CN112226748B - Plating process of plastic part with metal - Google Patents
Plating process of plastic part with metal Download PDFInfo
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- CN112226748B CN112226748B CN202011085491.6A CN202011085491A CN112226748B CN 112226748 B CN112226748 B CN 112226748B CN 202011085491 A CN202011085491 A CN 202011085491A CN 112226748 B CN112226748 B CN 112226748B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
Abstract
The invention provides a plating process of a plastic part with metal. The plating process comprises the steps of: grafting an unsaturated monomer which has a functional group capable of adsorbing and complexing metal ions and can react with the plastic base material of the plastic part on the surface of the plastic base material of the plastic part, and initiating polymerization to obtain a grafted and modified plastic part; contacting the grafted and modified plastic part with a reduced complex solution of metal ions with catalytic capability to enable the surface of the plastic base material to adsorb the metal ions, and then reducing the metal ions into metal particles to obtain the plastic part with the metal particles adsorbed on the surface of the plastic base material; and depositing metal on the surface of the plastic base material of the plastic part adsorbed with the metal particles to obtain the plastic part with a metal coating. The plating process provided by the invention effectively solves the problem that the strength and the performance of the plastic part are reduced because the metal in the plastic part with the metal needs to be shielded during the traditional plastic electroplating process so as to avoid chemical or physical damage to the plastic part.
Description
Technical Field
The invention relates to the technical field of material plating metal, in particular to a plating process of a plastic part with metal.
Background
The plastic has the characteristics of high strength, easy processing and forming, insulation, light weight and the like, and therefore, the plastic is widely applied to the fields of electronics, electric appliances, communication and the like. With the rapid development of the electronic industry and the 5G technology, the number of various civil and military electronic products is rapidly increased, and the electromagnetic interference gradually becomes a new social hazard. Although the common plastic has excellent insulation, the common plastic can hardly absorb and reflect electromagnetic waves and has no electromagnetic interference resistance and shielding capability. Therefore, the universal plastic is endowed with shielding performance, can provide good means and guarantee for military affairs, communication, confidentiality, computer system engineering, electronic control engineering, bioengineering and high-tech electromagnetic compatibility, and has important significance for social life and national defense construction.
The electromagnetic shielding materials of polymer plastics are generally classified into two types, i.e., composite type and intrinsic type. The intrinsic electromagnetic shielding material is formed by chemically and electrochemically doping a polymer with conjugated pi bonds, and the conductivity of the intrinsic electromagnetic shielding material is changed from an insulator to a conductor through doping, such as a polyaniline material. The composite electromagnetic shielding material is mainly a surface conductive shielding material and a filling type shielding material, wherein the surface conductive shielding material is a very thin metal layer obtained on the surface of a plastic by using methods of sticking a metal foil, melting metal, plating or chemically plating a plastic product with conductive paint and the like, so that the purpose of shielding is achieved; the filling type shielding material is filled with metal powder such as copper, nickel and the like, stainless steel wire carbon fiber, graphite fiber and the like, so that the shielding purpose is achieved. The plating layer prepared by chemical plating on the surface of the plastic has uniform components and is easy to control, the bonding force of the plating layer is strong and is not limited by the size and the shape of a part, and the deposited metal plating layer has higher electromagnetic shielding capability and environmental reliability, so the chemical plating is a common method for preparing the electromagnetic shielding composite layer.
CN104141121A discloses a method for chemical silver plating of small plastic pieces and chlorination of silver plating thereof, which comprises the following steps: a) Washing and removing oil; b) Coarsening, namely soaking the substrate by adopting a solution consisting of concentrated sulfuric acid and hydrogen peroxide to increase the roughness and the surface wettability of the surface of the substrate; c) Sensitizing, namely adsorbing a layer of substance which is easy to oxidize on the surface of the base material; d) Activating, namely dipping by adopting an aqueous solution consisting of palladium chloride and hydrochloric acid to form a thin catalytic active layer on the surface of the base material; e) Reducing, namely presoaking the substrate by using a reducing solution of the chemical silver plating solution; f) Chemical silver plating, namely mixing silver salt solution and reducing solution after respectively preparing the silver salt solution and the reducing solution for chemical silver plating; g) Activating the silver coating by acid, and cleaning the silver coating by using dilute nitric acid; h) The silver layer is chloridized, and ferric trichloride is adopted to convert the silver coating into a silver/silver chloride electrode. When the technical scheme is used for plating silver on the small plastic part, the plastic part needs to be coarsened by using sulfuric acid and hydrogen peroxide, so that the strength and the performance of the body of the plastic part are reduced, and the environment is harmed.
CN102409319A discloses a preparation method of a plastic product and the plastic product. The technology comprises the following steps: 1) Molding a plastic substrate; the plastic matrix contains chemical plating accelerant; the chemical plating accelerant is Ni 2 O 3 、Co 2 O 3 、CuSiO 3 、CuC 2 O 4 One or more of Cu/Fe/Mn or Cu/Fe/Al ternary co-sintered oxide and Cu/Fe/Al/Mn quaternary co-sintered oxide; 2) Laser gasifying the surface of the plastic substrate to expose the chemical plating accelerant; 3) And (3) electroless copper plating or electroless nickel plating, and continuing to perform at least one time of electroless plating and/or electroplating to form a metal layer on the surface of the plastic substrate. ByWhen the technology is used for preparing plastic products with metal layers, the chemical plating accelerant is required to be contained in the plastic substrate, and the technology is not suitable for other plastic substrates.
CN101654775A discloses an electroless plating material and a preparation method thereof. The technology comprises the steps of contacting a plastic substrate with a reducing agent aqueous solution and a divalent copper salt aqueous solution to enable an elemental copper particle layer to be attached to the surface of the plastic substrate, then carrying out metal deposition to form a metal coating, wherein the elemental copper particle layer and the metal coating form a chemical coating, the reducing agent reduces the divalent copper salt into elemental copper particles with the particle diameter of 15-100 nanometers under the contact condition, and the bonding force between the chemical coating and the plastic substrate is 100-400 MPa. The aqueous solution of cupric salt used in this technical solution may cause a displacement reaction with the metal in the plastic part with metal, resulting in a decrease in strength and performance of the plastic part, and thus this technical solution is not suitable for plating the plastic part with metal.
Therefore, it is an urgent need to provide a plating process suitable for a plastic part with metal, without shielding the metal material and causing environmental damage.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide a process for plating plastic parts with metal. The plating process effectively solves the problem that the traditional plastic piece with metal needs to be shielded when being subjected to chemical plating so as to avoid chemical or physical damage to the metal and further reduce the strength and the performance of the plastic piece.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a plating process of a plastic part with metal, which comprises the following steps:
(1) Grafting an unsaturated monomer which has a functional group for adsorbing and complexing metal ions and can react with the plastic base material of the plastic part on the surface of the plastic base material with metal, and initiating polymerization to obtain a grafted and modified plastic part;
(2) Contacting the plastic part obtained in the step (1) with a reduced complex solution of metal ions with catalytic capability to obtain the plastic part with the metal ions adsorbed on the surface of the plastic base material;
(3) Reducing the metal ions adsorbed on the surface of the plastic base material of the plastic part obtained in the step (2) to obtain the plastic part with metal nano particles adsorbed on the surface of the plastic base material;
(4) Depositing metal on the surface of the plastic base material of the plastic part obtained in the step (3) to obtain the plastic part with a metal coating;
the metal ion is Pd 2+ ；
The complex is selected from any one or a combination of at least two of ethylenediamine, disodium ethylene diamine tetraacetate, tetramethylenediamine and diethylenetriamine;
the molar ratio of the metal ion to the complex is 1.
In the present invention, pd is mentioned 2+ The supply source of (b) may be a water-soluble palladium ion compound, and may be, for example, palladium chloride, palladium sulfate or palladium acetate.
In the prior art, the pretreatment method of plastic surface chemical plating is usually chemical roughening and physical roughening, but when chemical plating is performed on a plastic part with a special metal structure, the metal in the plastic part is usually required to be shielded to prevent mechanical damage and corrosion from strong acid during pretreatment, and metal ions can generate a replacement reaction with the metal in the plastic part in an ion exchange process to affect the surface state and electrical performance of the metal and damage the strength and performance of the plastic part. However, in the invention, by using the coordination of the specific kind of metal ions and the complex, the concentration of free metal ions in the solution is reduced, the strength and performance of the plastic part are prevented from being damaged due to the replacement reaction between the metal ions and the metal in the plastic part, and the bonding strength between the metal plating layer on the surface of the chemically plated plastic substrate and the plastic substrate is high, so that the peel is not easy to fall off.
According to the invention, by controlling the molar ratio of the metal ions to the complex compound within the range, more metal ions can be adsorbed on the surface of the plastic base material, after chemical plating, the metal plating layer on the surface of the plastic base material and the plastic base material have higher bonding strength, and meanwhile, the phenomenon that the metal ions in the solution have more displacement reaction with the metal in the plastic part to influence the surface state and the electrical performance of the metal and damage the strength and the performance of the plastic part can be avoided.
The following are preferred embodiments of the present invention, but the present invention is not limited thereto, and the objects and advantages of the present invention can be achieved by the following preferred embodiments.
As a preferred embodiment of the present invention, the metal on the plastic part is selected from one or a combination of at least two of copper, copper alloy and silver, wherein a typical but non-limiting combination is: a combination of copper and copper alloys; a combination of copper alloy and silver; a combination of copper and silver.
Preferably, the plastic substrate of the plastic part is selected from one or a combination of at least two of polymers containing readily abstractable hydrogen atoms, readily abstractable halogen atoms and/or unsaturated chemical bonds in the molecular chain structure, further preferably one or a combination of at least two of PA (polyamide), PBT (polytetramethylene terephthalate) and PP (polypropylene), and exemplarily, the halogen atom may be a F atom; the unsaturated chemical bond may be a carbon-carbon double bond.
In the present invention, the polymer having a hydrogen atom which is easily abstracted in the molecular chain means that the molecular chain of the polymer contains a hydroxyl group, an amine group or a carboxyl group.
As a preferred technical scheme of the invention, the grafting method in the step (1) is any one or a combination of at least two of ultraviolet light-initiated plastic surface grafting modification, thermal-initiated plastic surface grafting modification, plasma plastic surface grafting modification and radiation plastic material surface grafting modification.
Preferably, the functional group capable of adsorbing the complex metal ion in step (1) is a carboxyl group and/or an acid anhydride.
Preferably, the unsaturated monomer in step (1) is selected from any one of acrylic acid, maleic anhydride, acrylamide and methacrylic acid or a combination of at least two thereof.
Preferably, the method for initiating polymerization in step (1) is to initiate the unsaturated monomer to perform polymerization reaction by the first initiator.
Preferably, the first initiator is benzophenone and/or mikrolon.
Preferably, the polymerization reaction time is 5-10min, for example, 5min, 6min, 7min, 8min, 9min, 10min, etc.
As a preferred technical scheme of the invention, the metal ions in the step (2) are Pd 2+ The complex is ethylenediamine.
Preferably, the concentration of the metal ions in the complex solution of the metal ions is 0.02 to 0.1mol/L. For example, it may be 0.02mol/L, 0.03mol/L, 0.4mol/L, 0.5mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, or 0.1mol/L.
Preferably, the concentration of the complex in the complex solution of the metal ion is 0.15 to 1mol/L, and may be, for example, 0.15mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, or the like.
As a preferred technical scheme of the invention, the reduction method in the step (3) is reduction by a reducing agent or catalytic reduction by a catalyst under ultraviolet light.
Preferably, the reducing agent is selected from any one of sodium borohydride, stannous chloride and ascorbic acid or a combination of at least two thereof.
Preferably, the catalyst is potassium chloride and/or sodium formate.
As a preferred technical scheme of the invention, the deposition method in the step (4) is electroless plating.
Preferably, the metal deposited in step (4) is copper and/or nickel.
As a preferred embodiment of the present invention, the plating process further comprises pretreating the plastic part before performing step (1).
Preferably, the pretreatment is to perform degreasing and oil removing treatment on the surface of the plastic substrate of the plastic part and perform degreasing and oxide removing treatment on metal on the plastic part.
As a preferred embodiment of the present invention, the plating process further comprises swelling the pretreated plastic part with an organic solvent between the pretreatment and step (1).
Preferably, the organic solvent is formic acid and/or ethanol.
Preferably, the organic solvent contains a second initiator.
Preferably, the second initiator is a photoinitiator or a thermal initiator.
Preferably, the second initiator is benzophenone and/or michaelis-ler ketone.
Preferably, the swelling time is 10-60min, such as 10min, 20min, 30min, 40min, 50min or 60min.
In a preferred embodiment of the present invention, the plating process further comprises cleaning the plastic part obtained in step (1) before step (2).
Preferably, the cleaning method is cleaning by pure water.
Preferably, the temperature of the pure water is 60 to 90 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃ and the like.
As a preferred embodiment of the present invention, the plating process includes the steps of:
(1) Carrying out degreasing and oil removing treatment on a plastic substrate of a plastic piece with metal, and carrying out degreasing and oxide removing treatment on the metal on the plastic piece;
(2) Soaking the plastic part obtained in the step (1) in an organic solvent containing a second initiator for swelling for 10-60min to obtain a swelled plastic part;
(3) Grafting an unsaturated monomer which has carboxyl and can react with the plastic part substrate on the surface of the plastic part substrate obtained in the step (2), and initiating a polymerization reaction by a first initiator for 5-10min to obtain a grafted and modified plastic part;
(4) Obtained in the step (3)Cleaning the plastic part with pure water at 60-90 ℃, and soaking the plastic part in Pd, the molar ratio of which is 1 2+ In the ethylene diamine solution, pd is adsorbed on the surface of the obtained plastic substrate 2+ The plastic part of (1);
(5) Adsorbing Pd on the surface of the plastic base material of the plastic part obtained in the step (4) 2+ Reducing to obtain a plastic piece with palladium nanoparticles with the particle size of 5-20nm adsorbed on the surface of the plastic base material;
(6) And (5) performing chemical plating and metal deposition on the surface of the plastic base material of the plastic part obtained in the step (5) to obtain the plastic part with a metal plating layer.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method for processing the plastic surface by matching the surface grafting and the metal ion complex solution does not damage the strength and the performance of the body of the plastic material, does not need mechanical coarsening and chemical coarsening, does not use substances such as chromic anhydride, fluoride, sulfuric acid and the like which are harmful to the environment, does not need shielding treatment on the metal material, and does not damage the strength and the performance of the metal material.
(2) According to the invention, by selecting specific types of metal ions and complexes, when a plastic part with metal is subjected to chemical plating, the complexes of the metal ions do not generate a replacement reaction with the metal in the plastic part, shielding treatment on the metal in the plastic part is not required, the strength and performance of the plastic part are not damaged, and no harm is generated to the environment, meanwhile, the bonding strength of the metal coating and the plastic substrate is higher, the bonding strength of the metal coating and the plastic is not lower than 20N/cm, the bonding strength is not lower than 15N/cm after the plastic coating and the plastic are subjected to warm punching circulation at-55 ℃ to +125 ℃ for 5 times, and the degree of reduction of the bonding degree is less than or equal to 25%. For a plated piece of high-temperature nylon, the bonding strength of the metal plating layer and the high-temperature nylon is not lower than 24N/cm, and is not lower than 20N/cm after the plated piece is subjected to temperature impact cycling for 5 times at minus 55 ℃ to plus 125 ℃, and the degree of reduction of the bonding strength is less than or equal to 20 percent.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It will be appreciated that these embodiments are merely provided to facilitate an understanding of the present invention and should not be considered as specific limitations of the invention.
Some of the raw material sources in the examples are as follows:
PA10T: guangzhou Jinfa science and technology, inc., R630NH;
PA46: imperial groups of the Netherlands (DSM), PA46-GF20FR (40);
PBT: taiwan New light, 301-G20F (Gray).
Example 1
The embodiment provides a plating process of a PA10T plastic package copper strip, which comprises the following steps:
(1) Carrying out degreasing and oil removing treatment on a PA10T base material of the PA10T plastic package copper belt material, and carrying out degreasing and oxide removing treatment on metal copper;
(2) Soaking the PA10T plastic-packaged copper strip material obtained in the step (1) in an ethanol solution containing 2g/L of benzophenone and 10wt% of formic acid for swelling, wherein the swelling time is 40min, and the temperature is 25 ℃, so as to obtain a swollen plastic part of the PA10T plastic-packaged copper strip material;
(3) Immersing the plastic part obtained in the step (2) into an acrylic acid aqueous solution containing benzophenone, and carrying out ultraviolet irradiation grafting modification by using an ultraviolet mercury lamp with power of 2000W to obtain a grafted and modified plastic part, wherein the mass concentration of acrylic acid is 35%, the mass ratio of benzophenone to acrylic acid is 0.005;
(4) Cleaning the plastic part obtained in the step (3) by pure water at 70 ℃, soaking the plastic part in an aqueous solution of palladium chloride/ethylenediamine, wherein the concentration of the palladium chloride in the solution is 0.05mol/L, the concentration of the ethylenediamine is 0.4mol/L, the soaking time is 5min, and then washing the plastic part by pure water to obtain the plastic substrate with Pd adsorbed on the surface 2+ The plastic part of (1);
(5) Adsorbing Pd on the surface of the plastic base material of the plastic part obtained in the step (4) 2+ Reducing by sodium borohydride solution with the concentration of 0.1mol/L to obtain a plastic piece, wherein Pd nano-particles with the particle size of 5-20nm are adsorbed on the surface of the plastic base material;
(6) And (5) depositing metal copper on the surface of the plastic base material of the plastic part obtained in the step (5) through chemical plating to obtain the plastic part of the PA10T plastic packaging copper belt material with a copper plating layer.
The plating solution composition and the process conditions of the chemical plating in the step (6) are as follows:
wherein the mass percent of the formaldehyde is 37%.
Example 2
The embodiment provides a plating process of a PA46 plastic packaging copper strip, which comprises the following steps:
(1) Carrying out degreasing and deoiling treatment on a PA46 base material of the PA46 plastic-packaged copper strip material, and carrying out degreasing and oxide removing treatment on metal copper;
(2) Soaking the PA46 plastic package copper belt material obtained in the step (1) in an ethanol solution containing 2g/L of benzophenone and 10wt% of formic acid for swelling, wherein the swelling time is 20min, and the temperature is 25 ℃, so as to obtain a plastic piece of the swelled PA46 plastic package copper belt material;
(3) Immersing the plastic part obtained in the step (2) into an acrylic acid aqueous solution containing benzophenone, and carrying out ultraviolet irradiation grafting modification by using an ultraviolet mercury lamp with power of 2000W to obtain a grafted and modified plastic part, wherein the mass concentration of acrylic acid is 30%, the mass ratio of benzophenone to acrylic acid is 0.005;
(4) Cleaning the plastic part obtained in the step (3) by pure water at 60 ℃, soaking the plastic part in an aqueous solution of palladium chloride/ethylenediamine, wherein the concentration of the palladium chloride in the solution is 0.05mol/L, the concentration of the ethylenediamine is 0.4mol/L, the soaking time is 5min, and then washing the plastic part by pure water to obtain the plastic substrate with Pd adsorbed on the surface 2+ The plastic part of (1);
(5) Adsorbing Pd on the surface of the plastic base material of the plastic part obtained in the step (4) 2+ Reducing by using 0.1mol/L sodium borohydride solution to obtain a plastic piece, wherein Pd nanoparticles with the particle size of 5-20nm are adsorbed on the surface of the plastic base material;
(6) And (5) depositing metal copper on the surface of the plastic base material of the plastic part obtained in the step (5) through chemical plating to obtain the plastic part of the PA46 plastic packaging copper belt material with a copper plating layer.
The plating solution composition and process conditions of the above electroless plating were the same as in example 1.
Example 3
The embodiment provides a plating process of a PBT plastic package copper insert, which comprises the following steps:
(1) Carrying out degreasing and oil removing treatment on the PBT base material of the PBT plastic package copper insert, and carrying out degreasing and oxide removing treatment on metal copper;
(2) Soaking the PBT plastic package copper insert obtained in the step (1) in an ethanol solution containing 2g/L of benzophenone and 10wt% of formic acid for swelling, wherein the swelling time is 45min, and the temperature is 25 ℃, so as to obtain a plastic piece of the swelled PBT plastic package copper band;
(3) Immersing the plastic part obtained in the step (2) into acrylic acid aqueous solution containing benzophenone, and carrying out ultraviolet irradiation grafting modification by using an ultraviolet mercury lamp with power of 2000W, wherein the mass concentration of acrylic acid is 30%, the mass ratio of benzophenone to acrylic acid is 0.005;
(4) Cleaning the plastic part obtained in the step (3) by pure water at the temperature of 80 ℃, soaking the plastic part in an aqueous solution of palladium chloride/diethylenetriamine, wherein the concentration of the palladium chloride in the solution is 0.05mol/L, the concentration of the diethylenetriamine in the solution is 0.4mol/L, the soaking time is 5min, and then washing the plastic part by the pure water to obtain the plastic substrate with Pd adsorbed on the surface 2+ The plastic part of (1);
(5) Adsorbing Pd on the surface of the plastic base material of the plastic part obtained in the step (4) 2+ Reducing with 0.1mol/L ascorbic acid solution to obtain plastic part with Pd nanoparticles with particle size of 5-20nm adsorbed on the surface of plastic substrate;
(6) And (5) depositing metal copper on the surface of the plastic base material of the plastic part obtained in the step (5) through chemical plating to obtain the plastic part of the PBT plastic package copper belt material with the copper coating.
The plating solution composition and process conditions of the above electroless plating were the same as in example 1.
Example 4
The embodiment provides a plating process of a PBT plastic package copper insert, which comprises the following steps:
(1) Degreasing and deoiling the PBT base material of the PBT plastic package copper insert, and degreasing and deoxidizing metal copper;
(2) Soaking the PBT plastic package copper insert obtained in the step (1) in an ethanol solution containing 2g/L and 10wt% of formic acid for swelling, wherein the swelling time is 60min, and the temperature is 25 ℃, so as to obtain a plastic part of the swelled PBT plastic package copper strip;
(3) Soaking the plastic part obtained in the step (2) in acetone containing maleic anhydride and benzophenone, taking out after 20min, volatilizing the acetone, and carrying out ultraviolet irradiation grafting modification by using an ultraviolet mercury lamp with power of 2000W to obtain a grafting modified plastic part, wherein the mass ratio of maleic anhydride to acetone is 1;
(4) Cleaning the plastic part obtained in the step (3) by pure water at 90 ℃, soaking the plastic part in an aqueous solution of palladium sulfate/disodium ethylene diamine tetraacetate, wherein the concentration of the palladium sulfate in the solution is 0.1mol/L, the concentration of the disodium ethylene diamine tetraacetate is 0.3mol/L, and the soaking time is 5min, and then washing the plastic part by the pure water to obtain the plastic substrate with Pd adsorbed on the surface 2+ The plastic part of (1);
(5) Adsorbing Pd on the surface of the plastic base material of the plastic part obtained in the step (4) 2+ Reducing with 0.1mol/L ascorbic acid solution to obtain plastic part with Pd nanoparticles with particle size of 5-20nm adsorbed on the surface of plastic substrate;
(6) And (5) depositing metal copper on the surface of the plastic base material of the plastic part obtained in the step (5) through chemical plating to obtain the plastic part of the PBT plastic-packaged copper strip material with the copper coating.
The plating solution composition and process conditions of the above electroless plating were the same as in example 1.
Example 5
The embodiment provides a plating process of a PA46 plastic package copper insert, which comprises the following steps:
(1) Carrying out degreasing and oil removing treatment on a PA46 base material of the PA46 plastic package copper insert, and carrying out degreasing and oxide removing treatment on metal copper;
(2) Soaking the PA46 plastic-packaged copper insert obtained in the step (1) in an ethanol solution containing 2g/L of benzophenone and 10wt% of formic acid for swelling, wherein the swelling time is 20min, and the temperature is 25 ℃, so as to obtain a swollen plastic piece of the PA46 plastic-packaged copper strip;
(3) Immersing the plastic part obtained in the step (2) into an aqueous solution of methacrylic acid containing michelson ketone, and carrying out ultraviolet irradiation grafting modification by using an ultraviolet mercury lamp with the power of 2000W to obtain a grafted and modified plastic part, wherein the mass concentration of the methacrylic acid is 30%, the mass ratio of the michelson ketone to the methacrylic acid is 0.005;
(4) Cleaning the plastic part obtained in the step (3) by pure water at the temperature of 80 ℃, soaking the plastic part in an aqueous solution of palladium acetate/tetramethylenediamine, wherein the concentration of palladium acetate in the solution is 0.02mol/L, the concentration of tetramethylenediamine is 0.3mol/L, the soaking time is 5min, and then washing the plastic part by pure water to obtain the plastic substrate with Pd adsorbed on the surface 2+ The plastic part of (1);
(5) Adsorbing Pd on the surface of the plastic base material of the plastic part obtained in the step (4) 2+ Reducing by stannous chloride solution with concentration of 0.1mol/L to obtain a plastic piece with Pd nano-particles with particle size of 5-20nm adsorbed on the surface of the plastic base material;
(6) And (5) depositing metal copper on the surface of the plastic base material of the plastic part obtained in the step (5) through chemical plating to obtain the plastic part of the PA46 plastic package copper belt material with the copper plating layer.
The plating solution composition and process conditions of the above electroless plating were the same as in example 1.
Example 6
The only difference from example 2 is that the concentration of palladium chloride in step (4) was 0.04mol/L and the concentration of ethylenediamine was 0.15mol/L, and the other conditions were the same as in example 2.
Example 7
The only difference from example 2 is that the concentration of palladium chloride in step (4) was 0.08mol/L and the concentration of ethylenediamine was 1mol/L, and the other conditions were the same as in example 2.
Example 8
The only difference from example 2 is that step (2) was not performed, and the other conditions were the same as example 2.
Comparative example 1
The only difference from example 7 is that in step (4), the concentration of ethylenediamine was 0.16mol/L, the molar ratio of palladium chloride to ethylenediamine was 1.
Comparative example 2
The only difference from example 2 is that in step (4), the concentration of ethylenediamine was 0.8mol/L, the molar ratio of palladium chloride to ethylenediamine was 1.
Comparative example 3
The difference from the embodiment 1 is only that the PA10T plastic-packaged copper strip material is replaced by the PA10T plastic-packaged copper strip material with a pre-plated silver layer on the metal copper in the plastic part, and the thickness of the pre-plated silver layer is 0.2 mu m; in the step (4), the palladium chloride/ethylenediamine solution was replaced with a silver nitrate solution having a concentration of 0.05mol/L, and the other conditions were the same as in example 1.
Comparative example 4
The only difference from example 2 is that in step (4), the palladium chloride/ethylenediamine solution was replaced with a silver nitrate/ethylenediamine solution having a silver nitrate concentration of 0.05mol/L, and the other conditions were the same as in example 2.
Comparative example 5
The only difference from example 2 is that in step (4), the concentration of palladium chloride/ethylenediamine solution was changed to 0.4mol/L by palladium chloride/ethanolamine, and the other conditions were the same as in example 2.
Comparative example 6
The only difference from example 2 is that in step (4), the palladium chloride/ethylenediamine solution was replaced with a palladium chloride solution having a concentration of 0.05mol/L, and the other conditions were the same as in example 2.
The performance of the metal-coated plastic parts provided in the above examples and comparative examples, which were metal-coated by the coating process, was tested as follows:
coating bonding strength: taking the sectional area (S) as 1cm 2 The copper column (or the aluminum column) and the plastic piece with the metal coating are bonded through an adhesive, the mixture is pressurized and cured for 24 hours at room temperature, then the adhesive around the copper column (or the aluminum column) is removed through a knife, and the coating around the copper column (or the aluminum column) is cut off (the plastic base body is cut), so that a sample is obtained. Loading the sample on a tensile machine, performing pull-off experiment with a force perpendicular to the surface of the plated part until the metal coating is separated from the plastic substrate, recording the tensile value (N), and calculating to obtain the peel strength F r ：
F H ＝N/S；
F r ＝F H ·σ 3/4 /5.5；
Wherein, F H The pull-off strength (N/cm) of the plastic coating 2 )，F r Is the peel strength (N/cm) of the plastic coating, and σ is the thickness (cm) of the metal layer to be peeled;
in the present case, the peel strength of the metal layer and the plastic substrate can be quantitatively regarded as the bonding strength of the plating layer.
Bonding strength of a hot stamping circulating plating layer at-55 ℃ to +125 ℃: and (2) sequentially placing the plastic piece with the metal piece and the metal coating at the temperature of minus 55 ℃ for 60 minutes, at the temperature of 25 ℃, for 60 minutes, at the temperature of 125 ℃, for 60 minutes and at the temperature of 25 ℃ for 60 minutes to complete 1-55-125 ℃ warm punching cycle. And (3) performing 5-55 to +125 ℃ warm punching cycles on the plastic part with the metal coating, observing whether the metal coating of the plastic part has bubbles, peeling or other visible deformation and damage, and performing coating bonding strength test on the plastic part subjected to the 5-55 to 125 ℃ warm punching cycles if the metal coating of the plastic part has no visible deformation and damage.
Solvent resistance: and completely immersing the plastic part with the metal coating into acetone for 24h, taking out and airing, and checking whether the metal coating on the surface of the plastic part has bubbles or peels.
The examples and comparative examples provided metal-coated plastic parts that were metal-coated by a plating process and tested as shown in table 1 below:
TABLE 1
From the results in table 1, it can be seen that, by selecting the specific types and molar ratios of the metal ions and the complexes, when the plastic part with metal is subjected to chemical plating, the complexes of the metal ions do not generate a displacement reaction with the metal in the plastic part, the metal in the plastic part does not need to be shielded, the strength and performance of the plastic part are not damaged, and the environment is not damaged, meanwhile, the bonding strength of the metal plating layer and the plastic substrate is high, the bonding strength of the metal plating layer and the plastic is not lower than 20N/cm, and is not lower than 15N/cm after being subjected to warm-punching circulation at-55 ℃ to +125 ℃ for 5 times, and the degree of bonding reduction is not more than 25%. For a plated piece of high-temperature nylon, the bonding strength of the metal plating layer and the high-temperature nylon is not lower than 24N/cm, and is not lower than 20N/cm after the plated piece is subjected to temperature impact cycling for 5 times at minus 55 ℃ to plus 125 ℃, and the degree of reduction of the bonding strength is less than or equal to 20 percent.
In contrast to example 7, if the molar ratio of palladium chloride/ethylenediamine solution is greater than 1 2+ Pd in the palladium chloride/ethylenediamine solution when the metal-bearing plastic part is contacted with the palladium chloride/ethylenediamine solution 2+ The metal in the plastic piece is subjected to replacement reaction, so that the surface state and the electrical performance of the metal are influenced, and the strength and the performance of the plastic piece are damaged; if the molar ratio of palladium chloride/ethylenediamine solution is less than 1 2+ Too large concentration ratio affects the ion adsorption speed and the metal ion capturing capability of carboxyl, slight plating leakage occurs, and the binding force of a plating layer is poor.
In comparison with example 1, if the metal in the plastic part is pre-coated with silver (comparative example 3), the palladium chloride/ethylenediamine solution is replaced by silver nitrate solution and the plastic part is coated with silver nitrate solutionMetal will still be mixed with Ag + A substitution reaction occurs, which affects the surface state of the metal and increases the production cost. In comparison with example 2, if palladium chloride is replaced by silver nitrate (comparative example 4), ag in solution + Will react with the metal in the plastic part to affect the surface state of the metal; if the ethylenediamine solution was replaced with an ethanolamine solution of the same concentration (comparative example 5), pd 2+ The metal plating layer is not easy to be adsorbed on the surface of the plastic piece, and the finally formed metal plating layer is incomplete; if the palladium chloride/ethylenediamine solution is replaced by PdCl with the same concentration 2 Solution (comparative example 6), pdCl 2 The solution has a large amount of free Pd 2+ The solution is unstable and is easy to generate black precipitates, and the solution can be used as a plastic piece with metal and PdCl 2 Pd in the solution when the solution is contacted 2+ The metal in the plastic piece is subjected to replacement reaction, so that the surface state and the electrical performance of the metal are influenced, and the strength and the performance of the plastic piece are damaged.
In conclusion, the plating performance of the part prepared by the process which does not need chemical roughening or mechanical roughening, does not need to protect the metal material part and can prevent metal replacement obtains excellent effect. And is suitable for continuous industrial production of certain parts.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (23)
1. A process for plating a plastic part with a metal, the process comprising the steps of:
(1) Grafting an unsaturated monomer which has a functional group for adsorbing and complexing metal ions and can react with the plastic substrate on the surface of the plastic substrate with metal, and initiating polymerization to obtain a grafted and modified plastic part;
(2) Contacting the plastic part obtained in the step (1) with a reduced complex solution of metal ions with catalytic activity to obtain the plastic part with the metal ions adsorbed on the surface of the plastic substrate;
(3) Reducing the metal ions adsorbed on the surface of the plastic base material of the plastic part obtained in the step (2) to obtain the plastic part with metal nano particles adsorbed on the surface of the plastic base material;
(4) Depositing metal on the surface of the plastic base material of the plastic part obtained in the step (3) to obtain the plastic part with a metal coating;
wherein the metal ion is Pd 2+ ；
The complex is selected from any one or a combination of at least two of ethylenediamine, disodium ethylene diamine tetraacetate, tetramethylenediamine and diethylenetriamine;
the molar ratio of the metal ion to the complex is 1;
the metal carried on the plastic part in the step (1) is any one or the combination of at least two of copper, copper alloy and silver;
the plastic base material of the plastic part is any one or the combination of at least two of PA, PBT and PP; the functional group for adsorbing the complex metal ions in the step (1) is carboxyl and/or anhydride;
the unsaturated monomer in the step (1) is selected from any one of acrylic acid, maleic anhydride, acrylamide and methacrylic acid or the combination of at least two of the acrylic acid, the maleic anhydride, the acrylamide and the methacrylic acid;
the deposition method in the step (4) is chemical plating.
2. A process for coating a metal-loaded plastic part according to claim 1, wherein the grafting in step (1) is performed by any one or a combination of at least two of uv light-initiated plastic surface grafting modification, thermal-initiated plastic surface grafting modification, plasma plastic surface grafting modification and radiation plastic material surface grafting modification.
3. A process for coating a metal-coated plastic part according to claim 1 wherein the step (1) initiates polymerization of the unsaturated monomer by a first initiator.
4. A process for plating a metal-loaded plastic part according to claim 3, wherein the first initiator is benzophenone and/or michael's ketone.
5. A process for coating a metal-loaded plastic part according to claim 3, wherein the polymerization time is 5-10 min.
6. A process for plating a metal-bearing plastic part according to claim 1, wherein the complex is ethylenediamine.
7. A process for plating a metal loaded plastic part according to claim 1 wherein the concentration of metal ions in the metal ion complex solution is 0.02 to 0.1mol/L.
8. A process for plating a metal-loaded plastic part according to claim 1, wherein the concentration of the complex in the solution of the metal ion complex is 0.15 to 1mol/L.
9. A process for plating a metal-loaded plastic part according to claim 1, wherein the reduction in step (3) is by a reducing agent or catalyzed by a catalyst under uv light.
10. A process for plating a metal-loaded plastic part according to claim 9, wherein the reducing agent is selected from any one or a combination of at least two of sodium borohydride, stannous chloride and ascorbic acid.
11. A process for coating a metal-loaded plastic part according to claim 9, wherein the catalyst is potassium chloride and/or sodium formate.
12. A process for coating a metal-loaded plastic part according to claim 1, wherein the metal deposited in step (4) is copper and/or nickel.
13. A process for plating a metal-bearing plastic part according to claim 1, further comprising pretreating the plastic part prior to step (1).
14. A process for plating a metal-loaded plastic part according to claim 13, wherein the pre-treatment comprises degreasing the plastic substrate surface of the plastic part and degreasing and deoxidizing the metal on the plastic part.
15. A process for plating a metal-loaded plastic part according to claim 13, further comprising swelling the pretreated plastic part with an organic solvent between the pretreating and step (1).
16. A process for plating a metal-loaded plastic part according to claim 15, wherein the organic solvent is formic acid and/or ethanol.
17. A process for plating a metal on a plastic part according to claim 15 wherein the organic solvent includes a second initiator.
18. A process for plating a metal-bearing plastic part according to claim 17, wherein the second initiator is a photoinitiator or a thermal initiator.
19. A process for plating a metal loaded plastic part according to claim 18 wherein the second initiator is benzophenone and/or michael's ketone.
20. A process for coating a metal-loaded plastic part according to claim 15, wherein the swelling time is 10-60min.
21. A process for coating a metal-loaded plastic part according to claim 1, further comprising cleaning the plastic part obtained in step (1) prior to performing step (2).
22. A process for coating a plastic part with a metal according to claim 21, wherein the cleaning is carried out by pure water.
23. A process for coating a plastic part with a metal according to claim 22, wherein the pure water is at a temperature of 60-90 ℃.
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| EP0340513A1 (en) * | 1988-04-29 | 1989-11-08 | Bayer Ag | Metallising process |
| CN101509130A (en) * | 2009-03-12 | 2009-08-19 | 浙江大学 | Method for producing film metal fine device on PDMS surface |
| CN101654775A (en) * | 2008-08-21 | 2010-02-24 | 比亚迪股份有限公司 | Chemical plating material and preparation method thereof |
| CN102400115A (en) * | 2011-10-20 | 2012-04-04 | 复旦大学 | Preparation method of flexible copper electrode pattern in micron level wire width |
| CN103525154A (en) * | 2013-09-29 | 2014-01-22 | 哈尔滨工业大学 | Ion metallic paint for electroless copper plating pretreatment of plastic matrix and process |
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| EP0340513A1 (en) * | 1988-04-29 | 1989-11-08 | Bayer Ag | Metallising process |
| CN101654775A (en) * | 2008-08-21 | 2010-02-24 | 比亚迪股份有限公司 | Chemical plating material and preparation method thereof |
| CN101509130A (en) * | 2009-03-12 | 2009-08-19 | 浙江大学 | Method for producing film metal fine device on PDMS surface |
| CN102400115A (en) * | 2011-10-20 | 2012-04-04 | 复旦大学 | Preparation method of flexible copper electrode pattern in micron level wire width |
| CN103525154A (en) * | 2013-09-29 | 2014-01-22 | 哈尔滨工业大学 | Ion metallic paint for electroless copper plating pretreatment of plastic matrix and process |
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