Composite coating, preparation method thereof and bathroom product

Abstract

The invention relates to a composite coating, a preparation method thereof and a sanitary product. The preparation method of the composite coating comprises the following steps: forming the metal base layer on the surface of the base material; n B layers and n C layers are formed on the surface of the metal base layer, and a composite coating is prepared; wherein n is larger than or equal to 1, the n B layers and the n C layers are alternately arranged in the thickness direction of the composite coating, the B layer closest to the metal base layer is closer to the metal base layer than the C layer closest to the metal base layer, the materials of the B layers comprise Ti and SiO, the materials of the C layers comprise TiOx and SiOy, the C layers are formed in a sputter coating mode, and the thickness of the C layers is smaller than that of the C layers. The negative bias voltage is switched between a first negative bias voltage and a second negative bias voltage once every 180-480 s, the first negative bias voltage is smaller than or equal to 100 V, and the second negative bias voltage is larger than or equal to 800 V. According to the preparation method of the composite coating, the scratch resistance of the coating is improved, the service life is prolonged, and the composite coating has excellent waterlogging resistance.

Description

Technical Field

[0001] The present application relates to the field of sanitary ware, and in particular to a composite coating and a preparation method thereof, and sanitary ware products. Background Art

[0002] As we all know, since bathroom products are used in water environments such as bathrooms and washbasins, their surfaces will be contaminated with water droplets. If the water droplets stay on the surface of bathroom products for a long time, they will be contaminated by dust in the air. As the water droplets evaporate, the dust will form water stains and remain on the surface of the bathroom products. Over time, the surface of the bathroom products will become very dirty and difficult to clean, requiring users to clean them regularly.

[0003] In order to solve the above problems, traditional technology prevents water from remaining and causing water stains by changing the appearance structure of bathroom products, such as setting a water-conducting layer. However, this method requires adjustment of the product structure, and bathroom products are diverse and the structures are ever-changing. Not all products are suitable for changing the structure, and changing the structure will also increase the cost of the product. Therefore, some researchers have solved the problem of increased costs caused by adjusting the product structure by coating the surface of bathroom products with a fluorine-containing organic hydrophobic coating to prevent water from remaining. However, the above method still has the following problems: the fluorine-containing organic coating has poor wear resistance and a short lifespan during use. When the user touches the product with the coating with his hands or a rag, the organic coating on the surface is easily damaged or scraped off, causing the product to lose the effect of being waterproof and easy to clean. Summary of the invention

[0004] Based on this, the present application provides, on the one hand, a composite coating having a good water stain-proof effect while improving scratch resistance and increasing service life, and a preparation method thereof.

[0005] In addition, the present application also provides a bathroom product on the other hand.

[0006] A method for preparing a composite coating comprises the following steps:

[0007] Forming a metal primer layer on the surface of the substrate;

[0008] Forming n layers of B layer and n layers of C layer on the surface of the metal base layer to prepare a composite coating;

[0009] Wherein, n ≥ 1, along the thickness direction of the composite coating, n layers of B layers and n layers of C layers are alternately arranged, and the B layer closest to the metal base layer is closer to the metal base layer than the C layer closest to the metal base layer, the material of the B layer includes Ti and SiO, and the material of the C layer includes TiO x and SiO yThe C layer is formed by sputtering, and the negative bias is switched between a first negative bias and a second negative bias every 180s to 480s, wherein the first negative bias is less than or equal to 100V, and the second negative bias is greater than or equal to 800V.

[0010] Optionally, the first negative bias voltage is 30V~100V, and the second negative bias voltage is 800V~1000V.

[0011] Optionally, the steps of preparing each of the C layers include:

[0012] Filling the coating chamber with argon and oxygen, wherein the argon flow rate is 20 sccm~60 sccm, and the oxygen flow rate is 20 sccm~60 sccm;

[0013] The target material is set to a Ti-doped SiO composite target, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300W~800W, the chamber temperature is 50℃~150℃, the negative bias voltage is switched between the first negative bias voltage and the second negative bias voltage every 180s~480s, and the coating time is 2100s~4500s to obtain each C layer.

[0014] Optionally, in the Ti-doped SiO composite target, the mass percentages of Ti and SiO are 60% to 80% and 20% to 40%, respectively; and / or,

[0015] The thickness of each C layer is 50nm~100nm.

[0016] Optionally, the steps of preparing each of the B layers include:

[0017] Filling the coating chamber with argon gas, wherein the argon gas flow rate is 20 sccm~60 sccm;

[0018] The target material is set to a Ti-doped SiO composite target, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300 W, the chamber temperature is 50° C. to 150° C., the negative bias voltage is 50V to 150V, and the coating time is 1500s to 2000s to obtain each of the B layers.

[0019] Optionally, in the Ti-doped SiO composite target, the mass percentages of Ti and SiO are 60% to 80% and 20% to 40%, respectively; and / or,

[0020] The thickness of each B layer is 50nm~100nm.

[0021] Optionally, the metal base layer is formed by multi-arc ion plating.

[0022] Optionally, the steps of preparing the metal primer layer include:

[0023] Filling the coating chamber with argon gas, wherein the argon gas flow rate is 20 sccm~60 sccm;

[0024] One or more of Zr, Ti, Cr and Ta are used as target materials, and a multi-arc ion plating method is adopted. The power supply voltage is set to 20V~40V, the current is set to 50A~150A, the negative bias voltage is set to 100V~300V, the chamber temperature is set to 50℃~150℃, and the plating time is set to 60s~120s to obtain the metal base layer.

[0025] Optionally, the thickness of the metal base layer is 10 nm to 50 nm.

[0026] A composite coating is prepared by the above-mentioned preparation method.

[0027] A sanitary ware product comprises the above-mentioned composite coating.

[0028] The preparation method of the composite coating comprises forming a metal primer layer, n layers of B layers and n layers of C layers alternately arranged on the surface of the substrate, wherein the metal primer layer is beneficial to improving the adhesion between the composite coating and the substrate, so that the composite coating is not easy to fall off from the substrate, the material of the B layer comprises Ti and SiO, the material of the C layer comprises TiO x and SiO y , adding SiO or SiO to the B and C layers y , improving the scratch resistance of the coating. In addition, the B layer can play a transitional role between the metal base layer and the C layer, and on the other hand, cooperate with the C layer to improve the density of the composite coating. At the same time, the C layer adopts a high and low negative bias alternating method, which is conducive to covering the loose holes in the B layer, so that the surface density of the composite coating is good, further improving the scratch resistance, and making it difficult for water stains to penetrate into the coating, thereby improving the waterproof performance of the coating.

[0029] Therefore, the preparation method of the composite coating can improve the scratch resistance and increase the service life while having a good water stain prevention effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0031] Figure 1 A schematic diagram of a process flow of a method for preparing a composite coating according to some embodiments of the present application;

[0032] Figure 2 This is a scanning electron microscope image of the composite coating of Example 1 of the present application;

[0033] Figure 3 This is a scanning electron microscope image of the composite coating of Example 2 of the present application;

[0034] Figure 4 This is a scanning electron microscope image of the composite coating of Example 3 of the present application;

[0035] Figure 5 This is a scanning electron microscope image of the composite coating of Comparative Example 1 of the present application;

[0036] Figure 6 This is a scanning electron microscope image of the composite coating of Comparative Example 2 of the present application;

[0037] Figure 7 The total number spectrum of element distribution diagram of the composite coating of Example 1;

[0038] Figure 8 This is an atomic force microscope surface morphology image of Example 1 of the present application;

[0039] Fig. 9 This is a schematic diagram of the surface of Example 1 before the water stains are wiped with clean water and a dust-free cloth;

[0040] Fig.10 It is a schematic diagram after the water stain surface of Example 1 is cleaned with clean water and a dust-free cloth and then wiped with absorbent cotton;

[0041] Fig.11 This is a schematic diagram of the surface water stain of Comparative Example 1 before being wiped with clean water and a dust-free cloth;

[0042] Fig.12 This is a schematic diagram of cleaning the water-stained surface of Comparative Example 1 with clean water and a dust-free cloth and then wiping it with absorbent cotton. DETAILED DESCRIPTION

[0043] In order to facilitate the understanding of the present application, the present application will be described more comprehensively below in conjunction with the specific embodiments. The preferred embodiments of the present application are provided in the specific embodiments. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present application belongs. The terms used herein in the specification of the present application are only for the purpose of describing specific embodiments and are not intended to limit the present application. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0045] Unless otherwise specified or there is a contradiction, the terms and phrases used in this application have the following meanings:

[0046] In this application, "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features.

[0047] In the description of the present application, “plurality” means at least two, for example, two, three, etc., unless otherwise clearly and specifically defined.

[0048] In this application, "one or several" refers to any one, any two or more of the listed items. Among them, "several" refers to any two or more of the listed items.

[0049] In this application, the percentage concentration involved, unless otherwise specified, refers to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of the component.

[0050] In this document, "further", "further", "particularly", "for example", "such as", "example", "for example", etc. are used for descriptive purposes, indicating that the previous and subsequent technical solutions are related in terms of the content covered, but should not be understood as limiting the previous technical solution, nor can they be understood as limiting the scope of protection of this document. In this document, unless otherwise specified, A (such as B) means that B is a non-limiting example of A, and it can be understood that A is not limited to B.

[0051] Herein, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel schemes of "yes" or "no". If multiple "optional" items appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" item is independent of each other. In this application, descriptions such as "optionally contain", "optionally include", etc. mean "contain or not contain". "Optional component X" means that component X exists or does not exist, or means that component X is contained or not contained.

[0052] When a numerical range is disclosed in this application, the above range is considered to be continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed in this application should be understood to include any and all subranges included therein.

[0053] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0054] The terms "including" and "having" and any variations thereof in the embodiments of the present application are intended to cover non-exclusive inclusions. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units that are not listed, or may optionally include other steps or components that are inherent to these processes, methods, products, or devices.

[0055] Reference to "embodiments" in this application means that a particular feature, structure, or characteristic described in conjunction with the embodiments may be included in at least one embodiment of the present application. The appearance of the phrase in various locations in the specification does not necessarily refer to the same embodiment, nor is it an independent or alternative embodiment that is mutually exclusive with other embodiments. It is explicitly and implicitly understood by those skilled in the art that the embodiments described in this application may be combined with other embodiments.

[0056] As described in the background technology, some researchers have solved the problem of residual water stains on the surface of bathroom products by changing the structure of bathroom products. However, bathroom products are diverse and their structures are ever-changing. Not all products are suitable for changing the structure, and changing the structure will also increase the cost of the product. Other researchers have prevented residual water stains by setting a fluorine-containing organic coating. However, the fluorine-containing organic coating sprayed by this method is not wear-resistant and has a short lifespan during use. When the user touches the product with the coating with his hands or a rag, the organic coating on the surface is easily damaged or scraped off, causing the product to lose the effect of being waterproof and easy to clean.

[0057] Based on this, the present application provides a composite coating and preparation method that can prevent water stains from remaining without changing the structure of the bathroom product, while improving scratch resistance and increasing service life.

[0058] In a first aspect, the present application provides a method for preparing a composite coating, comprising the following steps:

[0059] Forming a metal primer layer on the surface of the substrate;

[0060] Forming n layers of B layer and n layers of C layer on the surface of the metal base layer to prepare a composite coating;

[0061] Wherein, n ≥ 1, along the thickness direction of the composite coating, n layers of B layers and n layers of C layers are alternately arranged, and the B layer closest to the metal base layer is closer to the metal base layer than the C layer closest to the metal base layer, the material of the B layer includes Ti and SiO, and the material of the C layer includes TiO x and SiO y, a C layer is formed by sputtering, and the negative bias is switched between a first negative bias and a second negative bias every 180s to 480s, wherein the first negative bias is less than or equal to 100V, and the second negative bias is greater than or equal to 800V.

[0062] The preparation method of the composite coating comprises forming a metal primer layer, n layers of B layers and n layers of C layers alternately arranged on the surface of the substrate, wherein the metal primer layer is beneficial to improving the adhesion between the composite coating and the substrate, so that the composite coating is not easy to fall off from the substrate, the material of the B layer comprises Ti and SiO, the material of the C layer comprises TiO x and SiO y , adding silicon oxide to the B layer and the C layer improves the wear resistance of the coating. In addition, the B layer can play a transitional role between the metal base layer and the C layer, and on the other hand, cooperate with the C layer to improve the density of the composite coating. At the same time, the C layer adopts a high and low negative bias alternating method, which is conducive to covering the loose holes in the B layer, so that the surface density of the composite coating is good, further improving the scratch resistance, and making it difficult for water stains to penetrate into the coating, thereby improving the waterproof performance of the coating.

[0063] Therefore, the preparation method of the composite coating can improve the scratch resistance and increase the service life while having a good water stain prevention effect.

[0064] In addition, experiments have shown that if other coating methods such as multi-arc ion plating are used to form the C layer, due to the fast deposition rate of ion plating, more "large droplets" are generated in the coating, and the coating is relatively loose and porous, which can easily lead to residual water stains. Therefore, in some embodiments of the present application, sputtering coating is used to form the C layer. In addition, if the composite coating does not contain the B layer, and the C layer is directly formed on the metal base layer, the bonding force between the metal base layer and the C layer is not good, and the water stain effect and friction resistance of the coating are not good; if the B layer is directly used as the surface layer, the water stain effect and friction resistance of the coating will also be reduced.

[0065] By setting a metal base layer, it is beneficial to improve the bonding force between the composite coating and the substrate. In some embodiments, the metal base layer is formed by multi-arc ion plating. Multi-arc ion plating is a method of directly evaporating metal on a solid cathode target material by arc discharge, and the evaporant is the ions of the cathode material emitted from the bright point of the cathode arc, so as to be deposited on the surface of the substrate as a thin film. This method uses the ions generated by arc discharge to bombard the substrate, causing the metal to evaporate and form a thin film on the substrate. The use of multi-arc ion plating to form a metal base layer is beneficial to improve the deposition rate and adhesion.

[0066] Specifically, the preparation steps of the metal primer layer include:

[0067] Filling the coating chamber with argon gas, wherein the argon gas flow rate is 20 sccm~60 sccm;

[0068] Using one or more of Zr, Ti, Cr and Ta as target materials, adopting multi-arc ion plating method, setting the power supply voltage to 20V~40V, the current to 50A~150A, the negative bias voltage to 100V~300V, the chamber temperature to 50℃~150℃, and the coating time to 60s~120s, the coating is carried out to obtain a metal base layer.

[0069] Specifically, before the step of filling the coating chamber with argon gas, the coating chamber is pre-evacuated to a vacuum degree of 8×10 -4 ~1×10 -2 Pa.

[0070] In some embodiments, the steps of preparing the metal primer layer include:

[0071] Step S112: pre-evacuate the coating chamber to a vacuum degree of 8×10 -4 ~1×10 -2 Pa, argon gas was filled into it with a flow rate of 20sccm~60sccm to maintain the gas pressure at 3×10 -2 ~6×10 -1 Pa;

[0072] Step S114: Use one or more of Zr, Ti, Cr and Ta as target materials, adopt multi-arc ion plating method, set the power supply voltage to 20V~40V, the current to 50A~150A, the negative bias voltage to 100V~300V, the chamber temperature to 50℃~150℃, and the coating time to 60s~120s to perform coating.

[0073] In some of the embodiments, in step S112, the argon gas flow rate may be, but is not limited to, 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm or a range consisting of any two of these values.

[0074] In some embodiments, in step S114, the power supply voltage may be, but is not limited to, 20V, 22V, 25V, 28V, 30V, 32V, 35V, 38V, 40V, or a range consisting of any two of these values. The current may be, but is not limited to, 50A, 60A, 80A, 100A, 120A, 140A, 150A, or a range consisting of any two of these values.

[0075] In step S114, the negative bias voltage may be, but is not limited to, 100 V, 120 V, 150 V, 180 V, 200 V, 220 V, 250 V, 280 V, 300 V, or a range consisting of any two of these values.

[0076] In step S114, the chamber temperature may be, but is not limited to, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 140°C, 150°C or a range consisting of any two of these values.

[0077] In step S114, the coating time may be, but is not limited to, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 120 s or a range consisting of any two of these values.

[0078] In some embodiments, the thickness of the metal base layer is 10 nm to 50 nm. For example, the thickness of the metal base layer can be, but is not limited to, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, or a range consisting of any two of these values.

[0079] In some embodiments, before preparing the metal base layer, a pre-treatment step of the substrate is also included. Specifically, the pre-treatment step includes: electroplating bright chrome, degreasing, dewaxing, washing, acid activation and baking. The specific processes can be commonly used in the art and are not particularly limited here.

[0080] In a specific example, the step of pre-treating the substrate includes:

[0081] Plating bright chrome on the substrate;

[0082] The substrate is subjected to ultrasonic degreasing, two-step water washing, ultrasonic dewaxing, two-step water washing, acid activation, four-step water washing, slow pulling and baking in sequence.

[0083] Specifically, double washing means washing twice. Quadruple washing means washing four times. Slow pulling means pulling out from the washing tank very slowly to avoid too much water remaining on the surface of the substrate.

[0084] By pre-treating the substrate, a relatively clean surface can be obtained, which facilitates the adhesion of the subsequent composite coating on the substrate surface.

[0085] In some embodiments, each B layer is prepared by sputtering. Specifically, the steps of preparing each B layer include:

[0086] Filling the coating chamber with argon gas, wherein the argon gas flow rate is 20 sccm~60 sccm;

[0087] The target material is set to a Ti-doped SiO composite target, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300 W, the chamber temperature is 50°C~150°C, the negative bias voltage is 50V~150V, the coating time is 1500s~2000s, and the B layer is obtained by sputtering coating.

[0088] Specifically, in the Ti-doped SiO composite target, the mass percentages of Ti and SiO are 60% to 80% and 20% to 40%, respectively. For example, in the Ti-doped SiO composite target, the mass percentages of Ti and SiO can be, but are not limited to, 60% and 40%, 68% and 32%, 65% and 35%, 62% and 38%, 70% and 30%, 72% and 28%, 75% and 25%, 78% and 22%, 80% and 20%, etc.

[0089] In some of the embodiments, the Ti-doped SiO composite target is prepared by the following steps: Ti and SiO powders are uniformly mixed in a ratio of 60% to 80% and 20% to 40% by mass, respectively, and a target having a specific shape is prepared by hot pressing and sintering.

[0090] Specifically, before the step of filling the coating chamber with argon gas, the coating chamber is pre-evacuated to a vacuum degree of 8×10 -4 ~1×10 -2 Pa.

[0091] In some embodiments, the steps of preparing layer B include:

[0092] Step S212: Pre-evacuate the coating chamber to a vacuum degree of 8×10 -4 ~1×10 -2 Pa, argon gas was filled into it with a flow rate of 20sccm~60sccm to maintain the gas pressure at 3×10 -2 ~6×10 -1 Pa;

[0093] Step S214: using Ti-doped SiO composite targets with mass percentages of 60%-80% and 20%-40% respectively as targets, adopting RF sputtering coating method, setting RF power to 300W-800W, chamber temperature to 50℃-150℃, negative bias voltage to 50V-150V, coating time to 1500s-2000s, to obtain each B layer.

[0094] In one example, in step S212, the argon gas flow rate may be, but is not limited to, 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm, or a range consisting of any two of these values.

[0095] In one example, in step S214, the coating time may be, but is not limited to, 1500 s, 1600 s, 1700 s, 1800 s, 1900 s, 2000 s, or a range consisting of any two of these values.

[0096] In one example, in step S214, the negative bias voltage may be, but is not limited to, 50 V, 60 V, 70 V, 80 V, 90 V, 100 V, 110 V, 120 V, 130 V, 140 V, 150 V, or a range consisting of any two of these values.

[0097] In one example, in step S214, the chamber temperature may be, but is not limited to, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 140°C, 150°C or a range consisting of any two of these values.

[0098] In some embodiments, the thickness of each B layer is 50 nm to 100 nm. For example, the thickness of each B layer can be, but is not limited to, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, or a range consisting of any two of these values.

[0099] In some embodiments, the first negative bias voltage is 30V to 100V, and the second negative bias voltage is 800V to 1000V. For example, the first negative bias voltage may be, but is not limited to, 30V, 40V, 50V, 60V, 70V, 80V, 90V, 100V, or a range consisting of any two of these values. The second negative bias voltage may be, but is not limited to, 800V, 820V, 850V, 880V, 900V, 920V, 950V, 980V, 1000V, or a range consisting of any two of these values.

[0100] It can be understood that in the step of preparing each C layer, switching the negative bias voltage between the first negative bias voltage and the second negative bias voltage once every 180s~480s means switching the negative bias voltage from the first negative bias voltage to the second negative bias voltage, or from the second negative bias voltage to the first negative bias voltage every 180s~480s. Take every 300s as an example, for example, when the coating time is 0s, the negative bias voltage is the first negative bias voltage and the coating is performed at the first negative bias voltage, when the coating reaches 300s, the negative bias voltage is switched from the first negative bias voltage to the second negative bias voltage and the coating is performed at the second negative bias voltage, when the coating reaches 600s, the negative bias voltage is switched from the second negative bias voltage to the first negative bias voltage and the coating is performed at the first negative bias voltage, and so on.

[0101] In some embodiments, x and y are each 1 to 2. For example, x and y are each 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, or a range consisting of any two of these values. It is understood that the values ​​of x and y can be the same or different, and are not particularly limited.

[0102] In some embodiments, the steps of preparing each C layer include:

[0103] Filling the coating chamber with argon and oxygen, wherein the argon flow rate is 20 sccm~60 sccm, and the oxygen flow rate is 20 sccm~60 sccm;

[0104] The target material is set to a Ti-doped SiO composite target, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300W~800W, the chamber temperature is set to 50℃~150℃, and the negative bias is switched between the first negative bias and the second negative bias every 180s~480s. The coating time is 2100s~4500s to obtain each C layer.

[0105] Specifically, in the Ti-doped SiO composite target, the mass percentages of Ti and SiO are 60% to 80% and 20% to 40%, respectively. For example, in the Ti-doped SiO composite target, the mass percentages of Ti and SiO can be, but are not limited to, 60% and 40%, 68% and 32%, 65% and 35%, 62% and 38%, 70% and 30%, 72% and 28%, 75% and 25%, 78% and 22%, 80% and 20%, etc.

[0106] Specifically, before the step of filling the coating chamber with argon and oxygen, the coating chamber is pre-evacuated to a vacuum degree of 8×10 -4 ~1×10 -2 Pa.

[0107] In some embodiments, the steps of preparing layer C include:

[0108] Step S312: pre-evacuate the coating chamber to a vacuum degree of 8×10 -4 ~1×10 -2 Pa, argon and oxygen were filled into it, the argon flow rate was 20sccm~60sccm, and the oxygen flow rate was 20sccm~60sccm, so that the pressure was maintained at 3×10 -2 ~6×10 -1 Pa;

[0109] Step S314: the target material is set to a Ti-doped SiO composite target material, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300W~800W, the chamber temperature is 50℃~150℃, and the negative bias voltage is switched between the first negative bias voltage and the second negative bias voltage every 180s~480s. The coating time is 2100s~4500s to obtain each C layer.

[0110] In step S312, the argon flow rate may be, but is not limited to, 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm, or a range consisting of any two of these values. The oxygen flow rate may be, but is not limited to, 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm, or a range consisting of any two of these values.

[0111] In step S314, the coating time may be, but is not limited to, 2100s, 2300s, 2500s, 2700s, 2800s, 3000s, 3200s, 3500s, 3600s, 3800s, 4000s, 4200s, 4500s or a range consisting of any two of these values.

[0112] In step S314, the negative bias voltage is switched between 30V and 800V, or 50V and 900V, or 100V and 1000V every 180s to 480s.

[0113] In step S314, the chamber temperature may be, but is not limited to, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 140°C, 150°C or a range consisting of any two of these values.

[0114] In some embodiments, the thickness of each C layer is 50 nm to 100 nm. For example, the thickness of each C layer can be, but is not limited to, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, or a range consisting of any two of these values.

[0115] The preparation method of the above-mentioned composite coating optimizes the vacuum coating parameters and uses high and low bias voltages alternately during the coating process to cleverly construct the microstructure of the product surface and improve the density of the coating, thereby improving the water stain resistance of the coating.

[0116] In the above preparation method, in the B layer and the C layer, a certain amount of silicon oxide is added to the titanium target to prepare a Ti-doped SiO composite target, which increases the Si content in the coating to a certain extent, thereby improving the wear resistance of the coating.

[0117] In addition, the use of this composite coating does not require changing the product structure or spraying fluorine-containing organic substances for sanitary products, making it more suitable for widespread promotion and mass production.

[0118] See also Figure 1 In some embodiments, the method for preparing the composite coating comprises the following steps:

[0119] Step S112: pre-evacuate the coating chamber to a vacuum degree of 8×10 -4 Pa~1×10 -2 Pa, argon gas was filled into it with a flow rate of 20sccm~60sccm to maintain the gas pressure at 3×10 -2 Pa~6×10 -1 Pa.

[0120] Step S114: Use one or more of Zr, Ti, Cr and Ta as target materials, adopt multi-arc ion plating method, set the power supply voltage to 20V~40V, the current to 50A~150A, the negative bias voltage to 100V~300V, the chamber temperature to 50~150℃, and the coating time to 60s~120s to obtain a metal base layer.

[0121] Step S212: Pre-evacuate the coating chamber to a vacuum degree of 8×10 -4 Pa~1×10 -2 Pa, argon gas was filled into it with a flow rate of 20sccm~60sccm to maintain the gas pressure at 3×10 -2 Pa~6×10 -1 Pa.

[0122] Step S214: the target material is set to a Ti-doped SiO composite target material, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300W~800W, the chamber temperature is set to 50℃~150℃, the negative bias voltage is set to 50V~150V, and the coating time is set to 1500s~2000s to obtain a B layer.

[0123] Step S312: pre-evacuate the coating chamber to a vacuum degree of 8×10 -4 Pa~1×10 -2 Pa, argon and oxygen were filled into it, the argon flow rate was 20sccm~60sccm, and the oxygen flow rate was 20sccm~60sccm, so that the pressure was maintained at 3×10 -2 Pa~6×10 -1 Pa.

[0124] Step S314: the target material is set to a Ti-doped SiO composite target material, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300W~800W, the chamber temperature is 50℃~150℃, and the negative bias voltage is switched between the first negative bias voltage and the second negative bias voltage every 180s~480s. The coating time is 2100s~4500s to obtain a C layer.

[0125] In some embodiments, the composite coating includes a metal base layer, a B layer, and a C layer stacked in sequence, or the composite coating includes a metal base layer, a B layer, a C layer, a B layer, and a C layer stacked in sequence. It can be understood that in other embodiments, the number of layers of the composite coating is not limited to three or five layers, but may also be seven, nine, eleven, etc., so that the B layer and the C layer are alternately stacked.

[0126] It can be understood that when there are two or more B layers and C layers, the material, thickness, etc. of each B layer can be the same or different. Similarly, the material, thickness, etc. of each C layer can be the same or different.

[0127] It can be understood that in some embodiments, the number of layers B and C is more than two, and the preparation steps of the composite coating further include sequentially repeating step S212, step S214, step S312, and step S314 at least once.

[0128] Figure 1 This is a schematic diagram of a process for preparing a composite coating according to an embodiment of the present invention. It should be understood that although Figure 1 The steps in the flowchart are shown in sequence as indicated by the arrows, but these steps are not necessarily performed in the order indicated by the arrows. Unless otherwise specified in this document, there is no strict order restriction for the execution of these steps, and they can be performed in other orders. Figure 1 At least part of the steps may include multiple sub-steps or multiple stages. These sub-steps or stages are not necessarily executed at the same time, but can be executed at different times. The order of execution is not necessarily sequential, but can be executed in turn or alternately with other steps or at least part of other sub-steps or stages.

[0129] The second aspect of the present application provides a composite coating, which is prepared by the method for preparing a composite coating according to the first aspect.

[0130] The third aspect of the present application provides a bathroom product, comprising the above-mentioned composite coating.

[0131] In order to make the purpose and advantages of the present application clearer, the composite coating of the present application and its effects are further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and shall not be used to limit the present application. The following embodiments do not include other components except for unavoidable impurities unless otherwise specified. The drugs and instruments used in the embodiments are conventionally selected in the art unless otherwise specified. The experimental methods for which specific conditions are not specified in the embodiments are implemented according to conventional conditions, such as the conditions described in the literature and books or the methods recommended by the manufacturer.

[0132] Example 1

[0133] This embodiment provides a composite film layer, and the preparation steps are as follows:

[0134] 1. Preparation of titanium-doped silicon oxide target

[0135] Ti and SiO powders were uniformly mixed in a ratio of 60% and 40% by mass respectively, and a target material with a specific shape was prepared by a hot pressing sintering method.

[0136] 2. Pre-treat the substrate

[0137] (1) The substrate is subjected to bright chromium electroplating treatment in a conventional manner in the art.

[0138] (2) The substrate is pre-treated and cleaned, and the process is as follows: ultrasonic degreasing, two-step water washing, ultrasonic dewaxing, two-step water washing, acid activation, four-step water washing, slow pulling and baking.

[0139] 3. Preparation of composite coating

[0140] Install the corresponding target materials in the PVD coating chamber. In the multi-arc ion coating system, there are two chromium targets, and in the RF sputtering coating system, there is a titanium-doped silicon oxide target. Place the pre-treated and baked substrate in the vacuum coating machine and prepare the corresponding film layer in the following steps:

[0141] (1) Prepare the metal base layer in the following steps: Use a multi-arc ion plating system to pre-evacuate the vacuum to 6×10 -3 Pa, argon gas was filled in at a flow rate of 30 sccm to maintain the gas pressure at 4.5×10 -1 Pa. Turn on the multi-arc ion plating power supply, the voltage is 22V, the current is 70A, the plating time is 120s, the negative bias voltage is 200V during plating, the chamber temperature is 80℃, and a metal base layer with a thickness of 10nm~50nm and a material of Cr is obtained.

[0142] (2) Preparation of layer B, the steps are as follows: turn off the multi-arc ion plating system used to prepare the metal base layer in (1), use the radio frequency sputtering coating system, pre-evacuate the vacuum to 6×10 -3 Pa, argon gas was filled in at a flow rate of 30 sccm to maintain the gas pressure at 4.5×10 -1 Pa. With titanium-doped silicon oxide target as the target material, the RF sputtering coating power supply was turned on, the power was 300W, the negative bias voltage was 100V during coating, the chamber temperature was 100℃, the coating time was 1800s, and a B layer with a thickness of 50nm~100nm was obtained.

[0143] (3) Preparation of C layer, the steps are as follows: Use RF sputtering coating system, pre-vacuum, vacuum degree to 6×10 -3 Pa, argon and oxygen were filled in, with the argon flow rate of 30 sccm and the oxygen flow rate of 30 sccm, so that the gas pressure was maintained at 5×10 -1 Pa. With titanium-doped silicon oxide target as the target material, the RF sputtering coating power supply was turned on, the RF power was 500W, the negative bias voltage was switched every 300s during coating, from 50V to 900V or 900V to 50V, the chamber temperature was 100℃, the coating time was 2100s, and a C layer with a thickness of 50nm~100nm was obtained.

[0144] The composite coating of this embodiment is obtained through the above steps.

[0145] Example 2

[0146] This embodiment provides a composite coating, and the preparation steps are similar to those of embodiment 1, except that: in the titanium-doped silicon oxide target, the mass percentage of Ti and SiO powder is 70:30; when preparing the metal base layer, the target material used is a Zr target; the steps for preparing the C layer are as follows: using a radio frequency sputtering coating system, pre-evacuate the vacuum to 6×10 -3 Pa, argon and oxygen were filled in, with the argon flow rate of 30 sccm and the oxygen flow rate of 30 sccm, so that the gas pressure was maintained at 5×10 -1 Pa. A titanium-doped silicon oxide target was used as the target material, and the RF sputtering coating power supply was turned on with a power of 300 W. During coating, the negative bias voltage was switched every 300 s, from 30 V to 800 V or 800 V to 30 V. The chamber temperature was 100 ° C. The coating time was 2100 s, and a C layer with a thickness of 50 nm to 100 nm was obtained. The other steps are the same as those in Example 1 and will not be repeated here.

[0147] Example 3

[0148] This embodiment provides a composite coating, and the preparation steps are similar to those of embodiment 1, except that: in the titanium-doped silicon oxide target, the mass percentage of Ti and SiO powder is 80:20; the target material used to prepare the metal base layer is a Ti target; the steps for preparing the C layer are as follows: a radio frequency sputtering coating system is used, and a vacuum degree of 6×10 -3 Pa, argon and oxygen were filled in, with the argon flow rate of 30 sccm and the oxygen flow rate of 30 sccm, so that the gas pressure was maintained at 5×10 -1 Pa. A titanium-doped silicon oxide target was used as the target material, and the RF sputtering coating power supply was turned on. The RF power was 800W. During coating, the negative bias voltage was switched every 300s, from 100V to 1000V or from 1000V to 100V. The chamber temperature was 100°C, and the coating time was 2100s to obtain a C layer with a thickness of 50nm to 100nm. The other steps were the same as those in Example 1 and will not be repeated here.

[0149] The process parameters in the preparation process of the composite coating in the above-mentioned Examples 1 to 3 are shown in Table 1 below:

[0150] Table 1

[0151]

[0152] Comparative Example 1

[0153] Comparative Example 1 provides a composite coating, and the preparation steps are as follows:

[0154] 1. Pre-treat the substrate

[0155] (1) The substrate is subjected to bright chromium electroplating treatment in a conventional manner in the art.

[0156] (2) The substrate is pre-treated and cleaned, and the process is as follows: ultrasonic degreasing, two-step water washing, ultrasonic dewaxing, two-step water washing, acid activation, four-step water washing, slow pulling and baking.

[0157] 2. Preparation of composite coating

[0158] Install the target material in the PVD coating chamber. In the multi-arc ion coating system, there are two titanium targets. Place the pre-treated and baked substrate in the vacuum coating machine and prepare the corresponding film layer in the following steps:

[0159] (1) Preparation of metal base layer

[0160] Use multi-arc ion plating system to pre-evacuate to a vacuum degree of 6×10 -3 Pa, argon gas was filled in at a flow rate of 30 sccm to maintain the gas pressure at 4.5×10 -1Pa. Turn on the multi-arc ion plating power supply, use titanium target as target material, set the voltage to 24V, the current to 90A, the negative bias voltage to 200V during plating, the chamber temperature to 80℃, the plating time to 120s, and obtain a Ti base layer with a thickness of 10nm~50nm.

[0161] (2) Preparation of titanium oxide layer

[0162] Use multi-arc ion plating system to evacuate the vacuum to a level of 6×10 -3 Pa, argon and oxygen were filled in, the argon flow rate was 30sccm, the oxygen flow rate was 30sccm, and the gas pressure was maintained at 6×10 -1 Pa. Turn on the multi-arc ion plating power supply, use titanium target as target material, set the voltage to 24V, the current to 90A, the negative bias voltage to 100V during plating, the chamber temperature to 75℃, the plating time to 120s, and obtain a titanium oxide layer with a thickness of 10nm~50nm.

[0163] The composite coating of Comparative Example 1 is obtained through the above steps.

[0164] Comparative Example 2

[0165] Comparative Example 2 provides a composite coating, and the preparation steps are as follows:

[0166] 1. Pre-treat the substrate

[0167] (1) The substrate is subjected to bright chromium electroplating treatment in a conventional manner in the art.

[0168] (2) The substrate is pre-treated and cleaned, and the process is as follows: ultrasonic degreasing, two-step water washing, ultrasonic dewaxing, two-step water washing, acid activation, four-step water washing, slow pulling and baking.

[0169] 2. Preparation of composite coating

[0170] The corresponding target materials are installed in the PVD coating chamber. In the multi-arc ion coating system, two Cr targets are provided, and in the radio frequency sputtering coating system, one titanium oxide target is provided. The substrate after pretreatment and baking is placed in the vacuum coating machine for coating, and the corresponding film layer is prepared in the following steps:

[0171] (1) Preparation of metal base layer

[0172] Use multi-arc ion plating system, pre-vacuum, vacuum degree to 6×10 -3 Pa, argon gas was filled in at a flow rate of 30 sccm to maintain the gas pressure at 4.5×10 -1Pa. Turn on the multi-arc ion plating power supply, set the voltage to 22V, the current to 70A, the negative bias voltage to 200V during plating, the chamber temperature to 80℃, the plating time to 120s, and obtain a Cr base layer with a thickness of 10nm~50nm.

[0173] (2) Preparation of titanium oxide layer

[0174] The multi-arc ion plating system used to prepare the metal base layer in (1) was turned off, and the radio frequency sputtering coating system was used. The titanium oxide target was turned on and the vacuum was evacuated to a background vacuum of 6×10 -3 Pa, argon gas was filled in with a flow rate of 30 sccm to maintain the gas pressure at 4.5×10 -1 Pa, turn on the RF sputtering coating power supply, the power is 500 W, the negative bias voltage is 100 V during coating, the chamber temperature is 65 ° C, the coating time is 1800 s, and a titanium oxide layer with a thickness of 30nm~80nm is obtained.

[0175] The composite coating of Comparative Example 2 was prepared through the above steps.

[0176] Comparative Example 3

[0177] Comparative Example 3 provides a composite coating, and the preparation steps are similar to those of Example 1, except that the preparation steps of the C layer are different. In Comparative Example 3, the preparation steps of the C layer include: using a radio frequency sputtering coating system, pre-evacuating the vacuum to a vacuum degree of 6×10 - 3 Pa, argon and oxygen were filled in, with the argon flow rate of 30 sccm and the oxygen flow rate of 30 sccm, so that the gas pressure was maintained at 5×10 -1 Pa. With titanium-doped silicon oxide target as the target material, the RF sputtering coating power supply was turned on, the RF power was 500W, the negative bias voltage during coating was 300V, the chamber temperature was 100℃, the coating time was 2100s, and a C layer with a thickness of 50nm~100nm was obtained.

[0178] The composite coatings prepared in the above embodiments and comparative examples were tested as follows:

[0179] (1) Water stain test method: Use toothpaste water, shampoo water, and shower gel water (the solution is completely dissolved without solid precipitation) to drop 2 to 3 drops on the surface of the test piece. After drying naturally at room temperature (about 16 hours), wipe the surface with clean water and a dust-free cloth, and wipe it with absorbent cotton. Under natural light, observe the surface of the test piece from all angles at a distance of about 400 mm from the surface of the test piece. The surface water stains are wiped off and there is no residue.

[0180] (2) Salt spray test method: Test according to GB / T 10125. AASS test for 48 hours, at any 650mm 2There should be no more than 2 surface defects within a product, and no more than 3 surface defects within any 25mm length of the product connection line and parting line. The defect diameter should not be greater than 1.6mm.

[0181] (3) Friction resistance test method: The test shall be conducted in accordance with the provisions of Appendix D of QB / T 5419-2019. The ABS substrate shall be rubbed for 1000 cycles and other substrates shall be rubbed for 2500 cycles.

[0182] The test results of the composite coatings of the above embodiments and comparative examples are shown in Table 2 below:

[0183] Table 2

[0184]

[0185] The scanning electron microscope (SEM) images of the composite coatings prepared in the above embodiments and comparative examples are as follows: Figures 2 to 6 As shown. Among them, Figure 2 This is a scanning electron microscope image of the composite coating prepared in Example 1. Figure 3 This is a scanning electron microscope image of the composite coating prepared in Example 2. Figure 4 This is a scanning electron microscope image of the composite coating prepared in Example 3. Figure 5 This is a scanning electron microscope image of the composite coating prepared in Comparative Example 1. Figure 6 This is a scanning electron microscope image of the composite coating prepared in Comparative Example 2.

[0186] From Table 2 and Figure 2~Figure 6 It can be seen from the SEM image that the composite coating prepared in the embodiment is more dense and has a special microstructure due to the alternating high and low bias voltages, so that it can maintain a good waterproof effect. In addition, the composite coating is deposited by combining multi-arc ion plating and radio frequency sputtering, and the Si content in the coating is increased, and the coating hardness is improved to improve the surface scratch resistance. However, the multi-arc ion plating titanium oxide coating has a fast ion plating deposition rate, and more "large droplets" are generated in the coating. The coating is relatively loose and porous, resulting in residual water stains.

[0187] Figure 7 This is a total spectrum of element distribution of the composite coating prepared in Example 1. The element distribution of the composite coating of Example 1 is shown in Table 3 below:

[0188] Table 3

[0189]

[0190] Figure 8 This is an atomic force microscope surface morphology image of the composite coating prepared in Example 1 of the present application. Figure 7 and Figure 8It can be seen that after the Ti-doped SiO composite target is formed by RF sputtering, elements such as Ti, Si, and O have been deposited on the surface of the product. Moreover, the film is deposited evenly, and the surface roughness and nanoparticle size are relatively uniform, achieving better water stain resistance and friction resistance of the film layer.

[0191] Fig. 9 This is a water stain residue diagram of the composite coating prepared in Example 1 before water stain test. Fig.10 This is a picture of a water stain test performed on the composite coating prepared in Example 1 after the water stain was wiped with clean water and a dust-free cloth and then wiped with absorbent cotton. Fig.11 This is a water stain residue image of the composite coating prepared in Comparative Example 1 before the water stain test. Fig.12 The composite coating prepared in Comparative Example 1 was subjected to a water stain test. The water stain was wiped with clean water and a dust-free cloth and then wiped with absorbent cotton. Figure 9~Figure 12 It can be seen that the composite coating prepared in Example 1 has less water stains before wiping, and the water stains can be completely removed by wiping the surface with clean water and a dust-free cloth and wiping with absorbent cotton. However, the composite coating of Comparative Example 1 has more water stains before wiping, and there are still water stains after wiping the surface with clean water and a dust-free cloth and wiping with absorbent cotton.

[0192] It can be seen from the above experimental data that the composite coating prepared by the embodiment of the present application not only has good wear resistance, but also has good water stain resistance effect, and can be used in bathroom products.

[0193] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0194] The above-described embodiments only express several implementation methods of the present application, which is convenient for understanding the technical solution of the present application in detail, but it cannot be understood as limiting the scope of protection of the invention patent. It should be pointed out that for ordinary technicians in this field, without departing from the concept of the present application, several modifications and improvements can be made, which all belong to the scope of protection of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments on the basis of the technical solutions provided in the present application are all within the scope of protection of the claims attached to the present application. Therefore, the scope of protection of the patent of this application shall be based on the contents of the attached claims, and the description and drawings can be used to explain the contents of the claims.

Claims

1. A method for preparing a composite coating, characterized in that: The steps include: Forming a metal primer layer on the surface of the substrate; Forming n layers of B layer and n layers of C layer on the surface of the metal base layer to prepare a composite coating; Wherein, n ≥ 1, along the thickness direction of the composite coating, n layers of B layers and n layers of C layers are alternately arranged, and the B layer closest to the metal base layer is closer to the metal base layer than the C layer closest to the metal base layer, the material of the B layer includes Ti and SiO, and the material of the C layer includes TiO x and SiO y The C layer is formed by sputtering, and the negative bias is switched between a first negative bias and a second negative bias every 180s to 480s, wherein the first negative bias is less than or equal to 100V, and the second negative bias is greater than or equal to 800V.

2. The method for preparing a composite coating according to claim 1, characterized in that: The first negative bias voltage is 30V~100V, and the second negative bias voltage is 800V~1000V.

3. The method for preparing a composite coating according to claim 1 or 2, characterized in that: The steps of preparing each of the C layers include: Filling the coating chamber with argon and oxygen, wherein the argon flow rate is 20 sccm~60 sccm, and the oxygen flow rate is 20 sccm~60 sccm; The target material is set to a Ti-doped SiO composite target, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300W~800W, the chamber temperature is 50℃~150℃, the negative bias voltage is switched between the first negative bias voltage and the second negative bias voltage every 180s~480s, and the coating time is 2100s~4500s to obtain each C layer.

4. The method for preparing the composite coating according to claim 3, characterized in that: In the Ti-doped SiO composite target, the mass percentages of Ti and SiO are 60% to 80% and 20% to 40% respectively; and / or, The thickness of each C layer is 50nm~100nm.

5. The method for preparing a composite coating according to claim 1, characterized in that: The steps of preparing each of the B layers include: Filling the coating chamber with argon gas, wherein the argon gas flow rate is 20 sccm~60 sccm; The target material is set to a Ti-doped SiO composite target, and a radio frequency sputtering coating method is adopted. The radio frequency power is set to 300 W, the chamber temperature is 50° C. to 150° C., the negative bias voltage is 50V to 150V, and the coating time is 1500s to 2000s to obtain each of the B layers.

6. The method for preparing the composite coating according to claim 5, characterized in that: In the Ti-doped SiO composite target, the mass percentages of Ti and SiO are 60% to 80% and 20% to 40% respectively; and / or, The thickness of each B layer is 50nm~100nm.

7. The method for preparing a composite coating according to any one of claims 1, 2 and 4 to 6, characterized in that: The metal base layer is formed by multi-arc ion plating.

8. The method for preparing a composite coating according to claim 7, characterized in that: The preparation steps of the metal primer layer include: Filling the coating chamber with argon gas, wherein the argon gas flow rate is 20 sccm~60 sccm; One or more of Zr, Ti, Cr and Ta are used as target materials, and a multi-arc ion plating method is adopted. The power supply voltage is set to 20V~40V, the current is set to 50A~150A, the negative bias voltage is set to 100V~300V, the chamber temperature is set to 50℃~150℃, and the plating time is set to 60s~120s to obtain the metal base layer.

9. The method for preparing a composite coating according to claim 8, characterized in that: The thickness of the metal base layer is 10nm-50nm.

10. A composite coating, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 9.

11. A bathroom product, characterized in that: Comprising the composite coating as claimed in claim 10.

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