CN111962111A

CN111962111A - Mobile phone material containing cobalt alloy coating and preparation method thereof

Info

Publication number: CN111962111A
Application number: CN202010774686.5A
Authority: CN
Inventors: 王小锋
Original assignee: Shenzhen Shengli Technology Co ltd
Current assignee: Shenzhen Shengli Technology Co ltd
Priority date: 2020-08-04
Filing date: 2020-08-04
Publication date: 2020-11-20

Abstract

The invention relates to the technical field of electroplating, and particularly provides a mobile phone material containing a cobalt alloy plating layer and a preparation method thereof. The invention provides a mobile phone material with a cobalt-containing alloy coating, which sequentially comprises a metal coating and a plastic bracket from top to bottom; the metal plating layer contains a cobalt alloy plating layer.

Description

Mobile phone material containing cobalt alloy coating and preparation method thereof

Technical Field

The invention relates to the technical field of support materials, and particularly provides a mobile phone material containing a cobalt alloy plating layer and a preparation method thereof.

Background

ABS resin is one of five synthetic resins, its impact resistance, heat resistance, low temperature resistance, chemical resistance and electrical property are excellent, and it also has the characteristics of easy processing, stable product size and good surface gloss, and can be easily coated and colored, and can also be used for secondary processing of surface spraying metal, electroplating, welding, hot-pressing and bonding, etc., and can be extensively used in the industrial fields of machinery, automobile, electronic and electric appliances, instruments and meters, textile and building, etc., so that it is a thermoplastic engineering plastic with extensive application. Cobalt alloys are alloys formed by adding other alloying elements on the basis of cobalt. Common cobalt alloys include platinum-cobalt alloys, samarium-cobalt alloys, zirconium-cobalt alloys, tungsten-cobalt alloys, and the like. Electroplating is carried out on the surface of the ABS plastic, namely plastic electroplating, and the ABS plastic has the advantages of light weight, easiness in processing, good surface gloss, good leveling property and the like.

However, many currently used electroplated cobalt alloys have some defects, for example, the cobalt alloy electroplating solution is easy to have unstable liquid transfer and uneven plating thickness in the deposition process on the surface of the ABS plastic, thereby affecting the properties of the plating such as hardness and corrosion resistance; in addition, the obtained plating layer has high resistance and magnetic permeability, and mobile phone materials used in smart phones and cameras are liable to have adverse effects on signals and the like.

Disclosure of Invention

In order to solve the technical problems, the invention provides a mobile phone material with a cobalt-containing alloy coating, which comprises a metal coating and a plastic bracket from top to bottom in sequence; the metal plating layer contains a cobalt alloy plating layer.

As a preferred technical scheme of the invention, the cobalt alloy plating layer is prepared from cobalt alloy electroplating solution; the raw materials for preparing the cobalt alloy electroplating solution comprise cobalt salt, inorganic acid and salt thereof and a complexing agent.

As a preferred technical scheme of the invention, the concentration of the cobalt salt is 200-300 g/L; the concentration of the inorganic acid and the salt thereof is 50-130 g/L; the concentration of the complexing agent is 10-40 g/L.

As a preferable technical scheme of the invention, the cobalt salt is selected from one or a combination of more of cobalt sulfate, basic cobalt carbonate, cobalt sulfamate, cobalt acetate, cobalt methane sulfonate, cobalt chloride, cobalt nitrate and cobalt acetate.

As a preferred technical scheme of the invention, the complexing agent is organic acid; the organic acid is selected from one or more of citric acid, malic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, hydroxyethylidene diphosphonic acid and ethylenediamine tetraacetic acid.

As a preferable technical scheme, the concentration of the citric acid is 5-15 g/L; the concentration of the malic acid is 5-25 g/L.

As a preferable technical scheme of the invention, the hardness of the mobile phone material is more than 550 HV.

As a preferable technical solution of the present invention, the resistance value of the mobile phone material is less than 1.0, and the magnetic permeability is less than 1.1.

The second aspect of the invention provides a preparation method of a mobile phone material containing a cobalt alloy plating layer, which comprises the following steps: roughening and neutralizing the surface of the plastic support, activating palladium and dispergating; and then carrying out chemical copper plating engraving and copper plating, then carrying out cobalt alloy plating and chromium plating, and drying to obtain the product.

As a preferred technical scheme of the invention, the cobalt alloy plating process comprises the following steps: sending the plastic bracket after the copper plating into a plating bath containing cobalt alloy electroplating solution, wherein the current density is 0.2-2A/dm²(ii) a The pH value of the plating solution is 2-3.5, and the plating temperature is 55-65 ℃.

Has the advantages that: the invention provides a mobile phone material containing a cobalt alloy coating, which sequentially comprises a metal coating and a plastic bracket from top to bottom; the metal plating layer contains a cobalt alloy plating layer, the alloy plating layer is prepared from a cobalt alloy electroplating solution, the preparation raw materials of the cobalt alloy electroplating solution comprise specific cobalt salt, inorganic acid and salt thereof, and complexing agent, the concentration of the cobalt salt, the inorganic acid and the salt thereof is limited, the components interact with each other, so that the cobalt alloy plating layer has high adhesive force and is not easy to fall off, the obtained material has high hardness and good corrosion resistance, and meanwhile, the magnetic conductivity is less than 1.1, and the resistance value is less than 1.0; in the preparation process of the mobile phone material containing the cobalt alloy coating, specific substances and process parameters are selected, so that the coating is more tightly combined with plastics, the phenomena of looseness, bubbling, cracking and the like of the coating after electroplating are avoided, the surface durability of the product is prolonged, the comprehensive performances of high temperature resistance, corrosion resistance and the like are further improved, the magnetic conductivity and the resistance value are further reduced, and the service performance is excellent.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.

In one embodiment, the cobalt alloy coating is prepared from a cobalt alloy electroplating bath.

In a preferred embodiment, the raw materials for preparing the cobalt alloy electroplating solution comprise cobalt salt, inorganic acid and salt thereof, and complexing agent.

In a more preferred embodiment, the concentration of the cobalt salt is 200 to 300 g/L; the concentration of the inorganic acid and the salt thereof is 50-130 g/L; the concentration of the complexing agent is 10-40 g/L.

In a more preferred embodiment, the concentration of the cobalt salt is 250 g/L; the concentration of the inorganic acid and the salt thereof is 90 g/L; the concentration of the complexing agent is 25 g/L.

Cobalt salt

In one embodiment, the cobalt salt is selected from one or more of cobalt sulfate, cobalt carbonate hydroxide, cobalt sulfamate, cobalt acetate, cobalt methane sulfonate, cobalt chloride, cobalt nitrate and cobalt acetate.

In a preferred embodiment, the cobalt salt is cobalt sulfate.

The method for preparing the cobalt-plated alloy layer by using the electroplating method is characterized in that cobalt sulfate is used as a main salt to provide cobalt metal, ammonium salt cannot be used, and the problem that the pH value of a system is changed rapidly in the construction process so as to influence the stability of a plating solution is solved, mainly because the electroplating is carried out at 55-65 ℃, the ammonium salt is unstable so as to cause the instability of the pH value in an electroplating solution system so as to influence the uniform formation of a plating layer, and when the pH value is too low, a large amount of hydrogen is generated so as to influence the deposition of cobalt.

Inorganic acids and salts thereof

In one embodiment, the inorganic acid and salts thereof are phosphorus-containing inorganic acids and salts thereof.

In a preferred embodiment, the phosphorus-containing inorganic acid and its salt are meant to include phosphorus-containing inorganic acids and their corresponding phosphorus-containing inorganic acid salts.

Based on the double consideration of the pH value buffering effect of the plating solution and the magnetism of the obtained plating layer, the applicant finds in the experimental process that not all inorganic acids and salts thereof have a good pH buffering effect in the system of the application and can simultaneously enable the magnetic permeability of the obtained plating layer to be low, the technology of the effect is good when phosphorus-containing inorganic acids and salts thereof are adopted, and when boric acid and salts thereof are adopted in the system, the obtained plating solution system is unstable in the electroplating process, the obtained plating layer is easy to have the problems of hardness and wear resistance reduction, probably because hydrogen ions in the system are consumed in the electroplating process, the hydrogen ions in the system are greatly changed in concentration in a short time, the pH of the system is increased, impurities with a large content are formed, the mechanical property of the obtained plating layer is influenced, and the change degree of the pH can be reduced by the phosphorus-containing inorganic acids and salts thereof, the impurity content in the coating is reduced, so that the influence of the impurity content on the obtained coating is reduced; in addition, the magnetic permeability of the obtained product is also reduced, and probably because phosphorus in the obtained coating does not have symmetry and periodic repeatability in a part of the structure of the formed cobalt-phosphorus coating, the amorphous isotropy of the part of the structure is formed, and the magnetic permeability of the obtained coating is reduced.

In a more preferred embodiment, the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: (1-1.5); more preferably, the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1.2.

in a more preferred embodiment, the phosphorus-containing inorganic acid is selected from one or a combination of phosphorous acid, hypophosphorous acid and orthophosphoric acid.

In a more preferred embodiment, the phosphorus-containing inorganic acid is phosphorous acid and/or hypophosphorous acid.

In a more preferred embodiment, the phosphorus-containing inorganic acid is hypophosphorous acid; more preferably, the phosphorus-containing inorganic acid salt is a hypophosphite salt; more preferably, the hypophosphite salt is sodium/potassium hypophosphite.

The phosphorous acid, the phosphite, the hypophosphorous acid and the hypophosphite are adopted, so that the inorganic acid and the inorganic acid salt have synergistic effect and are used as components of the electroplating solution to provide a source for phosphorus of a plating layer, and the hardness and the corrosion resistance of the plating layer are improved.

Complexing agents

In one embodiment, the complexing agent is an organic acid.

In a preferred embodiment, the organic acid is selected from one or more of citric acid, malic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, hydroxyethylidene diphosphonic acid and ethylenediamine tetraacetic acid.

In a more preferred embodiment, the organic acid comprises citric acid and malic acid.

In a more preferred embodiment, the concentration of the citric acid is 5-15 g/L; the concentration of the malic acid is 5-25 g/L.

In a more preferred embodiment, the citric acid is present at a concentration of 10g/L citric acid; the concentration of the malic acid is 15 g/L.

The malic acid is D-malic acid (CAS number 636-61-3).

The concentration of the components in the cobalt alloy plating solution is the concentration of the plating solution.

Although the specific phosphorus-containing inorganic acid and the salt thereof are added into the main salt of the cobalt sulfate to be beneficial to reducing the magnetic permeability of the product, the applicant also finds that the reduction degree of the magnetic permeability is variable, the mechanical property, the wear resistance, the corrosion resistance and the like of the obtained plating layer are not ideal, the resistance value of the obtained plating layer is high, and the plating layer is not very suitable for being applied to the formation of the plating layer of a mobile phone camera frame, when citric acid and malic acid are added into the system, particularly when the concentration of the citric acid is 5-15 g/L and the concentration of the malic acid is 5-25 g/L, the obtained plating layer can realize the low magnetic permeability and the low resistance value, the magnetic permeability is less than 1.1 and the resistance value is less than 1.0, and the hardness, the corrosion resistance and the wear resistance of the plating layer are improved, probably because hypophosphorous acid or hypophosphite is oxidized into a phosphorous substance in the system under the condition that the pH is 2, the phosphorous acid substance can keep the valence state and is further complexed with cobalt in the system, but because the solubility of a complex compound in the system is limited, the complex compound is easy to form colloid to be separated out, and simultaneously, the formation of crystal grains of the cobalt is influenced, so that the hardness or compactness of a plating layer is influenced, and even the plating layer is cracked; the malic acid and the citric acid with specific concentration are added into the system to act together, so that a better complex can be formed with cobalt, colloid precipitation is avoided, refinement and reduction of cobalt in a plating layer are promoted, the dispersibility of cobalt and phosphorus in the plating layer is improved, phosphorus content in the plating layer is moderate based on the synergistic effect of phosphorus content with specific content and the malic acid and the citric acid, the great influence of impurities on the resistance of the plating layer is reduced, and the formation of an asymmetric and periodic repetitive structure in the plating layer structure is promoted.

The plastic bracket of the invention is an ABS plastic bracket which is purchased from ABS 920 of New Eurona materials Co., Ltd, Dongguan city.

The second aspect of the invention provides a preparation method of a mobile phone material containing a cobalt alloy plating layer, which comprises the following steps: coarsening, neutralizing, palladium activating, dispergating, chemical copper plating, carving, copper plating, cobalt alloy plating, chromium plating and drying.

In a preferred embodiment, the preparation method of the mobile phone material containing the cobalt alloy plating layer comprises the following steps: roughening and neutralizing the surface of the plastic support, activating palladium and dispergating; and then carrying out chemical copper plating engraving and copper plating, then carrying out cobalt alloy plating and chromium plating, and drying to obtain the product.

In one embodiment, the roughening process is: and (3) conveying the plastic support into a roughening tank containing roughening liquid, wherein the roughening temperature is 68-73 ℃, the roughening time is 8-15 min, and conveying the plastic support into a cleaning tank for cleaning after treatment.

In a preferred embodiment, the roughening liquid comprises the following components in the following concentrations: chromic anhydride 350-450 g/L and sulfuric acid 350-420 g/L.

In a more preferred embodiment, the roughening liquid comprises the following components in the following concentrations: chromic anhydride 400g/L and sulfuric acid 385 g/L.

In one embodiment, the neutralization process is: and (3) feeding the roughened plastic support into a neutralizing tank containing a neutralizing solution, wherein the neutralizing temperature is 25 ℃, the neutralizing time is 1-3 min, and feeding the treated plastic support into a cleaning tank for cleaning.

In a preferred embodiment, the neutralizing solution is a mixed water solution containing chloride ions, and comprises the following components in concentration: 200-400 g/L of chloride ions; the chloride ion source is any one of hydrochloric acid, potassium chloride, lithium chloride, calcium chloride and copper chloride; more preferably, the chloride ion is 300g/L and the source is hydrochloric acid.

The roughening solution has stronger roughening capability on the electric ABS plastic under the action of the roughening solution, and can oxidize butadiene in the ABS or the ABS containing PC to form an anchoring point, SO that more hydrophilic polar groups such as C-O, -OH, -SO3H, COOH and the like are generated on the surface of the plastic, and due to the existence of the groups, the hydrophilicity of the surface of the plastic is greatly improved, the chemical bonding is facilitated, and the bonding force of a plating layer is improved; the sulfuric acid can react with styrene to increase the bonding force of palladium; but the formed hexavalent chromium is relatively polluted and is relatively harmful to human bodies, and on the basis of the consideration, the reagent containing 200-400 g/L of chloride ions is adopted to neutralize the hexavalent chromium ions at room temperature; the method is matched with a specific palladium activation process, namely, 12-30 ppm of palladium ions, 220-320 mL/L of hydrochloric acid and 2-6 g/L of stannous chloride are adopted to treat a workpiece at 6-32 ℃ for 1-6 min, and particularly when the method is used together with 80-100 mL of hydrochloric acid dispergation liquid, the charged palladium ions and groups on the surface of plastic act to change non-conductive plastic into a conductive surface so as to promote the binding force between the non-conductive plastic and a plating layer, and the stannous ions in the system are favorable for improving the stability of the palladium ions and avoiding the inactivation of the palladium ions, but not all systems of the palladium ions, the stannous chloride and the hydrochloric acid are suitable, and on one hand, the content relation between the stannous chloride and the hydrochloric acid needs to be controlled, the method adopts 220-320 mL/L of hydrochloric acid and 2-6 g/L of stannous chloride, and when the concentration of the hydrochloric acid in the system is relatively high and the stannous chloride is relatively, the oxidation degree of stannous chloride in the system is increased, which not only causes the difficulty in the peptizing process to be increased, but also causes the aggregation of a glue layer on the surface of the plastic, influences the formation of a subsequent plating layer to cause the problem of plating leakage and influences the performance of the plating layer; but also causes the stability of the system palladium ions to be reduced and the binding force of the plating layer to be reduced; when the content of hydrochloric acid is low, the pH value of the system is increased, the stability of stannous chloride is poor, the stability of palladium ions of the system is reduced, and the binding force of a plating layer is reduced.

In addition, when the concentration of palladium ions in the system is controlled within the range of 12-30 ppm, the obtained plating layer has good binding force and good compactness, and when the concentration of the palladium ions is higher or lower, the properties of the obtained plating layer can be influenced; when the content of the organic acid is less, the activity is lower, and the binding force between the plastic and the coating is reduced.

In one embodiment, the palladium activation process is: and (3) feeding the neutralized plastic support into a palladium activation tank containing a palladium activation solution, wherein the palladium activation temperature is 26-32 ℃, the palladium activation time is 1-6 min, and feeding the plastic support into a cleaning tank for cleaning after treatment.

In a preferred embodiment, the palladium activation solution is a mixed aqueous solution containing palladium ions, and comprises the following components in concentration: 12-30 ppm of palladium ions, 220-320 ml/L of hydrochloric acid and 2-6 g/L of stannous chloride; the source of the palladium ions is palladium water or palladium salt; the palladium salt is any one of tetraamminepalladium sulfate, diammine palladium sulfate, tetraamminepalladium chloride, diammine palladium chloride and palladium tetrachloro ammonia; more preferably, the palladium activation solution is a mixed aqueous solution containing palladium ions, and comprises the following components in concentration: 21ppm of palladium ions, 270ml/L of hydrochloric acid and 4g/L of stannous chloride; the source of palladium ions is tetraamminepalladium sulfate.

In one embodiment, the dispergation process is: and (3) conveying the plastic support activated by the palladium into a degumming tank containing a degumming solution, wherein the degumming temperature is 35-50 ℃, and the degumming time is 1-4 min.

In a preferred embodiment, the dispergation solution comprises the following components in the following concentrations: 80-100 ml/L of hydrochloric acid; more preferably, the dispergation solution comprises the following components in concentration: hydrochloric acid 90 ml/L.

In one embodiment, the electroless copper plating process is: and (3) conveying the dispergated plastic support into a plating bath containing chemical copper plating solution, wherein the chemical copper plating temperature is 45-58 ℃, and the chemical copper plating time is 2-8 min.

In a preferred embodiment, the electroless copper plating solution includes the following concentrations of components: 60-90 ml/L of formaldehyde, 45-75 g/L of copper sulfate, 5-10 g/L of sodium citrate and 2.5-4.5 g/L of sodium gluconate; the electroless copper plating solution has a pH greater than 10.

In a more preferred embodiment, the electroless copper plating solution includes the following concentrations of components: 75ml/L of formaldehyde, 60g/L of copper sulfate, 7g/L of sodium citrate and 3.5g/L of sodium gluconate.

The chemical copper plating is used as an intermediate layer between the plastic and the electroplated layer, has an important effect on the binding force between the finally obtained metal plating layer and the metal, and adopts a plating layer formed by formaldehyde and copper sulfate at the pH value of more than 10, particularly 60-90 ml/L of formaldehyde, 45-75 g/L of copper sulfate, 5-10 g/L of sodium citrate and 2.5-4.5 g/L of sodium gluconate; under the condition of 45-58 ℃, the obtained material has high binding force, and can still keep good binding force under high temperature or ultraviolet irradiation, sodium citrate is probably high in stability and not easy to oxidize, and a complex animal formed by sodium gluconate is stable in structure, so that the complex animal is beneficial to reduction of copper ions at a stable speed under the synergistic action of the complex animal, forms fine-grained sediment, is uniformly deposited on the surface of plastic and forms high binding force with palladium ions, copper powder generated due to reduction of metal copper is avoided, a plating layer is rough, and the binding force is reduced; in addition, when the pH is higher or lower, the deposition rate of copper is higher or the efficiency is lower, resulting in rough plating and poor bonding force, thereby affecting the overall properties of the resulting plating.

In one embodiment, the engraving process is: and forming a pattern on the plastic support subjected to electroless copper plating by utilizing laser engraving marks.

In one embodiment, the copper plating process is: the carved plastic bracket is sent into a plating bath containing copper plating solution, the plating voltage is 2-4V, and the plating current density is 0.1-0.3A/dm²The electroplating temperature is 25-35 ℃, and the electroplating time is 5-15 min.

In a preferred embodiment, the copper electroplating bath comprises the following concentrations of components: 150-220 g/L of copper sulfate and 60-80 g/L of sulfuric acid.

In a more preferred embodiment, the copper electroplating bath comprises the following concentrations of components: 185g/L of copper sulfate and 70g/L of sulfuric acid.

In one embodiment, the cobalt alloy plating process is: feeding the plastic support after copper plating into a plating bath containing the cobalt alloy electroplating solution, wherein the current density is 0.2-2A/dm²(ii) a The pH value of the plating solution is 2-3.5, the plating temperature is 55-65 ℃, and the plating time is 5-15 min.

The electroplating time is determined by the electroplating thickness and is generally 5-15 min.

The pH value is 2.0-3.5, the temperature is 55-65 ℃, and the current density is 0.2-2A/dm²The electroplating conditions and the specific electroplating solution have synergistic effect, so that the technical effects of low magnetic permeability and low resistance of the obtained plating layer are realized, the comprehensive performance of the obtained plating layer is good, and when the pH is low or high, the stability of an electroplating solution system can be influenced, the solubility of phosphorus-containing inorganic acid and salt thereof can be influenced, and the deposition of a cobalt complex compound can be influenced, so that the structure of the plating layer is influenced, and the resistance value, the magnetic permeability and the comprehensive performance of the plating layer are influenced; the problem of plating leakage or partial non-plating layer can occur due to low temperature in the electroplating process, and the deposition speed of the plating layer can be accelerated when the temperature is high, so that the refining degree and the dispersion condition of metal can be influenced, and the comprehensive performance is deteriorated.

In one embodiment, the chrome plating process is: the plastic bracket after being plated with the cobalt alloy is sent into a plating bath containing chromium plating solution, the plating voltage is 3-5V, and the plating current is 3-5A/dm²The electroplating temperature is 40-60 ℃, and the electroplating time is 5-15 min.

In a preferred embodiment, the chromium electroplating bath comprises the following concentrations of components: 45-65 g/L of trivalent chromium and 40-70 g/L of hydrochloric acid.

In a more preferred embodiment, the chromium electroplating bath comprises the following concentrations of components: 55g/L of trivalent chromium and 55g/L of hydrochloric acid.

In one embodiment, the drying process is: and (3) drying the chromium-plated plastic support in an oven at the temperature of 35-40 ℃ for 10-30 min to obtain the chromium-plated plastic support.

The solvent of the coarsening solution, the peptizing solution, the chemical copper electroplating solution, the cobalt alloy electroplating solution and the chromium electroplating solution is deionized water.

When the mobile phone material is electroplated, carbon, platinum, electroplated platinum, cobalt and the like can be used as an anode; preferably, platinum; the cathode is a target workpiece, and the target workpiece is ABS.

The third aspect of the invention provides application of a mobile phone material containing a cobalt alloy coating, which is applied to a camera support of a smart phone to realize the installation and fixation of a camera.

Examples

In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.

Practice ofExample 1

Embodiment 1 of the invention provides a mobile phone material with a cobalt-containing alloy coating, which sequentially comprises a metal coating and a plastic support from top to bottom; the metal plating layer contains a cobalt alloy plating layer.

The cobalt alloy plating layer is prepared from cobalt alloy electroplating solution; the raw materials for preparing the cobalt alloy electroplating solution comprise 210g/L of cobalt salt, 60g/L of phosphorus-containing inorganic acid and salt thereof and 15g/L of complexing agent.

The cobalt salt is cobalt sulfate.

The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and corresponding phosphorus-containing inorganic acid salt; the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1; the phosphorus-containing inorganic acid is hypophosphorous acid; the phosphorus-containing inorganic acid salt is hypophosphite; the hypophosphite is sodium hypophosphite.

The complexing agent is organic acid; the organic acid comprises 6g/L citric acid and 7g/L malic acid.

The malic acid is D-malic acid.

The pH value of the cobalt alloy electroplating solution is 2-3.5.

The preparation method of the mobile phone material containing the cobalt alloy plating layer comprises the following steps: roughening and neutralizing the surface of the plastic support, activating palladium and dispergating; and then carrying out chemical copper plating engraving and copper plating, then carrying out cobalt alloy plating and chromium plating, and drying to obtain the product.

The coarsening process comprises the following steps: and (3) conveying the plastic support into a roughening tank containing roughening liquid, wherein the roughening temperature is 70 ℃, the roughening time is 11min, and conveying the plastic support into a cleaning tank for cleaning after treatment.

The coarsening liquid comprises the following components in concentration: chromic anhydride 400g/L and sulfuric acid 385 g/L.

The neutralization process is as follows: and (3) feeding the roughened plastic support into a neutralizing tank containing a neutralizing solution, wherein the neutralizing temperature is 25 ℃, the neutralizing time is 2min, and feeding the plastic support into a cleaning tank for cleaning after treatment.

The neutralizing solution is a mixed water solution containing chloride ions and comprises the following components in concentration: 300g/L of chloride ions; the source of chloride ions is hydrochloric acid.

The palladium activation process is as follows: and (3) conveying the neutralized plastic support into a palladium activation tank containing a palladium activation solution, wherein the palladium activation temperature is 29 ℃, the palladium activation time is 4min, and conveying the plastic support into a cleaning tank for cleaning after treatment.

The palladium activating solution is a mixed aqueous solution containing palladium ions and comprises the following components in concentration: 12ppm of palladium ions, 220ml/L of hydrochloric acid and 2g/L of stannous chloride; the source of palladium ions is tetraamminepalladium sulfate.

The degumming process comprises the following steps: and (3) conveying the plastic support activated by the palladium into a degumming tank containing a degumming solution, wherein the degumming temperature is 42 ℃, and the degumming time is 3 min.

The peptizing solution comprises the following components in concentration: hydrochloric acid 80 ml/L.

The chemical copper plating process comprises the following steps: and (3) conveying the dispergated plastic support into a plating bath containing chemical copper plating solution, wherein the chemical copper plating temperature is 51 ℃, and the chemical copper plating time is 5 min.

The electroless copper plating solution includes the following components in concentrations: 60ml/L of formaldehyde, 45g/L of copper sulfate, 5g/L of sodium citrate and 2.5g/L of sodium gluconate.

The copper plating process comprises the following steps: the carved plastic bracket is sent into a plating bath containing copper plating solution, the plating voltage is 3V, and the plating current density is 0.2A/dm²The electroplating temperature is 30 ℃ and the electroplating time is 10 min.

The copper electroplating solution includes the following components in concentration: 185g/L of copper sulfate and 70g/L of sulfuric acid.

The cobalt alloy plating process comprises the following steps: the plastic bracket after copper plating is sent into a plating bath containing the cobalt alloy electroplating solution, the current efficiency is 80 percent, and the current density is 0.2A/dm²(ii) a The electroplating temperature is 55 ℃ and the electroplating time is 10 min.

The chromium plating process comprises the following steps: the plastic bracket after being plated with the cobalt alloy is sent into a plating bath containing chromium plating solution, the plating voltage is 4V, and the plating current is 4A/dm²The electroplating temperature is 50 ℃ and the electroplating time is 10 min.

The chromium electroplating solution comprises the following components in concentration: 55g/L of trivalent chromium and 55g/L of hydrochloric acid.

The drying process comprises the following steps: and (3) placing the chromium-plated plastic support in a 37 ℃ oven for drying for 20min to obtain the electroplated plastic workpiece.

In the case of electroplating, carbon may be used as an anode; the cathode is a target workpiece, which is an ABS plastic bracket, and is purchased from ABS 920 of New materials, Inc. of PolyOucan, Dongguan.

Example 2

Embodiment 2 of the present invention provides a mobile phone material with a cobalt-containing alloy plating layer, which comprises a metal plating layer and a plastic support in sequence from top to bottom; the metal plating layer contains a cobalt alloy plating layer.

The cobalt alloy plating layer is prepared from cobalt alloy electroplating solution; the raw materials for preparing the cobalt alloy electroplating solution comprise 290g/L of cobalt salt, 120g/L of phosphorus-containing inorganic acid and salt thereof and 35g/L of complexing agent.

The cobalt salt is cobalt sulfate.

The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and corresponding phosphorus-containing inorganic acid salt; the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1.5; the phosphorus-containing inorganic acid is hypophosphorous acid; the phosphorus-containing inorganic acid salt is hypophosphite; the hypophosphite is sodium hypophosphite.

The complexing agent is organic acid; the organic acid comprises 14g/L of citric acid and 23g/L of malic acid.

The malic acid is D-malic acid (CAS number 636-61-3).

The pH value of the cobalt alloy electroplating solution is 2-3.5.

The coarsening process comprises the following steps: and (3) conveying the plastic substrate into a roughening tank containing roughening liquid, wherein the roughening temperature is 70 ℃, the roughening time is 11min, and conveying the treated plastic substrate into a cleaning tank for cleaning.

The neutralization process is as follows: and (3) feeding the roughened plastic base material into a neutralizing tank containing a neutralizing solution, wherein the neutralizing temperature is 25 ℃, the neutralizing time is 2min, and feeding the treated plastic base material into a cleaning tank for cleaning.

The palladium activation process is as follows: and (3) feeding the neutralized plastic base material into a palladium activation tank containing a palladium activation solution, wherein the palladium activation temperature is 29 ℃, the palladium activation time is 4min, and feeding the plastic base material into a cleaning tank for cleaning after treatment.

The palladium activating solution is a mixed aqueous solution containing palladium ions and comprises the following components in concentration: 30ppm of palladium ions, 320ml/L of hydrochloric acid and 6g/L of stannous chloride; the source of palladium ions is tetraamminepalladium sulfate.

The degumming process comprises the following steps: and (3) conveying the plastic base material activated by the palladium into a degumming tank containing a degumming solution, wherein the degumming temperature is 42 ℃, and the degumming time is 3 min.

The peptizing solution comprises the following components in concentration: hydrochloric acid 100 ml/L.

The chemical copper plating process comprises the following steps: and (3) conveying the dispergated plastic substrate into a plating tank containing chemical copper plating solution, wherein the chemical copper plating temperature is 51 ℃, and the chemical copper plating time is 5 min.

The electroless copper plating solution includes the following components in concentrations: 90ml/L of formaldehyde, 75g/L of copper sulfate, 10g/L of sodium citrate and 4.5g/L of sodium gluconate.

The copper plating process comprises the following steps: the engraved plastic substrate was placed in a plating bath containing a copper plating solution at a plating voltage of 3V and a plating current density of 0.2A/dm²The electroplating temperature is 30 ℃ and the electroplating time is 10 min.

The cobalt alloy plating process comprises the following steps: the plastic substrate after copper plating is sent into a plating bath containing the cobalt alloy electroplating solution, the current efficiency is 80 percent, and the current density is 2A/dm²(ii) a The electroplating temperature is 65 ℃ during electroplatingThe time interval is 10 min.

The chromium plating process comprises the following steps: the plastic base material plated with the cobalt alloy is sent into a plating bath containing chromium plating solution, the plating voltage is 4V, and the plating current is 4A/dm²The electroplating temperature is 50 ℃ and the electroplating time is 10 min.

The drying process comprises the following steps: and (3) placing the chromium-plated plastic base material in a 37 ℃ oven for drying for 20min to obtain the electroplated plastic workpiece.

Example 3

Embodiment 3 of the present invention provides a mobile phone material with a cobalt-containing alloy plating layer, which comprises a metal plating layer and a plastic support in sequence from top to bottom; the metal plating layer contains a cobalt alloy plating layer.

The cobalt alloy plating layer is prepared from cobalt alloy electroplating solution; the raw materials for preparing the cobalt alloy electroplating solution comprise 250g/L of cobalt salt, 90g/L of phosphorus-containing inorganic acid and salt thereof and 250g/L of complexing agent.

The cobalt salt is cobalt sulfate.

The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and corresponding phosphorus-containing inorganic acid salt; the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1.2; the phosphorus-containing inorganic acid is hypophosphorous acid; the phosphorus-containing inorganic acid salt is hypophosphite; the hypophosphite is sodium hypophosphite.

The complexing agent is organic acid; the organic acid comprises 10g/L of citric acid and 15g/L of malic acid.

The malic acid is D-malic acid (CAS number 636-61-3).

The pH value of the cobalt alloy electroplating solution is 2-3.5.

The palladium activating solution is a mixed aqueous solution containing palladium ions and comprises the following components in concentration: 21ppm of palladium ions, 270ml/L of hydrochloric acid and 4g/L of stannous chloride; the source of palladium ions is tetraamminepalladium sulfate.

The peptizing solution comprises the following components in concentration: hydrochloric acid 90 ml/L.

The electroless copper plating solution includes the following components in concentrations: 75ml/L of formaldehyde, 60g/L of copper sulfate, 7g/L of sodium citrate and 3.5g/L of sodium gluconate.

The copper plating process comprises the following steps: the engraved plastic substrate was placed in a plating bath containing a copper plating solution at a plating voltage of 3V and a plating current density of 0.2A/dm²Plating temperatureThe temperature is 30 ℃, and the electroplating time is 10 min.

The cobalt alloy plating process comprises the following steps: the plastic substrate after copper plating is sent into a plating bath containing the cobalt alloy electroplating solution, the current efficiency is 80 percent, and the current density is 1.1A/dm²(ii) a The electroplating temperature is 60 ℃ and the electroplating time is 10 min.

Comparative example 1

Comparative example 1 of the present invention provides a mobile phone material containing a cobalt alloy plating layer, which is the same as example 3 in the specific embodiment except that the inorganic acid and the salt thereof are boric acid and sodium borate corresponding thereto; the weight ratio of the boric acid to the sodium borate is 1: 1.2.

comparative example 2

Comparative example 2 of the present invention provides a mobile phone material including a cobalt alloy plating layer, which is the same as example 3 in the specific embodiment except that the phosphorus-containing inorganic acid is orthophosphoric acid; the phosphorus-containing inorganic acid salt is sodium orthophosphate.

Comparative example 3

Comparative example 3 of the present invention provides a cellular phone material with a cobalt alloy plating layer, and the specific embodiment thereof is the same as example 3, except that the concentration of the phosphorus-containing inorganic acid and the salt thereof is 150 g/L.

Comparative example 4

Comparative example 4 of the present invention provides a mobile phone material with a cobalt-containing alloy plating layer, which is the same as example 3 in the specific embodiment, except that the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 10; the pH of the cobalt alloy electroplating solution is greater than 3.5.

Comparative example 5

Comparative example 5 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and its specific embodiment is the same as example 3, except that the palladium ion concentration of the palladium activation solution is 35 ppm.

Comparative example 6

Comparative example 6 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and its specific embodiment is the same as example 3, except that the palladium ion concentration of the palladium activation solution is 9 ppm.

Comparative example 7

Comparative example 7 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and its specific embodiment is the same as example 3, except that the hydrochloric acid concentration of the palladium activation solution is 330 ml/L.

Comparative example 8

Comparative example 8 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and its specific embodiment is the same as example 3, except that the hydrochloric acid concentration of the palladium activation solution is 210 ml/L.

Comparative example 9

Comparative example 9 of the present invention provides a mobile phone material with a cobalt alloy plating layer, and the specific implementation manner thereof is the same as example 3, except that the stannous chloride concentration of the palladium activation liquid is 8 g/L.

Comparative example 10

A comparative example 10 of the present invention provides a mobile phone material with a cobalt alloy plating layer, which is the same as example 3 in the specific implementation manner, except that the stannous chloride concentration of the palladium activation solution is 1 g/L.

Comparative example 11

Comparative example 11 of the present invention provides a mobile phone material with a cobalt alloy plating layer, and the specific embodiment thereof is the same as example 3, except that hydrochloric acid in the peptizing solution is replaced by sodium hydroxide.

Comparative example 12

Comparative example 12 of the present invention provides a mobile phone material comprising a cobalt alloy plating layer, and its specific embodiment is the same as example 3, except that malic acid is replaced with lactic acid.

Comparative example 13

Comparative example 13 of the present invention provides a material for a mobile phone including a cobalt alloy plating layer, and the detailed embodiment thereof is the same as example 4, except that malic acid is replaced with ethylenediaminetetraacetic acid.

Comparative example 14

Comparative example 14 of the present invention provides a cobalt alloy plated cellular phone material, and the detailed embodiment thereof is the same as example 3, except that malic acid is replaced with ethylenediaminetetraacetic acid.

Comparative example 15

Comparative example 15 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and the specific embodiment thereof is the same as example 3, except that the concentration of malic acid is 2 g/L.

Comparative example 16

Comparative example 16 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and its specific embodiment is the same as example 3, except that the plating temperature in the cobalt alloy plating process is 75 ℃.

Comparative example 17

Comparative example 17 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and the specific embodiment thereof is the same as example 3, except that the plating temperature in the cobalt alloy plating process is 45 ℃.

Comparative example 18

Comparative example 18 of the present invention provides a cellular phone material including a cobalt alloy plating layer, and its specific embodiment is the same as example 3, except that sodium citrate in the electroless copper plating solution is replaced with citric acid.

Comparative example 19

Comparative example 19 of the present invention provides a mobile phone material including a cobalt alloy plating layer, and the specific embodiment thereof is the same as example 3, except that sodium gluconate in the electroless copper plating solution is replaced with malic acid.

Comparative example 20

A comparative example 20 of the present invention provides a mobile phone material with a cobalt alloy plating layer, which is implemented in the same manner as in example 3, except that sodium gluconate in the electroless copper plating solution is replaced with sodium tartrate.

Performance testing

Carrying out the following performance tests 1-13 on the mobile phone material samples prepared in the above embodiments 1-3; carrying out performance tests of the following 1, 2, 5 and 10-12 on the mobile phone material samples prepared in the comparative examples 1-4 and 12-17; the mobile phone material samples prepared in the comparative examples 5-11 and 18-20 are subjected to the following performance tests 1, 5, 6 and 8-10. Appearance no anomaly in the following tests means: no discoloration, no bubbling, no cracking, no corrosion, no delamination and no shedding; otherwise, recording an exception.

1. Pencil hardness test

Marking 3 lines with the length of 1.0 +/-0.2 cm on the surface of a sample from different directions at an angle of 45 degrees under the load of 500gf by using a Mitsubishi pencil (UNI series), wiping off the trace of the pencil by using an eraser, sequentially testing from hard to soft from the hardest pencil until a pencil with a coating which is not scratched is found, and recording the hardness value at the moment, wherein the hardness value is A above 7H, B above 5-7H, C below 4-5H (excluding 5H), and D below 4H.

2. Rubber rub test

A500 g load was applied to the sample and a special rubber was used to rub the surface of the material back and forth for 200 cycles. The lateral edges are subjected to 100 cycles, wherein 45 +/-5 times per minute and 20mm of stroke are carried out, the rubber cannot be separated from the sample, the rubber is exposed by 30-40% when the rubber moves to two ends in the small product stroke, and whether the plating layer falls off or not and whether the substrate texture is exposed or not are observed and recorded; wherein, the texture of the coating at the wear-resistant part which does not fall off and expose the substrate is recorded as qualified, otherwise, the coating is unqualified; 10 parallel samples were set and the number was recorded as acceptable.

3. Hexavalent chromium test

Taking 150mL of a proper amount of purified water by using a beaker, taking 12pcs of a product (a sample needs to peel apart TPU and ABS electroplated parts), and simultaneously placing the TPU and the ABS electroplated parts in the beaker; boiling the solution until the volume of the solution is more than 30mL and less than or equal to 50mL, if the volume of the solution is less than 50m, adding purified water to 50mL, and pouring the solution into a color developing bottle with the scale mark on the color developing bottle as the standard (about 15 mL); a small amount of reagent medicine (uniformly using water quality rapid test reagent produced by Guangdong Huanji Microbiol. Tech Co., Ltd.) is taken out from the hexavalent chromium determination kit and added into the color developing bottle, and then the bottle cap is covered and shaken up until the medicine is completely dissolved (the test only aims at plating a side key). After standing for about 10 minutes, taking out the chromium colorimetric card from the hexavalent chromium determination kit, and comparing the color of the solution in the color developing bottle with the color of the solution in the color developing bottle. If the solution in the color developing bottle is colorless and transparent, the sample to be detected does not contain hexavalent chromium; if the solution in the color developing bottle is red, indicating that the sample to be detected contains hexavalent chromium; and marking that the alloy is qualified if the alloy does not contain hexavalent chromium, otherwise, the alloy is unqualified.

4. Alcohol resistance test

Rubbing the sample surface with 99.8% absolute ethanol under 500g pressure at 50 + -5 times/min for 200 times while keeping the flannel moist; observing whether the film is decolorized, falls off or shows the phenomenon of exposing the substrate; wherein, the base material without decolorization, falling off and exposure is marked as qualified, otherwise, the base material is marked as unqualified; 10 parallel samples were set and the number was recorded as acceptable.

5. Salt spray test

Using a NaCl solution with the pH value of 6.5-7.2 and the concentration of 5 wt%, the temperature of a test groove is 33-37 ℃, the test time is 96h, cleaning with clear water after the test, and drying at 50-60 ℃; the coating adhesion was tested using 3M610 gummed paper, where no appearance abnormality and adhesion above 3B was designated A, no appearance abnormality and adhesion between 2B and 3B was designated B, appearance abnormality or adhesion between 1B and 2B (excluding 2B) was designated C, and appearance abnormality or adhesion below 1B was designated D.

6. High temperature storage test

Standing at 73-77 ℃ for 48h, standing at normal temperature for at least 2h, and observing the appearance, wherein no abnormal appearance is recorded as qualified, and abnormal appearance is recorded as unqualified; 10 parallel samples were set and the number was recorded as acceptable.

7. Cosmetic resistance test

The surface of the product is wiped clean by cotton cloth, and cosmetics are uniformly coated on the surface of the sample, wherein each cosmetic is coated with 2 samples. The cosmetics are as follows: nivea sunscreen SPF30PA + +; nivea hand cream; q1a yulan oil sun SPF15PA +; d. liushen mosquito-repellent toilet water; e. baique Ling olive essential oil. Temperature: 55. + -.1 ℃ humidity: 93% -95% RH; time: 48H; after at least 2H is recovered at normal temperature, checking whether the surface of the sample is foamed or not, whether a paint film is obviously abnormal such as falling, separation and the like or not, whether a material is cracked or not and whether the appearance of a product is abnormally changed or not; wherein, the sample surface has no bubble, the paint film has no drop, no separation, no cracking of the material, no abnormal change of the appearance is marked as qualified, otherwise, the sample surface is marked as unqualified; 10 parallel samples were set and the number was recorded as acceptable.

8. Artificial sweat resistance test

Preparing a solution according to an artificial juice preparation instruction, wherein the pH value is 4.6 +/-0.1; the dust-free cloth for soaking the solution is stuck on the surface of the sample and sealed in a constant temperature and humidity box by a sealing rubber bag; temperature: 55. + -.2 ℃ humidity: 93 plus or minus 2 percent; storage time: 48 h; after the test, wiping the solution on the surface of the product, standing for at least 2h at room temperature, observing the appearance, and carrying out an adhesion test; wherein, no bubble, no plating corrosion, no paint film falling, no separation, no black spot with the diameter less than 0.5mm on the silver edge, no flake black block on the silver edge are marked as qualified, otherwise, the silver edge is marked as unqualified; 10 parallel samples were set and the number was recorded as acceptable.

9. Temperature impact resistance test

Keeping at-40 deg.C + -2 deg.C for 1h, and transferring to 75 deg.C + -2 deg.C within 1min and keeping for 1 h; the samples were tested for 20 cycles for 40 h; after the test, the sample is kept stand at normal temperature for at least 2h, and then the appearance is observed, and the adhesive force is tested; directly sticking the plastic water electroplated part on the surface of the sample crystal by using a 3M610 adhesive tape for 3 times without scratching grids; wherein, the appearance is not abnormal and the adhesive force is more than 3B and is marked as A, the appearance is not abnormal and the adhesive force is 2B to 3B and is marked as B, the appearance is abnormal or the adhesive force is 1B to 2B (excluding 2B) and is marked as C, and the appearance is abnormal or the adhesive force is less than 1B and is marked as D.

10. Ultraviolet aging test

Sticking black gummed paper or wrapping the non-irradiated surface of the sample by a dark thick paperboard; setting the power of the lamp tube to be 0.63W/m2, placing a sample into a test box, directly irradiating ultraviolet rays on the surface of the paint for 4 hours at the temperature of 60 ℃, then condensing for 4 hours at the temperature of 50 ℃, wherein the cycle is one cycle, taking out the sample after 12 cycles (96 hours), cooling for at least 2 hours at normal temperature, and then inspecting the surface of the paint; the paint surface is not faded, discolored, grains, cracked or peeled, the adhesive force is more than 3B and is marked as A, the paint surface is not faded, discolored, grains, cracked or peeled, the adhesive force is 2B-3B and is marked as B, the paint surface is faded, discolored, grains, cracked or peeled, the adhesive force is less than 1B-2B (excluding 2B) and is marked as C, and the paint surface is faded, discolored, grains, cracked, peeled or adhered, the adhesive force is less than 1B and is marked as D.

11. Permeability test

And testing the magnetic permeability of the sample by using an inductance test, wherein the magnetic permeability is less than Q and not equal to 1.01 and is recorded as A, the magnetic permeability is 1.01-1.1 and is recorded as B, the magnetic permeability is 1.1-1.6 and is recorded as C, and the magnetic permeability is more than 1.6 and is recorded as D.

12. Resistance value test

And (3) performing a resistance value test on the sample according to GB/T6146-2010, wherein the resistance value is less than 1 omega and is recorded as A, the resistance value is 1-1.5 omega and is recorded as B, the resistance value is 1.5-2 omega and is recorded as B, and the resistance value is more than 2 omega and is recorded as C.

TABLE 1

	Example 1	Example 2	Example 3
				Hardness of pencil	A	A	A
Rubber friction	8	8	8
				Hexavalent chromium	Qualified	Qualified	Qualified
Alcohol resistance	10	10	10
				Salt fog	A	A	A
High temperature storage	10	10	10
				Cosmetic product	10	10	10
Artificial sweat resistance water	10	10	10
				Temperature shock resistance	A	A	A
Ultraviolet aging	A	A	A
				Magnetic permeability	A	A	A
Resistance value	A	A	A

TABLE 2

TABLE 3

From the data in the table, the mobile phone material containing the cobalt alloy coating prepared by the invention sequentially comprises a metal coating and a plastic support from top to bottom; the metal plating layer contains a cobalt alloy plating layer, the alloy plating layer is prepared from a cobalt alloy electroplating solution, the preparation raw materials of the cobalt alloy electroplating solution comprise specific cobalt salt, inorganic acid and salt thereof, and complexing agent, the concentration of the cobalt salt, the inorganic acid and the salt thereof is limited, the components interact with each other, so that the cobalt alloy plating layer has high adhesive force and is not easy to fall off, the obtained material has high hardness and good corrosion resistance, and meanwhile, the magnetic conductivity is less than 1.1, and the resistance value is less than 1.0; in the preparation process of the mobile phone material containing the cobalt alloy coating, specific substances and process parameters are selected, so that the coating is more tightly combined with plastics, the phenomena of looseness, bubbling, cracking and the like of the coating after electroplating are avoided, the surface durability of the product is prolonged, the comprehensive performances of high temperature resistance, corrosion resistance and the like are further improved, the magnetic conductivity and the resistance value are further reduced, and the service performance is excellent.

The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.

Claims

1. The mobile phone material containing the cobalt alloy coating is characterized by comprising a metal coating and a plastic bracket from top to bottom in sequence; the metal plating layer contains a cobalt alloy plating layer.

2. The cobalt-alloy-plated mobile phone material as claimed in claim 1, wherein the cobalt alloy plating layer is prepared from a cobalt alloy electroplating solution; the raw materials for preparing the cobalt alloy electroplating solution comprise cobalt salt, inorganic acid and salt thereof and a complexing agent.

3. The cobalt-containing alloy plated mobile phone material as claimed in claim 2, wherein the concentration of the cobalt salt is 200-300 g/L; the concentration of the inorganic acid and the salt thereof is 50-130 g/L; the concentration of the complexing agent is 10-40 g/L.

4. The material for mobile phone with cobalt-containing alloy coating as claimed in claim 2 or 3, wherein the cobalt salt is selected from one or more of cobalt sulfate, cobalt carbonate hydroxide, cobalt sulfamate, cobalt acetate, cobalt methanesulfonate, cobalt chloride, cobalt nitrate, and cobalt acetate.

5. The cobalt-containing alloy coated mobile phone material as claimed in claim 2, wherein the complexing agent is an organic acid; the organic acid is selected from one or more of citric acid, malic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, hydroxyethylidene diphosphonic acid and ethylenediamine tetraacetic acid.

6. The cobalt-containing alloy plated mobile phone material as claimed in claim 5, wherein the concentration of citric acid is 5-15 g/L; the concentration of the malic acid is 5-25 g/L.

7. The cobalt-containing alloy plated cellular phone material as set forth in claim 1, wherein the hardness of the cellular phone material is more than 550 HV.

8. The cobalt-containing alloy plated mobile phone material as claimed in claim 1, wherein the mobile phone material has a resistance value of less than 1.0 and a magnetic permeability of less than 1.1.

9. The method for preparing the mobile phone material with the cobalt-containing alloy coating according to claims 1-9, comprising the following steps: roughening and neutralizing the surface of the plastic support, activating palladium and dispergating; and then carrying out chemical copper plating engraving and copper plating, then carrying out cobalt alloy plating and chromium plating, and drying to obtain the product.

10. The method for preparing a mobile phone material with a cobalt-containing alloy coating according to claim 9, wherein the cobalt alloy coating process comprises: sending the plastic bracket after the copper plating into a plating bath containing cobalt alloy electroplating solution, wherein the current density is 0.2-2A/dm²(ii) a The pH value of the plating solution is 2-3.5, and the plating temperature is 55-65 ℃.