CN111534798A - Base material dry-type surface treatment method and bathroom accessory applying same - Google Patents
Base material dry-type surface treatment method and bathroom accessory applying same Download PDFInfo
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- CN111534798A CN111534798A CN202010241805.0A CN202010241805A CN111534798A CN 111534798 A CN111534798 A CN 111534798A CN 202010241805 A CN202010241805 A CN 202010241805A CN 111534798 A CN111534798 A CN 111534798A
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B1/00—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means
- B05B1/14—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means with multiple outlet openings; with strainers in or outside the outlet opening
- B05B1/18—Roses; Shower heads
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03C—DOMESTIC PLUMBING INSTALLATIONS FOR FRESH WATER OR WASTE WATER; SINKS
- E03C1/00—Domestic plumbing installations for fresh water or waste water; Sinks
- E03C1/02—Plumbing installations for fresh water
- E03C1/04—Water-basin installations specially adapted to wash-basins or baths
- E03C1/0412—Constructional or functional features of the faucet handle
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16K—VALVES; TAPS; COCKS; ACTUATING-FLOATS; DEVICES FOR VENTING OR AERATING
- F16K27/00—Construction of housing; Use of materials therefor
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Public Health (AREA)
- Water Supply & Treatment (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A dry-type surface treatment method for a substrate and bathroom accessories applying the method comprise the steps of cleaning the substrate, spraying ultraviolet curing coating on the surface of the substrate to form a primer layer, baking and leveling by infrared rays, curing the primer layer by ultraviolet irradiation, and carrying out physical vapor deposition on the primer layer. The ultraviolet curing coating comprises polybutadiene resin, an acrylate monomer, a photoinitiator, an aromatic solvent and an alcohol solvent. And the physical vapor deposition is carried out by multi-arc sputtering to deposit at least one metal nitride coating film and at least one metal coating film on the primer layer in sequence. The target material for physical vapor deposition is selected from chromium, aluminum, zirconium or titanium, the current is 65-80A, the voltage is 50-80V, the argon flow rate is 50-92sccm, the nitrogen flow rate is 0-80sccm, the gas flow ratio of argon to nitrogen is 92:0-50:80, the duty ratio is 50-80%, the deposition time is 3-5 minutes, the total thickness of the metal coating film and the metal nitride coating film is 0.02-5 mu m, and the metal coating film accounts for 10-30% of the total thickness.
Description
Technical Field
The present invention relates to a method for treating a surface of a substrate, and more particularly, to a method for treating a surface of a substrate by a dry method and a sanitary fitting using the same.
Background
The water and hardware related industries comprise hardware needed to be used by reservoirs, tap water or household water, such as valves, bolts, pumps and the like of sanitary equipment commonly called as taps, the surfaces of water and hardware products need to have corrosion resistance, so the surfaces of the water and hardware products are mostly treated by a water electroplating process, a large amount of water is needed to be used as an operation interface in the water electroplating process, and the used water often contains a plurality of toxic heavy metals such as nickel, zinc, copper and the like, even contains extremely toxic cyanide and is in a state of strong acid and strong alkali; if the waste water is directly discharged into rivers without being treated, ecological destruction can be caused. The water and electricity plating waste water is also subjected to environmental protection treatment to generate a large amount of sludge containing heavy metals, and the toxic sludge is also hazardous waste, so that the cost for effectively remedying pollution is also high.
Because the dependence of hardware and water related industries on electroplating technology is extremely high, the process of performing hardware and water surface treatment must be replaced by a non-toxic dry process, such as Physical Vapor Deposition (PVD) for aesthetic and corrosion-resistant treatment of the product surface, which is an important issue. Therefore, how to carry out effective and proper-price coating treatment on the surface of the water hardware product is an important technology.
Disclosure of Invention
In summary, the present invention utilizes dry physical vapor deposition to directly deposit the metal coating and the metal nitride coating in alternating layers on the polymer coating on the substrate, so that the final product, such as the surface of various sanitary fittings, has good mechanical properties such as corrosion resistance, wear resistance, etc., and simultaneously solves the problem of waste soil and waste water treatment generated in the water electroplating process.
Therefore, the invention provides a method for dry surface treatment of a substrate, which comprises the following steps. Cleaning a substrate, spraying an ultraviolet curing coating on the surface of the substrate to form a primer layer, baking the primer layer by infrared rays to level, irradiating the cured primer layer by ultraviolet light, and carrying out physical vapor deposition on the primer layer. Wherein, the material of the base material is metal alloy or plastic. The ultraviolet curing coating comprises 20-60% of polybutadiene resin, 20-40% of acrylate monomer, 1-10% of photoinitiator, 10-30% of aromatic solvent and 8-20% of alcohol solvent, wherein the photoinitiator is selected from a group consisting of 4-dimethylamino ethyl benzoate, 2-alkyl-2-methyl-1-phenyl-1-acetone, benzophenone, tertiary amine, dibutyltin dilaurate, triethylene diamine, stannous octoate and zinc naphthenate. The baking temperature of the infrared baking leveling is 30-60 ℃, and the baking time is 3-10 minutes; the ultraviolet irradiation energy is 1500-3000mJ/cm2, and the thickness of the formed primer layer is 10-70 μm. And sequentially depositing at least one metal nitride coating and at least one metal coating on the primer layer by physical vapor deposition through multi-arc sputtering, wherein the target material of the physical vapor deposition is selected from the group consisting of chromium, aluminum, zirconium and titanium. The current of the physical vapor deposition is 65-80A, the voltage is 50-80V, the flow rate of argon is 50-92sccm, the flow rate of nitrogen is 0-80sccm, the gas flow ratio of argon to nitrogen is 92:0-50:80, the duty ratio is 50-80%, the deposition time is 3-5 minutes, the total thickness of the metal nitride coating film and the metal coating film is 0.02-5 mu m, and the metal coating film accounts for 10-30% of the total thickness.
According to an embodiment of the present invention, at least two metal plating films and at least two metal nitride plating films are formed during the physical vapor deposition, and the two metal plating films and the two metal nitride plating films are alternately stacked.
According to another embodiment of the present invention, during the physical vapor deposition, the nitrogen flow is changed in a gradient manner to deposit a plurality of metal nitride films, and then a metal coating film is deposited thereon.
According to another embodiment of the present invention, the method for dry surface treatment of a substrate further comprises coating a coupling agent on the surface of the substrate after cleaning the surface of the substrate. The coupling agent is silane coupling agent, aluminum zirconate coupling agent, titanate coupling agent or phosphated acrylate, and the weight percentage concentration of the coupling agent is 5-50%.
According to another embodiment of the present invention, the method for dry surface treatment of a substrate further comprises spraying a polymer coating on the surface of the metal coating to form a top coating layer, wherein the thickness of the top coating layer is 5-50 μm, and the polymer coating is an ultraviolet curable coating or a perfluoropolyether coating.
According to another embodiment of the present invention, the physical vapor deposition of the substrate dry surface treatment method is performed by multi-arc sputtering and intermediate frequency sputtering, wherein the current is 20-50A, the voltage is 50-100V, the argon flow rate is 50-92sccm, the nitrogen flow rate is 0-50sccm, the duty ratio is 50-80%, and the deposition time is 6-10 minutes.
According to still another embodiment of the present invention, the acrylate monomer in the uv curable coating used in the method for dry surface treatment of a substrate is selected from the group consisting of methyl acrylate, methyl methacrylate, trimethylolpropane triacrylate, isobornyl acrylate, dipropylene glycol diacrylate, dipentaerythritol hexaacrylate and 1, 6-hexanediol diacrylate.
According to another embodiment of the present invention, the aromatic solvent in the uv curable coating used in the above method for dry surface treatment of a substrate is toluene, xylene or dimethylformamide.
According to still another embodiment of the present invention, the alcohol solvent in the uv curable coating used in the method for dry surface treatment of a substrate is ethanol, isopropanol, butanol, diacetone alcohol or glycerol.
According to another embodiment of the present invention, the ultraviolet curable coating used in the method for dry surface treatment of a substrate further includes 5-25% of an ester solvent, wherein the ester solvent is ethyl acetate, ethyl acetate or butyl acetate.
According to another embodiment of the present invention, the uv curable coating used in the above method for dry surface treatment of a substrate further comprises 0.01 to 1% of a leveling agent or 0.01 to 1% of an antifoaming agent.
According to another embodiment of the present invention, the UV-curable coating used in the method for dry surface treatment of a substrate comprises 1-10% of alkyd resin mixed with polybutadiene resin.
The invention also provides a bathroom accessory, which is provided with the base material with the dry surface treatment method, and the surface treatment is carried out on the base material by the dry surface treatment method, wherein the bathroom accessory can be a faucet body, a shower head body or a handle.
Drawings
In order to make the aforementioned and other objects, features, advantages and embodiments of the invention more comprehensible, the following description is given:
FIG. 1 is a schematic cross-sectional view of a final product after physical vapor deposition according to one embodiment of the present invention;
FIG. 2 is a schematic cross-sectional view of a final product after physical vapor deposition according to another embodiment of the present invention;
FIG. 3 is an electron microscope result of a finished product made in accordance with an embodiment of the present invention;
FIG. 4 is an electron microscope image of a finished product made in accordance with another embodiment of the present invention;
FIG. 5 is a schematic view of the finished product obtained by the dry surface treatment method of the present invention, showing the faucet body;
FIG. 6 shows the final product of the substrate dry surface treatment method of the present invention, and shows the final product is a shower body;
FIG. 7 is a schematic representation of the finished product made by the substrate dry surface treatment process of the present invention, and showing the finished product as a handle.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following describes a specific implementation of the present invention in more detail with reference to specific embodiments:
the invention provides a substrate dry surface treatment method, which comprises the following steps. Cleaning a substrate, spraying an ultraviolet curing coating on the surface of the substrate to form a primer layer, baking the primer layer by infrared rays and leveling the primer layer, irradiating the primer layer by ultraviolet light and curing the primer layer, and performing Physical Vapor Deposition (PVD) on the primer layer.
The base material is metal alloy or plastic. Cleaning the substrate, in order to remove stains and oil stains on the surface of the substrate, a hydrocarbon vacuum cleaning mode is utilized, and the surface is dried to finish the surface cleaning of the substrate. And the static electricity on the surface of the base material can be removed by an ion gun, so that external dust or cotton wool pollution is prevented.
Then, a high molecular coating, such as an ultraviolet light curing coating, is sprayed on the surface of the substrate in a dust-free room to form a primer layer, and then the primer layer is baked and leveled by using infrared rays and the primer layer is cured by ultraviolet light irradiation. The operation in a clean room ensures that no dust or lint is adhered to the process. The leveling temperature of the infrared baking is 30-60 ℃, and the baking time is 3-10 minutes. The energy is 1500-3000mJ/cm2 when the ultraviolet light irradiates and cures. According to one embodiment of the present invention, the thickness of the primer layer is 10-70 μm, preferably 10-60 μm, more preferably 10-40 μm, or 15-20 μm, and the primer layer can resist the temperature of 160-180 ℃ so that the substrate can resist the temperature generated in the subsequent PVD step.
According to an embodiment of the present invention, the uv curable coating material includes 20 to 60% of polybutadiene resin, 20 to 40% of acrylate monomer, 1 to 10% of photoinitiator, 10 to 30% of aromatic solvent, and 8 to 20% of alcohol solvent. Wherein the acrylate monomer is selected from the group consisting of methyl acrylate, methyl methacrylate, trimethylolpropane triacrylate, isobornyl acrylate, dipropylene glycol diacrylate, dipentaerythritol hexaacrylate and 1, 6-hexanediol diacrylate. The photoinitiator is selected from the group consisting of ethyl 4-dimethylaminobenzoate (EDAB), 2-alkyl-2-methyl-1-phenyl-1-propanone (HMPP), benzophenone, tertiary amines, dibutyltin dilaurate, triethylene diamine, stannous octoate and zinc naphthenate. The aromatic solvent is toluene, xylene or dimethylformamide. The alcohol solvent is ethanol, isopropanol, butanol, diacetone alcohol or glycerol. The primer layer formed by using the ultraviolet curing coating can ensure that the surface after final treatment has good corrosion resistance and glossiness.
According to an embodiment of the present invention, the ultraviolet light curable coating further includes 5-25% of an ester solvent, wherein the ester solvent is ethyl acetate, ethyl acetate or butyl acetate. According to another embodiment of the present invention, the uv curable coating material may also include 0.01 to 1% of an auxiliary agent, such as a leveling agent or an antifoaming agent. In addition, polybutadiene resin in the ultraviolet curing coating can be mixed with 1-10% of alkyd resin.
And then, carrying out physical vapor deposition on the primer layer, and depositing a metal coating and a metal nitride coating on the surface of the primer layer by utilizing a multi-arc sputtering mode or a multi-arc sputtering mode and a medium-frequency sputtering mode so as to form the appearance which is the same as that of the traditional water electroplating process. The target material for physical vapor deposition is selected from the group consisting of chromium (Cr), aluminum (Al), zirconium (Zr) and titanium (Ti), such that the total thickness of the metal plating film and the metal nitride plating film is 0.02-5 μm, and all the metal plating films account for 10-30% of the total thickness. Different target materials can be used for depositing different appearance colors of the final finished product, and the change of the decorative coating layer is increased. For example, titanium nitride (TiN) appears golden yellow, zirconium nitride (ZrN) appears light gold, and chromium nitride (CrN) appears silver gray.
According to one embodiment of the invention, when the physical vapor deposition is performed by using multi-arc sputtering, the current is 65-80A, the voltage is 50-80V, the argon flow rate is 50-92sccm, the nitrogen flow rate is 0-80sccm, the gas flow ratio of argon to nitrogen is 92:0-50:80, the duty ratio is 50-80%, and the deposition time is 3-5 minutes.
According to another embodiment of the present invention, multi-arc sputtering is used in combination with intermediate frequency sputtering to perform physical vapor depositionAt the time, the current is 20-50A, the voltage is 50-100V, and the argon flow rate is 50-92sccmThe nitrogen flow rate is 0-50sccmThe duty ratio is 50-80%, and the deposition time is 6-10 minutes.
Specifically, when physical vapor deposition is used, the nitrided metal coating and the metal coating which are alternately laminated are deposited on the primer layer according to different gas flow ratios of argon gas and nitrogen gas, and the final layer is the metal coating. The "alternate lamination" refers to, for example, a lamination of a metal nitride plating film, a metal nitride plating film, and a metal plating film in this order, or a lamination of a metal plating film, a metal nitride plating film, and a metal plating film in this order. However, the above description is merely exemplary of "alternate layers" and is not intended to limit the present invention. According to one embodiment of the invention, when the target material is chromium, the target material can directly generate an appearance color similar to that of a general water electroplated bright chromium color finished product after physical vapor deposition without color mixing.
FIG. 1 is a schematic cross-sectional view of a final product after physical vapor deposition according to one embodiment of the present invention. According to one embodiment of the present invention, the PVD metal target is chromium (Cr), wherein alternating layers of chromium (Cr) and chromium nitride (CrN) are formed by different gas flow ratios of argon (Ar) and nitrogen (N2) during PVD, and the cross-section of the resulting product is shown in FIG. 1, wherein the substrate (Prim) is treated with a chemical vapor deposition processer) the flow conditions of argon and nitrogen gas for physical vapor deposition on the surface are in sequence 1 to sequence 4, and sequence 4 is the final surface layer.
Watch 1
| Sequence of steps | Ar(sccm) | N2(sccm) | Deposition time (seconds) | Kind of coating film |
| 4 | 92～50 | 0 | 60～90 | Cr |
| 3 | 50 | 30 | 60～120 | CrN |
| 2 | 50 | 50 | 60～120 | CrN |
| 1 | 50～92 | 0 | 120～180 | Cr |
FIG. 2 is a schematic cross-sectional view after physical vapor deposition according to another embodiment of the present invention. According to an embodiment of the present invention, the physical vapor deposition metal target is chromium (Cr), in which the nitrogen flow is changed in a Gradient manner to deposit a plurality of metal nitride coatings (Gradient coatings) on which metal coatings are deposited. Table two shows that during physical vapor deposition, alternating chromium plating films (Cr) and chromium nitride plating films (CrN) are formed by using different gas flow ratios of argon (Ar) and nitrogen (N2), and the cross-sectional view of the resulting product is shown in fig. 2, where the flow ratio of argon (Ar) and nitrogen (N2) is used to control the structure of each layer of plating film. Wherein the flow conditions of argon and nitrogen gas for physical vapor deposition on the surface of the substrate (Primer) are in sequence 1 to sequence 8, and sequence 8 is the final surface layer.
Watch two
| Sequence of steps | Ar(sccm) | N2(sccm) | Deposition time (sec) | Kind of coating film |
| 8 | 92 | 0 | 30～60 | Cr |
| 7 | 92 | 10 | 10～30 | CrN |
| 6 | 80 | 25 | 10～30 | CrN |
| 5 | 65 | 35 | 10～30 | CrN |
| 4 | 50 | 50 | 10～30 | CrN |
| 3 | 65 | 65 | 10～30 | CrN |
| 2 | 80 | 80 | 10～30 | CrN |
| 1 | 92 | 0 | 60～90 | Cr |
In the above-mentioned substrate dry surface treatment method, if the substrate material is a metal alloy, after the substrate is cleaned and before the polymer coating (ultraviolet curable coating) is coated, a coupling agent may be coated on the surface of the substrate, and the surface sealing treatment is performed to increase the adhesion between the subsequent polymer coating (ultraviolet curable coating) and the metal surface. According to one embodiment of the present invention, the coupling agent is a silane coupling agent, an aluminum zirconate coupling agent, a titanate coupling agent or a phosphated acrylate, and the coupling agent is present in a concentration of 5 to 50% by weight, preferably 5 to 30% by weight, more preferably 10 to 30% by weight.
In addition, according to another embodiment of the present invention, a surface paint layer is formed by spraying a polymer coating on the surface of the final metal plating film, wherein the thickness of the surface paint layer is 5-50 μm, preferably 10-20 μm, to improve the wear resistance of the surface of the final product. The high molecular coating is ultraviolet light curing coating or perfluoropolyether coating. According to an embodiment of the present invention, the finish paint layer formed by perfluoropolyether coating can provide fingerprint resistance and hydrophobicity to the final product. Alternatively, the top coat layer is formed using the same uv curable coating as the primer layer.
In the substrate dry surface treatment method, the temperature resistance of the primer layer after curing reaches 180 ℃, and a metal target can be directly used on the primer layer to react with nitrogen to generate a plurality of layers of nitrided metal coating films and metal coating films, so that the final surface color of the manufactured finished product approaches to that of the finished product in a general water electroplating process, and the finished product has good mechanical properties such as corrosion resistance, wear resistance and the like, thereby replacing the traditional water electroplating process and solving the problem of waste soil and waste water treatment in the water electroplating process. The steps and the characteristics of the substrate dry surface treatment method of the present invention will be described below in each experimental example.
EXAMPLES 1-3 primer compositional component testing
Table III shows the results of tests on the primer compositions and their final products of examples 1-3. The tests included surface gloss, pencil hardness test, and corrosion resistance test (CASS). Wherein the surface gloss is measured by a color difference meter for LAB values of the finished product, the pencil hardness test is performed according to ASTM D-3363, and the corrosion resistance test is performed according to ASTM B-368.
Test results of the primer compositions and finished products thereof of experimental examples 1-3
According to the test, the LAB value of the finished surface further formed using the primer layer formed using the primer composition of experimental example 1 was 83.77/-0.72/-1.61, while the LAB value of the conventional water-electroplated bright chrome color was 83.74/-0.78/-0.64, so that both represent gloss L values were similar, showing that the primer layer formed using the primer composition of experimental example 1 can make the surface gloss of the final product good, similar to that of the conventional water-electroplated chrome, and it can also pass the corrosion resistance for 24 hours (CASS) test and the 3H pencil hardness test. The primer composition of Experimental example 2 also exhibited a surface having gloss but a yellowish color, which passed the 12 hour corrosion resistance (CASS) test and the 3H pencil hardness test. The primer layer composed of the primer of the experimental example 3 has insufficient glossiness, and cannot enable the metal coating film of the subsequent physical vapor deposition to be adhered and deposited, and can enable the metal to be ashed; in addition, the CASS test can only be maintained for less than 2 hours, the hardness is relatively insufficient, and the 2H pencil hardness test can only be passed. Therefore, it can be seen from table three that both experimental examples 1 and 2 can achieve the same surface gloss as the conventional water-electroplated bright chrome color, and the results of the CASS test and the pencil hardness test show that the primer layers formed by the experimental examples 1 and 2 have the mechanical properties of corrosion resistance and wear resistance.
Experimental examples 4-8 different physical vapor deposition conditions and coating film test results
Examples 4 to 8 were conducted by depositing a metal plating film and a metal nitride plating film under different physical vapor deposition conditions and examining the color of the surface of the plated product. The compositions of the primers used in examples 4-7 were as described in experiment 1, and experiment 8 was conducted under different PVD conditions using the composition of the primer described in example 3.
Watch four
As can be seen from table four, experimental example 4 and experimental example 5 are physical vapor deposition using multi-arc sputtering, and the difference between them is that the current and bias voltage used are different and the deposition time is different. The result is that the surface color of the finished product produced in experimental example 4 approaches to the color produced by the traditional electro-plating bright chrome color process, and the color difference values are respectively: the LAB value of the water electroplating process is 83.74/-0.78/-0.64, while the LAB value of the substrate dry surface treatment method of the present invention is 83.77/-0.72/-1.61. The surface of the product produced in Experimental example 5 was observed to have cracks under a microscope.
In the experimental examples 6-8, the pvd was performed by using multi-arc sputtering and medium frequency sputtering, wherein the difference between the experimental example 6 and the experimental example 7 is the nitrogen flow rate during the pvd. As a result, it was found that the surface color of the product of Experimental example 6 is close to the color produced by the conventional water electroplating process, and the color difference values are: the LAB value of the water electroplating process is 83.74/-0.78/-0.64, while the LAB value of the substrate dry surface treatment method of the present invention is 77.47/-0.76/-1.68. The surface of the product of example 7 was black. In addition, the above examples 4-7 performed PVD with the same primer but under different conditions, and the results of the final products were not completely the same, showing that the primer composition still had to be matched with proper PVD conditions to produce the same results as the conventional water-electroplated bright chrome. In addition, in experimental example 8, the primer resin used was a water-based UV paint, which apparently cannot withstand the temperature and voltage under the conditions of physical vapor deposition, thereby causing cracks in the formed primer layer and failure of adhesion of the coating film to cause white fogging.
Experimental examples 9-10 lamination test of metal plating film and nitrided metal plating film
Experimental example 9 is a double-layer coating design (CrN + Cr) in which a chromium nitride coating and a chromium coating are sequentially formed on a substrate by physical vapor deposition using a chromium target on the substrate using the substrate dry surface treatment method of the present invention. In experimental example 10, a chromium target was used to perform physical vapor deposition on a substrate by using the dry surface treatment method for a substrate according to the present invention, and four coating designs (CrN + Cr + CrN + Cr) were formed on the substrate in this order, i.e., a chromium nitride coating, a chromium nitride coating, and a chromium coating. And the finished products of experimental examples 9 and 10 were subjected to corrosion resistance test (CASS) and corrosion potential (Ecorr) and corrosion current (Icorr) were measured. And the substrate itself, the single-layer chromium plating film, and the single-layer chromium nitride plating film were used as comparative examples 1 to 3. The corrosion resistance test was performed as a copper salt accelerated acetate spray test. Table V shows the results of measuring the corrosion potential and the corrosion current of the experimental examples 9 to 10 and the comparative examples 1 to 3.
Watch five
The corrosion current is equal to the corrosion rate, with higher values indicating greater corrosion. According to the test results, it was found that the laminate designs of the multi-layered metal plating film and the metal nitride plating film of experimental examples 9 and 10 both have lower corrosion current than the single-layered metal plating film or the single-layered metal nitride plating film. In addition, in the corrosion resistance test, the experimental example 10 having a four-layer coating film stack exhibited the least corrosion points after 4 hours of the salt spray test, and had a color similar to that of a general water electroplating appearance. It is shown that the laminate coating film formed by the dry surface treatment method of a substrate according to the present invention can have corrosion resistance.
Experimental examples 11-12 functional testing of the final product
According to the results of the above examples, Experimental example 11 is a finished product formed by selecting the primer composition of Experimental example 1 and performing physical vapor deposition under the conditions of Experimental example 4; in experiment example 12, the primer composition of experiment example 1 was selected and the final product was formed by physical vapor deposition under the conditions of experiment example 6, and in both experiment examples 11 and 12, the final metallic plating film was coated with a topcoat, and then the functional test of the final product was performed. The test contents comprise a corrosion resistance test, a pencil hardness test, a hundred-grid test, a shakeout test, a chemical resistance test, a water immersion test, a cold and hot cycle test and a surface color difference measurement. Wherein the corrosion resistance test is according to ASTM B-368, the pencil hardness test is according to ASTM D-3363, the hundred grid test is according to ASTM D3359, the shakeout test is according to ASTM D-968, the chemical resistance test is according to ASTM D-1308, and the water immersion test is according to ASTM D-870. The cold-hot cycle test was performed under the following conditions: 40 minutes at-40. + -. 2 ℃, 30 minutes at 20. + -. 5 ℃, 40 minutes at 75. + -. 2 ℃ and finally 30 minutes at 20. + -. 2 ℃. Table six shows the results of the functional tests on the final products of experimental examples 9 and 10.
Table six final product function test results
According to the results listed in table six, the surfaces of the final products of experimental examples 11 and 12 have mechanical properties such as corrosion resistance and wear resistance, and the difference is not easily perceived by naked eyes compared with the surface color of the final product produced by the conventional electro-plating process.
Fig. 3 is an electron microscope result of a finished product made in accordance with an embodiment of the present invention. The thickness of the finished product of Experimental example 12 was measured by an electron microscope. The primer layer thickness was seen to be 33 μm at a magnification of 2000, where the total thickness of the metal plating film formed via physical vapor deposition was 0.12 μm.
Fig. 4 is an electron microscope result of a finished product made according to another embodiment of the present invention. The thickness of the finished product of Experimental example 11 was measured by an electron microscope. At a magnification of 1000, it can be seen that the primer layer (Base coating) has a thickness of 40 μm and the Top coating layer (Top coating) has a thickness of 34 μm, with a coating (PVD coating) having a thickness of 0.05 μm in between.
In summary, the substrate dry surface treatment method of the present invention forms a polymer coating (primer layer) on the substrate, and then forms an alternate stacked metal coating and metal nitride coating by physical vapor deposition on the polymer coating and directly using a metal target to react with nitrogen, so that the surface of the final product has good mechanical properties such as corrosion resistance and wear resistance, and if the target is chromium, the color formation similar to the appearance of the general water electroplating bright chromium color can be directly generated, and the paint is not required to be additionally used for color matching, so as to solve the problem of waste soil and waste water treatment generated in the water electroplating process.
It should be noted that the final product of the present invention can be various conventional sanitary fittings, such as the faucet body 10, the shower body 20, or the handle 30, as shown in fig. 5 to 7, and it can be easily understood that the sanitary fittings have a substrate on which a surface treatment is performed by a dry surface treatment method.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (16)
1. A method for dry surface treatment of a substrate, comprising:
cleaning a base material, wherein the base material is metal alloy or plastic;
spraying ultraviolet curing coating on the surface of the base material to form a primer layer, wherein the thickness of the primer layer is 10-70 μm, and the ultraviolet curing coating comprises:
20-60% of polybutadiene resin;
20-40% of acrylate monomer;
1-10% of a photoinitiator selected from the group consisting of ethyl 4-dimethylaminobenzoate, 2-alkyl-2-methyl-1-phenyl-1-propanone, benzophenone, tertiary amines, dibutyltin dilaurate, triethylene diamine, stannous octoate and zinc naphthenate;
10-30% of aromatic solvent; and
8-20% of an alcohol solvent;
leveling the primer layer by infrared baking, wherein the baking temperature is 30-60 ℃, and the baking time is 3-10 minutes;
curing the primer layer by ultraviolet irradiation, wherein the ultraviolet irradiation energy is 1500-3000mJ/cm 2; and
performing physical vapor deposition on the primer layer, and sequentially depositing at least one metal nitride coating and at least one metal coating on the primer layer by multi-arc sputtering, wherein a target of the physical vapor deposition is selected from the group consisting of chromium, aluminum, zirconium and titanium, the current is 65-80A, the voltage is 50-80V, the argon flow rate is 50-92sccm, the nitrogen flow rate is 0-80sccm, the gas flow ratio of argon to nitrogen is 92:0-50:80, the duty ratio is 50-80%, the deposition time is 3-5 minutes, so that the total thickness of the metal nitride coating and the metal coating is 0.02-5 mu m, and the metal coating accounts for 10-30% of the total thickness.
2. The dry surface treatment method according to claim 1, wherein at least two metal plating films and at least two metal nitride plating films are formed while the physical vapor deposition is performed, and the two metal plating films and the two metal nitride plating films are alternately stacked.
3. The dry surface treatment method according to claim 1, wherein a nitrogen flow rate is changed in a gradient manner to deposit a plurality of metal nitride plating films and the metal plating films are deposited thereon while the physical vapor deposition is performed.
4. The dry surface treatment method according to claim 1, further comprising:
after the surface of the base material is cleaned, coating a coupling agent on the surface of the base material, wherein the coupling agent is a silane coupling agent, an aluminum zirconate coupling agent, a titanate coupling agent or a phosphated acrylate, and the weight percentage concentration of the coupling agent is 5-50%.
5. The dry surface treatment method according to claim 1, further comprising:
and spraying a high polymer coating on the surface of the metal coating to form a finish coating layer, wherein the thickness of the finish coating layer is 5-50 mu m, and the high polymer coating is an ultraviolet curing coating or a perfluoropolyether coating.
6. The dry surface treatment method as claimed in claim 1, wherein the physical vapor deposition is performed by multi-arc sputtering and intermediate frequency sputtering, the current is 20-50A, the voltage is 50-100V, the argon gas flow rate is 50-92sccm, the nitrogen gas flow rate is 0-50sccm, the duty ratio is 50-80%, and the deposition time is 6-10 minutes.
7. The dry surface treatment method according to claim 1, wherein the acrylate monomer of the uv-curable coating material is selected from the group consisting of methyl acrylate, methyl methacrylate, trimethylolpropane triacrylate, isobornyl acrylate, dipropylene glycol diacrylate, dipentaerythritol hexaacrylate and 1, 6-hexanediol diacrylate.
8. The dry surface treatment method according to claim 1, wherein the aromatic solvent of the uv-curable coating material is toluene, xylene, or dimethylformamide.
9. The dry surface treatment method according to claim 1, wherein the alcohol solvent of the ultraviolet-curable coating material is ethanol, isopropanol, butanol, diacetone alcohol, or glycerol.
10. The dry surface treatment method according to claim 1, wherein the uv curable coating further comprises 5 to 25% of an ester solvent, wherein the ester solvent is ethyl acetate, or butyl acetate.
11. The dry surface treatment method according to claim 1, wherein the uv-curable coating material further comprises 0.01 to 1% of a leveling agent or 0.01 to 1% of an antifoaming agent.
12. The dry surface treatment method according to claim 1, wherein the polybutadiene resin of the uv-curable coating is blended with 1 to 10% alkyd resin.
13. A sanitary fitting, characterized in that the substrate having the dry surface treatment method according to claim 1 is subjected to surface treatment by the dry surface treatment method.
14. The sanitary fitting according to claim 13, wherein said sanitary fitting is a faucet body.
15. The sanitary fitting according to claim 13, wherein said sanitary fitting is a shower body.
16. The sanitary fitting according to claim 13, wherein said sanitary fitting is a handle.
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| CN114457309A (en) * | 2022-02-11 | 2022-05-10 | 九牧厨卫股份有限公司 | Method for treating easy-to-clean surface of hardware |
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