 80 degrees Celsius for drying. Using the same method as in Example 1, the surface of the aluminum alloy sheet after electrolysis was measured to obtain a loose layer having a thickness of 6 μm to 7 μm, a barrier layer having a thickness of 80 nm to 100 nm, and a corrosion thickness of 100 nm to 30 μm. Floor. The pore size of the anodized film micropores in the loose layer is 15 nm to 30 μm; the pore size of the barrier layer in the barrier layer is 20 nm to 800 nm; and the pore size of the aluminum alloy etching hole in the etching layer is 60 nm to 100 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 5

The aluminum alloy resin composites A5 and B5 were prepared in the same manner as in Example 1, except that the time of etching the bubble was 3 minutes in the surface treatment 2, and the electrolysis was carried out in the same manner as in Example 1. The surface of the rear aluminum alloy sheet is made into a loose layer having a thickness of 5 μm to 6 μm, a barrier layer having a thickness of 80 nm to 100 nm, and an etching layer having a thickness of 80 nm to 50 μm. The pore size of the anodized film micropores in the loose layer is 20 nm to 65 μm; the pore size of the barrier layer in the barrier layer is 25 nm to 2 μm; and the pore diameter of the aluminum alloy etching hole in the etching layer is 50 nm to 300 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 6

Aluminum alloy resin composite A6 group and B6 were prepared in the same manner as in Example 4. The difference was that the etching solution in the surface treatment 2 was 15 wt% hydrochloric acid, and the surface of the aluminum alloy sheet after electrolysis was measured in the same manner as in Example 1 to obtain a loose layer having a thickness of 4.5 μm to 5.5 μm. It is a barrier layer of 80 nm to 100 nm and an etching layer of 100 nm to 60 μm in thickness. The pore size of the anodized film micropores in the loose layer is 20 nm to 70 μm; the pore size of the barrier layer in the barrier layer is 30 nm to 3 μm; and the pore size of the aluminum alloy etching hole in the etching layer is 50 nm to 400 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 7

The aluminum alloy resin composites A7 and B7 were prepared in the same manner as in Example 1, except that the dried aluminum alloy sheets were immersed in a 2 wt% polyvinyl alcohol solution for 5 minutes before being formed, and taken out. Dry and put in the mold.

Example 8

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. 2; Surface treatment 1: The above aluminum alloy sheet is placed as an anode in an H2SO4 anodizing bath containing a concentration of about 20% by weight, electrolyzed at 20 volts, 18 degrees Celsius for 5 minutes, and dried at 80 degrees Celsius for 20 minutes; Surface treatment 2: Prepare 500 mL of 5 wt% hydrochloric acid and 10 wt% sodium chloride mixed solution in a beaker, put it into a 25 ° C thermostat and raise the temperature to 25 ° C, and put it into the temperature. The measurement point is placed at the center of the solution. Take the above-mentioned aluminum alloy sheet 20PCS, divide into two batches, each batch of 10PCS, one batch is immersed in it, take it out after 2 minutes, record the temperature of the etching liquid in the beaker before taking out, and immediately put in the second batch of aluminum alloy piece, at the same time The first batch of aluminum alloy pieces are immersed in a beaker containing water for 2 minutes, the second batch of aluminum alloy pieces are taken out from the etching liquid, the temperature is recorded before taking out, and the first batch of aluminum alloy pieces are placed in the etching liquid. At the same time, the second batch of aluminum alloy sheets are immersed in water, so that the two batches of aluminum alloy sheets are soaked in the etching liquid 5 times, and the temperature is recorded before each aluminum alloy sheet is taken out from the acid liquid. A graph of temperature versus time (as in Figure 1).

Comparative example 1

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was subjected to etch treatment for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 s, and then washed with water to obtain a pretreated aluminum alloy sheet. ;

2. Surface treatment: The aluminum alloy substrate is immersed in 500 mL of hydrochloric acid having a concentration of 10 wt%, and placed in a 25 ° C thermostat to raise the temperature to 25 ° C. The obtained aluminum alloy sheet 10PCS is immersed therein, and after 2 minutes, it is taken out. Soak in a beaker filled with water for 2 minutes, add a blisters to the etch bubble once as a loop, and then loop back 5 times. After the last water immersion, place the aluminum alloy piece in an oven at 80 ° C to dry.

An etching layer having a thickness of 500 nm to 100 μm was obtained by the same method as in Example 1. The pores in the corrosion layer have a pore size of from about 500 nm to about 500 microns.

3. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and a batch of polyphenylene sulfide (PPS) tree containing 30wt% glass fiber is injected. The fat composition, another batch of injection molded nylon resin, was released from the mold and cooled to obtain an aluminum alloy resin composite C1 group and D1 group of the aluminum alloy and the resin composition which were firmly bonded together.

Comparative example 2

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. sheet;

2. Surface treatment: The above aluminum alloy sheet was placed as an anode in an H2SO4 anodizing bath containing a concentration of about 20 wt%, electrolyzed at 15 volts for 10 minutes, and blown dry; measured by the same method as in Example 1. The pores of the anodized film have a pore diameter of from 10 nm to 100 nm and a pore depth of from 9 μm to 10 μm.

3. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and one batch of polyphenylene sulfide (PPS) resin composition containing 30wt% glass fiber is injected, and the other is The nylon resin was batch-molded, and both were released from the mold and cooled to obtain an aluminum alloy resin composite C2 group and D2 group of the aluminum alloy and the resin composition which were firmly bonded together.

Comparative example 3

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. sheet; 2. Surface treatment: 500 mL of 5 wt% hydrochloric acid and 10 wt% sodium chloride mixed solution was prepared in a beaker, placed in a 25 ° C thermostat to raise the temperature to 25 ° C, and placed in a thermometer so that the measurement point was at the center of the solution. Take the above-mentioned aluminum alloy sheet 20PCS, divide into two batches, each batch of 10PCS, one batch is immersed in it, take it out after 2 minutes, record the temperature of the etching liquid in the beaker before taking out, and immediately put in the second batch of aluminum alloy piece, at the same time The first batch of aluminum alloy pieces are immersed in a beaker containing water for 2 minutes, the second batch of aluminum alloy pieces are taken out from the etching liquid, the temperature is recorded before taking out, and the first batch of aluminum alloy pieces are placed in the etching liquid. At the same time, the second batch of aluminum alloy sheets are immersed in water, so that the two batches of aluminum alloy sheets are soaked in the etching liquid 5 times, and the temperature is recorded before each aluminum alloy sheet is taken out from the acid liquid. A graph of temperature versus time (as in Figure 1).

Performance Testing:

Bonding force between aluminum alloy and resin: The aluminum alloy resin composites prepared in Examples 1-7 and Comparative Examples 1-2 were fixed on a universal material testing machine for product tensile test. The maximum load in the test results can be regarded as aluminum alloy and resin. The magnitude of the binding force between the test results is shown in Table 2.

Table 1

It can be seen from the table that the surface pore structure of the aluminum alloy substrate prepared by the invention is unique In particular, it has a high bonding strength with resin and can reach more than 800 N, which is much higher than the prior art, and has a wide application range, and the process is simple and easy to mass-produce. At the same time, it can be seen from FIG. 1 that the technical solution of the present invention has less heat release, slower temperature rise of the etching liquid, is more suitable for mass production, consumes less etching liquid, and has less corrosion to equipment.

Example 9

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. 2; Surface treatment 1: The above aluminum alloy sheet is placed as an anode in an H2SO4 anodizing bath containing a concentration of about 20% by weight, electrolyzed at 15 volts, 18 degrees Celsius for 5 minutes, and dried at 80 degrees Celsius for 20 minutes; Surface treatment 2: 500 mL of 10 wt% hydrochloric acid was prepared in a beaker, placed in a 25 ° C thermostat, and the obtained aluminum alloy sheet 10PCS was immersed therein, and after 2 minutes, it was taken out and placed in a beaker containing water for 2 minutes. Add a blisters of hydrochloric acid once as a loop, and then loop back 5 times. After the last water soak, the aluminum alloy pieces are placed in an oven at 80 degrees Celsius for drying.

The cross section of the surface treated aluminum alloy sheet was observed by a metallographic microscope and an SEM field emission scanning electron microscope, and a loose layer having a thickness of 6 μm to 7 μm was obtained on the surface of the aluminum alloy sheet, and the thickness was 80 nm to 100 nm. The barrier layer and the etching layer having a thickness of 100 nm to 30 μm.

Anodized film in loose layer was measured by SEM field emission scanning electron microscope The pore diameter of the micropores is 15 nm to 30 μm; the pore diameter of the barrier etching pores in the barrier layer is 20 nm to 25 μm by observing the cross section; the pore diameter of the aluminum alloy etching pores in the etching layer is 30 nm to 100 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other. 4. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and one batch of polyphenylene sulfide (PPS) resin composition containing 30wt% glass fiber is injected, and the other is The nylon resin was batch-molded, and after being released from the mold and cooled, an aluminum alloy resin composite group A1 and B1 in which the aluminum alloy and the resin composition were firmly bonded together were obtained.

Example 10

The aluminum alloy resin composites A2 and B2 were prepared in the same manner as in Example 9, except that the surface treatment 2 was to prepare 500 mL of 10 wt% hydrochloric acid in a beaker, and the temperature was raised to 25 ° C in a 25 ° C thermostat. The aluminum alloy sheet 10PCS obtained as described above was immersed therein, and after 10 minutes, it was taken out, and then immersed in a beaker containing water for 2 minutes, and then the aluminum alloy was placed in an oven at 80 ° C to be dried.

The surface of the aluminum alloy sheet after electrolysis was measured in the same manner as in Example 9 to obtain a loose layer having a thickness of 5 μm to 5.5 μm, a barrier layer having a thickness of 80 nm to 100 nm, and an etching layer of 200 nm to 50 μm. . The pore size of the anodized film micropores in the loose layer is 20 nm to 50 μm; the pore size of the barrier layer in the barrier layer is 25 nm to 50 μm; and the pore size of the aluminum alloy etching hole in the etching layer is 50 nm to 150 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 11

Aluminum alloy resin composite A3 was prepared in the same manner as in Example 9. Group, group B3, the difference is: the surface concentration of hydrochloric acid in the concentration of 5 wt%, placed in a 25 ° C constant temperature bath to 25 ° C, the aforementioned aluminum alloy sheet 10PCS immersed in it, 2 minutes later Take out, put in a beaker filled with water for 2 minutes, add a blisters of hydrochloric acid once to make a loop, so loop 5 times, after the last water soak, put the aluminum alloy sheet in an oven at 80 ° C to dry. .

The surface of the aluminum alloy sheet after electrolysis was measured in the same manner as in Example 9 to obtain a loose layer having a thickness of 7 μm to 8 μm, a barrier layer having a thickness of 80 nm to 100 nm, and an etching layer of 50 nm to 15 μm. . The pore size of the anodized film micropores in the loose layer is about 15 nm to 10 μm; the pore size of the barrier layer in the barrier layer is about 20 nm to 15 μm; and the pore size of the aluminum alloy etching hole in the etching layer is 30 nm to 50 μm. about. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 12

The aluminum alloy resin composites A4 and B4 were prepared in the same manner as in Example 9, except that the concentration of hydrochloric acid in the surface treatment 2 was 15% by weight, and it was placed in a 25 degree Celsius bath to obtain the aforementioned aluminum. The alloy sheet 10PCS was immersed in it, and after 2 minutes, it was taken out, and it was immersed in a beaker containing water for 2 minutes, and once a hydrochloric acid bubble was added as a loop, so that it was looped 5 times, and after the last water immersion, The aluminum alloy sheets are dried in an oven at 80 degrees Celsius.

The surface of the aluminum alloy sheet after electrolysis was measured in the same manner as in Example 9 to obtain a loose layer having a thickness of 4 μm to 5 μm, a barrier layer having a thickness of 80 nm to 100 nm, and a thickness of 150 nm to 60 μm. Corrosion layer. The pore size of the anodized film micropores in the loose layer is 25 nm to 60 μm; the pore size of the barrier layer in the barrier layer is 30 nm to 60 μm; the aluminum in the etching layer The corrosion hole of the alloy has a pore diameter of 50 nm to 200 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 13

The aluminum alloy resin composites A5 and B5 were prepared in the same manner as in Example 9, except that the dried aluminum alloy sheets were placed in a 2 wt% polyvinyl alcohol solution for 5 minutes before being formed, and taken out. Dry and put in the mold.

Example 14

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. 2; Surface treatment 1: The above aluminum alloy sheet was placed as an anode in an H2SO4 anodizing bath containing a concentration of about 20 wt%, electrolyzed at 15 volts, 18 degrees for 5 minutes, and dried at 80 degrees Celsius for 20 minutes; Surface treatment 2: Prepare 500 mL of 10 wt% hydrochloric acid in a beaker, place it in a 25 ° C thermostat to raise the temperature to 25 ° C, and place the thermometer so that the measurement point is at the center of the solution. Take the above-mentioned aluminum alloy sheet 20PCS, divide into two batches, each batch of 10PCS, one batch is immersed in it, take it out after 2 minutes, record the temperature of the etching liquid in the beaker before taking out, and immediately put in the second batch of aluminum alloy piece, at the same time The first batch of aluminum alloy sheets were immersed in a beaker containing water for 2 minutes, and the second batch of aluminum alloy sheets were taken out from the etching liquid, and the temperature was recorded before taking out, and the first batch of aluminum alloy sheets were placed in the engraved form. In the etched liquid, the second batch of aluminum alloy sheets are simultaneously immersed in water, and then looped until the two batches of aluminum alloy sheets are soaked 5 times in the etching liquid, and each time the aluminum alloy sheets are taken out from the acid liquid before recording Temperature, a graph of temperature versus time (as shown in Figure 2).

Comparative example 4

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. sheet;

2. Surface treatment: The aluminum alloy substrate is immersed in 500 mL of hydrochloric acid having a concentration of 10 wt%, and placed in a 25 ° C thermostat to raise the temperature to 25 ° C. The obtained aluminum alloy sheet 10PCS is immersed therein, and after 2 minutes, it is taken out. Soak in a beaker filled with water for 2 minutes, add a blisters to the etch bubble once as a loop, and then loop back 5 times. After the last water immersion, place the aluminum alloy piece in an oven at 80 ° C to dry.

An etching layer of 200 nm to 100 μm was obtained in the same manner as in Example 9. The pores in the corrosion layer have a pore size of from 100 nm to 500 microns.

3. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and one batch of polyphenylene sulfide (PPS) resin composition containing 30wt% glass fiber is injected, and the other is The nylon resin was batch-molded, and both were released from the mold and cooled to obtain an aluminum alloy resin composite C1 group and D1 group of the aluminum alloy and the resin composition which were firmly bonded together.

Comparative example 5

1. Pre-treatment: Cut the commercially available 1mm thick 6063 aluminum alloy plate into 15mm A rectangular piece of ×80 mm is placed in a polishing machine for grinding, then degreased and cleaned, and then etched for 10 seconds in a solution having a sodium hydroxide content of 40 g/L at 60 ° C. After washing with water, the water is washed. The mixture was neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy sheet;

2. Surface treatment: The above aluminum alloy sheet was placed as an anode in an H2SO4 anodizing bath containing a concentration of about 20 wt%, electrolyzed at 15 volts for 10 minutes, and blown dry; measured by the same method as in Example 9. The pore size of the anodized film is from about 10 nm to about 100 nm, and the pore depth is from about 9 μm to about 10 μm.

3. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and one batch of polyphenylene sulfide (PPS) resin composition containing 30wt% glass fiber is injected, and the other is The nylon resin was batch-molded, and both were released from the mold and cooled to obtain an aluminum alloy resin composite C2 group and D2 group of the aluminum alloy and the resin composition which were firmly bonded together.

Comparative example 6

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. 2; Surface treatment: Prepare 500mL of 10wt% hydrochloric acid in a beaker, put it into 25 ° C temperature bath to 25 ° C, and put a thermometer, so that the measurement point is at the center of the solution. Take the above-mentioned aluminum alloy sheet 20PCS, divide into two batches, each batch of 10PCS, one batch is immersed in it, take it out after 2 minutes, record the temperature of the etching liquid in the beaker before taking out, and put it into the second batch immediately. Aluminum alloy sheet, while the first batch of aluminum alloy sheets are immersed in a beaker containing water for 2 minutes, the second batch of aluminum alloy sheets are taken out from the etching liquid, the temperature is recorded before taking out, and the first batch of aluminum alloy sheets are placed. Into the etching solution, simultaneously immerse the second batch of aluminum alloy sheets in water, and loop back until the two batches of aluminum alloy sheets are soaked in the etching solution 5 times, each time the aluminum alloy sheets are taken out from the acid liquid. Record the temperature before, and get a graph of temperature and time (as shown in Figure 2).

Performance Testing:

Bonding force between aluminum alloy and resin: The aluminum alloy resin composites prepared in Examples 9-13 and Comparative Examples 4-5 were fixed to a universal material testing machine for product tensile test. The maximum load in the test results can be regarded as aluminum alloy and resin. The magnitude of the binding force between the test results is shown in Table 4.

It can be seen from the table that the aluminum alloy substrate prepared by the invention has unique surface pore structure and high binding force with resin, and can reach more than 800 N, which is far higher than the prior art, and has wide application range, and can be applied not only to PPS. And can be combined with nylon, strong bonding, simple and easy to mass production. At the same time, it can be seen from FIG. 2 that the technical solution of the present invention has less heat release, slower temperature rise of the etching liquid, is more suitable for mass production, consumes less etching liquid, and has less corrosion to equipment.

Example 15

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. sheet;

2. Surface treatment 1: The above aluminum alloy sheet is placed as an anode in an H2SO4 anodizing bath containing a concentration of about 15% by weight, electrolyzed at 15 volts, 18 degrees Celsius for 5 minutes, and dried at 80 degrees Celsius for 20 minutes;

3. Surface treatment 2: Prepare water-soluble solution containing 10wt% H3PO4 in a beaker 500 mL of the solution, the above-mentioned aluminum alloy sheet 10PCS was immersed therein at room temperature, and after 2 minutes, it was taken out, and immersed in a beaker containing water for 2 minutes, and a blister was added once in a H3PO4 aqueous solution as a loop. After looping 2 times, after the last water immersion, the aluminum alloy piece was placed in an oven at 80 degrees Celsius for drying.

The cross section of the surface treated aluminum alloy sheet was observed by a metallographic microscope and an SEM field emission scanning electron microscope, and a loose layer having a thickness of 6 μm to 6.5 μm was obtained on the surface of the aluminum alloy sheet, and the thickness was 80 nm to 110 nm. The barrier layer and the corrosion layer having a thickness of 20 nm to 40 μm.

The pore size of the anodized film micropores in the loose layer was measured by SEM field emission scanning electron microscope to be 20 nm to 20 μm; the pore size of the barrier layer in the barrier layer was observed to be 25 nm to 25 μm; The corrosion hole of the alloy has a pore diameter of 50 nm to 120 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

4. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, one batch of injection nylon resin, and the other batch of polyphenylene sulfide (PPS) containing 30wt% glass fiber. The resin composition was released from the mold and cooled to obtain an aluminum alloy resin composite group A1 and Group B1 of the aluminum alloy and the resin composition which were firmly bonded together.

Example 16

The aluminum alloy resin composites A2 and B2 were prepared in the same manner as in Example 15, except that the surface treatment 2 was to prepare 500 ml of an aqueous solution containing 10 wt% of H3PO4 in a beaker, and the obtained aluminum alloy sheet 10PCS was immersed at room temperature. Among them, after 10 minutes, it was taken out, and then immersed in a beaker containing water for 2 minutes, and then the aluminum alloy was placed in an oven at 80 ° C for drying. The surface of the aluminum alloy sheet after electrolysis was measured in the same manner as in Example 15 to obtain a loose layer having a thickness of 5 μm to 6 μm, a barrier layer having a thickness of 75 nm to 100 nm, and a thickness of 25 nm to 50 μm. Corrosion layer. The pore size of the anodized film micropores in the loose layer is 30 nm to 45 μm; the pore size of the barrier layer in the barrier layer is 30 nm to 50 μm; and the pore diameter of the aluminum alloy etching hole in the etching layer is 60 nm to 200 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 17

The aluminum alloy resin composites A3 and B3 were prepared in the same manner as in Example 1, except that the mass concentration of H3PO4 in the surface treatment 2 was 5 wt%, and the obtained aluminum alloy sheet 10PCS was immersed therein at room temperature. After 2 minutes, take it out and put it in a beaker filled with water for 2 minutes. Add a blister to the H3PO4 aqueous solution as a loop. So loop 2 times. After the last water soak, place the aluminum alloy sheet. Dry in an oven at 80 degrees Celsius. A porous layer having a thickness of 7 μm to 7.5 μm, a barrier layer having a thickness of 80 nm to 100 nm, and a thickness of 15 nm to 25 μm were obtained by measuring the surface of the aluminum alloy sheet after electrolysis in the same manner as in Example 15. Corrosion layer. The pore size of the anodized film micropores in the loose layer is about 15 nm to 10 μm; the pore size of the barrier layer in the barrier layer is about 20 nm to 15 μm; and the pore size of the aluminum alloy etching hole in the etching layer is 40 nm to 60 μm. about. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 18

The aluminum alloy resin composites A4 and B4 were prepared in the same manner as in Example 1, except that the mass concentration of H3PO4 in the surface treatment 2 was 20% by weight, and the obtained aluminum alloy sheet 10PCS was immersed therein at room temperature. , take it out after 2 minutes, put it in a water-filled Soak for 2 minutes in the cup, add a blisters in a H3PO4 aqueous solution as a loop, and then loop 2 times. After the last water soak, the aluminum alloy pieces are placed in an oven at 80 degrees Celsius for drying. The surface of the aluminum alloy sheet after electrolysis was measured in the same manner as in Example 15 to obtain a loose layer having a thickness of 3 μm to 4 μm, a barrier layer having a thickness of 80 nm to 100 nm, and a thickness of 30 nm to 80 μm. Corrosion layer. The pore size of the anodized film micropores in the loose layer is 30 nm to 60 μm; the pore size of the barrier layer in the barrier layer is 40 nm to 80 μm; and the pore size of the aluminum alloy etching hole in the etching layer is 80 nm to 300 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 19

The aluminum alloy resin composites A5 and B5 were prepared in the same manner as in Example 1, except that the surface treatment 2 was to prepare 500 mL of an aqueous solution containing 10 wt% of H3PO4 and 1 wt% of NaCl in a beaker. Using the same method as in Example 15, the surface of the aluminum alloy sheet after electrolysis was measured to obtain a loose layer having a thickness of 4.5 μm to 5 μm, a barrier layer having a thickness of 80 nm to 100 nm, and a thickness of 25 nm to 60 μm. Corrosion layer. The pore size of the anodized film micropores in the loose layer is 25 nm to 50 μm; the pore size of the barrier layer in the barrier layer is 30 nm to 50 μm; and the pore size of the aluminum alloy etching hole in the etching layer is 50 nm to 250 μm. It can also be observed that there are three layers of three-dimensional pore structure on the surface of the treated aluminum alloy, and the anodized film micropores, the barrier corrosion holes and the aluminum alloy corrosion holes communicate with each other.

Example 20

The aluminum alloy resin composites A6 and B6 were prepared in the same manner as in Example 15, except that the dried aluminum alloy sheets were placed in a 2 wt% polyvinyl alcohol solution for 5 minutes before being formed, and taken out. Dry and put in the mold.

Example 21

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. 2; Surface treatment 1: The above aluminum alloy sheet is placed as an anode in an H2SO4 anodizing bath containing a concentration of about 15% by weight, electrolyzed at 15 volts, 18 degrees Celsius for 5 minutes, and dried at 80 degrees Celsius for 20 minutes; Surface treatment 2: 500 mL of an aqueous solution containing 10 wt% of H3PO4 was prepared in a beaker, placed in a 25 ° C thermostat to raise the temperature to 25 ° C, and placed in a thermometer so that the measurement point was at the center of the solution. Take the above-mentioned aluminum alloy sheet 20PCS, divide into two batches, each batch of 10PCS, one batch is immersed in it, take it out after 2 minutes, record the temperature of the etching liquid in the beaker before taking out, and immediately put in the second batch of aluminum alloy piece, at the same time The first batch of aluminum alloy pieces are immersed in a beaker containing water for 2 minutes, the second batch of aluminum alloy pieces are taken out from the etching liquid, the temperature is recorded before taking out, and the first batch of aluminum alloy pieces are placed in the etching liquid. At the same time, the second batch of aluminum alloy sheets are immersed in water, so that the two batches of aluminum alloy sheets are soaked in the etching liquid 5 times, and the temperature is recorded before each aluminum alloy sheet is taken out from the acid liquid. A graph of temperature versus time (as in Figure 3).

Comparative example 7

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution with sodium content of 40g/L was etched for 10 seconds, and washed with water. The mixture was neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy sheet;

2. Surface treatment: The aluminum alloy substrate is immersed in 500 mL of a phosphoric acid aqueous solution having a concentration of 10 wt%, and placed in a 25 ° C thermostat to raise the temperature to 25 ° C. The obtained aluminum alloy sheet 10PCS is immersed therein, and taken out after 2 minutes. Soak it in a beaker filled with water for 2 minutes, add a blisters as a loop in one etching bubble, and then loop back 5 times. After the last water soak, place the aluminum alloy sheet in an oven at 80 ° C to dry. .

An etching layer having a thickness of 300 nm to 120 μm was obtained by the same method as in Example 15. The pores in the corrosion layer have a pore size of from 300 nm to 400 microns.

3. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and one batch of polyphenylene sulfide (PPS) resin composition containing 30wt% glass fiber is injected, and the other is The nylon resin was batch-molded, and both were released from the mold and cooled to obtain an aluminum alloy resin composite C1 group and D1 group of the aluminum alloy and the resin composition which were firmly bonded together.

Comparative example 8

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. sheet;

2. Surface treatment: The above aluminum alloy sheet was placed as an anode in an H2SO4 anodizing bath containing a concentration of about 20 wt%, electrolyzed at 15 volts for 10 minutes, and blown dry; measured by the same method as in Example 15. Anodized film mesopores The pore size is from about 10 nm to about 100 nm, and the pore depth is from about 9 microns to about 10 microns.

3. Molding: The dried aluminum alloy sheets are divided into two batches, each batch of 5PCS, which are respectively inserted into the injection molding mold, and one batch of polyphenylene sulfide (PPS) resin composition containing 30wt% glass fiber is injected, and the other is The nylon resin was batch-molded, and both were released from the mold and cooled to obtain an aluminum alloy resin composite C2 group and D2 group of the aluminum alloy and the resin composition which were firmly bonded together.

Comparative example 9

1. Pre-treatment: The commercially available 1mm thick 6063 aluminum alloy plate is cut into 15mm×80mm rectangular pieces, which are placed in a polishing machine for grinding, then degreased and then oxidized at 60 degrees Celsius. The solution having a sodium content of 40 g/L was etched for 10 seconds, washed with water, and neutralized in a neutralization tank having a HNO3 content of about 6 wt% for 30 seconds, and then washed with water to obtain a pretreated aluminum alloy. 2; Surface treatment: Prepare 500 mL of 10% by weight aqueous phosphoric acid solution in a beaker, place it in a 25 ° C thermostat to raise the temperature to 25 ° C, and put a thermometer so that the measurement point is at the center of the solution. Take the above-mentioned aluminum alloy sheet 20PCS, divide into two batches, each batch of 10PCS, one batch is immersed in it, take it out after 2 minutes, record the temperature of the etching liquid in the beaker before taking out, and immediately put in the second batch of aluminum alloy piece, at the same time The first batch of aluminum alloy pieces are immersed in a beaker containing water for 2 minutes, the second batch of aluminum alloy pieces are taken out from the etching liquid, the temperature is recorded before taking out, and the first batch of aluminum alloy pieces are placed in the etching liquid. At the same time, the second batch of aluminum alloy sheets are immersed in water, so that the two batches of aluminum alloy sheets are soaked in the etching liquid 5 times, and the temperature is recorded before each aluminum alloy sheet is taken out from the acid liquid. A graph of temperature versus time (as in Figure 3).

Performance Testing:

Aluminum alloy and resin binding force: Preparation of Examples 15-20 and Comparative Examples 7-8 The aluminum alloy resin composite is fixed on the universal material testing machine for product tensile test. The maximum load in the test results can be regarded as the bonding strength between the aluminum alloy and the resin. The test results are shown in Table 6.

It can be seen from the table that the aluminum alloy substrate prepared by the invention has unique surface pore structure and high binding force with resin, and can reach more than 900 N, which is far higher than the prior art, and has wide application range, and can be applied not only to PPS. And can be combined with nylon, strong bonding, simple and easy to mass production. At the same time, it can be seen from FIG. 1 that the technical solution of the present invention has less heat release, slower temperature rise of the etching liquid, is more suitable for mass production, consumes less etching liquid, and has less corrosion to equipment.

In the description of the present specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" and the like means a specific feature described in connection with the embodiment or example. A structure, material or feature is included in at least one embodiment or example of the invention. In the present specification, the schematic representation of the above terms does not necessarily mean the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in a suitable manner in any one or more embodiments or examples.

Although the embodiments of the present invention have been shown and described, it is understood that the foregoing embodiments are illustrative and not restrictive In the case of the present invention Variations, modifications, alterations and variations of the embodiments described above are possible.

Claims (29)

A method for treating a metal surface, comprising the steps of: anodizing a metal substrate to obtain a metal substrate having an anodized film on the surface, wherein the metal substrate is an aluminum alloy substrate or an aluminum base Surface treating the metal substrate having an anodized film on the surface with an etching solution to obtain a surface-treated metal substrate; wherein the etching solution contains at least one of a chloride ion and a phosphate ion, The concentration of H+ in the etching solution is 0.55-5.5 mol/L. The method of claim 1, wherein the etching solution is at least one selected from the group consisting of a hydrochloric acid solution and a phosphoric acid solution. The method according to claim 2, characterized in that the content of hydrogen chloride is from 2% by weight to 20% by weight based on the total weight of the hydrochloric acid solution. The method of claim 2, wherein the content of H3PO4 is from 3 wt% to 40 wt% based on the total weight of the phosphoric acid solution. The method of claim 4, wherein the phosphoric acid solution further contains an inorganic halide. The method of claim 5, wherein the inorganic halide is a soluble hydrochloride. The method of claim 6, wherein the soluble hydrochloride salt is present in an amount of from 0.01% by weight to 10% by weight based on the total weight of the phosphoric acid solution. The method of claim 6, wherein the soluble hydrochloride salt is at least one selected from the group consisting of sodium chloride, potassium chloride or aluminum chloride. The method of claim 1, wherein the surface treatment of the metal substrate having the anodized film on the surface by using the etching solution comprises: treating the surface at a temperature of 18 degrees Celsius to 35 degrees Celsius The metal substrate having an anodized film is immersed in the etching solution for 1 minute to 60 minutes. The method of claim 1, wherein the anodizing the metal substrate comprises: placing the metal substrate in a sulfuric acid solution having a concentration of 10 wt% to 30 wt% as an anode, and Electrolysis is carried out at a temperature of 10 volts to 30 degrees Celsius at a voltage of 5 volts to 100 volts for 1 minute to 40 minutes to form an oxide film layer on the surface of the metal substrate, wherein the oxide film layer has a thickness of 1 μm. ~20 microns. A surface-treated metal characterized in that the surface-treated metal is obtained by the method described in any one of claims 1-10. A surface-treated metal, comprising: a metal substrate, wherein the metal substrate is an aluminum alloy substrate or an aluminum substrate; and an anodized film layer, wherein the anodized layer is formed on the metal substrate a surface; wherein the anodized film layer includes: a barrier layer in contact with the metal substrate; and a loose layer formed on a surface of the barrier layer away from the metal substrate And an etching layer formed on the surface of the barrier layer adjacent to the metal substrate. The surface-treated metal according to claim 12, wherein the barrier layer has a thickness of 5 nm to 5 μm, and the barrier layer contains a barrier etching hole, and the barrier layer is corroded. The pore size is from 10 nm to 800 μm; the thickness of the loose layer is from 100 nm to 100 μm, and the porous layer contains anodization Membrane micropores, the pores of the anodized film have a pore diameter of 10 nm to 800 μm; the thickness of the etching layer is 5 nm to 200 μm, the corrosion layer contains a metal corrosion hole, and the pore of the metal corrosion hole It is 10 nanometers to 1 millimeter. The surface-treated metal according to claim 12, wherein the barrier etching hole, the anodized film micropore, and the metal etching hole are in communication with each other. A method of producing a metal resin composite, comprising the steps of: providing a surface-treated metal according to any one of claims 11 to 14; and injection molding the resin composition onto the surface The surface of the treated metal to obtain the metal resin composite. The method of claim 15, wherein the surface-treated metal is immersed in a water-soluble polymer prior to injection molding the resin composition onto the surface of the surface-treated metal. The solution is treated in a solution. The method of claim 16, wherein the surface-treated metal is immersed in the solution containing the water-soluble polymer for 1 minute to 30 minutes at a temperature of 15 degrees Celsius to 60 degrees Celsius. The method of claim 16, wherein the water-soluble polymer solution contains 1 wt% to 20 wt% of a water-soluble polymer based on the total weight of the water-soluble polymer solution, wherein The water-soluble polymer is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylate, polymethacrylic acid, polymethacrylate, polyvinylsulfonic acid, polyvinylsulfonate, polystyrenesulfonate. At least one of an acid or a polystyrene sulfonate. The method of claim 15, wherein the injection molding conditions are: a mold temperature of 50 degrees Celsius to 300 degrees Celsius, a nozzle temperature of 200 degrees Celsius to 450 degrees Celsius, and a dwell time of 1 second to 50 degrees. In seconds, the injection pressure is 50 MPa to 300 MPa, the injection time is 1 second to 30 seconds, the delay time is 1 second to 30 seconds, and the cooling time is 1 second to 60 seconds. The method according to claim 15, wherein the resin composition is a thermoplastic resin composition. The method of claim 20, wherein the thermoplastic resin composition comprises a host resin and a polyolefin resin, the polyolefin resin having a melting point of 65 degrees Celsius to 105 degrees Celsius, wherein the host resin is One selected from the group consisting of a mixture of polyphenylene ether and polyphenylene sulfide, wherein the weight ratio of polyphenylene ether to polyphenylene sulfide in the host resin is from 3:1 to 1:3; polyphenylene ether and poly a mixture of guanamine wherein the weight ratio of polyphenylene ether to polyamine in the host resin is from 3:1 to 1:3; and polycarbonate. The method of claim 21, wherein the polyolefin resin is a grafted polyethylene. The method according to claim 21, wherein the amount of the host resin is 70 to 95 parts by weight, and the amount of the polyolefin resin is 5 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin. . The method according to claim 23, wherein the thermoplastic resin further contains 1 to 5 parts by weight of a fluidity improver based on 100 parts by weight of the thermoplastic resin, and the fluidity improver is cyclic Polyester. The method of claim 23, wherein the resin composition contains a filler, the filler comprising at least one selected from the group consisting of a fibrous filler and an inorganic powder filler, wherein the fibrous filler is selected from the group consisting of a fibrous filler and an inorganic powder filler. At least one of glass fiber, carbon fiber, and polyamide fiber, the inorganic powder filler being at least one selected from the group consisting of cerium oxide, talc, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, glass, and kaolin . A metal-resin composite obtained by the method according to any one of claims 15 to 25. A metal-resin composite characterized by comprising: a metal layer, the metal layer being the surface-treated metal according to any one of claims 11 to 14, wherein the metal layer has anodization a film micropore, a barrier etching hole, and a metal etching hole; and a resin layer, the resin layer being bonded to the surface of the metal layer, wherein a resin composition forming the resin layer is filled in the anodized film micropore, The barrier layer is etched into the hole and the metal is etched into the hole. The metal-resin composite according to claim 27, wherein the anodic oxide film pores, the barrier etch holes, the metal corrosion holes or the metal substrate surface further contain a water-soluble polymer. Wherein, the water-soluble polymer is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylate, polymethacrylic acid, polymethacrylate, polyvinylsulfonic acid, polyvinylsulfonate, polyphenylene. At least one of ethylene sulfonic acid or polystyrene sulfonate. The metal-resin composite according to claim 27, wherein the resin layer has a thickness of 0.5 mm to 10 mm.