WO2016101694A1

WO2016101694A1 - Surface-treated metal substrate material and metal-resin composite and manufacturing method and application thereof, and electronic product outer shell and manufacturing method thereof

Info

Publication number: WO2016101694A1
Application number: PCT/CN2015/092725
Authority: WO
Inventors: 孙剑; 吴彦琴; 宋文广; 陈梁
Original assignee: 比亚迪股份有限公司
Priority date: 2014-12-25
Filing date: 2015-10-23
Publication date: 2016-06-30
Also published as: CN105522782A

Abstract

A surface-treated metal substrate material and manufacturing method thereof, and a metal-resin composite, the metal being aluminium or aluminium alloy, said metal substrate material comprising a metal substrate and a hard anodised film layer attached to at least part of the surface of the metal substrate, first etched holes being distributed on the surface of the hard anodised film layer.

Description

经表面处理的金属基材和金属-树脂复合体及制备方法和应用以及电子产品外壳及制备方法Surface treated metal substrate and metal-resin composite, preparation method and application thereof, electronic product outer casing and preparation method

相关申请的交叉引用Cross-reference to related applications

本申请主张在2014年12月25日在中国提交的中国专利申请号No.201410826354.1的优先权，其全部内容通过引用包含于此。The present application claims priority to Chinese Patent Application No. 201410826354.1, filed on Jan. 25, 2014, in

技术领域Technical field

本公开涉及一种经表面处理的金属基材及其制备方法和应用，具体地涉及一种金属-树脂复合体及其制备方法和应用，以及一种电子产品外壳及其制备方法。The present disclosure relates to a surface-treated metal substrate and a preparation method and application thereof, and in particular to a metal-resin composite, a preparation method and application thereof, and an electronic product casing and a preparation method thereof.

背景技术Background technique

在汽车、家用电器制品、工业机器等的零件制造领域中，需要铝或铝合金与树脂一体化成型技术。In the field of parts manufacturing of automobiles, household appliances, industrial machines, etc., an integrated molding technology of aluminum or aluminum alloy and resin is required.

目前常用的将铝或铝合金和树脂相结合的方法是胶合技术。该方法通过化学胶粘剂将铝或铝合金与已成型树脂结合在一起得到复合体。但是，由该方法得到的复合体中，铝或铝合金与树脂的结合力较差，且胶粘剂结合层不耐酸碱，影响复合体的使用场合。另外，由于胶粘剂结合层具有一定的厚度，因而会影响最终产品的尺寸。A commonly used method of combining aluminum or an aluminum alloy with a resin is a gluing technique. The method combines aluminum or an aluminum alloy with a formed resin by a chemical adhesive to obtain a composite. However, in the composite obtained by the method, the bonding strength of aluminum or aluminum alloy to the resin is poor, and the adhesive bonding layer is not resistant to acid and alkali, which affects the use of the composite. In addition, since the adhesive bonding layer has a certain thickness, it affects the size of the final product.

针对胶粘剂法存在的上述不足，研究人员开发了其它用于将铝或铝合金与树脂结合的方法。In response to the aforementioned deficiencies in the adhesive process, the researchers have developed other methods for combining aluminum or aluminum alloys with resins.

一种方法是采用胺类物质，例如：氨基甲酸酯、一水合肼、乙二胺等的水溶液对铝或铝合金进行表面腐蚀，以在铝或铝合金表面形成纳米级的微孔，并把胺类物质保留在形成的微孔中，然后将树脂注塑在经处理的表面，通过胺类物质与树脂之间的反应，将树脂与铝或铝合金结合到一起，从而得到具有一定拉伸剪切强度的铝塑一体化产品。但是，采用上述胺类物质对铝或铝合金进行蚀刻，在铝或铝合金表面形成的孔洞太小，树脂难以直接注塑进入纳米级的微孔中，以致难以明显提高铝合金和树脂的结合强度。One method is to surface-etch aluminum or aluminum alloy with an amine substance such as an aqueous solution of urethane, hydrazine monohydrate or ethylenediamine to form nano-scale micropores on the surface of aluminum or aluminum alloy, and The amine substance is retained in the formed micropores, and then the resin is injection molded on the treated surface, and the resin is combined with the aluminum or the aluminum alloy by a reaction between the amine substance and the resin, thereby obtaining a certain stretching. Aluminium-plastic integrated product with shear strength. However, the aluminum or aluminum alloy is etched by using the above amine substances, and the pores formed on the surface of the aluminum or aluminum alloy are too small, and the resin is difficult to be directly injected into the micropores of the nanometer order, so that it is difficult to significantly improve the bonding strength between the aluminum alloy and the resin. .

另一种方法是采用含无机卤素化合物的酸性蚀刻液直接对铝合金表面进行腐蚀，然后注塑树脂得到铝塑一体化产品。但是，采用这种方法得到的铝塑一体化产品，铝合金与树脂之间的结合强度仍有待于进一步提高。Another method is to directly corrode the surface of the aluminum alloy with an acidic etching solution containing an inorganic halogen compound, and then inject the resin to obtain an aluminum-plastic integrated product. However, the aluminum-plastic integrated product obtained by this method, the bonding strength between the aluminum alloy and the resin still needs to be further improved.

此外，还可以在铝合金表面进行阳极氧化从而在铝合金表面形成多孔性氧化铝膜层，然后将树脂注塑在具有氧化铝膜层的表面得到铝塑一体化产品。但是，采用该方法得到的铝塑一体化产品中，铝合金和树脂的结合强度也不高。Further, an anodizing may be performed on the surface of the aluminum alloy to form a porous aluminum oxide film layer on the surface of the aluminum alloy, and then the resin is injection molded on the surface having the aluminum oxide film layer to obtain an aluminum-plastic integrated product. However, the method obtained by this method In the aluminum-plastic integrated product, the bonding strength between the aluminum alloy and the resin is not high.

发明内容Summary of the invention

本公开的目的在于克服现有的金属-树脂复合体中，金属基材与树脂层之间的结合强度不高的技术问题。The purpose of the present disclosure is to overcome the technical problem that the bonding strength between the metal substrate and the resin layer is not high in the conventional metal-resin composite.

根据本公开的第一方面，本公开提供了一种经表面处理的金属基材，所述金属为铝或铝合金，该金属基材包括金属基体以及形成于所述金属基体的至少部分表面上的硬质阳极氧化膜层，所述硬质阳极氧化膜层的表面分布有第一腐蚀孔。According to a first aspect of the present disclosure, the present disclosure provides a surface-treated metal substrate, the metal being aluminum or an aluminum alloy, the metal substrate comprising a metal substrate and being formed on at least a portion of a surface of the metal substrate A hard anodized film layer having a first etching hole distributed on the surface of the hard anodized film layer.

根据本公开的第二个方面，本公开提供了一种金属基材的表面处理方法，所述金属为铝或铝合金，该方法包括提供金属基材，所述金属基材包括金属基体以及形成于所述金属基体的至少部分表面的硬质阳极氧化膜层；将所述金属基材进行第一蚀刻，以在所述硬质阳极氧化膜层中形成第一腐蚀孔。According to a second aspect of the present disclosure, the present disclosure provides a surface treatment method of a metal substrate, the metal being aluminum or an aluminum alloy, the method comprising providing a metal substrate including a metal substrate and forming a hard anodized film layer on at least a portion of the surface of the metal substrate; the metal substrate is subjected to a first etching to form a first etching hole in the hard anodized film layer.

根据本公开的第三个方面，本公开提供了一种由根据本公开的第二个方面的方法制备的经表面处理的金属基材。According to a third aspect of the present disclosure, the present disclosure provides a surface treated metal substrate prepared by the method according to the second aspect of the present disclosure.

根据本公开的第四个方面，本公开提供了一种金属-树脂复合体，所述金属为铝或铝合金，该复合体包括金属基材和树脂层，所述金属基材为本公开提供的经表面处理的金属基材，所述树脂层附着在所述金属基材的至少部分表面上，所述树脂层中的部分树脂向下延伸并填充于金属基材的第一腐蚀孔或者第一腐蚀孔和第二腐蚀孔中。According to a fourth aspect of the present disclosure, the present disclosure provides a metal-resin composite, the metal being aluminum or an aluminum alloy, the composite comprising a metal substrate and a resin layer, the metal substrate being provided for the present disclosure a surface-treated metal substrate, the resin layer being attached to at least a portion of a surface of the metal substrate, a portion of the resin in the resin layer extending downward and filling a first etching hole of the metal substrate or A corrosion hole and a second corrosion hole.

根据本公开的第五个方面，本公开提供了一种金属-树脂复合体的制备方法，所述金属为铝或铝合金，所述金属-树脂复合体包括金属基材以及附着在所述金属基材的至少部分表面的树脂层，所述金属基材为本公开提供的经表面处理的金属基材，该方法包括向金属基材的至少部分表面注入含有树脂的组合物并使部分组合物填充于金属基材的第一腐蚀孔或者第一腐蚀孔和第二腐蚀孔中，成型后形成树脂层。According to a fifth aspect of the present disclosure, the present disclosure provides a method of producing a metal-resin composite, the metal being aluminum or an aluminum alloy, the metal-resin composite including a metal substrate and attached to the metal a resin layer of at least a portion of a surface of the substrate, the metal substrate being a surface treated metal substrate provided by the present disclosure, the method comprising injecting a resin-containing composition onto at least a portion of a surface of the metal substrate and causing a partial composition The first etching hole or the first etching hole and the second etching hole are filled in the metal substrate, and a resin layer is formed after molding.

根据本公开的第六个方面，本公开提供了一种由根据本公开的第五个方面的方法制备的金属-树脂复合体。According to a sixth aspect of the present disclosure, the present disclosure provides a metal-resin composite prepared by the method according to the fifth aspect of the present disclosure.

根据本公开的第七个方面，本公开提供了根据本公开的金属-树脂复合体在制备电子产品外壳中的应用。According to a seventh aspect of the present disclosure, the present disclosure provides an application of a metal-resin composite according to the present disclosure in preparing an electronic product casing.

根据本公开的第八个方面，本公开提供了一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，其中，所述金属壳本体为根据本公开的金属基材。According to an eighth aspect of the present disclosure, the present disclosure provides an electronic product housing including a metal shell body and at least one resin member attached to at least a portion of an inner surface and/or at least a portion of an outer surface of the metal shell body Wherein the metal shell body is a metal substrate according to the present disclosure.

根据本公开的第九个方面，本公开提供了一种电子产品外壳的制备方法，该方法包括在金属壳本体的至少部分内表面和/或至少部分外表面形成至少一个树脂件，其中，采用根据本公开的金属-树脂复合体的制备方法来形成所述树脂件。According to a ninth aspect of the present disclosure, the present disclosure provides a method of fabricating an electronic product housing, the method comprising At least one resin member is formed on at least a portion of the inner surface and/or at least a portion of the outer surface of the metal shell body, wherein the resin member is formed using the method of preparing the metal-resin composite according to the present disclosure.

根据本公开的金属-树脂复合体，树脂与金属基材之间的结合强度高，树脂层不易从金属基材表面脱落，因而本公开提供的金属-树脂复合体具有较高的结构稳定性，能够满足对结构稳定性要求较高的使用场合的要求，例如可以作为各种电子产品的外壳。According to the metal-resin composite of the present disclosure, the bonding strength between the resin and the metal substrate is high, and the resin layer is not easily peeled off from the surface of the metal substrate, and thus the metal-resin composite provided by the present disclosure has high structural stability. It can meet the requirements of applications requiring high structural stability, for example, as an outer casing for various electronic products.

附图说明DRAWINGS

图1为用于示意性地说明根据本公开的手机外壳的剖视图，包括主视图和俯视图；1 is a cross-sectional view for schematically illustrating a cellular phone case according to the present disclosure, including a front view and a top view;

图2为用于示意性地说明根据本公开的智能表外壳的剖视图。2 is a cross-sectional view for schematically illustrating a smart watch case in accordance with the present disclosure.

具体实施方式detailed description

本文中，金属可以为纯铝，也可以为铝合金。所述铝合金是指以铝作为基础元素加入其它元素形成的合金，可以为常见的各种铝合金。金属基材是用铝或铝合金形成的各种成型体，根据具体使用要求可以具有各种形状。Herein, the metal may be pure aluminum or aluminum alloy. The aluminum alloy refers to an alloy formed by adding other elements to aluminum as a base element, and may be various common aluminum alloys. The metal substrate is various molded bodies formed of aluminum or an aluminum alloy, and may have various shapes depending on specific use requirements.

根据本公开的第一个方面，本公开提供了一种经表面处理的金属基材，所述金属为铝或铝合金，该金属基材包括金属基体以及形成于所述金属基体的至少部分表面上的硬质阳极氧化膜层，所述硬质阳极氧化膜层的表面分布有第一腐蚀孔。According to a first aspect of the present disclosure, the present disclosure provides a surface treated metal substrate, the metal being aluminum or an aluminum alloy, the metal substrate comprising a metal substrate and at least a portion of a surface formed on the metal substrate A hard anodized film layer having a first etching hole distributed on the surface of the hard anodized film layer.

在经表面处理的金属基材用于与树脂结合以制备金属-树脂复合体时，所述第一腐蚀孔可以用于容纳树脂，从而将树脂锚定在金属基材表面。通过选择第一腐蚀孔的尺寸可以提高树脂与金属基材之间的结合强度。When the surface-treated metal substrate is used in combination with a resin to prepare a metal-resin composite, the first etching hole may be used to accommodate a resin to anchor the resin to the surface of the metal substrate. The bonding strength between the resin and the metal substrate can be increased by selecting the size of the first etching hole.

所述第一腐蚀孔的孔径可以在10-200nm的范围内。在所述第一腐蚀孔的孔径处于上述范围之内时，一方面不会对硬质阳极氧化膜层本身的强度产生不利影响，另一方面在用于制备金属-树脂复合体时，还能将树脂层稳固地锚定在金属基材中，使树脂层与金属基材之间具有较高的结合强度，从而使得金属-树脂复合体具有较高的结构稳定性。从进一步提高由该经表面处理的金属基材与树脂一体化成型而制备的金属-树脂复合体中，金属基材与树脂层之间的结合强度的角度出发，所述第一腐蚀孔的孔径可以在50-200nm的范围内，例如在80-200nm的范围内，如在100-200nm的范围内。本文中，用于说明数值范围的术语“在……的范围内”均包括两个端值。The pore diameter of the first etching hole may be in the range of 10 to 200 nm. When the pore diameter of the first etching hole is within the above range, on the one hand, it does not adversely affect the strength of the hard anodized film layer itself, and on the other hand, when used for preparing the metal-resin composite body, The resin layer is firmly anchored in the metal substrate to have a high bonding strength between the resin layer and the metal substrate, thereby making the metal-resin composite have high structural stability. From the viewpoint of further improving the bonding strength between the metal substrate and the resin layer in the metal-resin composite prepared by integrally molding the surface-treated metal substrate and the resin, the pore diameter of the first etching hole It may be in the range of 50-200 nm, for example in the range of 80-200 nm, such as in the range of 100-200 nm. Herein, the term "within the range of" includes the two end values.

所述第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值可以在0.1-1：1的范围内，例如在0.2-1：1的范围内，如在0.5-1：1的范围内。诸如，至少部分第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1，如至少50％、至少60％、至少70％的第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1。The ratio of the depth of the first etching hole to the thickness of the hard anodized film layer may be in the range of 0.1 to 1:1, for example, in the range of 0.2 to 1:1, such as 0.5 to 1:1. In the range. For example, the ratio of the depth of at least a portion of the first etching holes to the thickness of the hard anodized film layer is 1:1, such as at least 50%, at least 60%, at least 70% of the first The ratio of the depth of a corrosion hole to the thickness of the hard anodized film layer is 1:1.

本文中，腐蚀孔的孔径是指腐蚀孔的上端口(即，位于表面的端口)在径向的最大尺寸，腐蚀孔的深度是指一腐蚀孔的两端之间的垂直距离。腐蚀孔的孔径和深度可以采用电镜法测定。Herein, the pore diameter of the etching hole refers to the maximum dimension of the upper port of the etching hole (that is, the port located at the surface) in the radial direction, and the depth of the etching hole refers to the vertical distance between the both ends of a corrosion hole. The pore size and depth of the corrosion hole can be determined by electron microscopy.

根据本公开的经表面处理的金属基材，所述金属基体的表面可以不存在腐蚀孔。According to the surface-treated metal substrate of the present disclosure, the surface of the metal substrate may be free from corrosion holes.

在一个具体实施方式中，所述金属基体包括基体层和腐蚀层，所述基体层与所述腐蚀层为一体结构，所述腐蚀层与所述硬质阳极氧化膜层相接并为一体结构，所述腐蚀层的表面分布有第二腐蚀孔，且至少部分第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1。在所述金属基体包括所述基体层和所述腐蚀层时，可以明显提高由该金属基材与树脂一体化成型而得到的金属-树脂复合体中，金属基材与树脂层之间的结合强度。In a specific embodiment, the metal substrate comprises a base layer and an etching layer, the base layer and the etching layer are integrated, and the etching layer is in contact with the hard anodized film layer and is an integral structure. The surface of the etching layer is distributed with a second etching hole, and a ratio of a depth of at least a portion of the first etching hole to a thickness of the hard anodized film layer is 1:1. When the metal substrate includes the base layer and the etching layer, the bonding between the metal substrate and the resin layer in the metal-resin composite obtained by integrally molding the metal substrate and the resin can be remarkably improved. strength.

本文中，出于清楚的目的，将分布在硬质阳极氧化膜层表面的腐蚀孔称为“第一腐蚀孔”，将分布在与硬质阳极氧化膜层相接的金属基体表面的腐蚀孔称为“第二腐蚀孔”。Herein, for the purpose of clarity, the etching holes distributed on the surface of the hard anodized film layer are referred to as "first etching holes", and the etching holes distributed on the surface of the metal substrate which is in contact with the hard anodized film layer It is called "second corrosion hole".

在该具体的实施方式中，所述基体层为致密层。即，所述基体层中没有腐蚀孔。In this particular embodiment, the base layer is a dense layer. That is, there are no corrosion holes in the base layer.

在该具体的实施方式中，所述第二腐蚀孔的孔径可以在200-2000nm的范围内，例如在400-2000nm的范围内，诸如在800-1500nm的范围内，如在1000-1500nm的范围内。所述第二腐蚀孔的深度在0.1-500μm的范围内，例如在10-400μm的范围内，诸如在50-200μm的范围内。In this specific embodiment, the pore diameter of the second etching hole may be in the range of 200-2000 nm, for example, in the range of 400-2000 nm, such as in the range of 800-1500 nm, such as in the range of 1000-1500 nm. Inside. The depth of the second etching hole is in the range of 0.1 to 500 μm, for example, in the range of 10 to 400 μm, such as in the range of 50 to 200 μm.

在该具体的实施方式中，至少部分第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1，例如至少50％、至少60％、至少70％的第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1。在该具体的实施方式中，所述第一腐蚀孔的孔径如前文所述，此处不再详述。In this specific embodiment, the ratio of the depth of at least a portion of the first etching holes to the thickness of the hard anodized film layer is 1:1, such as at least 50%, at least 60%, at least 70% of the first corrosion. The ratio of the depth of the hole to the thickness of the hard anodized film layer was 1:1. In this specific embodiment, the pore size of the first etching hole is as described above, and will not be described in detail herein.

根据本公开的经表面处理的金属基材，所述硬质阳极氧化膜层具有较高的硬度，其显微硬度一般为2000-2500HV，在该金属基材用于与树脂结合制备金属-树脂复合体时，与金属基材表面为阳极氧化膜层相比，能够更为牢固地将树脂固定在金属基材中，从而获得更高的结合强度。本公开对于所述硬质阳极氧化膜层的厚度没有特别限定。一般地，所述硬质阳极氧化膜层的厚度可以在0.1-500μm的范围内，例如在1-200μm的范围内，诸如在5-100μm的范围内，如在10-50μm的范围内。所述硬质阳极氧化膜层未经封孔处理。According to the surface-treated metal substrate of the present disclosure, the hard anodized film layer has a high hardness, and its microhardness is generally 2000-2500 HV, and the metal substrate is used for bonding with a resin to prepare a metal-resin. In the case of the composite, the resin can be more firmly fixed to the metal substrate than the surface of the metal substrate as the anodized film layer, thereby achieving higher bonding strength. The thickness of the hard anodized film layer is not particularly limited in the present disclosure. In general, the thickness of the hard anodized film layer may be in the range of 0.1 to 500 μm, for example, in the range of 1 to 200 μm, such as in the range of 5 to 100 μm, such as in the range of 10 to 50 μm. The hard anodized film layer is not sealed.

根据本公开的第二个方面，本公开提供了一种金属基材的表面处理方法，所述金属为铝或铝合金，该方法包括提供金属基材，所述金属基材包括金属基体以及形成于所述金属基体的至少部分表面的硬质阳极氧化膜层。本文中，“至少部分”表示部分或全部。According to a second aspect of the present disclosure, the present disclosure provides a surface treatment method of a metal substrate, the metal being aluminum or an aluminum alloy, the method comprising providing a metal substrate including a metal substrate and forming a hard anodized film layer on at least a portion of the surface of the metal substrate. As used herein, "at least a portion" means part or all.

可以采用常用的各种方法对金属基材进行硬质阳极氧化从而得到表面具有硬质氧化膜层的金属基材。具体地，可以在硬质阳极氧化条件下，将金属基材置于电解液中，以所述金属基材为阳极，以不与电解液反应的导电材料为阴极，使阴极和阳极分别与电源的正极和负极电连接，通电后，进行电解，从而在所述金属基体上形成硬质阳极氧化膜。所述电解液中的电解质可以为选自硫酸、草酸、甲酸和柠檬酸中的一种或两种以上。The metal substrate can be hard anodized by various methods commonly used to obtain a hard oxidation surface. The metal substrate of the film layer. Specifically, the metal substrate may be placed in an electrolyte under hard anodizing conditions, the metal substrate is used as an anode, and a conductive material that does not react with the electrolyte is used as a cathode, and the cathode and the anode are respectively connected to a power source. The positive electrode and the negative electrode are electrically connected, and after energization, electrolysis is performed to form a hard anodized film on the metal substrate. The electrolyte in the electrolytic solution may be one or more selected from the group consisting of sulfuric acid, oxalic acid, formic acid, and citric acid.

所述硬质阳极氧化的条件可以根据预期的硬质阳极氧化膜层的厚度进行选择。可选地，所述硬质阳极氧化使得形成的硬质阳极氧化膜层的厚度为0.1-500μm，例如为1-200μm，诸如为10-100μm，如为15-50μm。具体地，电压可以为10-100V，例如为40-80V；电解液的温度可以为0-60℃，例如为0-10℃。电解的时间可以根据具体的电解条件进行选择，以使形成的硬质阳极氧化膜层的厚度能够满足要求为准，一般地，所述电解的时间可以为1-60分钟，例如为10-30分钟。The conditions of the hard anodization may be selected according to the thickness of the intended hard anodized film layer. Alternatively, the hard anodization allows the formed hard anodized film layer to have a thickness of 0.1 to 500 μm, for example, 1 to 200 μm, such as 10 to 100 μm, such as 15 to 50 μm. Specifically, the voltage may be 10-100 V, for example 40-80 V; the temperature of the electrolyte may be 0-60 ° C, for example 0-10 ° C. The time of electrolysis can be selected according to specific electrolysis conditions, so that the thickness of the formed hard anodized film layer can meet the requirements. Generally, the electrolysis time can be 1-60 minutes, for example, 10-30. minute.

所述金属基材在进行硬质阳极氧化之前可选地采用本领域常用的各种方法进行前处理。一般地，所述前处理包括机械打磨或研磨，以去除金属基材表面明显的异物，然后对金属基材依次进行脱脂和清洗，以清除金属基材表面的油脂。The metal substrate is optionally pretreated by various methods commonly used in the art prior to hard anodization. Generally, the pretreatment includes mechanical grinding or grinding to remove foreign matter on the surface of the metal substrate, and then the metal substrate is sequentially degreased and cleaned to remove grease from the surface of the metal substrate.

根据本公开的方法，还包括将所述金属基材进行第一蚀刻，以在所述硬质阳极氧化膜层中形成第一腐蚀孔。The method according to the present disclosure further includes subjecting the metal substrate to a first etching to form a first etching hole in the hard anodized film layer.

所述第一蚀刻使得所述第一腐蚀孔的孔径可以在10-200nm的范围内，例如在50-200nm的范围内，诸如在80-200nm的范围内，如在100-200nm的范围内；所述第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值可以在0.1-1：1的范围内，例如在0.2-1：1的范围内，诸如在0.5-1：1的范围内，并且至少部分第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1，例如50％以上、诸如60％以上、如至少70％以上第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1。The first etching may cause the pore diameter of the first etching hole to be in the range of 10 to 200 nm, for example, in the range of 50 to 200 nm, such as in the range of 80 to 200 nm, such as in the range of 100 to 200 nm; The ratio of the depth of the first etching hole to the thickness of the hard anodized film layer may be in the range of 0.1 to 1:1, for example, in the range of 0.2 to 1:1, such as 0.5 to 1:1. And the ratio of the depth of at least a portion of the first etching hole to the thickness of the hard anodized film layer is 1:1, for example, 50% or more, such as 60% or more, such as at least 70% or more of the first etching hole The ratio of the depth to the thickness of the hard anodized film layer is 1:1.

可以采用常规的各种方法将金属基材进行第一蚀刻，从而在硬质阳极氧化膜层中形成第一腐蚀孔。The metal substrate may be subjected to a first etching by various conventional methods to form a first etching hole in the hard anodized film layer.

在一种实施方式中，所述第一蚀刻包括：将所述金属基材浸泡于碱性蚀刻液中，从而在硬质阳极氧化膜层中形成第一腐蚀孔。In one embodiment, the first etching includes: immersing the metal substrate in an alkaline etching solution to form a first etching hole in the hard anodized film layer.

所述碱性蚀刻液可以为常见的能够腐蚀硬质阳极氧化膜层的蚀刻液。可选地，所述蚀刻液为以下两种蚀刻液之一或两种的组合。采用以下两种蚀刻液之一或两种的组合对金属基材进行蚀刻，能够获得较好的蚀刻效果。以下对这两种蚀刻液分别进行说明。The alkaline etching solution may be a common etching liquid capable of etching a hard anodized film layer. Optionally, the etching solution is one or a combination of the following two etching liquids. The metal substrate can be etched by using one or a combination of the following two etching liquids, and a better etching effect can be obtained. The two etching solutions will be separately described below.

1、所述碱性蚀刻液为含有选自水溶性氢氧化物、水溶性碱性盐、氨、水溶性胺、肼以及一个或多个氢原子被烃基取代的肼衍生物中的一种或两种以上物质的水溶液。1. The alkaline etching solution is one containing an anthracene derivative selected from the group consisting of water-soluble hydroxides, water-soluble basic salts, ammonia, water-soluble amines, hydrazine, and one or more hydrogen atoms substituted by a hydrocarbon group. An aqueous solution of two or more substances.

所述水溶性氢氧化物可以为碱金属氢氧化物，可以为氢氧化钠和/或氢氧化钾，例如为氢氧化钠。The water-soluble hydroxide may be an alkali metal hydroxide, and may be sodium hydroxide and/or potassium hydroxide, for example Sodium hydroxide.

所述水溶性碱性盐是指其水溶液的pH值为大于7的水溶性碱性盐。具体地，所述水溶性碱性盐可以为水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐中的一种或两种以上。所述水溶性碱性盐可以为碱金属盐，例如为钠盐或钾盐，如为钠盐。可选地，所述水溶性碱性盐为Na₂CO₃、NaHCO₃、NaH₂PO₄、Na₂HPO₄、Na₃PO₄和Na₂B₄O₇中的一种或两种以上。The water-soluble basic salt refers to a water-soluble basic salt whose aqueous solution has a pH of more than 7. Specifically, the water-soluble basic salt may be a water-soluble carbonate, a water-soluble hydrogencarbonate, a water-soluble phosphate, a water-soluble monohydrogen phosphate, a water-soluble dihydrogen phosphate, and a water-soluble borate. One or two or more. The water-soluble basic salt may be an alkali metal salt such as a sodium salt or a potassium salt such as a sodium salt. Alternatively, the water-soluble basic salt is one or more of Na ₂ CO ₃ , NaHCO ₃ , NaH ₂ PO ₄ , Na ₂ HPO ₄ , Na ₃ PO ₄ and Na ₂ B ₄ O ₇ .

所述水溶性胺可以为常见的各种能够溶解于水的胺。可选地，所述水溶性胺为乙二胺、二乙基胺、乙醇胺、三甲基胺、甲基胺和二甲基胺中的一种或两种以上。The water-soluble amine may be a common variety of amines which are soluble in water. Alternatively, the water-soluble amine is one or more of ethylenediamine, diethylamine, ethanolamine, trimethylamine, methylamine, and dimethylamine.

所述肼衍生物是指肼(即，H₂N-NH₂)分子结构中的一个或多个氢原子被烃基取代形成的化合物，所述烃基可以为C₁-C₄的烷基，具体可以为一甲基肼和/或1,1-二甲基肼。The anthracene derivative refers to a compound in which one or more hydrogen atoms in the molecular structure of hydrazine (ie, H ₂ N—NH ₂ ) are substituted by a hydrocarbon group, and the hydrocarbon group may be a C ₁ -C ₄ alkyl group, specifically It may be monomethyl hydrazine and/or 1,1-dimethyl hydrazine.

所述碱性蚀刻液可以为含有水溶性氢氧化物和/或水溶性碱性盐的水溶液。可选地，所述碱性蚀刻液为含有水溶性碱性盐的水溶液，水溶性碱性盐例如可以为Na₂CO₃和/或NaHCO₃，诸如为Na₂CO₃或NaHCO₃。The alkaline etching solution may be an aqueous solution containing a water-soluble hydroxide and/or a water-soluble basic salt. Optionally, the alkaline etchant is an aqueous solution containing a water-soluble basic salt, such as Na ₂ CO ₃ and/or NaHCO ₃ , such as Na ₂ CO ₃ or NaHCO ₃ .

所述碱性蚀刻液的pH值可以The pH of the alkaline etching solution can be

在10-13的范围内，这样不仅能获得适宜的蚀刻速度，而且蚀刻过程温和易控。In the range of 10-13, not only can a suitable etching rate be obtained, but the etching process is gentle and easy to control.

2、所述碱性蚀刻液为碱性缓冲溶液，这样最终形成的腐蚀孔的分布更为均匀且孔径大小更为集中。2. The alkaline etching solution is an alkaline buffer solution, so that the finally formed corrosion holes are more evenly distributed and the pore size is more concentrated.

所述碱性蚀刻液可以为含有水溶性氢氧化物以及水溶性碱性盐的水溶液。所述水溶性氢氧化物和所述水溶性碱性盐的阳离子可以为相同，也可以为不同，例如为相同。The alkaline etching solution may be an aqueous solution containing a water-soluble hydroxide and a water-soluble basic salt. The cations of the water-soluble hydroxide and the water-soluble basic salt may be the same or different, for example, the same.

所述水溶性氢氧化物可以为碱金属氢氧化物，可以为氢氧化钠和/或氢氧化钾，例如为氢氧化钠。The water soluble hydroxide may be an alkali metal hydroxide, which may be sodium hydroxide and/or potassium hydroxide, such as sodium hydroxide.

所述水溶性碱性盐可以为水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐中的一种或两种以上。所述水溶性碱性盐可以为碱金属盐，例如为钠盐或钾盐，如为钠盐。可选地，所述水溶性碱性盐为Na₂CO₃、NaHCO₃、NaH₂PO₄、Na₂HPO₄、Na₃PO₄和Na₂B₄O₇中的一种或两种以上。可选地，所述水溶性碱性盐为水溶性磷酸一氢盐和/或水溶性磷酸二氢盐。可选地，所述水溶性碱性盐为水溶性磷酸二氢盐，如磷酸二氢钠、磷酸二氢钾、磷酸二氢铵和磷酸二氢铝中的一种或两种以上。The water-soluble basic salt may be one of a water-soluble carbonate, a water-soluble hydrogencarbonate, a water-soluble phosphate, a water-soluble monohydrogen phosphate, a water-soluble dihydrogen phosphate, and a water-soluble borate or Two or more. The water-soluble basic salt may be an alkali metal salt such as a sodium salt or a potassium salt such as a sodium salt. Alternatively, the water-soluble basic salt is one or more of Na ₂ CO ₃ , NaHCO ₃ , NaH ₂ PO ₄ , Na ₂ HPO ₄ , Na ₃ PO ₄ and Na ₂ B ₄ O ₇ . Optionally, the water-soluble basic salt is a water-soluble monohydrogen phosphate and/or a water-soluble dihydrogen phosphate. Alternatively, the water-soluble basic salt is a water-soluble dihydrogen phosphate such as one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium dihydrogen phosphate, and dihydrogen aluminum phosphate.

所述碱性蚀刻液也可以为含有水溶性正盐以及水溶性酸式盐的水溶液。所述正盐是指阳离子只含有金属离子和/或铵根离子的盐，所述酸式盐是指阳离子除含有金属离子和/或铵根离子外，还含有氢离子的盐。所述水溶性正盐与所述水溶性酸式盐的阳离子和酸根离子各自可以为相同，也可以为不同，例如为相同。The alkaline etching solution may also be an aqueous solution containing a water-soluble normal salt and a water-soluble acid salt. The normal salt refers to a salt in which a cation contains only a metal ion and/or an ammonium ion, and the acid salt refers to a salt containing a hydrogen ion in addition to a metal ion and/or an ammonium ion. The water-soluble normal salt and the cation and acid ion of the water-soluble acid salt Each may be the same or different, for example the same.

所述碱性蚀刻液可以为含有水溶性碳酸盐和水溶性碳酸氢盐的水溶液，或者含有水溶性磷酸盐和水溶性磷酸一氢盐的水溶液。具体地，所述碱性蚀刻液可以为含有Na₂CO₃和NaHCO₃的水溶液，或者含有Na₃PO₄和Na₂HPO₄的水溶液。The alkaline etching solution may be an aqueous solution containing a water-soluble carbonate and a water-soluble hydrogencarbonate, or an aqueous solution containing a water-soluble phosphate and a water-soluble monohydrogen phosphate. Specifically, the alkaline etching solution may be an aqueous solution containing Na ₂ CO ₃ and NaHCO ₃ or an aqueous solution containing Na ₃ PO ₄ and Na ₂ HPO ₄ .

所述碱性蚀刻液还可以为含有氨以及水溶性铵盐的水溶液。所述水溶性铵盐可以为NH₄Cl、(NH₄)₂SO₄、NH₄HCO₃和NH₄NO₃中的一种或两种以上。具体地，所述碱性蚀刻液可以为含有NH₃和NH₄Cl的水溶液、含有NH₃和(NH₄)₂SO₄的水溶液、含有NH₃和NH₄HCO₃的水溶液或者含有NH₃和NH₄NO₃的水溶液。The alkaline etching solution may also be an aqueous solution containing ammonia and a water-soluble ammonium salt. The water-soluble ammonium salt may be one or more of NH ₄ Cl, (NH ₄ ) ₂ SO ₄ , NH ₄ HCO ₃ and NH ₄ NO ₃ . Specifically, the alkaline etching solution may be an aqueous solution containing NH ₃ and NH ₄ Cl, an aqueous solution containing NH ₃ and (NH ₄ ) ₂ SO ₄ , an aqueous solution containing NH ₃ and NH ₄ HCO ₃ or containing NH ₃ and An aqueous solution of NH ₄ NO ₃ .

所述碱性蚀刻液可以为含有水溶性氢氧化物以及水溶性碱性盐的水溶液，或者为含有水溶性正盐以及水溶性酸式盐的水溶液，例如为含有水溶性正盐以及水溶性酸式盐的水溶液。The alkaline etching solution may be an aqueous solution containing a water-soluble hydroxide and a water-soluble basic salt, or an aqueous solution containing a water-soluble normal salt and a water-soluble acid salt, for example, containing a water-soluble normal salt and a water-soluble acid. An aqueous solution of a salt.

所述碱性蚀刻液可以为pH值为10-13的碱性缓冲溶液，这样能够获得适宜的蚀刻速度，而且蚀刻过程温和易控。The alkaline etching solution may be an alkaline buffer solution having a pH of 10-13, so that a suitable etching rate can be obtained, and the etching process is gentle and easy to control.

所述第一蚀刻中，碱性蚀刻液的温度可以为10-60℃，例如为20-40℃；第一蚀刻的时间可以为1-60分钟，例如为5-20分钟。In the first etching, the temperature of the alkaline etching solution may be 10-60 ° C, for example, 20-40 ° C; the first etching time may be 1-60 minutes, for example, 5-20 minutes.

经第一蚀刻在硬质阳极氧化膜层中形成了第一腐蚀孔的金属基材可以直接作为经表面处理的金属基材，与树脂一体化成型，以制备金属-树脂复合体。The metal substrate in which the first etching hole is formed in the hard anodized film layer by the first etching can be directly formed as a surface-treated metal substrate and integrally molded with the resin to prepare a metal-resin composite.

在一个具体实施方式中，将经第一蚀刻的金属基材进行第二蚀刻，以在与所述硬质阳极氧化膜层相接的金属基体表面形成第二腐蚀孔。将经第二蚀刻得到的经表面处理的金属基材用于与树脂结合制备金属-树脂复合体时，树脂层与金属基材之间显示出更高的结合强度。In a specific embodiment, the first etched metal substrate is subjected to a second etch to form a second etched hole on the surface of the metal substrate that is in contact with the hard anodized film layer. When the surface-treated metal substrate obtained by the second etching is used in combination with a resin to prepare a metal-resin composite, a higher bonding strength between the resin layer and the metal substrate is exhibited.

所述第二蚀刻使得所述第二腐蚀孔的孔径可以在200-2000nm的范围内，例如在400-2000nm的范围内，诸如在800-1500nm的范围内，如在1000-1500nm的范围内。从进一步提高由该经表面处理的金属基材与树脂一体化成型后形成的金属-树脂复合体中，金属基材与树脂层之间的结合强度的角度出发，所述第二蚀刻使得所述第二腐蚀孔的深度可以在0.1-500μm的范围内，例如在10-400μm的范围内，诸如在50-200μm的范围内。The second etching may cause the second etching hole to have a pore diameter in the range of 200 to 2000 nm, for example, in the range of 400 to 2000 nm, such as in the range of 800 to 1500 nm, such as in the range of 1000 to 1500 nm. From the viewpoint of further improving the bonding strength between the metal substrate and the resin layer in the metal-resin composite formed by integrally molding the surface-treated metal substrate and the resin, the second etching makes the The depth of the second etching hole may be in the range of 0.1 to 500 μm, for example, in the range of 10 to 400 μm, such as in the range of 50 to 200 μm.

可以采用各种方法来形成所述第二腐蚀孔。在一个具体实施方式中，所述第二蚀刻包括：将经第一蚀刻的金属基材浸泡于酸性蚀刻液中。Various methods can be employed to form the second etched holes. In a specific embodiment, the second etching comprises: immersing the first etched metal substrate in an acidic etchant.

所述酸性蚀刻液为含有酸的水溶液，所述酸为氢卤酸和/或H₃PO₄，例如为HCl或H₃PO₄。The acidic etching solution is an aqueous solution containing an acid which is a hydrohalic acid and/or H ₃ PO ₄ , such as HCl or H ₃ PO ₄ .

可选地，所述酸性蚀刻液还含有一种或两种以上水溶性盐，这样能够进一步提高蚀刻的稳定性。所述水溶性盐的酸根可以为与酸性蚀刻液中含有的酸的酸根相同。例如，在所述酸性蚀刻液为含有氢卤酸的水溶液时，所述酸性蚀刻液还可以含有一种或多种水溶性氢卤酸盐；在所述酸性蚀刻液为含有磷酸的水溶液时，所述酸性蚀刻液例如还含有一种或多种水溶性磷酸盐。具体地，所述酸性蚀刻液为盐酸时，所述水溶性盐可以为NaCl、KCl和AlCl₃中的一种或两种以上。所述酸性蚀刻液为磷酸时，所述水溶性盐为水溶性磷酸盐、水溶性磷酸一氢盐和水溶性磷酸二氢盐中的一种或两种以上，如NaH₂PO₄、Na₂HPO₄、Na₃PO₄、KH₂PO₄、K₂HPO₄和K₃PO₄中的一种或两种以上。Alternatively, the acidic etching solution further contains one or two or more water-soluble salts, which can further improve the stability of etching. The acid salt of the water-soluble salt may be the same as the acid group of the acid contained in the acidic etching solution. For example, when the acidic etching solution is an aqueous solution containing a halogen acid, the acidic etching solution may further contain one or more water-soluble hydrohalic acid salts; when the acidic etching liquid is an aqueous solution containing phosphoric acid, The acidic etching solution, for example, also contains one or more water soluble phosphate salts. Specifically, when the acidic etching solution is hydrochloric acid, the water-soluble salt may be one or more selected from the group consisting of NaCl, KCl, and AlCl ₃ . When the acidic etching solution is phosphoric acid, the water-soluble salt is one or more of a water-soluble phosphate, a water-soluble monohydrogen phosphate and a water-soluble dihydrogen salt, such as NaH ₂ PO ₄ , Na _{2 .} One or more of HPO ₄ , Na ₃ PO ₄ , KH ₂ PO ₄ , K ₂ HPO ₄ and K ₃ PO ₄ .

所述水溶性盐在所述酸性蚀刻液中的含量随酸性蚀刻液中酸的量而定。一般地，所述水溶性盐与所述酸的摩尔比可以为0.1-1：1，例如为0.2-0.8：1，诸如为0.4-0.6：1。The content of the water-soluble salt in the acidic etching solution depends on the amount of acid in the acidic etching solution. Generally, the molar ratio of the water soluble salt to the acid may range from 0.1 to 1:1, such as from 0.2 to 0.8:1, such as from 0.4 to 0.6:1.

所述酸性蚀刻液的pH值可以为1-3，这样形成的经表面处理的金属基材中腐蚀孔的分布更为均匀，孔径分布也更为集中，由该金属基材制备的金属-树脂复合体中树脂与金属基材的结合强度更高。The acidic etching solution may have a pH of 1-3, and the surface-treated metal substrate thus formed has a more uniform distribution of corrosion holes and a more concentrated pore size distribution, and the metal-resin prepared from the metal substrate. The bonding strength of the resin to the metal substrate in the composite is higher.

具体地，所述酸性蚀刻液的温度可以为20-30℃，金属基材在所述酸性蚀刻液中的浸泡时间可以为1-60分钟，例如为10-30分钟。Specifically, the temperature of the acidic etching solution may be 20-30 ° C, and the soaking time of the metal substrate in the acidic etching solution may be 1-60 minutes, for example, 10-30 minutes.

根据本公开的方法，在一个具体实例中，在所述第一蚀刻中，将所述金属基材浸泡于碱性蚀刻液中；在所述第二蚀刻中，将经第一蚀刻的金属基材浸泡于酸性蚀刻液中。采用这种方式进行蚀刻，在蚀刻过程中蚀刻放热小，蚀刻过程温和易控，形成的第一腐蚀孔和第二腐蚀孔的分布更为均匀，孔尺寸(包括孔径和深度)更为集中；并且，在将由该方法得到的经表面处理的金属基材用于与树脂结合制备金属-树脂复合体时，树脂层与金属基材之间显示出更高的结合强度。According to the method of the present disclosure, in one specific example, the metal substrate is immersed in an alkaline etchant in the first etch; and the first etched metal base is etched in the second etch The material is immersed in an acidic etching solution. Etching is performed in this way, the etching exotherm is small during the etching process, the etching process is gentle and easy to control, the distribution of the first etching hole and the second etching hole is more uniform, and the hole size (including the aperture and the depth) is more concentrated. And, when the surface-treated metal substrate obtained by the method is used for bonding with a resin to prepare a metal-resin composite, a higher bonding strength between the resin layer and the metal substrate is exhibited.

根据本公开的方法，所述第一蚀刻和所述第二蚀刻各自可以只进行一次，也可以分次，每次蚀刻的持续时间没有特别限定，只要总的蚀刻时间满足上述要求即可。在两次蚀刻之间用水进行洗涤，以除去前一次蚀刻残留的蚀刻液。According to the method of the present disclosure, the first etching and the second etching may each be performed only once or in stages, and the duration of each etching is not particularly limited as long as the total etching time satisfies the above requirements. The washing was performed with water between the two etchings to remove the etching liquid remaining in the previous etching.

所述经表面处理的金属基材及其制备方法在前文已经进行了详细的描述，此处不再详述。 The surface treated metal substrate and its preparation method have been described in detail above and will not be described in detail herein.

根据本公开的复合体，所述树脂层的厚度可以根据具体的使用场合进行选择。一般地，所述树脂层的厚度可以在0.1-10mm的范围内，例如在0.5-5mm的范围内。本文中，树脂层的厚度是指硬质阳极氧化膜层的上表面至树脂层的上表面之间的垂直距离。According to the composite of the present disclosure, the thickness of the resin layer can be selected depending on the specific use occasion. Generally, the thickness of the resin layer may be in the range of 0.1 to 10 mm, for example, in the range of 0.5 to 5 mm. Herein, the thickness of the resin layer means a vertical distance between the upper surface of the hard anodized film layer and the upper surface of the resin layer.

所述树脂层中的主体树脂可以根据具体的使用要求进行选择，只要该树脂能与铝或铝合金结合即可。一般地，所述树脂层中的主体树脂可以选自热塑性树脂，例如可以为聚苯硫醚、聚酯、聚酰胺、聚碳酸酯和聚烯烃中的一种或两种以上。所述聚酯可以为常见的由二羧酸与二醇缩合而成的聚合物，其具体实例可以包括但不限于聚对苯二甲酸丁二醇酯和/或聚对苯二甲酸乙二醇酯。所述聚酰胺可以为常见的由二胺与二羧酸缩合而成的聚合物，其具体实例可以包括但不限于聚己二酰己二胺、聚壬二酰己二胺、聚丁二酰己二胺、聚十二烷二酰己二胺、聚癸二酰己二胺、聚癸二酰癸二胺、聚十一酰胺、聚十二酰胺、聚辛酰胺、聚9-氨基壬酸、聚己内酰胺、聚对苯二甲酰苯二胺、聚间苯二甲酰己二胺、聚对苯二甲酰己二胺和聚对苯二甲酰壬二胺。所述聚烯烃的具体实例可以包括但不限于聚苯乙烯、聚丙烯、聚甲基丙烯酸甲酯和聚(丙烯腈-丁二烯-苯乙烯)。The host resin in the resin layer can be selected according to specific use requirements as long as the resin can be combined with aluminum or an aluminum alloy. In general, the host resin in the resin layer may be selected from a thermoplastic resin, and may be, for example, one or more of polyphenylene sulfide, polyester, polyamide, polycarbonate, and polyolefin. The polyester may be a common polymer obtained by condensing a dicarboxylic acid and a diol, and specific examples thereof may include, but are not limited to, polybutylene terephthalate and/or polyethylene terephthalate. ester. The polyamide may be a common polymer obtained by condensing a diamine and a dicarboxylic acid, and specific examples thereof may include, but are not limited to, polyhexamethylene adipamide, polysebacyldiamine, polysuccinic acid. Hexamethylenediamine, polydodecanediylhexyldiamine, polydecamethylenediamine, polysebacic acid diamine, polyundecamide, polydodecylamide, polyoctanoic acid, poly 9-aminononanoic acid , polycaprolactam, poly(p-phenylene diphenylene diamine), poly(phthalamide), poly(p-phenylene hexamethylene diamine) and poly(p-phenylene terephthalamide). Specific examples of the polyolefin may include, but are not limited to, polystyrene, polypropylene, polymethyl methacrylate, and poly(acrylonitrile-butadiene-styrene).

所述树脂层除含有主体树脂外，还可以含有至少一种填料。所述填料的种类可以根据具体的使用要求进行选择。所述填料可以为纤维型填料和/或粉末型填料。所述纤维型填料可以为选自玻璃纤维、碳纤维和芳族聚酰胺纤维中的一种或两种以上。所述粉末型填料可以为选自碳酸钙、碳酸镁、二氧化硅、重质硫酸钡、滑石粉、玻璃和粘土中的一种或两种以上。所述填料的含量可以为常规选择。一般地，可选地，以100重量份主体树脂为基准，所述填料的含量可以为20-150重量份，例如为25-100重量份，诸如为30-50重量份。The resin layer may contain at least one filler in addition to the host resin. The type of the filler can be selected according to specific use requirements. The filler may be a fibrous filler and/or a powder filler. The fibrous filler may be one or more selected from the group consisting of glass fibers, carbon fibers, and aramid fibers. The powder type filler may be one or more selected from the group consisting of calcium carbonate, magnesium carbonate, silica, heavy barium sulfate, talc, glass, and clay. The content of the filler may be a conventional selection. Generally, the filler may optionally be included in an amount of 20 to 150 parts by weight, for example, 25 to 100 parts by weight, such as 30 to 50 parts by weight, based on 100 parts by weight of the main body resin.

所述含树脂的组合物中的树脂(以下称为主体树脂)与前文所述树脂层中的主体树脂的种类相同，此处不再详述。所述含树脂的组合物除含有主体树脂外，还可以含有至少一种填料和/或至少一种流动性改进剂。所述填料的种类与前文所述树脂层中的填料的种类相同，此处不再详述。The resin in the resin-containing composition (hereinafter referred to as a host resin) is the same as the type of the host resin in the resin layer described above, and will not be described in detail herein. The resin-containing composition may contain, in addition to the host resin, at least one filler and/or at least one fluidity improver. The type of the filler is the same as that of the filler in the resin layer described above, and will not be described in detail herein.

所述填料的含量可以为常规选择。一般地，以100重量份主体树脂为基准，所述填料的含量可以为20-150重量份，例如为25-100重量份，诸如为30-50重量份。The content of the filler may be a conventional selection. Generally, the filler may be included in an amount of 20 to 150 parts by weight, for example, 25 to 100 parts by weight, such as 30 to 50 parts by weight, based on 100 parts by weight of the main body resin.

所述流动性改进剂用于提高主体树脂的流动能力，进一步提高金属基材与树脂之间的结合强度以及树脂的加工性能。所述流动性改进剂可以为各种能够实现上述效果的物质，例如为环状聚酯。The fluidity improver is used to improve the flowability of the host resin and further improve the relationship between the metal substrate and the resin. Bond strength and processing properties of the resin. The fluidity improver may be any of various substances capable of achieving the above effects, for example, a cyclic polyester.

所述流动性改进剂的用量以能够提高主体树脂的流动能力为准。可选地，相对于100重量份主体树脂，所述流动性改进剂的含量为1-5重量份。The amount of the fluidity improver is based on the ability to increase the flowability of the host resin. Alternatively, the fluidity improver is contained in an amount of 1 to 5 parts by weight based on 100 parts by weight of the main body resin.

所述含树脂的组合物根据具体使用要求还可以含有常见的各种助剂，如着色剂和/或抗氧剂，以改善最终形成的金属-树脂复合体中树脂层的性能或者赋予所述树脂层以新的性能。The resin-containing composition may further contain various conventional auxiliaries such as a colorant and/or an antioxidant in accordance with specific use requirements to improve the properties of the resin layer in the finally formed metal-resin composite or to impart the The resin layer has new properties.

含树脂的组合物可以通过将主体树脂、任选的填料、任选的流动性改进剂以及任选的助剂混合均匀而获得。一般地，可以将主体树脂、任选的填料、任选的流动性改进剂以及任选的助剂混合均匀，并进行挤出造粒而得到。The resin-containing composition can be obtained by uniformly mixing a host resin, an optional filler, an optional fluidity improver, and an optional auxiliary. In general, the host resin, the optional filler, the optional fluidity improver, and the optional auxiliary agent may be uniformly mixed and subjected to extrusion granulation.

可以采用常用的各种方法向金属基材的蚀刻表面注入所述含树脂的组合物。在本公开的一个具体实施方式中，将所述金属基材置于模具中，通过注塑的方法注入所述含树脂的组合物。The resin-containing composition can be injected into the etched surface of the metal substrate by various conventional methods. In a specific embodiment of the present disclosure, the metal substrate is placed in a mold, and the resin-containing composition is injected by injection molding.

所述注塑的条件可以根据含树脂的组合物中主体树脂的种类进行选择。可选地，所述注塑的条件包括：模具温度为50-300℃，喷嘴温度为200-450℃，保压时间为1-50秒，射出压力为50-300MPa，射出时间为1-30秒，延迟时间为1-30秒。The conditions of the injection molding may be selected depending on the kind of the host resin in the resin-containing composition. Optionally, the conditions of the injection molding include: a mold temperature of 50-300 ° C, a nozzle temperature of 200-450 ° C, a dwell time of 1-50 seconds, an injection pressure of 50-300 MPa, and an injection time of 1-30 seconds. The delay time is 1-30 seconds.

所述含树脂的组合物的注入量可以根据预期的树脂层厚度进行选择。一般地，所述含树脂的组合物的注入量使得形成的树脂层的厚度可以为0.1-10mm，例如为0.5-5mm。The amount of the resin-containing composition to be injected can be selected in accordance with the intended thickness of the resin layer. Generally, the resin-containing composition is injected in an amount such that the thickness of the formed resin layer may be from 0.1 to 10 mm, for example, from 0.5 to 5 mm.

根据本公开的方法，仅在金属基材的部分表面形成树脂层时，可以对无需形成树脂层的表面进行处理，以除去表面孔洞以及由于蚀刻而引起的表面颜色变化，该处理可以在注塑成型步骤之前进行，也可以在注塑成型步骤之后进行，没有特别限定。According to the method of the present disclosure, when a resin layer is formed only on a part of the surface of the metal substrate, the surface on which the resin layer is not formed may be treated to remove surface holes and surface color change due to etching, which may be in injection molding. It is also carried out before the step, and it can also be carried out after the injection molding step, and is not particularly limited.

根据本公开的第六个方面，本公开还提供了一种由根据本公开的第五个方面的方法制备的金属-树脂复合体。According to a sixth aspect of the present disclosure, the present disclosure also provides a metal-resin composite prepared by the method according to the fifth aspect of the present disclosure.

根据本公开的第八个方面，本公开提供了一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，其中，所述金属壳本体为根据本公开的金属基材。本公开中，所述外壳不仅包括为片状结构的外壳，也包括各种框架结构，如外框。According to an eighth aspect of the present disclosure, the present disclosure provides an electronic product housing including a metal shell body and at least one resin member attached to at least a portion of an inner surface and/or at least a portion of an outer surface of the metal shell body Wherein the metal shell body is a metal substrate according to the present disclosure. In the present disclosure, the outer casing includes not only an outer casing that is a sheet-like structure but also various frame structures such as an outer frame.

根据本公开的电子产品外壳，根据具体需要，所述金属壳本体上可以设置有至少一个开口，以在该开口的对应位置安装电子产品的需要避开金属壳本体的元件。在一种实施方式中，由于金属对电磁信号具有屏蔽作用，因此至少部分开口的位置可以对应于信号发射元件和/或信号接受元件的安装位置，此时所述开口位置可以设置树脂件，并使所述树脂件中的部分树脂填充于所述开口中，信号发射元件和/或信号接受元件可以安装在所述树脂件上。According to the electronic product casing of the present disclosure, according to a specific need, at least one opening may be disposed on the metal shell body to install an electronic product at a corresponding position of the opening to avoid the components of the metal shell body. In an implementation Wherein, since the metal has a shielding effect on the electromagnetic signal, the position of at least part of the opening may correspond to a mounting position of the signal transmitting element and/or the signal receiving element, and at this time, the opening position may be provided with a resin member, and the resin is provided A portion of the resin in the member is filled in the opening, and a signal emitting element and/or a signal receiving member may be mounted on the resin member.

根据本公开的电子产品外壳，所述金属壳本体可以为一体结构，也可以为拼接结构。所述拼接结构是指所述金属壳本体包括相互断开的至少两个部分，两个部分相互拼接在一起形成金属壳本体。According to the electronic product casing of the present disclosure, the metal shell body may be a unitary structure or a splicing structure. The splicing structure means that the metal shell body includes at least two portions that are disconnected from each other, and the two portions are spliced together to form a metal shell body.

在所述金属壳本体为拼接结构时，相邻两个部分可以用胶粘剂粘结在一起。在一个具体实施方式中，相邻两部分的拼接位置设置有所述树脂件，该树脂件分别与相邻两部分搭接并覆盖所述拼接位置(即该树脂件桥接该相邻两部分)，这样能够提高拼接位置的结合强度；并且，可以根据电子产品的内部结构，将金属壳本体分成多个部分，所述树脂件在起到使金属壳本体形成为一个整体的作用的同时，还能用作一些电子元件的安装基体。When the metal shell body is a spliced structure, the adjacent two portions may be bonded together with an adhesive. In a specific embodiment, the splicing positions of the adjacent two portions are provided with the resin member, and the resin members respectively overlap the adjacent two portions and cover the splicing position (ie, the resin member bridges the adjacent two portions) In this way, the bonding strength of the splicing position can be improved; and the metal shell body can be divided into a plurality of parts according to the internal structure of the electronic product, and the resin member functions to form the metal shell body as a whole, and Can be used as a mounting base for some electronic components.

根据本公开的电子产品外壳，所述金属壳本体的至少部分外表面可以附着有树脂件，所述树脂件可以覆盖整个外表面，也可以覆盖金属壳本体的部分外表面以形成图案，例如装饰性图案。According to the electronic product casing of the present disclosure, at least a part of the outer surface of the metal shell body may be attached with a resin member, which may cover the entire outer surface, or may cover a part of the outer surface of the metal shell body to form a pattern, such as decoration Sexual pattern.

根据本公开的电子产品外壳，所述金属壳本体的内表面附着有树脂件时，所述树脂件可以设置在需要的一个或多个位置。在一个具体实施方式中，所述树脂件附着于所述金属壳本体的整个内表面，此时所述树脂件例如可以为一体结构。根据该具体的实施方式，特别适用于金属壳本体为拼接结构的场合。According to the electronic product casing of the present disclosure, when the inner surface of the metal shell body is attached with a resin member, the resin member may be disposed at one or more positions required. In a specific embodiment, the resin member is attached to the entire inner surface of the metal shell body, and the resin member may be, for example, a unitary structure. According to this specific embodiment, it is particularly suitable for the case where the metal shell body is a spliced structure.

根据本公开的电子产品外壳，可以为各种需要以金属作为外壳的电子产品外壳，例如：移动终端的外壳或者外框，可穿戴电子设备的外壳或者外框。所述移动终端是指可以处于移动状态且具有无线传输功能的设备，例如：移动电话、便携式电脑(包括笔记本电脑和平板电脑)。所述可穿戴电子设备是指智能化的穿戴设备，例如：智能表、智能手环。所述电子产品具体可以为但不限于移动电话、便携式电脑(如笔记本电脑和平板电脑)、智能表和智能手环中的一种或两种以上。The electronic product casing according to the present disclosure may be any electronic product casing that requires a metal as a casing, such as a casing or a frame of a mobile terminal, a casing or a frame of the wearable electronic device. The mobile terminal refers to a device that can be in a mobile state and has a wireless transmission function, such as a mobile phone, a portable computer (including a laptop and a tablet). The wearable electronic device refers to an intelligent wearable device, such as a smart watch or a smart bracelet. The electronic product may specifically be, but not limited to, one or more of a mobile phone, a portable computer (such as a notebook computer and a tablet), a smart watch, and a smart wristband.

图1示出了所述电子产品外壳为手机外壳时的一种实施方式的主视图和俯视图。如图1所示，在手机金属壳本体1上开设有多个开口3，开口3的位置可以对应于安装天线的位置以及安装各种按键的位置。树脂层2附着在手机金属壳本体1的整个内表面，树脂层2为一体结构并且树脂层2中的部分树脂填充于开口3中。Fig. 1 shows a front view and a top view of an embodiment of the electronic product casing when it is a casing of a mobile phone. As shown in FIG. 1, a plurality of openings 3 are formed in the metal shell body 1 of the mobile phone. The position of the opening 3 may correspond to the position where the antenna is mounted and the position at which various buttons are mounted. The resin layer 2 is attached to the entire inner surface of the metal shell body 1 of the mobile phone, the resin layer 2 is an integral structure, and a part of the resin in the resin layer 2 is filled in the opening 3.

图2示出了所述电子产品外壳为智能表的外壳的一种实施方式的主视图。如2所示，智能表金属壳本体4上设置有对应于安装信号发射元件和/或信号接收元件的信号元件开口 6，智能表金属壳本体4的内表面附着有树脂内衬层5，树脂内衬层5中的部分树脂填充在信号元件开口6中，信号元件可以安装在树脂内衬层5上的相应位置。Fig. 2 shows a front view of an embodiment of the outer casing of the electronic product being a smart watch. As shown in FIG. 2, the smart watch metal case body 4 is provided with a signal element opening corresponding to the mounting signal transmitting element and/or the signal receiving element. 6. The inner surface of the smart watch metal shell body 4 is adhered with a resin inner liner 5, and a part of the resin in the resin inner liner layer 5 is filled in the signal element opening 6, and the signal element can be mounted at a corresponding position on the resin inner liner 5. .

根据本公开的第九个方面，本公开提供了一种电子产品外壳的制备方法，该方法包括在金属壳本体的至少部分内表面和/或至少部分外表面形成至少一个树脂件，其中，采用根据本公开的金属-树脂复合体的制备方法来形成所述树脂件。According to a ninth aspect of the present disclosure, the present disclosure provides a method of fabricating an electronic product casing, the method comprising forming at least one resin member on at least a portion of an inner surface and/or at least a portion of an outer surface of the metal shell body, wherein The resin member is formed according to a method of producing a metal-resin composite of the present disclosure.

以下结合实施例详细说明本公开，但并不因此限定本公开的范围。The present disclosure is described in detail below with reference to the embodiments, but does not limit the scope of the disclosure.

以下实施例和对比例中，参照ASTM D1002-10规定的方法，在INSTRON 3369型万能试验机上测定金属-树脂复合体中金属基体与树脂层之间的平均剪切强度。In the following examples and comparative examples, the average shear strength between the metal substrate and the resin layer in the metal-resin composite was measured on an INSTRON 3369 universal testing machine in accordance with the method specified in ASTM D1002-10.

以下实施例和对比例中，采用购自ZEISS的型号为Axio Imager Alm的金相显微镜测定阳极氧化膜层的厚度以及腐蚀孔的深度(对同一样品的五个不同位置进行观察，测定视野范围内出现的全部腐蚀孔的深度)，采用购自日本电子株式会社的型号为JSM-7600F的扫描电子显微镜测定腐蚀孔的孔径(对同一样品的五个不同位置进行观察，测定视野范围内出现的全部腐蚀孔的孔径)。In the following examples and comparative examples, the thickness of the anodized film layer and the depth of the etching hole were measured using a metallographic microscope of the model Axio Imager Alm available from ZEISS (five different positions of the same sample were observed, and the field of view was measured. The depth of all the corrosion holes that appeared) was measured by a scanning electron microscope of JSM-7600F model number from JEOL Ltd. (The five different positions of the same sample were observed, and all the fields appearing in the field of view were measured. Corrosion hole aperture).

以下实施例和对比例中，采用购自上海光学仪器一厂的型号为HX-1000TM/LCD显微硬度计测定硬质阳极氧化膜层的显微硬度。In the following examples and comparative examples, the microhardness of the hard anodized film layer was measured using a model HX-1000TM/LCD microhardness tester available from Shanghai Optical Instruments No. 1 Plant.

实施例1-12用于说明本公开。Examples 1-12 are used to illustrate the disclosure.

实施例1Example 1

(1)将市售厚度为1mm的5052铝合金板切成15mm×80mm的长方形片。将长方形片放入抛光机内进行抛光。接着用无水乙醇洗净，然后浸泡于浓度为2重量％的氢氧化钠水溶液中，2min后取出用去离子水冲洗干净，得到经过前处理的铝合金片。(1) A commercially available 5052 aluminum alloy plate having a thickness of 1 mm was cut into a rectangular piece of 15 mm × 80 mm. The rectangular piece is placed in a polishing machine for polishing. Then, it was washed with absolute ethanol, and then immersed in a 2% by weight aqueous sodium hydroxide solution. After 2 minutes, it was taken out and rinsed with deionized water to obtain a pretreated aluminum alloy sheet.

(2)将步骤(1)得到的铝合金片作为阳极放入含有1重量％的NaOH以及0.1重量％的硅酸钠的水溶液作为电解液的硬质阳极氧化槽中，以石墨碳板作为阴极，在60V的电压下，在10℃电解15分钟，以进行硬质阳极氧化。将经硬质阳极氧化的铝合金片取出并吹干，得到表面具有硬质阳极氧化膜层的铝合金片。用显微镜对该铝合金片的横截面进行观察，确定硬质阳极氧化膜层的厚度为25μm，硬质阳极氧化膜层的显微硬度为2200HV。(2) The aluminum alloy sheet obtained in the step (1) is placed as an anode in a hard anodizing bath containing an aqueous solution of 1% by weight of NaOH and 0.1% by weight of sodium silicate as an electrolytic solution, and a graphite carbon plate is used as a cathode. Electrolysis was carried out at 10 ° C for 15 minutes at a voltage of 60 V for hard anodization. The hard anodized aluminum alloy sheet was taken out and blown dry to obtain an aluminum alloy sheet having a hard anodized film layer on its surface. The cross section of the aluminum alloy sheet was observed with a microscope to confirm that the thickness of the hard anodized film layer was 25 μm, and the hardness of the hard anodized film layer was 2200 HV.

(3)将步骤(2)得到的表面具有硬质阳极氧化膜层的铝合金片浸泡于温度为20℃的作为蚀刻液的含有Na₂HPO₄的水溶液(pH＝11)中。15分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经碱蚀刻的铝合金片。(3) The aluminum alloy sheet having the hard anodized film layer on the surface obtained in the step (2) was immersed in an aqueous solution (pH = 11) containing Na ₂ HPO ₄ as an etching solution at a temperature of 20 °C. After 15 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an alkali-etched aluminum alloy sheet.

采用显微镜观察步骤(3)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在50-200nm范围内的腐蚀孔，该腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.2-1：1的范围内，60％以上的腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1。The cross section of the aluminum alloy sheet obtained by the step (3) was observed by a microscope, and it was found that a corrosion hole having a pore diameter in the range of 50-200 nm was distributed in the hard anodized film layer, and the depth of the etching hole was hard and an anodized film layer was formed. Ratio of thickness In the range of 0.2 to 1:1, the ratio of the depth of the corrosion hole of 60% or more to the thickness of the hard anodized film layer is 1:1.

(4)将步骤(3)得到的铝合金片置于注射成型模具中，在铝合金片的一个表面注塑含有玻璃纤维和聚苯硫醚(PPS)的树脂组合物(相对于100重量份PPS，玻璃纤维的含量为35重量份)，脱模并冷却。其中，注塑条件包括：模具温度为120℃，喷嘴温度为305℃，保压时间为5秒，射出压力为120MPa，射出时间为5秒，延迟时间为3秒。(4) placing the aluminum alloy sheet obtained in the step (3) in an injection molding mold, and molding a resin composition containing glass fiber and polyphenylene sulfide (PPS) on one surface of the aluminum alloy sheet (relative to 100 parts by weight of PPS) The content of the glass fiber was 35 parts by weight, which was released from the mold and cooled. Among them, the injection molding conditions include: the mold temperature is 120 ° C, the nozzle temperature is 305 ° C, the dwell time is 5 seconds, the injection pressure is 120 MPa, the injection time is 5 seconds, and the delay time is 3 seconds.

将冷却后的产品放入120℃的恒温干燥箱中保温1.5h，然后随炉自然冷却至室温，制得金属-树脂复合体(树脂层的厚度为5mm)，其平均剪切强度在表1中列出。The cooled product was placed in a constant temperature drying oven at 120 ° C for 1.5 h, and then naturally cooled to room temperature with the furnace to obtain a metal-resin composite (the thickness of the resin layer was 5 mm), and the average shear strength thereof is shown in Table 1. Listed in.

实施例2Example 2

采用与实施例1相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(2)中，使用的电解液为含有1重量％的NaOH以及0.1重量％的磷酸钠的水溶液，电解时间为10分钟。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 1 to prepare a metal-resin composite, except that in the step (2), the electrolytic solution used was 1% by weight of NaOH and 0.1% by weight of phosphoric acid. An aqueous solution of sodium, the electrolysis time is 10 minutes.

采用显微镜观察步骤(3)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在10-200nm范围内的腐蚀孔，该腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.1-1：1的范围内，50％以上的腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained in the step (3) was observed by a microscope, and it was found that a corrosion hole having a pore diameter in the range of 10 to 200 nm was distributed in the hard anodized film layer, and the depth of the etching hole and the hard anodized film layer were distributed. The ratio of the thickness is in the range of 0.1 to 1:1, and the ratio of the depth of the etching hole of 50% or more to the thickness of the hard anodized film layer is 1:1. The average shear strength of the prepared metal-resin composites is listed in Table 1.

实施例3Example 3

采用与实施例1相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3)中，蚀刻液为NaOH的水溶液(pH＝11)。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 1 to prepare a metal-resin composite, except that in the step (3), the etching liquid was an aqueous solution of NaOH (pH = 11).

对比例1Comparative example 1

(1)采用与实施例1步骤(1)相同的方法制备经过前处理的铝合金片。(1) A pretreated aluminum alloy sheet was prepared in the same manner as in the step (1) of Example 1.

(2)采用与实施例1步骤(4)相同的方法将树脂组合物注塑在对比例1步骤(1)得到的铝合金片的表面，形成树脂层，从而得到金属-树脂复合体，其平均剪切强度在表1中列出。 (2) The resin composition was injection molded on the surface of the aluminum alloy sheet obtained in the step (1) of Comparative Example 1 in the same manner as in the step (4) of Example 1, to form a resin layer, thereby obtaining a metal-resin composite, which averaged Shear strength is listed in Table 1.

对比例2Comparative example 2

(2)采用与实施例1步骤(2)相同的方法将对比例2步骤(1)得到的铝合金片进行硬质阳极氧化。(2) The aluminum alloy sheet obtained in the step (1) of Comparative Example 2 was subjected to hard anodization in the same manner as in the step (2) of Example 1.

(3)采用与实施例1步骤(4)相同的方法将树脂组合物注塑在对比例2步骤(2)得到的铝合金片的表面，形成树脂层，从而得到金属-树脂复合体，其平均剪切强度在表1中列出。(3) The resin composition was injection molded on the surface of the aluminum alloy sheet obtained in the step (2) of Comparative Example 2 in the same manner as in the step (4) of Example 1, to form a resin layer, thereby obtaining a metal-resin composite, which averaged Shear strength is listed in Table 1.

对比例3Comparative example 3

(2)将步骤(1)得到的铝合金片采用以下方法进行阳极氧化，得到经阳极氧化的铝合金片：(2) The aluminum alloy sheet obtained in the step (1) is anodized by the following method to obtain an anodized aluminum alloy sheet:

将步骤(1)得到的铝合金片作为阳极放入以浓度为20重量％的H₂SO₄水溶液作为电解液的阳极氧化槽中，以石墨碳板作为阴极，在18V的电压下，在20℃电解15分钟。将经阳极氧化的铝合金片取出并吹干，得到表面具有阳极氧化膜层的铝合金片。用显微镜对该铝合金片的横截面进行观察，确定阳极氧化膜层的厚度为25μm，显微硬度为200HV。The aluminum alloy sheet obtained in the step (1) is placed as an anode in an anodizing bath having a concentration of 20% by weight of an aqueous solution of H ₂ SO ₄ as an electrolytic solution, and a graphite carbon plate is used as a cathode at a voltage of 18 V at 20 Electrolyze at °C for 15 minutes. The anodized aluminum alloy sheet was taken out and blown dry to obtain an aluminum alloy sheet having an anodized film layer on its surface. The cross section of the aluminum alloy sheet was observed with a microscope to determine that the thickness of the anodized film layer was 25 μm and the microhardness was 200 HV.

(3)将步骤(2)得到的表面具有阳极氧化膜层的铝合金片浸泡于温度为20℃的含有Na₂HPO₄的水溶液(pH＝11)中。15分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经碱蚀刻的铝合金片。(3) The aluminum alloy sheet having the anodized film layer on the surface obtained in the step (2) was immersed in an aqueous solution (pH = 11) containing Na ₂ HPO ₄ at a temperature of 20 °C. After 15 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an alkali-etched aluminum alloy sheet.

采用显微镜观察步骤(3)得到的铝合金片的横截面，发现：阳极氧化膜层中分布有孔径在50-200nm范围内的腐蚀孔，该腐蚀孔的深度与阳极氧化膜层的厚度的比值在0.2-1：1的范围内，60％以上的腐蚀孔的深度与硬质氧化膜层的厚度的比值为1：1。The cross section of the aluminum alloy sheet obtained in the step (3) was observed by a microscope, and it was found that the anodized film layer was distributed with corrosion holes having a pore diameter in the range of 50 to 200 nm, and the ratio of the depth of the etching hole to the thickness of the anodized film layer. In the range of 0.2 to 1:1, the ratio of the depth of the corrosion hole of 60% or more to the thickness of the hard oxide film layer is 1:1.

(4)采用与实施例1步骤(4)相同的方法制备金属-树脂复合体，其平均剪切强度在表1中列出。(4) A metal-resin composite was prepared in the same manner as in the step (4) of Example 1, and the average shear strength thereof is shown in Table 1.

实施例4Example 4

采用与实施例1相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3)分为步骤(3-1)和步骤(3-2)，在步骤(3-1)中采用与实施例1步骤(3)相同的方法对经硬质阳极氧化的铝合金片进行蚀刻，在步骤(3-2)中采用酸性蚀刻液对经碱蚀刻的铝合金片进行蚀刻，步骤(3-2)具体如下：The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 1 to prepare a metal-resin composite, except that the step (3) was divided into the step (3-1) and the step (3-2), in the step ( In 3-1), the hard anodized aluminum alloy sheet is etched in the same manner as in the step (3) of the first embodiment, and the alkali etched aluminum alloy sheet is treated with the acidic etching solution in the step (3-2). Etching, step (3-2) is as follows:

将步骤(3-1)得到的经碱蚀刻的铝合金片浸泡于温度为20℃的作为蚀刻液的盐酸 (pH＝2)中。12分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经酸蚀刻的铝合金片。The alkali-etched aluminum alloy sheet obtained in the step (3-1) is immersed in hydrochloric acid as an etching solution at a temperature of 20 ° C. (pH = 2). After 12 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an acid-etched aluminum alloy sheet.

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在50-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.2-1：1的范围内，60％以上的第一腐蚀孔的深度与硬质氧化氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 50-200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard. The ratio of the thickness of the anodic oxide film layer is in the range of 0.2 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the hard oxide film layer of 60% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and an etching layer having a second etching hole, the etching layer is in contact with the hard anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 μm. Within the scope. The average shear strength of the prepared metal-resin composites is listed in Table 1.

对比例4Comparative example 4

采用与实施例4相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(2)采用与对比例3步骤(2)相同的方法在铝合金片表面形成阳极氧化膜层；The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 4 to prepare a metal-resin composite, except that the step (2) was carried out by forming an anode on the surface of the aluminum alloy sheet in the same manner as in the step (2) of Comparative Example 3. Oxide film layer;

步骤(3-1)中，将步骤(2)得到的表面具有阳极氧化膜层的铝合金片浸泡于温度为20℃的含有Na₂HPO₄的水溶液(pH＝11)中。15分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经碱蚀刻的铝合金片；In the step (3-1), the aluminum alloy sheet having the anodized film layer on the surface obtained in the step (2) was immersed in an aqueous solution (pH = 11) containing Na ₂ HPO ₄ at a temperature of 20 °C. After 15 minutes, the aluminum alloy piece was taken out, soaked in water for 1 minute, and then taken out and blown dry to obtain an alkali-etched aluminum alloy piece;

步骤(3-2)中，将步骤(3-1)得到的经碱蚀刻的铝合金片浸泡于温度为20℃的盐酸(pH＝2)中。12分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经酸蚀刻的铝合金片。In the step (3-2), the alkali-etched aluminum alloy sheet obtained in the step (3-1) is immersed in hydrochloric acid (pH = 2) at a temperature of 20 °C. After 12 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an acid-etched aluminum alloy sheet.

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：阳极氧化膜层中分布有孔径在50-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与阳极氧化膜层的厚度的比值在0.2-1：1的范围内，60％以上的第一腐蚀孔的深度与阳极氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 50-200 nm was distributed in the anodized film layer, and the depth of the first etching hole was anodized. The ratio of the thickness of the layer is in the range of 0.2 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the anodized film layer of more than 60% is 1:1; the aluminum alloy substrate is divided into a dense base layer and has A corrosion layer of the second etching hole, the etching layer is in contact with the anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 μm. The average shear strength of the prepared metal-resin composites is listed in Table 1.

对比例5Comparative example 5

采用与实施例1相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3)分为步骤(3-1)和步骤(3-2)，在步骤(3-1)中采用与实施例4中的步骤(3-2)相同的方法对经硬质阳极氧化的铝合金片进行蚀刻，在步骤(3-2)中采用与实施例1步骤(3)相同的方法对经酸蚀刻的铝合金片进行蚀刻。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 1 to prepare a metal-resin composite, except that the step (3) was divided into the step (3-1) and the step (3-2), in the step ( The hard anodized aluminum alloy sheet is etched in the same manner as the step (3-2) in the embodiment 4 in 3-1), and the step (3) is employed in the step (3-2). The same method etches the acid etched aluminum alloy sheet.

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在50-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.2-1：1的范围内，60％以上的第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在500-4500nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the hard anodized film layer was divided into Having a first etching hole having a pore diameter in the range of 50 to 200 nm, a ratio of a depth of the first etching hole to a thickness of the hard anodized film layer is in a range of 0.2 to 1:1, and a first etching hole of 60% or more The ratio of the depth to the thickness of the hard anodized film layer is 1:1; the aluminum alloy substrate is divided into a dense base layer and a corrosion layer having a second etching hole, and the corrosion layer is in contact with the hard anodized film layer, The pores of the second etching holes are in the range of 500-4500 nm, and the depth of the second etching holes is in the range of 0.1-400 μm. The average shear strength of the prepared metal-resin composites is listed in Table 1.

对比例6Comparative example 6

采用与实施例1相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3)中采用与实施例4步骤(3-2)相同的方法对经硬质阳极氧化的铝合金片进行蚀刻。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 1 to prepare a metal-resin composite, except that the same method as in the step (3-2) of Example 4 was used in the step (3). The anodized aluminum alloy sheet is etched.

采用显微镜观察步骤(3)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中基本没有腐蚀孔；铝合金基体分为致密的基体层和具有腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，腐蚀孔的孔径在800-5000nm范围内，腐蚀孔的深度在0.01-500μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3) was observed by a microscope, and it was found that there was substantially no corrosion hole in the hard anodized film layer; the aluminum alloy substrate was divided into a dense base layer and a corrosion layer having corrosion holes, and the corrosion layer and The hard anodized film layers are connected, the pores of the etching holes are in the range of 800-5000 nm, and the depth of the etching holes is in the range of 0.01-500 μm. The average shear strength of the prepared metal-resin composites is listed in Table 1.

实施例5Example 5

采用与实施例4相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3-2)中，蚀刻液为含有NaCl的盐酸(pH＝2)，NaCl与HCl的摩尔比为0.5：1。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 4 to prepare a metal-resin composite, except that in the step (3-2), the etching liquid was hydrochloric acid containing NaCl (pH=2), NaCl and The molar ratio of HCl was 0.5:1.

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在50-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.2-1：1的范围内，60％以上的第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在500-2000nm范围内，第二腐蚀孔的深度在50-200μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 50-200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard. The ratio of the thickness of the anodic oxide film layer is in the range of 0.2 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the hard anodized film layer of 60% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and an etching layer having a second etching hole, the etching layer is in contact with the hard anodized film layer, the second etching hole has a pore diameter in the range of 500-2000 nm, and the second etching hole has a depth in the range of 50-200 μm. Within the scope. The average shear strength of the prepared metal-resin composites is listed in Table 1.

实施例6Example 6

采用与实施例4相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3-1)中，蚀刻液为含有Na₃PO₄和Na₂HPO₄的水溶液(pH＝11)。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 4 to prepare a metal-resin composite, except that in the step (3-1), the etching liquid was an aqueous solution containing Na ₃ PO ₄ and Na ₂ HPO ₄ . (pH = 11).

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在100-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.5-1：1的范围内，70％以上的第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在1000-1500nm范围内，第二腐蚀孔的深度在10-300μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 100-200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard. The ratio of the thickness of the anodic oxide film layer is in the range of 0.5 to 1:1, and the depth of the first etching hole and the thickness of the hard anodized film layer are 70% or more. The ratio of the aluminum alloy is divided into a dense base layer and a corrosion layer having a second etching hole, the corrosion layer is in contact with the hard anodized film layer, and the second etching hole has a pore diameter in the range of 1000-1500 nm. The depth of the second etching hole is in the range of 10 to 300 μm. The average shear strength of the prepared metal-resin composites is listed in Table 1.

实施例7Example 7

(2)将步骤(1)得到的铝合金片作为阳极放入以浓度为20重量％的草酸作为电解液的硬质阳极氧化槽中，以石墨碳板作为阴极，在60V的电压下，在5℃电解15分钟，进行硬质阳极氧化。将经硬质阳极氧化的铝合金片取出并吹干，得到表面具有硬质阳极氧化膜层的铝合金片。用显微镜对该铝合金片的横截面进行观察确定硬质阳极氧化膜层的厚度为10μm，硬质阳极氧化膜层的显微硬度为2500HV。(2) The aluminum alloy sheet obtained in the step (1) is placed as an anode in a hard anodizing bath having a concentration of 20% by weight of oxalic acid as an electrolytic solution, and a graphite carbon plate is used as a cathode at a voltage of 60 V. Electrolysis was carried out at 5 ° C for 15 minutes for hard anodization. The hard anodized aluminum alloy sheet was taken out and blown dry to obtain an aluminum alloy sheet having a hard anodized film layer on its surface. The cross section of the aluminum alloy sheet was observed with a microscope to confirm that the thickness of the hard anodized film layer was 10 μm, and the hardness of the hard anodized film layer was 2500 HV.

(3-1)将步骤(2)得到的表面具有硬质阳极氧化膜层的铝合金片浸泡于温度为25℃的作为蚀刻液的Na₂CO₃和NaHCO₃的水溶液(pH＝12)中。20分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经碱蚀刻的铝合金片。(3-1) The aluminum alloy sheet having the hard anodized film layer on the surface obtained in the step (2) was immersed in an aqueous solution (pH=12) of Na ₂ CO ₃ and NaHCO ₃ as an etching solution at a temperature of 25 ° C. . After 20 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an alkali-etched aluminum alloy sheet.

(3-2)将步骤(3-1)得到的经碱蚀刻的铝合金片浸泡于温度为25℃的作为蚀刻液的盐酸(pH＝1)中。5分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经酸蚀刻的铝合金片。(3-2) The alkali-etched aluminum alloy sheet obtained in the step (3-1) was immersed in hydrochloric acid (pH = 1) as an etching solution at a temperature of 25 °C. After 5 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an acid-etched aluminum alloy sheet.

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在100-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.7-1：1的范围内，70％以上的第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在1000-1500nm范围内，第二腐蚀孔的深度在10-300μm的范围内。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 100-200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard. The ratio of the thickness of the anodic oxide film layer is in the range of 0.7 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the hard anodized film layer of 70% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and an etching layer having a second etching hole, the etching layer is in contact with the hard anodized film layer, the second etching hole has a pore diameter in the range of 1000-1500 nm, and the second etching hole has a depth in the range of 10-300 μm. Within the scope.

(4)将步骤(3-2)得到的铝合金片置于注射成型模具中，在铝合金片的一个表面注塑含有玻璃纤维和聚对苯二甲酸乙二醇酯(PET)的树脂组合物(相对于100重量份PET，玻璃纤维的含量为40重量份)，脱模并冷却。其中，注塑条件包括：模具温度为110℃，喷嘴温度为300℃，保压时间为8秒，射出压力为110MPa，射出时间为4秒，延迟时间为2秒。(4) The aluminum alloy sheet obtained in the step (3-2) is placed in an injection molding mold, and a resin composition containing glass fiber and polyethylene terephthalate (PET) is injection molded on one surface of the aluminum alloy sheet. (The content of the glass fiber was 40 parts by weight with respect to 100 parts by weight of PET), demolded and cooled. Among them, the injection molding conditions include: the mold temperature is 110 ° C, the nozzle temperature is 300 ° C, the dwell time is 8 seconds, the injection pressure is 110 MPa, the injection time is 4 seconds, and the delay time is 2 seconds.

将冷却后的产品放入120℃的恒温干燥箱中保温1.5h，然后随炉自然冷却至室温，制得金属-树脂复合体(树脂层的厚度为5mm)，其平均剪切强度在表1中列出。The cooled product was placed in a constant temperature drying oven at 120 ° C for 1.5 h, and then naturally cooled to room temperature with the furnace. A metal-resin composite (the thickness of the resin layer was 5 mm) was obtained, and the average shear strength thereof is listed in Table 1.

实施例8Example 8

采用与实施例7相同的方法对铝合金进行表面处理并制备铝合金-树脂复合体，不同的是，步骤(3-1)中，蚀刻液为乙二胺的水溶液(pH＝12)。The aluminum alloy was surface-treated in the same manner as in Example 7 to prepare an aluminum alloy-resin composite, except that in the step (3-1), the etching liquid was an aqueous solution of ethylenediamine (pH = 12).

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在10-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.1-1：1的范围内，50％以上的第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 10 to 200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard. The ratio of the thickness of the anodic oxide film layer is in the range of 0.1 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the hard anodized film layer of 50% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and an etching layer having a second etching hole, the etching layer is in contact with the hard anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 μm. Within the scope. The average shear strength of the prepared metal-resin composites is listed in Table 1.

实施例9Example 9

采用与实施例7相同的方法对铝合金进行表面处理并制备铝合金-树脂复合体，不同的是，步骤(3-1)中，蚀刻液为肼的水溶液(pH＝12)中。The aluminum alloy was surface-treated in the same manner as in Example 7 to prepare an aluminum alloy-resin composite, except that in the step (3-1), the etching liquid was an aqueous solution of hydrazine (pH = 12).

实施例10Example 10

(2)将步骤(1)得到的铝合金片作为阳极放入以浓度为20重量％的柠檬酸作为电解液的硬质阳极氧化槽中，以石墨碳板作为阴极，在60V的电压下，在20℃电解15分钟，以进行硬质阳极氧化。将经硬质阳极氧化的铝合金片取出并吹干，得到表面具有硬质阳极氧化膜的铝合金片。用显微镜对该铝合金片的横截面进行观察确定硬质阳极氧化膜层的厚度为21μm，硬质阳极氧化膜层的显微硬度为2000HV。 (2) The aluminum alloy sheet obtained in the step (1) is placed as an anode in a hard anodizing bath having a concentration of 20% by weight of citric acid as an electrolytic solution, and a graphite carbon plate is used as a cathode at a voltage of 60 V. Electrolysis was carried out at 20 ° C for 15 minutes for hard anodization. The hard anodized aluminum alloy sheet was taken out and blown dry to obtain an aluminum alloy sheet having a hard anodized film on its surface. The cross section of the aluminum alloy sheet was observed with a microscope to confirm that the thickness of the hard anodized film layer was 21 μm, and the hardness of the hard anodized film layer was 2000 HV.

(3-1)将步骤(2)得到的表面具有硬质阳极氧化膜层的铝片浸泡于温度为25℃的作为蚀刻液的NaOH水溶液(pH＝13)中。5分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经碱蚀刻的铝合金片。(3-1) The aluminum piece having the hard anodized film layer on the surface obtained in the step (2) was immersed in an aqueous NaOH solution (pH = 13) as an etching solution at a temperature of 25 °C. After 5 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an alkali-etched aluminum alloy sheet.

(3-2)将步骤(3-1)得到的经碱蚀刻的铝合金片浸泡于温度为30℃的作为蚀刻液的磷酸(pH＝3)中。20分钟后将铝合金片取出，在水中浸泡1分钟，然后取出吹干，得到经酸蚀刻的铝合金片。(3-2) The alkali-etched aluminum alloy sheet obtained in the step (3-1) was immersed in phosphoric acid (pH = 3) as an etching solution at a temperature of 30 °C. After 20 minutes, the aluminum alloy sheet was taken out, immersed in water for 1 minute, and then taken out and blown dry to obtain an acid-etched aluminum alloy sheet.

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在10-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.1-1：1的范围内，60％以上的第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在200-2000nm范围内，第二腐蚀孔的深度在0.1-400μm的范围内。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 10 to 200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard. The ratio of the thickness of the anodic oxide film layer is in the range of 0.1 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the hard anodized film layer of 60% or more is 1:1; the aluminum alloy substrate is divided into a dense base layer and an etching layer having a second etching hole, the etching layer is in contact with the hard anodized film layer, the second etching hole has a pore diameter in the range of 200-2000 nm, and the second etching hole has a depth in the range of 0.1-400 μm. Within the scope.

(4)将步骤(3-2)得到的铝合金片置于注射成型模具中，在铝合金片的一个表面注塑含有玻璃纤维和尼龙-66(PA-66)的树脂组合物(相对于100重量份PA-66，玻璃纤维的含量为50重量份)，脱模并冷却。其中，注塑条件包括：模具温度为100℃，喷嘴温度为300℃，保压时间为6秒，射出压力为100MPa，射出时间为5秒，延迟时间为5秒。(4) placing the aluminum alloy sheet obtained in the step (3-2) in an injection molding mold, and molding a resin composition containing glass fiber and nylon-66 (PA-66) on one surface of the aluminum alloy sheet (relative to 100) Parts by weight of PA-66, glass fiber content of 50 parts by weight), demolded and cooled. Among them, the injection molding conditions include: the mold temperature is 100 ° C, the nozzle temperature is 300 ° C, the dwell time is 6 seconds, the injection pressure is 100 MPa, the injection time is 5 seconds, and the delay time is 5 seconds.

实施例11Example 11

采用与实施例10相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3-1)中，蚀刻液(pH值与实施例10相同)还含有Na₂CO₃。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 10 to prepare a metal-resin composite, except that in the step (3-1), the etching liquid (the pH was the same as in Example 10) further contained Na _{2 .} CO ₃ .

采用显微镜观察步骤(3-2)得到的铝合金片的横截面，发现：硬质阳极氧化膜层中分布有孔径在80-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.5-1：1的范围内，60％以上的第一腐蚀孔的深度与硬质阳极膜层的厚度的比值为1：1；铝合金基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在1000-1500nm范围内，第二腐蚀孔的深度在10-300μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum alloy sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etching hole having a pore diameter in the range of 80-200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard. The ratio of the thickness of the anodic oxide film layer is in the range of 0.5 to 1:1, and the ratio of the depth of the first etching hole to the thickness of the hard anodic film layer of 60% or more is 1:1; the aluminum alloy substrate is classified into dense a base layer and an etching layer having a second etching hole, the etching layer is in contact with the hard anodized film layer, the second etching hole has a pore diameter in the range of 1000-1500 nm, and the second etching hole has a depth in the range of 10-300 μm. Inside. The average shear strength of the prepared metal-resin composites is listed in Table 1.

实施例12Example 12

采用与实施例10相同的方法对铝合金片进行表面处理并制备金属-树脂复合体，不同的是，步骤(3-2)中，蚀刻液(pH值与实施例10相同)还含有Na₂HPO₄，Na₂HPO₄与H₃PO₄的摩尔比为0.3：1。The aluminum alloy sheet was subjected to surface treatment in the same manner as in Example 10 to prepare a metal-resin composite, except that in the step (3-2), the etching liquid (the pH was the same as in Example 10) further contained Na _{2 .} The molar ratio of HPO ₄ , Na ₂ HPO ₄ to H ₃ PO ₄ was 0.3:1.

采用显微镜观察步骤(3-2)得到的铝片的横截面，发现：硬质阳极氧化膜层中分布有孔径在10-200nm范围内的第一腐蚀孔，第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值在0.1-1：1，60％以上的第一腐蚀孔的深度与硬质阳极氧化膜层的厚度的比值为1：1；铝基体分为致密的基体层和具有第二腐蚀孔的腐蚀层，腐蚀层与硬质阳极氧化膜层相接，第二腐蚀孔的孔径在400-2000nm范围内，第二腐蚀孔的深度在50-200μm的范围内。制备的金属-树脂复合体的平均剪切强度在表1中列出。The cross section of the aluminum sheet obtained by the step (3-2) was observed by a microscope, and it was found that the first etched hole having a pore diameter in the range of 10 to 200 nm was distributed in the hard anodized film layer, and the depth of the first etching hole was hard and hard. The ratio of the thickness of the anodized film layer is 0.1-1:1, and the ratio of the depth of the first etching hole to the thickness of the hard anodized film layer is 1:1; the aluminum substrate is divided into a dense base layer and An etching layer having a second etching hole, the etching layer is in contact with the hard anodized film layer, the second etching hole has a pore diameter in the range of 400-2000 nm, and the second etching hole has a depth in the range of 50-200 μm. The average shear strength of the prepared metal-resin composites is listed in Table 1.

将实施例1与对比例1-3进行比较可以看出，将根据本公开的经表面处理的金属基材与树脂一体化成型而制备的金属-树脂复合体中，树脂层与金属基材之间具有更高的平均剪切强度(即，具有更高的结合强度)，因而复合体具有更高的结构稳定性。 Comparing Example 1 with Comparative Examples 1-3, it can be seen that in the metal-resin composite prepared by integrally molding the surface-treated metal substrate according to the present disclosure with a resin, the resin layer and the metal substrate There is a higher average shear strength (i.e., a higher bond strength), and thus the composite has higher structural stability.

表1Table 1

编号Numbering	平均剪切强度(MPa)Average shear strength (MPa)
实施例1Example 1	18.118.1
实施例2Example 2	17.617.6
实施例3Example 3	19.419.4
对比例1Comparative example 1	0.20.2
对比例2Comparative example 2	44
对比例3Comparative example 3	10.410.4
实施例4Example 4	23.523.5
对比例4Comparative example 4	14.914.9
对比例5Comparative example 5	7.27.2
对比例6Comparative example 6	5.55.5
实施例5Example 5	24.724.7
实施例6Example 6	25.325.3
实施例7Example 7	22.122.1
实施例8Example 8	20.520.5
实施例9Example 9	20.320.3
实施例10Example 10	18.818.8
实施例11Example 11	21.621.6
实施例12Example 12	20.220.2

Claims

一种经表面处理的金属基材，所述金属为铝或铝合金，该金属基材包括金属基体以及形成于所述金属基体的至少部分表面上的硬质阳极氧化膜层，所述硬质阳极氧化膜层的表面分布有第一腐蚀孔。A surface treated metal substrate, the metal being aluminum or an aluminum alloy, the metal substrate comprising a metal substrate and a hard anodized film layer formed on at least a portion of a surface of the metal substrate, the hard The surface of the anodized film layer is distributed with a first etching hole.
根据权利要求1所述的经表面处理的金属基材，其中所述第一腐蚀孔的孔径在10-200nm的范围内，优选在50-200nm的范围内，更优选在80-200nm的范围内，进一步优选在100-200nm的范围内；所述第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值在0.1-1：1的范围内，优选在0.2-1：1的范围内，更优选在0.5-1：1的范围内。The surface-treated metal substrate according to claim 1, wherein the first etching hole has a pore diameter in the range of 10 to 200 nm, preferably in the range of 50 to 200 nm, more preferably in the range of 80 to 200 nm. Further preferably in the range of 100 to 200 nm; a ratio of a depth of the first etching hole to a thickness of the hard anodized film layer is in the range of 0.1 to 1:1, preferably 0.2 to 1:1 Within the range, it is more preferably in the range of 0.5 to 1:1.
根据权利要求1或2所述的经表面处理的金属基材，其中至少部分第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1，优选50％以上的第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1。The surface-treated metal substrate according to claim 1 or 2, wherein a ratio of a depth of at least a portion of the first etching holes to a thickness of the hard anodized film layer is 1:1, preferably 50% or more The ratio of the depth of a corrosion hole to the thickness of the hard anodized film layer is 1:1.
根据权利要求1-3中任意一项所述的经表面处理的金属基材，其中所述金属基体包括基体层和腐蚀层，所述基体层与所述腐蚀层为一体结构，所述腐蚀层与所述硬质阳极氧化膜层相接并为一体结构，所述腐蚀层的表面分布有第二腐蚀孔。The surface-treated metal substrate according to any one of claims 1 to 3, wherein the metal substrate comprises a base layer and an etching layer, the base layer being integrated with the etching layer, the etching layer The hard anodized film layer is connected to the integrated structure, and the surface of the etching layer is distributed with a second etching hole.
根据权利要求4所述的经表面处理的金属基材，其中所述第二腐蚀孔的孔径在200-2000nm的范围内，优选在400-2000nm的范围内，更优选在800-1500nm的范围内。The surface-treated metal substrate according to claim 4, wherein the second etching hole has a pore diameter in the range of 200 to 2000 nm, preferably in the range of 400 to 2000 nm, more preferably in the range of 800 to 1500 nm. .
根据权利要求4或5所述的经表面处理的金属基材，其中所述第二腐蚀孔的深度在0.1-500μm的范围内，优选在10-400μm的范围内，更优选在50-200μm的范围内。The surface-treated metal substrate according to claim 4 or 5, wherein the second etching hole has a depth in the range of 0.1 to 500 μm, preferably in the range of 10 to 400 μm, more preferably 50 to 200 μm. Within the scope.
根据权利要求4-6中任意一项所述的经表面处理的金属基材，其中所述基体层为致密层。The surface treated metal substrate according to any one of claims 4-6, wherein the base layer is a dense layer.
根据权利要求1-7中任意一项所述的经表面处理的金属基材，其中所述硬质阳极氧化膜层的厚度在0.1-500μm的范围内。 The surface-treated metal substrate according to any one of claims 1 to 7, wherein the hard anodized film layer has a thickness in the range of 0.1 to 500 μm.
一种金属基材的表面处理方法，所述金属为铝或铝合金，该方法包括提供金属基材，所述金属基材包括金属基体以及形成于所述金属基体的至少部分表面的硬质阳极氧化膜层；将所述金属基材进行第一蚀刻，以在所述硬质阳极氧化膜层中形成第一腐蚀孔。A surface treatment method for a metal substrate, the metal being aluminum or an aluminum alloy, the method comprising providing a metal substrate comprising a metal substrate and a hard anode formed on at least a portion of a surface of the metal substrate An oxide film layer; the metal substrate is subjected to a first etching to form a first etching hole in the hard anodized film layer.
根据权利要求9所述的方法，其中所述第一蚀刻使得所述第一腐蚀孔的孔径在10-200nm的范围内，优选在50-200nm的范围内，更优选在80-200nm的范围内，进一步优选在100-200nm的范围内；所述第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值在0.1-1：1的范围内，优选在0.2-1：1的范围内，更优选在0.5-1：1的范围内。The method according to claim 9, wherein said first etching is such that the pore diameter of said first etching hole is in the range of 10 to 200 nm, preferably in the range of 50 to 200 nm, more preferably in the range of 80 to 200 nm. Further preferably in the range of 100 to 200 nm; a ratio of a depth of the first etching hole to a thickness of the hard anodized film layer is in the range of 0.1 to 1:1, preferably 0.2 to 1:1 Within the range, it is more preferably in the range of 0.5 to 1:1.
根据权利要求9或10所述的方法，其中所述第一蚀刻使得至少部分第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1，优选50％以上的第一腐蚀孔的深度与所述硬质阳极氧化膜层的厚度的比值为1：1。The method according to claim 9 or 10, wherein said first etching is such that a ratio of a depth of at least a portion of the first etching holes to a thickness of said hard anodized film layer is 1:1, preferably 50% or more The ratio of the depth of a corrosion hole to the thickness of the hard anodized film layer is 1:1.
根据权利要求9-11中任意一项所述的方法，其中所述第一蚀刻包括：将所述金属基材浸泡于碱性蚀刻液中。The method of any of claims 9-11, wherein the first etching comprises immersing the metal substrate in an alkaline etchant.
根据权利要求12所述的方法，其中所述碱性蚀刻液为含有选自水溶性氢氧化物、水溶性碱性盐、氨、水溶性胺、肼以及一个或多个氢原子被烃基取代的肼衍生物中的一种或两种以上物质的水溶液。The method according to claim 12, wherein said alkaline etching solution contains a solvent selected from the group consisting of water-soluble hydroxides, water-soluble basic salts, ammonia, water-soluble amines, hydrazine, and one or more hydrogen atoms substituted by a hydrocarbon group. An aqueous solution of one or more of the anthracene derivatives.
根据权利要求13所述的方法，其中所述水溶性氢氧化物选自碱金属氢氧化物，优选为氢氧化钠和/或氢氧化钾；和/或The method of claim 13 wherein said water soluble hydroxide is selected from the group consisting of alkali metal hydroxides, preferably sodium hydroxide and/or potassium hydroxide; and/or

所述水溶性碱性盐选自水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐，优选选自Na₂CO₃、NaHCO₃、NaH₂PO₄、Na₂HPO₄、Na₃PO₄和Na₂B₄O₇；和/或The water-soluble basic salt is selected from the group consisting of water-soluble carbonates, water-soluble hydrogencarbonates, water-soluble phosphates, water-soluble monohydrogen phosphates, water-soluble dihydrogen phosphates, and water-soluble borates, preferably selected from Na. ₂ CO ₃ , NaHCO ₃ , NaH ₂ PO ₄ , Na ₂ HPO ₄ , Na ₃ PO ₄ and Na ₂ B ₄ O ₇ ; and/or

所述水溶性胺选自乙二胺、二乙基胺、乙醇胺、三甲基胺、甲基胺和二甲基胺；和/或The water soluble amine is selected from the group consisting of ethylenediamine, diethylamine, ethanolamine, trimethylamine, methylamine, and dimethylamine; and/or

所述肼衍生物选自一甲基肼和1,1-二甲基肼。The anthracene derivative is selected from the group consisting of monomethyl hydrazine and 1,1-dimethyl hydrazine.
根据权利要求12所述的方法，其中所述碱性蚀刻液为碱性缓冲溶液。 The method of claim 12 wherein said alkaline etchant is an alkaline buffer solution.
根据权利要求12所述的方法，其中所述碱性蚀刻液为含有水溶性氢氧化物以及水溶性碱性盐的水溶液，或者所述碱性蚀刻液为含有水溶性正盐以及水溶性酸式盐的水溶液，或者所述碱性蚀刻液为含有氨以及水溶性铵盐的水溶液。The method according to claim 12, wherein said alkaline etching solution is an aqueous solution containing a water-soluble hydroxide and a water-soluble basic salt, or said alkaline etching solution contains a water-soluble normal salt and a water-soluble acid form. The aqueous solution of the salt or the alkaline etching solution is an aqueous solution containing ammonia and a water-soluble ammonium salt.
根据权利要求16所述的方法，其中所述水溶性氢氧化物为氢氧化钠和/或氢氧化钾；所述水溶性碱性盐为水溶性碳酸盐、水溶性碳酸氢盐、水溶性磷酸盐、水溶性磷酸一氢盐、水溶性磷酸二氢盐和水溶性硼酸盐中的一种或两种以上，优选为水溶性磷酸二氢盐，更优选为磷酸二氢钠、磷酸二氢钾、磷酸二氢铵和磷酸二氢铝中的一种或两种以上。The method according to claim 16, wherein said water-soluble hydroxide is sodium hydroxide and/or potassium hydroxide; said water-soluble basic salt is water-soluble carbonate, water-soluble hydrogencarbonate, water-soluble One or more of phosphate, water-soluble monohydrogen phosphate, water-soluble dihydrogen phosphate, and water-soluble borate, preferably water-soluble dihydrogen phosphate, more preferably sodium dihydrogen phosphate or phosphoric acid One or more of potassium hydrogen, ammonium dihydrogen phosphate, and aluminum dihydrogen phosphate.
根据权利要求16所述的方法，其中所述碱性蚀刻液为含有水溶性碳酸盐和水溶性碳酸氢盐的水溶液，或者为含有水溶性磷酸盐和水溶性磷酸一氢盐的水溶液。The method according to claim 16, wherein said alkaline etching solution is an aqueous solution containing a water-soluble carbonate and a water-soluble hydrogencarbonate, or an aqueous solution containing a water-soluble phosphate and a water-soluble monohydrogen phosphate.
根据权利要求16所述的方法，其中所述水溶性铵盐选自NH₄Cl、(NH₄)₂SO₄、NH₄HCO₃和NH₄NO₃。The method of claim 16 wherein said water soluble ammonium salt is selected from the group consisting of NH ₄ Cl, (NH ₄ ) ₂ SO ₄ , NH ₄ HCO ₃ and NH ₄ NO ₃ .
根据权利要求12-19中任意一项所述的方法，其中所述碱性蚀刻液的pH值为10-13。The method according to any one of claims 12 to 19, wherein the alkaline etching solution has a pH of 10-13.
根据权利要求12-20中任意一项所述的方法，其中所述碱性蚀刻液的温度为10-60℃，优选为20-40℃；所述第一蚀刻的时间为1-60分钟，优选为5-20分钟。The method according to any one of claims 12 to 20, wherein the alkaline etching solution has a temperature of 10 to 60 ° C, preferably 20 to 40 ° C; and the first etching time is 1 to 60 minutes. It is preferably 5-20 minutes.
根据权利要求9-21中任意一项所述的方法，其中该方法还包括将经第一蚀刻的金属基材进行第二蚀刻，以在与所述硬质阳极氧化膜层相接的金属基体表面形成第二腐蚀孔。The method according to any one of claims 9 to 21, wherein the method further comprises performing a second etching on the first etched metal substrate to form a metal substrate in contact with the hard anodized film layer The surface forms a second etching hole.
根据权利要求22所述的方法，其中所述第二蚀刻使得所述第二腐蚀孔的孔径在200-2000nm的范围内，优选在400-2000nm的范围内，更优选在800-1500nm的范围内。The method according to claim 22, wherein said second etching is such that the pore diameter of said second etching hole is in the range of 200 to 2000 nm, preferably in the range of 400 to 2000 nm, more preferably in the range of 800 to 1500 nm. .
根据权利要求22或23所述的方法，其中所述第二蚀刻使得所述第二腐蚀孔的深度在0.1-500μm的范围内，优选在10-400μm的范围内，更优选在50-200μm的范围内。The method according to claim 22 or 23, wherein said second etching is such that the depth of said second etching hole is in the range of 0.1 to 500 μm, preferably in the range of 10 to 400 μm, more preferably 50 to 200 μm. Within the scope.
根据权利要求22-24中任意一项所述的方法，其中所述第二蚀刻包括：将经第一蚀刻的金属基材浸泡于酸性蚀刻液中。The method of any of claims 22-24, wherein the second etching comprises: The etched metal substrate is immersed in an acidic etchant.
根据权利要求25所述的方法，其中所述酸性蚀刻液为含有酸的水溶液，所述酸为氢卤酸和/或H₃PO₄，优选为HCl或H₃PO₄。The method according to claim 25, wherein said acidic etching solution is an aqueous solution containing an acid which is a hydrohalic acid and/or H ₃ PO ₄ , preferably HCl or H ₃ PO ₄ .
根据权利要求25或26所述的方法，其中所述酸性蚀刻液还含有一种或两种以上水溶性盐，所述水溶性盐为水溶性氢卤酸盐和/或水溶性磷酸盐。The method according to claim 25 or 26, wherein the acidic etching solution further contains one or two or more water-soluble salts, which are water-soluble hydrohalide salts and/or water-soluble phosphate salts.
根据权利要求27所述的方法，其中所述水溶性盐与所述酸的摩尔比为0.1-1：1，优选为0.2-0.8：1，更优选为0.4-0.6：1。The method according to claim 27, wherein the molar ratio of the water-soluble salt to the acid is from 0.1 to 1:1, preferably from 0.2 to 0.8:1, more preferably from 0.4 to 0.6:1.
根据权利要求25-28中任意一项所述的方法，其中所述酸性蚀刻液的pH值为1-3。The method according to any one of claims 25 to 28, wherein the acidic etching solution has a pH of 1-3.
根据权利要求25-29中任意一项所述的方法，其中所述酸性蚀刻液的温度为20-30℃，所述第二蚀刻的时间为1-60分钟，优选为10-30分钟。The method according to any one of claims 25 to 29, wherein the temperature of the acidic etching solution is 20-30 ° C, and the time of the second etching is 1-60 minutes, preferably 10-30 minutes.
根据权利要求9-30中任意一项所述的方法，其中提供金属基材的方法包括：将金属基材置于电解液中进行硬质阳极氧化，所述电解液中的电解质为草酸、磷酸盐、硅酸盐和铝酸盐中的一种或两种以上，所述硬质阳极氧化的条件包括：电压为10-100V，优选为40-80V；时间为1-60分钟，优选为10-30分钟；电解液的温度为0-60℃，优选为0-10℃。The method according to any one of claims 9 to 30, wherein the method of providing a metal substrate comprises: placing a metal substrate in an electrolyte for hard anodization, the electrolyte in the electrolyte being oxalic acid, phosphoric acid One or more of a salt, a silicate and an aluminate, the hard anodic oxidation conditions comprising: a voltage of 10-100 V, preferably 40-80 V; a time of 1-60 minutes, preferably 10 -30 minutes; the temperature of the electrolyte is 0-60 ° C, preferably 0-10 ° C.
根据权利要求9-31中任意一项所述的方法，其中所述硬质阳极氧化膜层的厚度在0.1-500μm的范围内。The method according to any one of claims 9 to 31, wherein the thickness of the hard anodized film layer is in the range of 0.1 to 500 μm.
权利要求9-32中任意一项所述的方法制备的经表面处理的金属基材。A surface treated metal substrate prepared by the method of any of claims 9-32.
一种金属-树脂复合体，所述金属为铝或铝合金，该复合体包括金属基材和树脂层，所述金属基材为权利要求1-8和33中任意一项所述的经表面处理的金属基材，所述树脂层附着在所述金属基材的至少部分表面上，所述树脂层中的部分树脂向下延伸并填充于金属基材的第一腐蚀孔或者第一腐蚀孔和第二腐蚀孔中。 A metal-resin composite, the metal being aluminum or an aluminum alloy, the composite comprising a metal substrate and a resin layer, the metal substrate being the surface of any one of claims 1-8 and 33 a treated metal substrate, the resin layer being attached to at least a portion of a surface of the metal substrate, a portion of the resin in the resin layer extending downward and filling a first etching hole or a first etching hole of the metal substrate And the second corrosion hole.
一种金属-树脂复合体的制备方法，所述金属为铝或铝合金，所述金属-树脂复合体包括金属基材以及附着在所述金属基材的至少部分表面的树脂层，所述金属基材为权利要求1-8和33中任意一项所述的经表面处理的金属基材，该方法包括向金属基材的至少部分表面注入含有树脂的组合物并使部分组合物填充于金属基材的第一腐蚀孔或者第一腐蚀孔和第二腐蚀孔中，成型后形成树脂层。A method for producing a metal-resin composite, the metal being aluminum or an aluminum alloy, the metal-resin composite comprising a metal substrate and a resin layer attached to at least a part of a surface of the metal substrate, the metal The substrate is a surface treated metal substrate according to any one of claims 1 to 8 and 33, the method comprising injecting a resin-containing composition onto at least a portion of a surface of the metal substrate and filling a portion of the composition with the metal The first etching hole of the substrate or the first etching hole and the second etching hole are formed into a resin layer after molding.
权利要求35所述的方法制备的金属-树脂复合体。A metal-resin composite prepared by the method of claim 35.
权利要求34或者权利要求36所述的金属-树脂复合体在制备电子产品壳体中的应用。Use of the metal-resin composite of claim 34 or claim 36 in the preparation of an electronic product casing.
一种电子产品外壳，该外壳包括金属壳本体以及附着于所述金属壳本体的至少部分内表面和/或至少部分外表面的至少一个树脂件，其中所述金属壳本体为权利要求1-8中任意一项所述的金属基材。An electronic product housing comprising a metal shell body and at least one resin member attached to at least a portion of an inner surface and/or at least a portion of an outer surface of the metal shell body, wherein the metal shell body is in accordance with claims 1-8 The metal substrate according to any one of the preceding claims.
一种电子产品外壳的制备方法，该方法包括在金属壳本体的至少部分内表面和/或至少部分外表面形成至少一个树脂件，其中采用权利要求35所述的方法形成所述树脂件。 A method of making an outer casing of an electronic product, the method comprising forming at least one resin member on at least a portion of an inner surface and/or at least a portion of an outer surface of the metal shell body, wherein the resin member is formed by the method of claim 35.