Composite film layer containing ternary black plating layer, preparation method of composite film layer and bathroom product

Abstract

The invention provides a composite film layer containing a ternary black coating, a preparation method of the composite film layer and a bathroom product. The composite film layer comprises a base material; a nickel layer on the substrate; a chromium layer over the nickel layer; the transition layer is positioned on the chromium layer; the ternary black plating layer is positioned on the transition layer; the anti-fingerprint layer is positioned on the ternary black plating layer; wherein the transition layer is formed by a physical vapor deposition method based on a first target material, and the first target material is selected from one of chromium, zirconium and titanium; the ternary black coating is formed through a physical vapor deposition method based on a second target material, the second target material is a CrxWySiz composite target material, x represents the atomic percent of chromium, y represents the atomic percent of tungsten, z represents the atomic percent of silicon, x is equal to 80-90, y is equal to 5-15, and z is equal to 3-10. The ternary black composite film layer has good water resistance, corrosion resistance and friction resistance.

Description

Technical Field

[0001] This application relates to the field of membrane materials, and more particularly to a composite membrane layer comprising a ternary black coating and its preparation method, for bathroom products. Background Technology

[0002] With the rapid development of modern technology and the continuous improvement of consumers' aesthetic demands, the appearance design of bathroom and home furnishing products is facing unprecedented opportunities and challenges. Among the many color options, black, with its unique visual charm—exuding a sense of luxury and mystery—is gradually becoming the preferred color for high-end bathroom products. However, currently, the market offers very few products that truly possess a metallic texture and meet the required blackness (L value). The black bathroom products category (30) remains largely untapped.

[0003] The preparation of black films is mainly achieved through traditional processes such as baking paint or powder coating, or physical vapor deposition (PVD). While baking paint or powder coating can achieve a black L-value, these techniques are not universally applicable. However, due to the limitations of coating leveling, its surface roughness is difficult to achieve the ideal metallic texture level. The film has poor metallic texture, mostly a matte effect, rough surface, and poor wear resistance and temperature resistance. PVD process usually uses metal targets such as chromium and titanium in combination with carbon source gases such as methane and acetylene to form a black coating. However, the black coating produced by the current PVD process is not black enough (L value is about 35), and the film quality is unstable. Moreover, when the L value drops below 35, the excessive carbon content will cause a surge in internal stress in the film, resulting in quality defects such as coating peeling and iridescent effect, which seriously restricts the application of black PVD coating in bathroom products.

[0004] Therefore, there is an urgent need for a composite film containing a ternary black coating that overcomes the above-mentioned shortcomings and its preparation method. Summary of the Invention

[0005] The following is an overview of the subject matter described in detail herein. This overview is not intended to limit the scope of protection of this application.

[0006] In one aspect, this application provides a composite film layer comprising a ternary black coating, including: Substrate; A nickel layer is located on the substrate; A chromium layer, which is situated on top of the nickel layer; A transition layer, which is located on top of the chromium layer; A ternary black coating, which is located above the transition layer; and An anti-fingerprint layer is located on top of the ternary black coating; The transition layer is formed by physical vapor deposition based on a first target material selected from chromium, zirconium, and titanium. The ternary black coating is formed by physical vapor deposition based on a second target material, which is Cr. x W y Si z Composite target material, where x represents the atomic percentage of chromium, y represents the atomic percentage of tungsten, and z represents the atomic percentage of silicon, where x = 80~90, y = 5~15, and z = 3~10.

[0007] In an exemplary embodiment, the LAB value of the ternary black coating is L 30, A=-1~1 and B=-1~1.5, and the 60° gloss is 20~50 GU.

[0008] In an exemplary embodiment, the thickness of the ternary black coating is 1~2μm.

[0009] In one exemplary embodiment, the second target material is Cr 85 W5Si 10 Cr 90 W5Si5 or Cr 85 W 10 Si5.

[0010] In one exemplary embodiment, the thickness of the nickel layer is 20~25 μm.

[0011] In one exemplary embodiment, the thickness of the chromium layer is 0.2~0.3 μm, and the chromium is trivalent white chromium or trivalent black chromium.

[0012] In one exemplary embodiment, the thickness of the transition layer is 10~50nm.

[0013] In one exemplary embodiment, the thickness of the anti-fingerprint layer is 5~10nm.

[0014] In an exemplary embodiment, the carbon content in the ternary black coating increases along the direction away from the transition layer.

[0015] On the other hand, this application provides a method for preparing the above-mentioned composite film layer, the method comprising the following steps: 1) Pre-treatment of the substrate; 2) The pretreated substrate is plated with nickel to form a nickel layer; 3) A chromium layer is formed by plating chromium onto the nickel layer; 4) A transition layer is formed on the chromium layer by physical vapor deposition; 5) A ternary black coating is formed on the transition layer by physical vapor deposition; and 6) An anti-fingerprint layer is formed on the ternary black coating by vacuum evaporation deposition or spraying; In step 5), under a protective atmosphere, acetylene or methane reaction gas is introduced. The flow rate of acetylene or methane gradually increases with the coating time, with an increase of 20~50 sccm every 10 minutes (20~50 sccm / 10min).

[0016] In an exemplary embodiment, in step 1), pretreatment of the substrate includes polishing and cleaning the substrate.

[0017] In an exemplary embodiment, in step 2), the nickel plating is performed by electroplating. The nickel plating solution includes 240 g / L to 300 g / L of nickel sulfate, 40 g / L to 55 g / L of nickel chloride, 40 g / L to 50 g / L of boric acid, and 10 to 50 ml / L of a composite additive. The composite additive is selected from two or three of butynediol propoxy ether, sodium allyl sulfonate, and saccharin. The pH range of the nickel plating solution is 3 to 4.5. The current density used for nickel plating is 5 to 12 A / dm³. 2 The nickel plating time is 15~20 minutes, and the temperature is 55℃ to 65℃.

[0018] In one exemplary embodiment, in step 3), the chromium plating is performed by electroplating, and the current density for chromium plating is 8~11 A / dm³. 2 The electroplating time is 5~10 minutes.

[0019] In an exemplary embodiment, in step 4), the substrate is placed in a vacuum coating machine for glow discharge cleaning to further clean the substrate surface; the multi-arc ion plating power supply is turned on to perform multi-arc ion plating, and the atmosphere and flow rate are: Ar 250~350sccm; negative bias voltage: -100~-200 V; arc source current: 60~80A; coating time: 2~5min.

[0020] In an exemplary embodiment, in step 5), the multi-arc ion plating power supply is turned off, and the medium-frequency magnetron sputtering power supply is turned on. The temperature of the vacuum chamber is 100~150°C. The protective atmosphere and flow rate are: Ar 200~400 sccm; the reaction atmosphere and flow rate are: acetylene or methane 50~500 sccm, increasing at a rate of 40~60 sccm / 10min when the flow rate is below 300 sccm, and increasing at a rate of 15~35 sccm / 10min when the flow rate is above 300 sccm; the working pressure is 0.1~2 Pa; the negative bias voltage is -30~-80 V; the target current is 10~30 A, the duty cycle is 45%~60%, and the total coating time is 120~180 min. After the coating is completed, the coating is removed after the temperature drops below 100°C.

[0021] In an exemplary embodiment, in step 6), the physical vapor deposition method employs a vacuum evaporation coating method.

[0022] In another aspect, this application provides a bathroom product having a composite film layer, wherein the composite film layer is the aforementioned composite film layer or is obtained by the aforementioned method.

[0023] In this application, the term "bathroom products" may refer to products whose surface has a composite film layer containing a ternary black coating as described in this application, including but not limited to faucets, showers, and bathroom cabinets.

[0024] This application proposes a ternary black composite coating technology with gradient carbon content. By controlling the flow rate of the reactive gas, the gradient distribution of carbon elements in the ternary black coating is achieved, which effectively avoids problems such as film peeling caused by a sudden increase in carbon content. This improves the stability of the coating.

[0025] This application further reduces the film blackness (L) by additional doping with W and Si elements. 30), and the color is pure black.

[0026] The composite film layer containing a ternary black coating obtained in this application has good water resistance, corrosion resistance and abrasion resistance.

[0027] Other features and advantages of this application will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the application. Other advantages of this application can be realized and obtained by means of the solutions described in the description and the accompanying drawings. Attached Figure Description

[0028] The accompanying drawings are used to provide an understanding of the technical solutions of this application and constitute a part of the specification. They are used together with the embodiments of this application to explain the technical solutions of this application and do not constitute a limitation on the technical solutions of this application.

[0029] Figure 1 A schematic cross-sectional view of a composite film layer provided according to an exemplary embodiment of the present disclosure; and Figure 2 SEM images of the composite film obtained according to Example 1 of this disclosure are shown. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this application clearer, the embodiments of this application are described in detail below. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be arbitrarily combined with each other.

[0031] Unless otherwise specified, all materials used in the following examples and comparative examples are commercially available.

[0032] refer to Figure 1 This application provides a composite film layer, including a substrate 10, a nickel layer 20 on the substrate 10, a chromium layer 30 on the nickel layer 20, a transition layer 40 on the chromium layer 30, a ternary black plating layer 50 on the transition layer 40, and an anti-fingerprint layer 60 on the ternary black plating layer 50.

[0033] In this application, the substrate 10 applicable to this application may include, but is not limited to, stainless steel, aluminum alloy, zinc alloy, copper alloy, and electroplatable plastic with electroplated copper, nickel, or chromium coatings.

[0034] In this application, the substrate 10 can be pretreated. The pretreatment can be carried out using conventional pretreatment methods in the art, such as polishing, degreasing with acetone and anhydrous ethanol, ultrasonic cleaning, acidic solution cleaning, alkaline solution neutralization, deionized water rinsing, and preservative rinsing.

[0035] Pretreatment can reduce the surface roughness of the substrate, giving it a bright and smooth mirror finish with Ra≤0.8μm.

[0036] In this application, the nickel layer 20 may consist of at least two of the following: an impact nickel layer, a semi-bright nickel layer, and a fully bright nickel layer. The total thickness of the nickel layer 20 may be 20-25 μm. Forming a nickel layer on the substrate can significantly improve the corrosion resistance of the substrate and provide a basic gloss level to the workpiece. The 60° gloss level of the nickel layer 20 may be in the range of 80-160 GU.

[0037] The 60° gloss test can be performed using a gloss meter to measure the 60° gloss of the product surface, and the average value is taken from 3 test points.

[0038] In this application, the nickel layer 20 can be prepared by electroplating. The nickel plating solution used in the electroplating method may include 240 g / L to 300 g / L nickel sulfate, 40 g / L to 55 g / L nickel chloride, 40 g / L to 50 g / L boric acid, and 10-50 ml / L of composite additives. The composite additives may consist of two or three of butynediol propoxy ether, sodium allyl sulfonate (ALS), and saccharin (C6H8O7). The process parameters for nickel plating may include a current density of 5-12 A / dm³. 2 The electroplating time is 15-20 minutes; the temperature is 55℃ to 65℃; and the pH range of the nickel plating solution is 3-4.5.

[0039] In this application, a chromium layer 30 can be formed by electroplating, and the thickness of the chromium layer can be 0.2~0.3μm.

[0040] In this application, the chromium plating solution can be either trivalent white chromium or trivalent black chromium. The trivalent white chromium can be one of the following products manufactured by Amtech Chemical Co., Ltd.: Trichrome ICE or Trichrome Plus; the trivalent black chromium can be one of the following products manufactured by Amtech Chemical Co., Ltd.: Trichrome phantom, Trichrome Shadow, Trichrome Titan, or Trichrome Graphite. The electroplating process parameters may include a current density of 8~11 A / dm³. 2 The electroplating time is 5~10 minutes.

[0041] In this application, the formation of chromium layer 30 can enhance the corrosion resistance and oxidation resistance of the workpiece, maintain a suitable surface condition for plating, and ensure good connection with subsequent PVD coating processes.

[0042] In this application, the thickness of the transition layer 40 is typically less than the thickness of the chromium layer. The transition metal layer in this application primarily serves to improve the adhesion between the chromium layer and the subsequent PVD black coating.

[0043] The thickness of the transition layer 40 can be in the range of 10~50nm.

[0044] In this application, a transition layer 40 can be formed in a vacuum environment containing an inert gas by physical vapor deposition based on a first target material selected from chromium, zirconium, and titanium. Physical vapor deposition methods may include ion plating, magnetron sputtering, and vacuum evaporation deposition, etc.

[0045] In this application, the physical vapor deposition method for forming the transition layer 40 can be an ion plating method, such as multi-arc ion plating. Multi-arc ion plating utilizes arc discharge to directly generate plasma, which has a high ionization rate, deposition rate, and good adhesion, making it suitable for forming the transition layer between the chromium layer and the subsequent PVD coating layer in this application.

[0046] In this application, a ternary black coating 50 can be formed by physical vapor deposition based on a second target. The second target is Cr. x W y Si z Composite target material, where x = 80~90, y = 5~15 and z = 3~10. x represents the atomic percentage of chromium, y represents the atomic percentage of tungsten, and z represents the atomic percentage of silicon.

[0047] Powder metallurgy and other methods can be used to prepare CrWSi targets. For example, chromium, tungsten, and silicon powders can be mixed uniformly in a certain proportion and then prepared into an alloy with a specific shape using powder metallurgy to serve as a second target.

[0048] The LAB value of the ternary black coating formed using the specific target material selected in this application is L. With an A value of -1 to 1 and a B value of -1 to 1.5, and a 60° gloss level of 20 to 50 GU, it exhibits an excellent deep black gloss effect.

[0049] In this application, the thickness of the ternary black coating can be 1~2μm.

[0050] In this application, the physical vapor deposition method for forming the ternary black coating 50 can be magnetron sputtering, such as intermediate frequency magnetron sputtering.

[0051] In this application, the anti-fingerprint layer 60 can be a nano-anti-fingerprint layer, used to improve the product's anti-fingerprint performance and stain resistance. The material of the anti-fingerprint layer 60 can be a perfluoropolyether type, and it can be deposited on the black coating layer 50 by physical vapor deposition or spraying.

[0052] In this application, the anti-fingerprint layer 60 can be formed using a physical vapor deposition method such as vacuum evaporation coating.

[0053] The thickness of the anti-fingerprint layer 60 can be in the range of 5~10nm.

[0054] This application also provides a method for preparing a composite film, the method comprising the following steps: 1) pretreating a substrate; 2) plating nickel onto the pretreated substrate to form a nickel layer; 3) plating chromium onto the nickel layer to form a chromium layer; 4) forming a transition layer on the chromium layer by physical vapor deposition; 5) forming a ternary black coating on the transition layer by physical vapor deposition; and 6) forming an anti-fingerprint layer on the ternary black coating by physical vapor deposition or spraying; wherein in step 5), under a protective atmosphere, acetylene or methane reaction gas is introduced, and the flow rate of acetylene or methane gradually increases with the coating time, with an increase rate of 20~50 sccm / 10min.

[0055] The following examples describe in detail the preparation method of the composite film layer of this application.

[0056] Example 1 (1) Polish the surface of the workpiece substrate (select copper alloy or stainless steel) to reduce the surface roughness and obtain a bright and smooth mirror effect with Ra≤0.8μm. Clean the workpiece to remove impurities, oil stains and other contaminants from the workpiece surface. (2) The cleaned workpiece was placed in a nickel plating bath (electroplating solution composition: nickel sulfate 275g / L, nickel chloride 45g / L, boric acid 45g / L, composite additive 30ml / L (butynediol propoxy ether 15ml / L + sodium allyl sulfonate 15ml / L), pH range 3.5) to electroplate nickel, resulting in a 25μm thick combination of impact nickel + semi-bright nickel + fully bright nickel three-layer nickel layer; the current density was 5A / dm 2 The electroplating time is 20 minutes, and the reaction temperature is 55℃. (3) Place the workpiece in a Trichrome ICE electroplating bath for trivalent white chromium deposition at a current density of 10 A / dm³. 2 The electroplating time is 5 minutes, and a chromium layer is obtained on the nickel layer; (4) Clean the workpiece again and place it in a vacuum coating machine for glow discharge cleaning to further clean the substrate surface. The specific parameters are as follows: vacuum degree is 2×10 -3 ~2.0×10 -2 Pa; Discharge voltage: 500~600 V; Atmosphere and flow rate: Ar 300~400 sccm; Cleaning time: 30~60 s; Coating fixture rotation speed: 15~20 r / min; Turn on the multi-arc ion plating power supply, using a chromium target, atmosphere and flow rate: Ar 100~200 sccm; Working gas pressure: 0.5~1.5 Pa; Negative bias voltage: -200~ -300 V; Arc source current: 80~100 A; Coating time: 1~2 min; Coating fixture rotation speed: 15~20 r / min; (5) Turn off the multi-arc ion plating power supply, heat the furnace cavity to 180°C, turn on the medium-frequency power supply, and select Cr 85 W 10 For Si5 target material, argon gas flow rate was 150 sccm, and acetylene flow rate was gradually increased from 50 sccm to 450 sccm. Specific parameters were as follows: negative bias voltage: -60 V; target current: 15 A; duty cycle: 50%; total coating time: 150 min. After coating, the product was removed only after the temperature dropped below 100℃. The change in acetylene flow rate with coating time is shown in Table 1. Table 1 (6) Transfer the above workpiece to the evaporation coating machine and coat it with an anti-fingerprint film for 20 minutes.

[0057] Figure 2 SEM images of the composite film layer prepared in this embodiment are shown. Figure 2 It can be seen that the microstructure of the composite film is uniform and has good density.

[0058] Example 2 The preparation process is basically the same as in Example 1, but the ternary black coating in step (5) uses Cr. 85 W5Si 10 The target material and reaction gas used are methane, and the coating temperature is 200℃.

[0059] Example 3 The preparation process is basically the same as in Example 1, but in step (5), the argon flow rate is 200 sccm, and the acetylene flow rate is gradually increased from 100 sccm to 420 sccm. The specific parameters are as follows: negative bias voltage: -70 V; target current: 10 A, duty cycle is 50%. The change of acetylene flow rate with coating time is shown in Table 2. Table 2 Example 4 The preparation process is basically the same as in Example 1, but the ternary black coating in step (5) uses Cr. 90 W5Si5 target material, methane as the reaction gas; negative bias: -70 V; target current: 10 A, duty cycle: 50%.

[0060] Comparative Example 1 The preparation process is basically the same as in Example 1, but in step (5), the argon flow rate is 150 sccm, and the acetylene flow rate does not change with the plating time, which is 350 sccm.

[0061] Comparative Example 2 The preparation process is basically the same as in Example 1, but in step (5), the argon flow rate is 200 sccm, and the acetylene flow rate does not change with the plating time, which is 400 sccm.

[0062] Comparative Example 3 The preparation process is basically the same as in Example 1, but step (6) is omitted.

[0063] Comparative Example 4 The preparation process is basically the same as in Example 1, but only a chromium target is used in step (5).

[0064] Performance testing The above Examples 1-4 and Comparative Examples 1-4 were tested for thermal shock, water quality degradation, salt spray, and color difference LAB value.

[0065] The thermal shock test procedure may include: placing the sample in an oven at the following specified temperatures for 60 minutes, removing it, and quickly immersing the sample completely in room temperature water for 2 minutes, then observing the coating surface. a) Copper alloy samples: (250±2)℃; b) Zinc alloy samples: (150±2)℃; and c) Stainless steel samples: (300±2)℃. The coating surface should be free from blistering, cracks, flaking, or other separation from the base material.

[0066] The water quality degradation test process may include: placing the sample in a constant temperature water bath containing distilled water at (65±1)℃, soaking for 100 h±10 min, and then observing the sample surface. The surface should be free of blistering, discoloration, peeling, corrosion, and other adverse phenomena.

[0067] The salt spray test procedure may include: conducting the test according to the provisions of GB / T 10125 and Table 1, AASS test for 48 h, and spraying salt spray on any 650 mm area of ​​the surface. 2 There should be no more than 2 surface defects within the product, and no more than 3 surface defects within any 25 mm length of the product connection line and parting line. The diameter of the defects should not be greater than 1.6 mm.

[0068] The color difference LAB value testing process may include: using a colorimeter to test the LAB value of the product surface, taking the average value of 3 test points to characterize the color of the product.

[0069] The test results are shown in Table 3: Table 3 As shown in Table 3, the chromium target Cr doped with W and Si elements... x W y Si z Composite targets are key to achieving black (L value) 30); Increasing the reaction atmosphere flow rate gradient is a key step in reducing internal stress in the film and ensuring coating stability. As the reaction atmosphere flow rate gradually increases, the C content gradient in the ternary black coating increases, avoiding a sudden increase in carbon content and effectively reducing internal stress in the film (the carbon content gradually increases with the thickness of the ternary black coating, thus achieving a gradient distribution of carbon elements); The anti-fingerprint coating can effectively improve the product's stain resistance, with a contact angle >110°.

[0070] In addition, as can be seen from the results in Table 3, since Comparative Examples 1 and 2 did not use the reaction atmosphere flow rate gradient but instead used a fixed flow rate, their membrane carbon content was high and the internal stress of the membrane was large. Under thermal shock and water quality degradation, they were prone to detachment, peeling and other defects. Therefore, their thermal shock and water quality degradation were both unqualified.

[0071] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A composite film layer comprising a ternary black coating, characterized in that, include: Substrate; A nickel layer is located on the substrate; A chromium layer, which is situated on top of the nickel layer; A transition layer, which is located on top of the chromium layer; A ternary black coating is located on the transition layer; as well as An anti-fingerprint layer is located on top of the ternary black coating; The transition layer is formed by physical vapor deposition based on a first target material selected from chromium, zirconium, and titanium. The ternary black coating is formed by physical vapor deposition based on a second target material, which is Cr. x W y Si z Composite target material, where x represents the atomic percentage of chromium, y represents the atomic percentage of tungsten, and z represents the atomic percentage of silicon, where x = 80~90, y = 5~15, and z = 3~10.

2. The composite film layer according to claim 1, characterized in that, The LAB value of the ternary black coating is L 30, A=-1~1 and B=-1~1.5, and a gloss level of 20~50 GU at 60°; and / or, The thickness of the ternary black coating is 1~2μm.

3. The composite film layer according to claim 1, characterized in that, The second target material is Cr 85 W5Si 10 Cr 90 W5Si5 or Cr 85 W 10 Si5.

4. The composite film layer according to claim 1, characterized in that, The thickness of the nickel layer is 20~25μm; and / or, The thickness of the chromium layer is 0.2~0.3 μm, and the chromium is trivalent white chromium or trivalent black chromium; and / or, The thickness of the transition layer is 10~50 nm; and / or, The thickness of the anti-fingerprint layer is 5~10nm.

5. The composite film layer according to any one of claims 1-4, characterized in that, In the ternary black coating, the carbon content increases along the direction away from the transition layer.

6. A method for preparing a composite film layer according to any one of claims 1-5, characterized in that, The method includes the following steps: 1) Pre-treatment of the substrate; 2) The pretreated substrate is plated with nickel to form a nickel layer; 3) A chromium layer is formed by plating chromium onto the nickel layer; 4) A transition layer is formed on the chromium layer by physical vapor deposition; 5) A ternary black coating is formed on the transition layer by physical vapor deposition; as well as 6) An anti-fingerprint layer is formed on the ternary black coating by physical vapor deposition or spraying; In step 5), under a protective atmosphere, acetylene or methane reaction gas is introduced, and the flow rate of acetylene or methane gradually increases with the coating time, with an increase of 20-50 sccm every 10 minutes.

7. The method according to claim 6, characterized in that, In step 1), pretreatment of the substrate includes polishing and cleaning the substrate; and / or, In step 2), nickel plating is performed using electroplating. The nickel plating solution includes 240 g / L to 300 g / L of nickel sulfate, 40 g / L to 55 g / L of nickel chloride, 40 g / L to 50 g / L of boric acid, and 10 to 50 ml / L of a composite additive. The composite additive is selected from two or three of butynediol propoxy ether, sodium allyl sulfonate, and saccharin. The pH range of the nickel plating solution is 3 to 4.

5. The current density used for nickel plating is 5 to 12 A / dm³. 2 The nickel plating time is 15~20 minutes, and the temperature is 55℃ to 65℃.

8. The method according to claim 6, characterized in that, In step 3), chromium plating is performed using electroplating, with a current density of 8~11 A / dm³. 2 The electroplating time is 5-10 minutes; and / or, In step 4), the substrate is placed in a vacuum coating machine for glow discharge cleaning to further clean the substrate surface; the multi-arc ion plating power supply is turned on for multi-arc ion plating, and the atmosphere and flow rate are: Ar 250~350 sccm; negative bias voltage: -100~ -200V; arc source current: 60~80A; coating time: 2~5min.

9. The method according to any one of claims 6-8, characterized in that, In step 5), turn off the multi-arc ion plating power supply and turn on the medium-frequency magnetron sputtering power supply. The temperature of the vacuum chamber is 100~150℃. Protective atmosphere and flow rate: Ar 200~400 sccm; reaction atmosphere and flow rate: acetylene or methane 50~500 sccm, increasing at a rate of 40~60 sccm / 10min when the flow rate is below 300 sccm, and increasing at a rate of 15~35 sccm / 10min when the flow rate is above 300 sccm; working pressure: 0.1~2Pa; negative bias: -30~-80 V; target current: 10~30A, duty cycle 45%~60%, total coating time 120~180min; after coating, wait for the temperature to drop below 100℃ before removing the coating; and / or, In step 6), the physical vapor deposition method employs vacuum evaporation coating.

10. A bathroom product having a composite film layer, characterized in that, The composite film is the composite film as described in any one of claims 1-5 or is prepared by any one of claims 6-9.

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