Patent Application
20130153407
1. Field of the Invention
The present invention relates to a method of forming a metal composite layer on an engineering plastic surface, in particular to a full-dry method of preparing a sandwich composite coating on an engineering plastic surface.
2. Description of Related Art
Products featuring high corrosion, abrasion resistance, flat mirror-surface and decoration can be produced by wet plating a plastic surface, and plastic metallization (plated Cu/Ni/Cr metal film) has been used extensively for a long time. However, the wet plating technology has the following drawbacks: (1) consuming much water and power and producing a large quantity of wastewater; (2) using toxic chemical electrolytes and additives; (3) discharging toxic waste gases; (4) consuming a large quantity of metal; (5) using hexavalent chromium which is harmful to human health; and (6) requiring a high-standard substrate surface, and providing a limited scope of applicability. Obviously, this prior art causing tremendous environmental pollutions and hazards requires improvements. Related researchers and manufacturers spare no effort to improve the conventional wet plating technology and achieve some preliminary results. The dry coating technology is well developed, and its applications have substituted some of the plastic plated products. In an automobile wheel cap coating method as disclosed in P.R.C. Pat. No. CN 101338409, the method comprises pre-processing, primer paint curing, ion-bombardment chromium plating, and finish paint light curing steps. The patented invention adopts a dry coating method to substitute the traditional wet electroplating method and an aluminum layer to substitute the traditional Ni—Cu—Cr metal coating. The dry coating method has the advantages of using no toxic matters, requiring no waste treatments, involving a simple manufacturing process, as well as causing no environmental pollution. In addition, the dry coating method has less bad impacts on workers' health since the workers can work under better working conditions. The method does not require any use of noble metals such as copper, nickel and chromium, but just uses a small quantity of aluminum and incurs a significantly lower cost, an easier technique, and a simpler manufacturing procedure. In this method, the power consumption is approximately equal to ⅕˜ 1/7 of that of the electroplating method, the water consumption is approximately equal to 1/10˜ 1/20 of that of the electroplating method, and the overall production cost is approximately equal to ½ of that of the electroplating method. Obviously, the method of the present invention is cost-effective and improves the conventional dispersing and mixing techniques by adding nano ceramic particles into a light curing finish paint material to enhance the surface abrasion resistance.
A surface treatment method applicable for metals and non-metals was disclosed in P.R.C. Pat. No. CN1468976, this patented technology overcomes the serious environmental pollution problem of the conventional surface treatment method, but the products so produced have the drawbacks of poor corrosion resistance and low surface luster. As a result, a conductive fixed rack is developed for positioning objects, and the objects are fixed onto the fixed rack, wherein a primer film is coated onto the objects, and then vacuumed and electroplated to form a metal plated layer. The fixed rack together with the objects are electrically coated, so that the surface of the plated layer becomes an acrylic layer having high corrosion resistance and abrasion resistance to overcome the existing problems of the conventional surface treatment method. The aforementioned dry coating also adopts an electrophoretic coating as the finish paint. However, the dry coating technology still has the following problems and drawbacks:
The objective of the present invention is to overcome the drawbacks of the conventional dry coating method by providing an environmentally friendly and water-saving method of preparing a sandwich composite coating on an engineering plastic surface, and the method can achieve the effects of improving the function and quality of a plastic coated metal product, lowering the production cost, and using no liquid water in the entire manufacturing process.
The method of the present invention comprises the following steps:
(1) A plastic blank is dry cleaned and activated. In the step (1), the plastic blank is made of thermoplastic or thermosetting plastic, and the thermoplastic is one selected from the group of ABS, PC/ABS, HIPS, PC, PPO, PP, PBT, PPS, PERT, HDPE, PA6, PA66, ABS/TPU and PMMA and fiberglass reinforced ABS, PC/ABS, HIPS, PC, PPO, PP, PBT, PPS, PERT, HDPE, PA6, PA66, ABS/TPU, and PMMA, and the thermosetting plastic is BMC. In the dry cleaning of the plastic blank, the plastic blank is wiped by a dry cloth and then placed into an electrostatic dust remover to blow away the dust. In the activation process, the cleaned plastic blank is transferred into a physical vapor deposition (PVD) furnace and processed by a plasma gas glow activation.
(2) The activated plastic blank is placed into the PVD furnace and a metal basal film is formed on the activated plastic blank.
In the step (2), the metal is one selected from the group of copper, nickel, chromium, aluminum, stainless steel, zirconium and titanium, and metal compounds of copper, nickel, chromium, aluminum, stainless steel, zirconium and titanium. The metal basal film layer has a thickness falling within a range of 0.05˜3 μm. The metal basal film M1 of the activated plastic blank has a vacuum pressure of 5×10−3 Pa, and the time for coating metal on the basal film layer falls within a range of 5˜60 min. The metal is coated onto the basal film layer by sputtering, arc plating or evaporation deposition.
(3) A plasma activation of the plastic blank is performed after the metal is coated onto the basal film layer, and then an organic coating is sputtered.
In the step (3), the organic coating has a thickness falling within a range of 5˜60 μm, and the organic coating is sputtered by the following method:
After the ion source in the PVD furnace is turned on, a protective gas is passed, and a plasma glow activation of the metal basal film layer is performed, the plastic blank is removed from the PVD furnace and transferred to a spray rotating line and sputtered with a light curing paint (UV) or baked paint layer, and then sent into an infrared oven for leveling and baking dry the spray paint layer, and the plastic blank is placed in an ultraviolet curing furnace and processed by a radiation curing crosslink or thermal curing crosslink.
The protective gas can be nitrogen, argon or oxygen; the plasma glow activation time falls within a range of 2˜10 min; the paint layer has a thickness falling within a range of 5˜60 μm; the baking temperature falls within a range of 40˜80° C.; the baking time falls within a range of 3˜10 min; the radiation curing crosslink time falls within a range of 10˜45 s; the thermal curing crosslink temperature falls within a range of 70˜180° C., the thermal curing crosslink time falls within a range of 10˜90 min; and the organic coating is sputtered by a liquid spray, electrophoretic deposition or powder spray method.
(4) The plastic blank obtained from the Step (3) is placed into PVD and coated with a metal film layer to obtain a metalized engineering plastic product.
In the step (4), the metal film layer has a thickness falling within a range of 0.05˜3 μm; the metal is copper, nickel, chromium, aluminum, stainless steel, zirconium or titanium, or a metal compound of copper, nickel, chromium, aluminum, stainless steel, zirconium or titanium; and the metal film layer is coated by a method as described below:
The plastic blank is transferred into a PVD furnace, an ion source is turned on, a protective gas is passed over, a plasma glow activation of the cured spray paint layer is performed; the ion source is turned off, an arc target is turned on, and a sputtering of the target or a steam source is supplied for coating a metal film.
The protective gas can be nitrogen, argon or oxygen; the plasma glow activation time falls within a range of 2˜10 min; and the chromium arc plating time falls within a range of 5˜60 min.
Since the coating of the present invention includes two metal layers, and an organic coating included between the two metal layers, the coating of the invention is called a sandwich composite coating, wherein the organic coating is provided for leveling the surface of the blank and covering defects formed on the surface of the blank to improve the luster of the product. Therefore, the present invention can be used to substitute the conventional wet electroplating method.
Tests show that the metalized engineering plastic product produced in accordance with the present invention not only has the advantages of being corrosion resistant, abrasion resistant, weather resistant, temperature resistant and ability to be multiple colors, but also provides a hard smooth surface with a quality comparable to the plastic products produced by the conventional wet electroplating, dispelling the need for roughening via conventional wet electroplating, and activation via a water rinsing process, and no harmful electrolytes are used, particularly the toxic hexavalent chromium. In addition, the invention consumes a small quantity of metal, discharges insignificant waste gas, and results in no release of wastewater in the process. The invention provides an economic and environmentally friendly coating technology to open up the field of plastic metallization and produce plated products with excellent functions and good appearance. The invention is suitable for the sanitary ware, electronics, electric appliance and automobile industries.
The invention, as well as its many advantages, may be further understood by the following detailed description and a related drawing in which:
In the first preferred embodiment, a chromium plated PC/ABS mirror casing is provided for the illustration of the present invention.
(1) A blank is formed by injecting PC/ABS for the injection molding, and sent into a physical vapor deposition (PVD) furnace and rinsed and activated by a plasma source glow (provided that the current is 0.3 A, the bias voltage is 100V, the flow of argon is 30 SCCM, the flow of oxygen is 20 SCCM, the vacuum pressure inside the furnace is 0.1 Pa, and the activation time is 5 min).
(2) The arc target in the PVD furnace is turned on, chromium is plated on a surface of a PC/ABS blank (provided that the current of the target source is 60 A, the bias voltage is 100V, the flow of argon is 50 SCCM, the vacuum pressure inside the furnace is 0.1 Pa, and the chromium plating time is 12 min).
(3) After the metal basal film is plated with chromium, the surface of the blank is activated by plasma (provided that the current of the ion source is 0.3 A, the bias voltage is 100V, the flow of the working gases is a mixed flow of Ar2 and O2, and the activation time is 5 min).
(4) Empty the blank from the furnace, and spray a UV paint of 10 μm thick onto the blank, and bake the painted layer by an IR lamp at 60° C. for 5 min. and then cure the blank by an UV lamp at 1000 J/m2×20 s.
(5) The photo-cured blank is transferred into the PVD furnace and processed by a plasma gas activation (provided that the current of the ion source is 0.3 A, the bias voltage is 100V, the vacuum pressure inside the furnace is 0.2 Pa, the flow of the working gases is a mixed flow of Ar2 and O2, the mixing ratio is 50 SCCM:50 SCCM, and the activation time is 5 min); and then a 0.2 μm-thick Cr layer is coated onto the paint surface (wherein the arc plating conditions include: the current of the chromium target is 60 A, the bias voltage is 100V, the flow of Ar2 is 30 SCCM, the vacuum pressure is 0.2 Pa, and the coating time is 20 min).
The product produced by this technology has a smooth and flat surface and passes the following functional tests:
(A) CASS Corrosion Resistance: 8 h;
(B) Thermal Shock Loop: 4 loops;
(C) Falling Sand Impact: 12 L of falling sand;
(D) Adhesion (Cross Cut): 5 A;
(E) Water immersion at 38° C.: 24 h;
(F) Pencil Hardness (Mitsubishi): 2H;
(G) RCA Abrasion Resistance Test: 450 times.
In the second preferred embodiment, an ABS plated nickel mirror frame is used as an example.
(1) ABS is injected to form a blank, and the blank is sent into a PVD furnace and processed by plasma gas rinsing (provided that the current of the ion source current is 1 A, the bias voltage is 100V, the vacuum pressure is 0.1 Pa, the working gas is 50 SCCM of Ar2, and the activation time is 3 min).
(2) A mid-frequency nickel target is provided in the PVD furnace, and nickel is plated onto a surface of the plastic blank (provided that the current of the target power is 10 A, the bias voltage is 90V, the vacuum pressure is 0.1 Pa, and the flow of the working gases is a mixed flow of 30 SCCM of Ar2 and 20 SCCM of O2, and the time for plating nickel is 10 min).
(3) A plasma activation of the surface of the plastic blank is performed after nickel is plated (onto the metal basal film) (provided that the current of the ion source is 1 A, the bias voltage is 90V, the flow of the working gas is a mixed flow of Ar2 and N2, the mixing ratio is 50 SCCM:50 SCCM, the vacuum pressure is 0.2 Pa, and the activation time is 5 min).
(4) The blank is removed from the furnace, and sprayed with a 25 μm-thick layer of UV paint. An IR lamp is used to bake the painted layer at 60° C. for 5 min, and then an UV lamp is used for curing (1100 J/m2×25 s).
(5) The light-cured blank is transferred and hung in a PVD furnace and processed by a plasma gas activation (provided that the current of the ion source is 1 A, the bias voltage is 100V, the vacuum pressure inside the furnace is 0.2 Pa, the flow of the working gas is a mixed flow of Ar2 and N2, the mixing ratio is 50 SCCM:50 SCCM, and the activation time is 5 min). An imitation nickel surface with a thickness of 0.1 μm is coated onto the painted surface (wherein the imitation nickel coating conditions include: the current of the zirconium target is 70 A, the bias voltage is 100V, the vacuum pressure of passing 300 SCCM of N2 and 100 SCCM of Ar2 is 0.5 Pa, and the time of coating the film is 10 min).
The product produced according to the aforementioned technology has a shiny mirror surface and passes the following functional tests:
(A) CASS Corrosion Resistance: 8 h;
(B) Thermal Shock Loop: 4 loops;
(C) Falling Sand Impact: 12 L of falling sand;
(D) Adhesion (Cross Cut): 5 B;
(E) Water immersion at 38° C.: 24 h;
(F) Pencil Hardness (Mitsubishi): 2H;
(G) RCA Abrasion Resistance Test: 450 times.
In the third preferred embodiment, a BMC thermosetting plastic blank of a refrigerator handle coated with stainless steel is used as an example.
(1) BMC is injected to form a blank, and the blank is placed into a PVD furnace and processed by an ion source glow rinsing and activation (provided that the current of the ion source is 1 A, the bias voltage is 100V, the gases used are 50 SCCM of N2 and 50 SCCM of Ar2, the vacuum pressure is 0.2 Pa, and the activation time is 5 min).
(2) An arc target in the PVD furnace is turned on, and chromium is plated on a surface of the BMC blank (provided that the current of the target source is 50 A, the bias voltage is 100V, the flow of Ar2 is 50 SCCM, the vacuum pressure is 0.1 Pa, and the chromium plating time is 10 min).
(3) A plasma activation is performed at the surface of the plastic blank which is coated with chromium (metal basal film) (provided that the current of the ion source is 2 A, the bias voltage is 100V, the flow of the working gas is a mixed flow of Ar2 and O2, the mixing ratio is 50 SCCM:50 SCCM, the vacuum pressure is 0.2 Pa, and the activation time is 5 min).
(4) The blank is removed from the furnace and sprayed with a 60 μm-thick powder layer. The coated powder layer is cured in an oven at 160° C. for 20 min).
(5) The thermal cured blank is transferred into the PVD furnace and processed by a plasma gas activation (provided that the current of the ion source is 2 A, the bias voltage is 100V, the vacuum pressure inside the furnace is 0.3 Pa, the flow of the working gas is a mixed flow of Ar2 and N2, the mixing ratio is 50 SCCM:50 SCCM, and the activation time is 5 min), and then an 1 μm-thick metal (stainless steel) layer is plated onto the powder coating (wherein the conditions of plating the stainless steel layer include: the current of the sputtered stainless steel target is 10 A, the bias voltage is 100V, the flow of Ar2 is 50 SCCM, the vacuum pressure is 0.1 Pa, and the coating time is 40 min).
The product produced according to the aforementioned technology has a smooth flat surface and passes the following functional tests:
(A) CASS Corrosion Resistance: 64 h;
(B) Thermal Shock Loop: 8 loops;
(C) Falling Sand Impact: 12 L of falling sand;
(D) Adhesion (Cross Cut): 4 A;
(E) Water immersion at 38° C.: 24 h;
(F) Pencil Hardness (Mitsubishi): 3H;
(G) RCA Abrasion Resistance Test: 500 times
In the fourth preferred embodiment, an application on a fiberglass reinforced PPO plastic substrate free of lead and copper is used as an example for the illustration of the invention.
(1) A blank made of the fiberglass reinforced (40%) PPO by plastic molding is sent into a PVD furnace, and processed by plasmas glow rinsing and activation (provided that the current of ion source is 1 A, the bias voltage is 160V, the vacuum pressure is 0.2 Pa, the gases are 50 SCCM of Ar2 and 50 SCCM of O2, and the activation time is 5 min).
(2) A mid-frequency sputtering source in the PVD furnace is turned on, and a copper-zinc (Cu/Zn) alloy target (having a zinc content of 40%) is used and spattered onto a surface of the fiberglass reinforced PPO blank (provided that the current of the target source is 10 A, the bias voltage is 110V, the vacuum pressure inside the furnace is 0.1 Pa, the gas is 50 SCCM of Ar2, and the time of coating the alloy is 15 min).
(3) A plasma activation of the surface of the copper alloy plated (which is the metal basal film) plastic blank is conducted (provided that the current of the ion source is 1 A, the bias voltage is 160V, the vacuum pressure inside the furnace is 0.1 Pa, and the activation time is 5 min).
(4) The blank is removed from the furnace, a layer of 45 μm-thick UV powder is sprayed, and an IR lamp is used to bake the paint layer at 120° C. for 5 min, and then a UV lamp is used to cure the blank (at 1100 J/M2×40 s).
(5) The cured blank is transferred into the PVD furnace and a plasma gas activation is carried out (provided that the current of the ion source is 1 A, the bias voltage is 160V, the vacuum pressure inside the furnace is 0.2 Pa, the flow of the working gas is a mixed flow of Ar2 and N2, the mixing ratio is 50 SCCM:50 SCCM, and the activation time is 5 min), and then a 0.5 μm-thick Cu/Zn alloy layer is coated onto the paint layer (wherein the conditions of the mid-frequency sputtering include: the current of the alloy target is 10 A, the bias voltage is 110V, the flow of Ar2 is 30 SCCM, the vacuum pressure is 0.1 Pa, and the coating time is 35 min).
The product produced according to the aforementioned technology has a smooth flat surface and passes the following functional tests:
(A) CASS Corrosion Resistance: 16 h;
(B) Thermal Shock Loop: 4 loops;
(C) Falling Sand Impact: 12 L of falling sand;
(D) Adhesion (Cross Cut): 5 B;
(E) Water immersion at 38° C.: 24 h;
(F) Pencil Hardness (Mitsubishi): 2H;
(G) RCA Abrasion Resistance Test: 500 times.
In the fifth preferred embodiment, a chromium plated faucet made of PA6 and added with fiberglass powder (enhanced PA6) is used as an example for illustrating the invention.
(1) A blank made of enhanced PA6 by injection molding is placed in a PVD furnace and processed by plasma glow rinsing and activation (provided that the current of the ion source is 1 A, the bias voltage is 100V, the flow of gases is a mixed flow of 50 SCCM of Ar2 and 50 SCCM of O2, the vacuum pressure is 0.2 Pa, and the activation time is 5 min).
(2) An arc target in the PVD furnace is turned on, and chromium is coated on the surface of the enhanced PA6 blank (provided that the current of the target power source is 100 A, the bias voltage is 100V, the vacuum pressure is 0.2 Pa, the gas is 50 SCCM of Ar2, and the chromium coating time is 20 min).
(3) A plasma activation of the chromium coating (which is the metal basal film) at the surface of the blank is conducted (provided that the current of the ion source is 2 A, the bias voltage is 100V, the flow of the working gases is a mixed flow of Ar2 and O2, the mixing ratio is 50 SCCM:50 SCCM, the vacuum pressure is 0.2 Pa, and the activation time is 5 min).
(4) A layer of 40 μm-thick electrophoretic paint is coated by electrophoretic deposition. The electrophoretic painted layer is baked and cured at 140° C. for 20 min in an oven.
(5) The thermally cured blank is transferred into the PVD furnace and processed by a plasma gas activation (provided that the current of the ion source is 2 A, the bias voltage is 100V, the flow of the working gas is a mixed flow of Ar2 and N2, the mixing ratio is 50 SCCM:50 SCCM, the vacuum pressure inside the furnace is 0.2 Pa, and the activation time is 5 min), and then a layer of 0.5 μm-thick metal (Cr/Ni/Cr) is coated onto the electrophoretic paint layer (wherein the conditions of arc plating the chromium include: the current of chromium target and nickel target is 50 A, the bias voltage is 100V, the gas is 50 SCCM of Ar2, the vacuum pressure is 0.2 Pa, the coating time is 20 min, the chromium coating time is 10 min).
The product produced according to the aforementioned technology has a smooth flat surface and passes the following functional tests:
(A) CASS Corrosion Resistance: 24 h;
(B) thermal shock loop: 4 loops;
(C) Falling Sand Impact: 12 L of falling sand;
(D) Adhesion (Cross Cut): 5 B;
(E) Water immersion at 38° C.: 24 h;
(F) Pencil Hardness (Mitsubishi): 3H;
(G) RCA Abrasion Resistance Test: 500 times.
The aforementioned function tests include:
1. Corrosion Resistance Function Tests:
2. Abrasion Resistance Function Test:
3. Adhesion Tests:
4. Weather Resistance Test:
5. Water Resistance Test:
6. Scratch Resistance Tests:
7. Chemical Resistance Test
Many changes and modifications in the above described embodiment of the invention can, of course, be carried out without departing from the scope thereof. Accordingly, to promote the progress in science and the useful arts, the invention is disclosed and is intended to be limited only by the scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201010585736.1 | Dec 2010 | CN | national |
