CN111197160A

CN111197160A - Method for forming copper metal layer on surface of non-metal material

Info

Publication number: CN111197160A
Application number: CN201811381803.0A
Authority: CN
Inventors: 古莞霖; 陈家庆; 张国兴; 赖中平
Original assignee: BGT Materials Ltd
Current assignee: BGT Materials Ltd
Priority date: 2018-11-20
Filing date: 2018-11-20
Publication date: 2020-05-26

Abstract

The invention provides a method for forming a copper metal layer on the surface of a non-metal material, which comprises the following steps: preparing carbon-based electroless plating catalyst (or catalyst) ink, wherein the ink at least comprises a carbon powder material containing an oxygen functional group; spraying carbon-based chemical plating catalyst ink on the surface of a non-metal material and then drying the carbon-based chemical plating catalyst ink; soaking the non-metal material with the carbon-based chemical plating catalyst ink on the surface in a chemical plating solution, and further forming a copper metal layer on the carbon-based chemical plating catalyst ink; the method can provide a substitute scheme for the catalyst used in the existing electroless copper plating process, realizes the aim of not using hexavalent chromium and palladium as the catalyst, and has the advantages of environmental protection, low cost and time saving.

Description

Method for forming copper metal layer on surface of non-metal material

Technical Field

The invention relates to the field of Chemical Plating (Chemical Plating) process, in particular to a method for forming a copper metal layer on the surface of a non-metal material.

Background

Electroplating has been widely used in industries on non-metallic materials (plastics, ceramics, glass, wood, etc.), and techniques of electroplating on non-metallic materials have been widely used in many products and industries such as automobiles, consumer goods, pipes, toys, foods and beverages, and cosmetics, because of the characteristics of corrosion resistance, toughness, wear resistance, and aesthetic appearance of the electroplated surfaces.

Electroless Plating (Electroless Plating), which is a metal Plating technique in which metal ions in an Electroless Plating solution are reduced to metal by an oxygen reduction reaction with the use of a suitable reducing agent without an external current and deposited on the surface of an activated part, is also known as chemical Plating. Firm electroplated metal is formed on the surface of the non-metallic material, and the non-metallic material needs to pass through a pretreatment step to enhance the adhesion of the electroplated metal on the surface of the non-metallic material.

Conventional electroplating procedures for non-metallic materials generally involve two steps: surface pretreatment and metal plating. Surface preparation involves several chemical treatments and reaction procedures, such as cleaning (cleaning), etching (etching), sensitization (sensitization), activation (activation) and acceleration (incubation). The surface is roughened using a strong oxidizing agent such as Chromium trioxide (Chromium trioxide) and sulfuric acid mixtures to obtain good mechanical adhesion, as well as creating microvoids to act as adhesion sites between the metal and the substrate.

The prior art pretreats the surface of non-metallic materials with a mixture of chromium trioxide, sulfuric acid and water, or a mixture of these inorganic components and phosphoric acid. However, this method has many disadvantages in that hexavalent chromium contained in the pretreatment solution is a carcinogen with genetic toxicity, and has a high risk. Workers exposed to hexavalent chromium are at risk of suffering lung cancer, asthma or damage to the nasal epithelium and skin. The use of hexavalent chromium may cause long-term environmental pollution and is widely banned in the electronics industry in the united states, europe and china. At the same time as the neutralization, large amounts of chromium hydroxide are formed, which treatment considerably hinders the removal of the compositions used. Furthermore, the pretreatment solution of the known method is very corrosive and requires a large amount of water to completely remove it from the surface of the non-metallic material. In addition, the conventional surface pretreatment process before electroplating is complicated and time-consuming. Because of the treatment of the pretreatment solution and the composition used therewith, it is necessary to reduce the hexavalent chromium compounds and to neutralize the reduction products in order to make it easier to treat the used pretreatment solution.

Disclosure of Invention

The invention aims to provide a method for forming a copper metal layer on the surface of a non-metal material.

The present invention has found that a functional carbon powder material can be used as a catalyst for electroless copper plating, and based on solving the above-mentioned technical problems, the present invention provides a preferable method for forming a copper metal layer on the surface of a non-metallic material, comprising the steps of: a method of forming a copper metal layer on a surface of a non-metallic material, comprising: preparing carbon-based chemical plating catalyst ink; spraying the carbon-based chemical plating catalyst ink on the surface of a non-metal material and then drying the carbon-based chemical plating catalyst ink; and soaking the non-metal material with the carbon-based chemical plating catalyst ink on the surface in a chemical plating solution, thereby forming a copper metal layer on the carbon-based chemical plating catalyst ink.

Wherein the non-metallic material comprises: any one of plastic, ceramic, wood, glass, and cloth.

The carbon-based electroless plating catalyst ink is a mixture consisting of a functional carbon powder material, a dispersant, a thickener (thicker) and a solvent.

Wherein the functional carbon powder material is a carbon powder material containing an oxygen functional group, and the oxygen content of the carbon powder material containing an oxygen functional group is 5 to 50 wt% of the carbon powder material containing an oxygen functional group.

Wherein the functional carbon powder material is further doped with any one or a combination of nitrogen (N), sulfur (S), boron (B), fluorine (F) and phosphorus (P), and the functional carbon powder material contains the combination of elements in an amount of 1 to 20 wt% of the functional carbon powder material.

Wherein the carbon powder material containing an oxygen functional group is an oxide of any one of graphene, graphite, carbon nanotubes, carbon black and activated carbon.

Wherein the content of the carbon powder material containing oxygen functional groups is 0.5 wt% to 30 wt% (weight percentage) of the mixture. The content of the dispersant is 0.05 wt% to 20 wt% (weight percentage) of the mixture, and the dispersant can be an ionic dispersant or a non-ionic dispersant. The solvent can be selected from organic, inorganic or aqueous systems, and the content of the solvent is 30 to 90 weight percent (weight percentage) of the mixture.

Wherein the components of the carbon-based electroless plating catalyst ink include a binder (adhesive) made of a polymer, a resin and a binder, and the content of the binder is 0.1 wt% to 30 wt% of the mixture.

Wherein the dispersant is an ionic dispersant or a nonionic dispersant, and the solvent is any one or a combination of pure water, an organic solvent and an inorganic solvent.

The method for forming the copper metal layer on the surface of the non-metallic material has the advantages that the method can provide a substitution scheme for the catalyst used in the existing chemical copper plating process, realizes the aim of not using hexavalent chromium and palladium as the catalyst, and has the advantages of environmental protection, low cost and time saving.

Other features and embodiments of the present invention will be described in detail below with reference to the drawings.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a flow chart of the steps of one embodiment of the method of the present invention for forming a copper metal layer on a surface of a non-metallic material;

FIGS. 2A and 2B are schematic views showing the constitution of the method for forming a copper metal layer on the surface of a non-metallic material according to the present invention;

FIG. 3 is a test sample of example 1 of the present invention;

FIG. 4 is a graph of example 2 test samples of the present invention;

FIG. 5 is a sample graph of the test of example 3 of the present invention.

Description of the symbols

10 carbon-based electroless plating catalyst ink

20 non-metallic material 30 copper metal layer

Detailed Description

The positional relationship described in the following embodiments includes: the top, bottom, left and right, unless otherwise indicated, are based on the orientation of the elements in the drawings.

Referring first to fig. 1, a flowchart of steps of a method for forming a copper metal layer on a surface of a non-metal material according to an embodiment of the present invention is shown. The preferred embodiment of the method of the present invention for forming a copper metal layer on a surface of a non-metallic material comprises the steps of:

a. preparing carbon-based chemical plating catalyst ink 10;

b. the carbon-based electroless plating catalyst ink 10 is sprayed (spraying) or coated by printing (printing) on the surface of the non-metallic material 20 (see fig. 2A), wherein the non-metallic material comprises: any one of plastic, ceramic, wood, glass, and cloth;

c. drying the carbon-based electroless plating catalyst ink 10 sprayed on the surface of the non-metallic material 20; and

d. the non-metal material 20 having the carbon-based electroless plating catalyst ink 10 on the surface thereof is immersed in a electroless plating solution, thereby forming a copper metal layer 30 on the carbon-based electroless plating catalyst ink 10 on the surface of the non-metal material 20 (see fig. 2B).

As a preferred embodiment of the method of the present invention for forming a copper metal layer on the surface of a non-metallic material, wherein the carbon-based electroless plating catalyst ink is a mixture consisting of a functional carbon powder material, a dispersant, a thickener (thicker) and a solvent. In a preferred embodiment, the functional carbon powder material is a carbon powder material containing an oxygen functional group, wherein the carbon powder material containing an oxygen functional group is an oxide of any one of graphene, graphite, carbon nanotube, carbon black and activated carbon, and the oxygen content of the carbon powder material containing an oxygen functional group is 5 wt% to 50 wt% of the carbon powder material containing an oxygen functional group.

The mixture as carbon-based electroless plating catalyst ink, wherein the content of the carbon powder material containing oxygen functional groups is 0.5 wt% to 30 wt% (weight percentage) of the mixture. The dispersant is used in an amount of 0.05 to 20 wt% (weight percent) of the mixture, and the dispersant may be an ionic dispersant or a non-ionic dispersant. The solvent can be selected from organic, inorganic or aqueous systems, and the content of the solvent accounts for 30 to 90 weight percent (weight percentage) of the mixture.

As a further preferred embodiment of the method of the present invention for forming a copper metal layer on a surface of a non-metallic material, wherein a functional carbon powder material further doped with any one or a combination of nitrogen (N), sulfur (S), boron (B), fluorine (F) and phosphorus (P) contains the combination of elements in an amount of 1 to 20 wt% of the functional carbon powder material.

As a further preferred embodiment of the method for forming a copper metal layer on a surface of a non-metallic material according to the present invention, the composition of the carbon-based electroless plating catalyst ink further includes a binder (adhesive) made of a polymer, a resin and a binder, and the content of the binder is 0.1 to 30 wt% of the mixture. One of the preferred embodiments includes the use of a resin or polymer as the adhesive and the application of at least one adhesive. It is to be noted that when graphene flakes (graphene flakes) or graphene oxide (graphene oxide) are used as the carbon powder material containing an oxygen functional group, it is not necessary to use any polymer or resin as a binder. The thickener can be prepared into suitable carbon-based electroless plating catalyst ink with the content of 0.01-10 wt% of the mixture.

Example 1

As an example of the method of forming a copper metal layer on a surface of a non-metallic material according to the present invention, the prepared carbon-based electroless plating catalyst ink is sprayed on the surface of the non-metallic material (see fig. 3(a)), and then dried in an oven at 100 ℃ for 20 minutes, and then placed in a plating bath of formaldehyde-based electroless plating solution at 50 to 70 ℃ for 30 to 120 minutes after the completion of drying, thereby obtaining uniform copper deposition on the carbon-based electroless plating catalyst ink (see fig. 3 (B)).

Example 2

As another example of the method for forming a copper metal layer on a surface of a non-metal material according to the present invention, a ceramic material is selected as a non-metal material, and the prepared carbon-based electroless plating catalyst ink is sprayed on the surface of the non-metal material (see fig. 4(a)), and then dried in an oven at 100 ℃ for 20 minutes, and after drying, the carbon-based electroless plating catalyst ink is placed in a plating bath at 50 to 70 ℃ for 30 to 120 minutes, so that uniform copper deposition can be obtained on the carbon-based electroless plating catalyst ink (see fig. 4 (B)).

Example 3

As another example of the method for forming a copper metal layer on a surface of a non-metal material according to the present invention, wood is selected as a non-metal material, and the prepared carbon-based electroless plating catalyst ink is sprayed on the surface of the non-metal material (see fig. 5(a)), and then dried in an oven at 100 ℃ for 20 minutes, and then placed in a plating bath of formaldehyde-based electroless plating solution at 50 ℃ to 70 ℃ for 30 to 120 minutes after drying, so that uniform copper deposition can be obtained on the carbon-based electroless plating catalyst ink (see fig. 5 (B)).

Example 3 test sample photograph

As can be understood from the above listed examples 1 to 3, the method of forming a copper metal layer on a surface of a non-metal material according to the present invention can be applied to various non-metal materials, provides an alternative to a catalyst used in an existing electroless copper plating process, realizes formation of copper metal on a surface of a non-metal material without using hexavalent chromium and palladium as a catalyst, and has the advantages of environmental protection, low cost, and time saving.

The above-described embodiments and/or implementations are only for illustrating the preferred embodiments and/or implementations of the present technology, and are not intended to limit the implementations of the present technology in any way, and those skilled in the art may make modifications or changes to other equivalent embodiments without departing from the scope of the technical means disclosed in the present disclosure, but should be construed as the technology or implementations substantially the same as the present technology.

Claims

1. A method of forming a copper metal layer on a surface of a non-metallic material, comprising:

preparing carbon-based chemical plating catalyst ink;

spraying the carbon-based chemical plating catalyst ink on the surface of a non-metallic material;

drying the carbon-based chemical plating catalyst ink sprayed on the surface of the non-metallic material; and

soaking the non-metal material with the carbon-based electroless plating catalyst ink on the surface in a electroless plating solution, and forming a copper metal layer on the carbon-based electroless plating catalyst ink on the surface of the non-metal material.

2. The method of forming a copper metal layer on a surface of a non-metallic material of claim 1, wherein: the non-metallic material comprises: any one of plastic, ceramic, wood, glass, and cloth.

3. The method of forming a copper metal layer on a surface of a non-metallic material of claim 1, wherein: the carbon-based electroless plating catalyst ink is a mixture consisting of a functional carbon powder material, a dispersant, a thickener and a solvent.

4. The method of claim 3, wherein the step of forming the copper metal layer on the surface of the non-metallic material comprises: the functional carbon powder material is an oxygen functional group-containing carbon powder material, and the oxygen content of the oxygen functional group-containing carbon powder material is 5 to 50 wt% of the oxygen functional group-containing carbon powder material.

5. The method of forming a copper metal layer on a surface of a non-metallic material of claim 4, wherein: the content of the carbon powder material containing the oxygen functional group is 0.5 to 30 weight percent of the mixture; the dosage of the dispersant is 0.05 wt% -20 wt% of the mixture, and the dosage of the solvent is 30 wt% -90 wt% of the mixture.

6. The method of claim 3, wherein the step of forming the copper metal layer on the surface of the non-metallic material comprises: the functional carbon powder material is further doped with any one or a combination of nitrogen, sulfur, boron, fluorine and phosphorus, and the functional carbon powder material contains the combination of the elements in an amount of 1 to 20 wt% of the functional carbon powder material.

7. The method of forming a copper metal layer on a surface of a non-metallic material of claim 4, wherein: the carbon powder material containing an oxygen functional group is an oxide of any one of graphene, graphite, carbon nanotubes, carbon black and activated carbon.

8. The method of claim 3, wherein the step of forming the copper metal layer on the surface of the non-metallic material comprises: the carbon-based electroless plating catalyst ink contains a binder made of a polymer, a resin and a binder in an amount of 0.1 to 30 wt% of the mixture.

9. The method of claim 3, wherein the step of forming the copper metal layer on the surface of the non-metallic material comprises: the dispersant is an ionic dispersant or a nonionic dispersant, and the solvent is any one or a combination of pure water, an organic solvent and an inorganic solvent.