WO2019228193A1 - Metal-plastic composite body, preparation method therefor and application thereof - Google Patents

Abstract

Provided are a metal-plastic composite body, a preparation method therefor and an application thereof. The metal-plastic composite body comprises a metal substrate, a metal-resin particle composite coating formed on the metal substrate, and a plastic layer formed on the metal-resin particle composite coating, wherein the metal-resin particle composite coating comprises a matrix metal layer and resin particles that are dispersed in the matrix metal layer, and at least a portion of the resin particles bond with the plastic layer.

Description

Metal-plastic composite body and preparation method and application thereof

Priority information

This application claims the priority and rights of the patent application filed with the State Intellectual Property Office of China on May 31, 2018, with a patent application number of 201810553630.X, which is hereby incorporated by reference in its entirety.

Technical field

The present application relates to the field of preparation of metal-plastic composites, and in particular, to a metal-plastic composite, a preparation method and applications thereof.

Background technique

At present, in the field of electronic equipment and vehicles such as mobile phones, automobiles, etc., it is often necessary to combine plastics with metal, ceramic, glass and other substrates to form composites. At present, the commonly used methods for combining plastic and metal, ceramic, glass and other substrates to form a composite body include adhesive bonding, using rivets, and buckle bonding. The above method increases the process flow, and the bonding strength of the substrate such as plastic and metal is low, and the sealing of the bonding interface is poor, which cannot meet the use requirements of electronic equipment and vehicles. Therefore, without the use of adhesives, rivets, etc., the direct integration of various substrates and plastics has become an industrial development requirement.

Summary of the Invention

One aspect of the present application is to provide a metal plastic composite body, which includes a metal substrate; a metal resin particle composite plating layer, the metal resin particle composite plating layer is located on the metal substrate; a plastic layer, the plastic The layer is located on a side of the metal resin particle composite plating layer away from the metal substrate, wherein the metal resin particle composite plating layer includes a matrix metal layer and resin particles dispersed in the matrix metal layer, and at least part of the Resin particles are combined with the plastic layer. Therefore, the structure of the metal-plastic composite substrate is simple, the bonding strength of the plastic layer and the metal substrate is high, and the performance is good.

Optionally, the metal plastic composite includes a metal substrate, a metal resin particle composite plating layer formed on the metal substrate, and a plastic layer formed on the metal resin particle composite plating layer, wherein the metal The resin particle composite plating layer includes a matrix metal layer and resin particles dispersed in the matrix metal layer, and at least part of the resin particles are combined with the plastic layer. Therefore, the structure of the metal-plastic composite substrate is simple, the bonding strength of the plastic layer and the metal substrate is high, and the performance is good.

Optionally, the resin particles and the plastic layer combined with the plastic layer are an integrated structure.

Optionally, the metal-resin particle composite plating layer is formed by co-depositing the resin particles and a matrix metal on a surface of the metal substrate by a dispersion plating method.

Optionally, the matrix metal includes one or more selected from the group consisting of nickel, copper, gold, iron, palladium, and tin.

Optionally, the thickness of the matrix metal layer is 5-50 μm.

Optionally, the material forming the resin particles includes a material selected from the group consisting of polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyamide, polyphenylene sulfide, polyphenylene ether, polypropylene, polyethylene, and styrene. -One or more of a butadiene-styrene block copolymer, a styrene-ethylene-butene-styrene block copolymer, and a thermoplastic polyurethane elastomer.

Optionally, the particle diameter of the resin particles is not greater than 30 μm.

Optionally, the metal substrate includes one or more of a stainless steel metal substrate, an aluminum metal substrate, a nickel metal substrate, and a copper metal substrate.

Optionally, the thickness of the metal substrate is 0.1-50 mm.

Optionally, the material forming the plastic layer includes a material selected from the group consisting of polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyamide, polyphenylene sulfide, polyphenylene ether, polypropylene, polyethylene, and styrene. -One or more of a butadiene-styrene block copolymer, a styrene-ethylene-butene-styrene block copolymer, and a thermoplastic polyurethane elastomer.

Optionally, the thickness of the plastic layer is 0.5-50 mm.

Optionally, the resin particles are formed from the same material as the plastic layer.

The present application also provides a method for preparing a metal-plastic composite, which includes the following steps: co-depositing resin particles and matrix metal on the surface of a metal substrate by a dispersion plating method to form a metal-resin particle composite plating layer; The resin particle composite plating layer is plastic injection-molded on a side far from the metal substrate, and the resin particles on the surface of the metal resin particle composite plating layer are at least partially combined with the plastic layer formed by injection molding. Therefore, the method has a simple manufacturing process, and does not need to make holes on the surface of the metal substrate by physical or chemical methods, and the formed metal resin particle composite coating layer does not need to undergo subsequent chemical treatment (such as hole expansion treatment or immersion in chemical solution to increase the plastic Adhesion, etc.), and the metal-plastic composite produced has high bonding strength and good performance.

Optionally, the dispersion electroplating method further includes: immersing the metal substrate in a plating solution for plating, wherein the liquid temperature of the plating solution is 50-90 ° C, the pH value is 3.5-5.5, Application time is 30-120 minutes.

Optionally, the plating solution includes a mixed solution of a metal plating solution and an aqueous dispersion of resin particles.

Optionally, in the plating solution, the concentration of the aqueous dispersion of the resin particles is 5-50 g / L.

Optionally, the aqueous dispersion of the resin particles includes the resin particles and a surfactant, and the surfactant includes a nonionic surfactant and a cationic surfactant. In the aqueous dispersion of the resin particles, The content of the resin particles is 0.05-0.25 g / mL, the mass of the non-ionic surfactant is 5-20 wt% of the resin particles, and the mass of the cationic surfactant is 0.2-2.0 of the resin particles wt%.

Optionally, the plating solution includes: 25-30g / L nickel sulfate hexahydrate, 0.5-10g / L borax, 5-15g / L aqueous dispersion of the resin particles, 10-50g / L malic acid , 10-50 / L succinic acid, 20-50g / L sodium hypophosphite.

The application also provides the application of the metal-plastic composite of the present application as a metal casing of a communication device.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a schematic structural diagram of a metal-plastic composite according to an embodiment of the present application; and

FIG. 2 shows a method flowchart of a method for preparing a metal-plastic composite according to an embodiment of the present application.

Reference signs:

1000: metal plastic composite; 100: metal substrate; 200: metal resin particle composite coating; 300: plastic layer.

Detailed ways

Hereinafter, embodiments of the present application are described in detail. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals represent the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the drawings are exemplary and are only used to explain the present application, and should not be construed as limiting the present application.

It should be noted that the features and effects described in the various aspects of this application can be applied to each other, and are not repeated here.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the end values of each range, between the end values of each range and individual point values, and between the individual point values, one or more new numerical ranges can be obtained by combining each other. These values The scope should be considered to be specifically disclosed herein.

This application is based on the inventor's discovery and knowledge of the following facts and problems:

Some current integrated plastic-metal forming methods require pore-forming treatment on the metal surface. Hole-making methods include anodic oxidation-strong acid treatment process, laser engraving process, immersion, etching and other treatment processes. All of the above methods have problems such as tedious process and high cost, and the treated metal substrate cannot be stored for a long time and needs to be stored in a short time. Proceed to the next stage of production.

In one aspect of the present application, the present application proposes a metal-plastic composite. Referring to FIG. 1, the metal-plastic composite 1000 of the present application includes a metal substrate 100 and a metal resin particle composite plating layer 200 formed on the metal substrate 100. And a plastic layer 300 formed on the metal resin particle composite plating layer 200, wherein the metal resin particle composite plating layer 200 includes a matrix metal layer and resin particles (not shown in the figure) dispersed in the matrix metal layer, and at least part of the resin The particles are combined with the plastic layer 300. Therefore, the metal-plastic composite 1000 has a simple structure, a high bonding strength between the metal substrate 100 and the plastic layer 300, and good useability.

In this application, "the composite coating of metal resin particles includes a matrix metal layer and resin particles dispersed in the matrix metal layer, and at least part of the resin particles are combined with the plastic layer" means that the resin particles are dispersed on the inside and the surface of the matrix metal layer, And at least part of the resin particles dispersed on the surface of the matrix metal layer is combined with the plastic layer. In order to further improve the bonding force between the metal substrate and the plastic layer, all the resin particles dispersed on the surface of the matrix metal layer can be combined with the plastic layer.

Optionally, in the metal-plastic composite according to the present application, the resin particles combined with the plastic layer and the plastic layer may be an integrated structure, and thus, the bonding force between the metal substrate and the plastic layer may be further improved.

Optionally, the metal-resin particle composite plating layer may be formed by a dispersion plating method, and the dispersion plating method may include co-depositing the resin particles and the matrix metal on the surface of the metal substrate. As a result, the resin particles can be uniformly distributed in the matrix metal to form a metal resin particle composite coating layer. The resin particles on the surface of the metal resin particle composite coating layer can be well fused with the plastic layer, and the metal substrate and plastic can be significantly improved. Cohesion between layers.

According to the embodiment of the present application, the matrix metal may be various metals commonly used in the art for dispersion plating. Optionally, the matrix metal may include one or more selected from nickel, copper, gold, iron, palladium, and tin. For example, the matrix metal may be nickel, may be copper, may be gold, may be iron, or may be Palladium may be tin, nickel copper, nickel palladium, nickel copper gold, or the like; specifically, the matrix metal may be nickel.

According to the embodiment of the present application, the material for forming the resin particles may include a material selected from polycarbonate (PC), acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (PA), polyphenylene sulfide (PPS ), Polyphenylene ether (PPO), polypropylene (PP), polyethylene (PE), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butene-styrene block One or more of a copolymer (SEBS) and a thermoplastic polyurethane elastomer (TPU). Specifically, the material forming the resin particles may be selected from one or more of PC, ABS, PA, and PPS. Specifically, the material forming the resin particles may be PA.

Optionally, the particle diameter of the resin particles may be 30 μm or less, that is, the particle diameter of the resin particles may not be greater than 30 μm; for example, the particle diameter of the resin particles may be 20 μm or less, and the particle diameter of the resin particles may be 1-10 μm, which may be 5 μm, and may be 8 μm or the like. Therefore, the particle diameter of the resin particles is within the above range, and the dispersion stability of the resin particles is good.

According to the metal-plastic composite of the present application, in order to further improve the bonding force between the metal substrate and the plastic layer, the thickness of the matrix metal layer may be 5-50 μm, for example, 10-30 μm, 15 μm, or 20 μm. It may be 25 μm, 40 μm, or the like.

According to the metal-plastic composite of the present application, the metal substrate may include one or more of a stainless steel metal substrate, an aluminum metal substrate, a nickel metal substrate, and a copper metal substrate. Optionally, the metal substrate may be a stainless steel metal substrate, an aluminum metal substrate, or a nickel metal substrate.

According to the embodiment of the present invention, the thickness of the metal substrate is not particularly limited, and a person skilled in the art can appropriately select according to its use. For example, when a metal substrate is used as a housing of a communication device, the thickness of the metal substrate can be selected from 0.1-50 mm, 0.2-25 mm, 0.5-10 mm, and 1-5 mm.

According to the metal-plastic composite of the present application, the material forming the plastic layer may include one or more selected from the group consisting of PC, ABS, PA, PPS, PPO, PP, PE, SBS, SEBS, and TPU; more optionally, The material forming the plastic layer may include one or more selected from PC, ABS, PA, PPS, PP, PE, and PPO; further optionally, the material forming the plastic layer may be selected from PC, ABS, PA, and PPS One or more of them.

Alternatively, the materials forming the resin particles and the plastic layer may be the same. As a result, the resin particles on the surface of the composite plating layer of the metal resin particles and the plastic layer can be better integrated into one body, and the bonding force between the metal substrate and the plastic layer is further improved.

Optionally, the thickness of the plastic layer may be 0.5-50 mm, may be 0.5-20 mm, more may be 1-10 mm, and further may be 1-3 mm.

In another aspect of the present application, the present application also provides a method for preparing a metal-plastic composite. According to the embodiment of the present invention, the method can prepare the metal-plastic composite body described above. Therefore, the metal-plastic composite body prepared by the method has all the features and advantages of the metal-plastic composite body described above. No longer.

The method includes the following steps:

1) a step of co-depositing the resin particles and the matrix metal on the surface of the metal substrate by dispersion electroplating;

2) A step of injection-molding plastic on the metal substrate having the composite plating layer obtained in step 1), and at least partially combining resin particles on the surface of the composite plating layer with the injection-molded plastic layer.

According to the method of the present application, resin particles and metal are co-deposited on the surface of a metal substrate by a dispersion plating method, thereby obtaining a metal-resin particle composite plating layer in which a resin particle structure is uniformly distributed in a matrix metal (or called host metal) layer By injecting plastic into a metal substrate on which a metal resin particle composite plating layer is formed, the resin particles on the surface of the metal resin particle composite plating layer can be integrated with the injection molded plastic layer, thereby significantly improving the metal substrate and the injection molding formed. Bonding force between plastic layers. In addition, the preparation process is simple, there is no need to make holes on the surface of the metal substrate by physical or chemical methods, and the formed metal resin particle composite coating does not need to be subjected to subsequent chemical treatments (such as hole expansion treatment or immersion in chemical solution to increase the adhesion of plastics). Etc.), environmentally friendly.

According to an embodiment of the present invention, referring to FIG. 2, the method includes the following steps:

S100: forming a metal resin particle composite coating on a metal substrate

In this step, the resin particles and the matrix metal are co-deposited on the surface of the metal substrate by a dispersion plating method to form a metal-resin particle composite plating layer.

According to the method of the present application, the matrix metal may be various metals commonly used in the art for dispersion electroplating. Optionally, the matrix metal may include one or more selected from the group consisting of nickel, copper, gold, iron, palladium, and tin; alternatively, the matrix metal may be nickel.

According to the method of the present application, the material forming the resin particles may include one or more selected from the group consisting of PC, ABS, PA, PPS, PPO, PP, PE, SBS, SEBS, and TPU; more optionally, forming the resin particles The material may include one or more selected from PC, ABS, PA, and PPS; optionally, the material forming the resin particles may be PA.

Optionally, the particle diameter of the resin particles may be 30 μm or less; more alternatively, the particle diameter of the resin particles may be 20 μm or less; and more alternatively, the particle diameter of the resin particles may be 1-10 μm. When the particle diameter of the resin particles is within the above range, the dispersion stability of the resin particles is good.

According to the method of the present application, the formed metal-resin particle composite plating layer includes a matrix metal layer and resin particles dispersed in the matrix metal layer. Specifically, the resin particles can be dispersed in the interior and surface layers of the matrix metal layer, and the resin particles dispersed in the surface layer of the matrix metal layer can be well combined with the plastic layer, further improving the bond between the metal substrate and the plastic layer formed by injection molding. force. In addition, in order to further improve the bonding force between the metal substrate and the plastic layer formed by injection molding, the thickness of the matrix metal layer may be selected from 5-50 μm, and may be selected from 10-30 μm.

According to the method of the present application, the metal substrate may include one or more of a stainless steel metal substrate, an aluminum metal substrate, a nickel metal substrate, and a copper metal substrate; the stainless steel metal substrate and the aluminum metal substrate may be selected. Or nickel metal substrate.

According to the embodiment of the present invention, the thickness of the metal substrate is not particularly limited, and those skilled in the art can appropriately select according to its use. For example, when a metal substrate is used as a housing of a communication device, the thickness of the metal substrate can be selected from 0.1-50 mm, 0.2-25 mm, 0.5-10 mm, and 1-5 mm.

According to the method of the present application, the above-mentioned dispersion plating can be performed in a plating solution containing metal ions and resin particles dispersed. Alternatively, the plating solution may include a mixed solution of a metal plating solution and an aqueous dispersion of resin particles.

According to the method of the present application, the aqueous dispersion of resin particles may include resin particles and a surfactant. Optionally, in the aqueous dispersion of resin particles, the content of the resin particles may be 0.05-0.25 g / mL, and may be 0.1-0.2 g / mL.

Optionally, the surfactant may be various surfactants commonly used in the art, and optionally, the surfactant may be one or more of a nonionic surfactant and a cationic surfactant.

Alternatively, the nonionic surfactant may include one or more of an alkylphenol polyoxyethylene ether, a fatty alcohol polyoxyethylene ether, and a polyether type nonionic surfactant. Examples of the alkylphenol polyoxyethylene ether include OP-10; examples of the fatty alcohol polyoxyethylene ether include AEO-9; and examples of the polyether nonionic surfactant include polypropylene glycol ethylene oxide adduct .

Alternatively, the cationic surfactant may include a quaternary ammonium salt type cationic surfactant.

According to the method of the present application, the amount of the surfactant may be 5-20% by weight of the resin particles, and may be 8-15% by weight of the resin particles.

According to an embodiment of the present invention, the aqueous dispersion of the resin particles may be prepared by a method generally used in the art to form an aqueous dispersion. In order to improve the dispersibility of the resin particles in the aqueous dispersion of the resin particles, in an optional embodiment of the present application, the resin particle aqueous dispersion is formed by the following steps:

(1) mixing the nonionic surfactant with the resin particles to obtain a mixed product, and the amount of the nonionic surfactant is 5-20% by weight of the resin particles;

(2) drying the mixed product to obtain a mixed powder, the drying conditions include: a drying temperature of 80-100 ° C, and a drying time of 1-10 hours;

(3) In the presence of a cationic surfactant, the mixed powder is dispersed with water, and the amount of the cationic surfactant is 0.2-2.0% by weight of the resin particles.

According to the method of the present application, the amount of the aqueous dispersion of resin particles in the plating solution can be determined according to the amount of the plating metal source compound. Optionally, the amount of the aqueous dispersion of the resin particles may be 5-50 g / L, and more preferably 5-15 g / L.

According to the method of the present application, the metal plating solution in the plating solution may include a nickel plating plating solution, and the aqueous dispersion of the resin particles may be an aqueous dispersion prepared by the above-mentioned optional embodiment.

In an optional embodiment of the present application, the composition of the plating solution for dispersion plating is as follows:

According to the method of the present application, optionally, the dispersion plating method may further include: immersing the metal substrate in a plating solution to perform composite plating, and the conditions of the dispersion plating may include: the liquid temperature of the plating solution is 50-90 ° C , PH value is 3.5-5.5, plating time is 30-120 minutes.

S200: Plastic injection, and the plastic layer is combined with at least part of the resin particles

In this step, the metal-resin particle composite plating layer formed in the previous step is injection-molded on the side far from the metal substrate, and the resin particles on the surface of the metal-resin particle composite plating layer are at least partially combined with the plastic layer formed by injection molding. According to the present application, the conditions for injection molding can be various conditions commonly used in injection molding in the art, which are not repeated here.

According to the method of the present application, optionally, the injection-molded plastic may include one or more selected from the group consisting of PC, ABS, PA, PPS, PPO, PP, PE, SBS, SEBS, and TPU; more optionally, injection molding The plastic can be selected from one or more of PC, ABS, PA, PPS, PP, PE, and PPO; further optionally, the injection molded plastic can be selected from one or more of PC, ABS, PA, and PPS Species.

Alternatively, the material of the resin particles and the injection-molded plastic may be the same. Thereby, the resin particles on the surface of the metal resin particle composite plating layer and the plastic layer formed by injection molding can be better integrated into one body, and the bonding force between the metal substrate and the plastic layer formed by injection molding can be improved.

According to the method of the present application, the thickness of the formed plastic layer can be 0.5-50 mm, optionally 0.5-20 mm, more preferably 1-10 mm, and further 1-3 mm.

The application also provides a metal plastic composite prepared by the preparation method of the application. Therefore, the metal-plastic composite has all the features and advantages of the metal-plastic composite prepared by the method for preparing a metal-plastic composite, which is not described herein again.

In addition, the present application also provides the application of the metal-plastic composite of the present application as a metal casing of a communication device.

The solution of the present application will be explained below with reference to the embodiments. Those skilled in the art will understand that the following examples are only used to illustrate the present application, and should not be regarded as limiting the scope of the present application. If the specific technology or conditions are not indicated in the examples, the technology or conditions described in the literature in the art or the product descriptions are performed.

Preparation Example 1

This preparation example is used to explain the preparation of an aqueous nylon dispersion.

(1) Weigh 10g of surfactant OP-10, 10g of surfactant F-68, heat and stir, and after the components are mutually soluble, stop operation and let it stand for later use;

(2) Weigh 20g of nylon powder (particle diameter: 5μm) into a 100mL jar, stir at high speed while slowly adding 2g of the above mixture, and quickly stir for 1h;

(3) Put the mixture of nylon powder and surfactant in a 100 ° C oven for 3 hours and continue to stir for 1 hour;

(4) Disperse the baked powder with 100 mL of deionized water, add 0.2 g of cationic surfactant F-134, stir for 0.5 h, and let it stand, to obtain a nylon aqueous dispersion W ₁ .

Preparation Example 2

This example is used to illustrate the preparation of an aqueous nylon dispersion.

(1) Weigh 5g of surfactant OP-10 and 15g of surfactant F-68, heat and stir. After the components are dissolved, stop operation and let it stand.

(2) Weigh 20g of nylon powder (particle size 5μm) into a 100ml jar, stir at high speed while slowly adding 2g of the above mixture, and quickly stir for 1h;

(3) Put the mixture of nylon powder and surfactant in a 100 ° C oven for 3 hours and continue to stir for 1 hour;

(4) Disperse the baked powder with 100 ml of deionized water, add 0.2 g of cationic surfactant F-134, stir for 0.5 h and let it stand, to obtain a nylon aqueous dispersion W ₂ .

Preparation Example 3

This preparation example is used to explain the preparation of an aqueous nylon dispersion.

(1) Weigh 10g of surfactant OP-10, 10g of surfactant F-68, heat and stir, and after the components are mutually soluble, stop operation and let it stand for later use;

(2) Weigh 20g of nylon powder (particle size 5μm) into a 100ml jar, stir at high speed while slowly adding 2g of the above mixture, and quickly stir for 1h;

(3) Put the mixture of nylon powder and surfactant in a 100 ° C oven for 3 hours, and then continue stirring for 1 hour;

(4) Disperse the baked powder with 100 ml of deionized water, add 0.1 g of cationic surfactant F-134, stir for 0.5 h, and let it stand, to obtain a nylon aqueous dispersion W ₃ .

Example 1

(1) Preparation of plating solution

Prepare plating solution A according to the following composition;

Nickel sulfate hexahydrate: 25g / L

Borax: 5g / L

Nylon water dispersion W ₁ : 7.5g / L

Malic acid: 25g / L

Lactic acid: 20g / L

Succinic acid: 5g / L

Sodium hypophosphite: 30g / L

(2) Dispersive plating

A stainless steel substrate (sus304, 1 mm thick) was immersed in the plating solution A for dispersion plating to obtain a metal substrate with a composite plating layer formed on the surface. The conditions for the dispersion plating were: the liquid temperature was 90 ° C and the pH was 4.5. , Wetting the plated substrate with the plating solution for 45 minutes to perform composite plating, and plating a composite coating film with uniformly distributed nylon particles in a Ni-P matrix on the surface of the substrate, the thickness of the coating film is 10 μm;

(3) Injection

The obtained metal substrate was put into a mold, and injection molding was performed at 290 ° C using commercially available nylon particles (PA6-8233G, BASF, Germany), and the mold temperature was 90 ° C to obtain a metal-plastic composite A ₁ . The thickness of the injection-molded plastic layer of the obtained metal-plastic composite was 2 mm.

Example 2

(1) Preparation of plating solution

The plating solution B was prepared according to the following composition.

Nickel sulfate hexahydrate: 25g / L

Borax: 5g / L

Nylon water dispersion W ₂ : 7.5g / L

Malic acid: 25g / L

Lactic acid: 20g / L

Succinic acid: 5g / L

Sodium hypophosphite: 30g / L

(2) Dispersive plating

A stainless steel substrate (sus304, thickness: 1 mm) was immersed in the plating solution B for dispersion plating to obtain a metal substrate with a composite plating layer formed on the surface. The conditions for the dispersion plating were: the liquid temperature was 90 ° C and the pH was 4.5 , Wetting the plated substrate with a plating solution for 60 minutes to perform composite plating, and plating a composite coating film with a uniform distribution of nylon particles in a Ni-P matrix on the surface of the substrate, the thickness of the coating film is 16 μm;

(3) Injection

The obtained metal substrate was put into a mold, and injection molding was performed at 290 ° C using commercially available nylon particles (PA6-8233G, BASF, Germany), and the mold temperature was 90 ° C to obtain a metal-plastic composite A ₂ . The thickness of the injection-molded plastic layer of the obtained metal-plastic composite was 2 mm.

Example 3

(1) Preparation of plating solution

A plating solution C was prepared according to the following composition.

Nickel sulfate hexahydrate: 25g / L

Borax: 5g / L

Nylon water dispersion W ₃ : 7.5g / L

Malic acid: 25g / L

Lactic acid: 20g / L

Succinic acid: 5g / L

Sodium hypophosphite: 30g / L

(2) Dispersive plating

A stainless steel substrate (sus304, 1 mm thick) was immersed in the plating solution C for dispersion plating to obtain a metal substrate with a composite plating layer formed on the surface. The conditions for the dispersion plating were that the liquid temperature was 90 ° C and the pH was 4.5. , Wetting the plated substrate with a plating solution for 90 minutes to perform composite plating, and plating a composite coating film with uniformly distributed nylon particles in a Ni-P matrix on the surface of the substrate, the thickness of the coating film is 25 μm;

(3) Injection

The obtained metal substrate was put into a mold, and injection molding was performed at 290 ° C with commercially available nylon particles (PA6-8233G, BASF, Germany), and the mold temperature was 90 ° C to obtain a metal-plastic composite A ₃ , and the obtained metal-plastic composite The thickness of the injection-molded plastic layer is 2mm.

Example 4

The method according to Example 1 was performed, except that the metal substrate was an aluminum metal substrate to obtain a metal-plastic composite A ₄ .

Example 5

The method was carried out according to Example 1, except that the amount of the nylon aqueous dispersion W ₁ was 15 g / L to obtain a metal-plastic composite A ₅ .

Test case

Preparation of test samples: The metal substrates coated with the composite coating on the surface of the substrate were prepared according to the steps (1) and (2) of Examples 1-5, and then the metal substrates obtained in step (2) were prepared. Put it into a mold, and use commercially available nylon particles (PA6-8233G, BASF, Germany) to perform injection molding at 290 ° C, and the mold temperature is 90 ° C to obtain metal-plastic composite test samples S ₁ -S ₅ and test samples S ₁ -S ₅ The size of the plastic part is 1 mm × 45 mm × 5 mm, and the bonding surface with the metal substrate is 0.5 cm ² (10 mm × 5 mm).

In addition, directly put the stainless steel substrate into the mold, and use commercially available nylon particles (PA6-8233G, BASF, Germany) to perform injection molding at 290 ° C, and the mold temperature was 90 ° C, and a metal-plastic composite test sample D _{1 was} also obtained. The size of the plastic part of D ₁ is 1 mm × 45 mm × 5 mm, and the bonding surface with the metal substrate is 0.5 cm ² (10 mm × 5 mm).

Test method: After 24 hours of injection, S ₁ -S ₅ and D ₁ were tested on a universal testing machine for pull-out bond strength. The results are shown in Table 1.

Zh Binding force (MPa) S ₁ 15 S ₂ 17 S ₃ 15.5 S ₄ 18 S ₅ 20 D ₁ less than 1

It can be seen from the results of the foregoing embodiments and Table 1 that the embodiments 1-5 using the method of the present application do not need to make holes on the surface of the metal substrate by physical or chemical methods, and do not need to perform chemical treatment after plating (such as Reaming treatment or immersion of chemical solution to increase the adhesion of plastics) has the advantages of simple process and environmental friendliness, and the obtained metal-plastic composite has high binding force between metal and plastic.

The embodiments of the present application have been described in detail above. However, the present application is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present application, various simple modifications can be made to the technical solution of the present application. It belongs to the protection scope of this application.

In addition, it should be noted that the specific technical features described in the foregoing specific embodiments can be combined in any suitable manner without conflict. In addition, various embodiments of the present application can also be arbitrarily combined, as long as it does not violate the idea of the present application, it should also be regarded as the content disclosed in the present application.

In the description of the present application, it should be understood that the orientation or position relationship indicated by the terms “up” and “down” is based on the orientation or position relationship shown in the drawings, and is only for the convenience of describing the application and simplifying the description. Rather than indicating or implying that the device or element referred to must have a particular orientation, be constructed and operate in a particular orientation, it cannot be understood as a limitation on this application.

Claims (19)

A metal-plastic composite includes: Metal substrate Metal resin particle composite plating layer, the metal resin particle composite plating layer is located on the metal substrate; A plastic layer located on a side of the metal resin particle composite plating layer away from the metal substrate, The metal-resin particle composite plating layer includes a matrix metal layer and resin particles dispersed in the matrix metal layer, and at least a part of the resin particles are combined with the plastic layer. The metal-plastic composite body according to claim 1, wherein the resin particles and the plastic layer combined with the plastic layer have an integrated structure. The metal-plastic composite body according to claim 1, wherein the metal-resin particle composite plating layer is formed by co-depositing the resin particles and a matrix metal on a surface of the metal substrate by a dispersion plating method. The metal-plastic composite according to claim 3, wherein the matrix metal comprises one or more selected from the group consisting of nickel, copper, gold, iron, palladium, and tin. The metal-plastic composite substrate according to claim 4, wherein the thickness of the matrix metal layer is 5-50 μm. The metal-plastic composite according to any one of claims 1-3, the material forming the resin particles comprises a material selected from the group consisting of polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyamide, and polyphenylene sulfide. One of ether, polyphenylene ether, polypropylene, polyethylene, styrene-butadiene-styrene block copolymer, styrene-ethylene-butene-styrene block copolymer, and thermoplastic polyurethane elastomer Multiple. The metal-plastic composite according to claim 6, wherein a particle diameter of the resin particles is not greater than 30 μm. The metal-plastic composite according to any one of claims 1-3, the metal substrate comprises one or more of a stainless steel metal substrate, an aluminum metal substrate, a nickel metal substrate, and a copper metal substrate. . The metal-plastic composite according to claim 8, wherein the thickness of the metal substrate is 0.1-50 mm. The metal-plastic composite according to any one of claims 1-3, the material forming the plastic layer comprises a material selected from the group consisting of polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyamide, and polyphenylene sulfide. One of ether, polyphenylene ether, polypropylene, polyethylene, styrene-butadiene-styrene block copolymer, styrene-ethylene-butene-styrene block copolymer, and thermoplastic polyurethane elastomer Multiple. The metal-plastic composite according to claim 10, wherein the thickness of the plastic layer is 0.5-50 mm. According to the metal-plastic composite body according to any one of claims 1-3, a material forming the resin particles and the plastic layer is the same. A method for preparing a metal-plastic composite. The method includes the following steps: Co-deposition of resin particles and matrix metal on the surface of a metal substrate by dispersion plating to form a composite coating of metal resin particles; Plastic is injection-molded on a side of the metal-resin particle composite plating layer remote from the metal substrate, and the resin particles on the surface of the metal-resin particle composite plating layer are at least partially combined with a plastic layer formed by injection molding. The method according to claim 13, wherein the dispersion plating method further comprises: immersing the metal substrate in a plating solution to perform plating, wherein a liquid temperature of the plating solution is 50-90 ° C and a pH value is 3.5-5.5, plating time is 30-120 minutes. The method according to claim 14, wherein the plating solution includes a mixed solution of a metal plating solution and an aqueous dispersion of resin particles. The method according to claim 15, wherein the concentration of the aqueous dispersion of the resin particles in the plating solution is 5-50 g / L. The method according to claim 15, wherein the aqueous dispersion of resin particles includes the resin particles and a surfactant, and the surfactant includes a nonionic surfactant and a cationic surfactant, In the aqueous dispersion of resin particles, the content of the resin particles is 0.05-0.25 g / mL, the mass of the non-ionic surfactant is 5-20 wt% of the resin particles, and the cationic surfactant The mass is 0.2-2.0 wt% of the resin particles. The method according to claim 15, wherein the plating solution comprises: 25-30 g / L nickel sulfate hexahydrate, 0.5-10 g / L borax, 5-15 g / L aqueous dispersion of the resin particles, 10- 50g / L malic acid, 10-50 / L succinic acid, 20-50g / L sodium hypophosphite. Use of the metal-plastic composite according to claims 1-12 or the metal-plastic composite prepared by the method according to claims 13-18 as a metal casing of a communication device.

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