Hydrophobic layer and preparation method thereof, hydrophobic composite layer and product

Abstract

The invention provides a hydrophobic layer and a preparation method thereof, a hydrophobic composite layer and a product. The preparation method of the hydrophobic layer comprises the following steps: in the presence of a nitrogen source, performing co-deposition on the surface of a binding layer by adopting direct-current magnetron sputtering and radio-frequency magnetron sputtering to form the hydrophobic layer, the target material of the direct current magnetron sputtering comprises one or more of Zr, Ti, Cr, Ta and compounds thereof; a target material of the radio frequency magnetron sputtering comprises Si. The surface of the prepared coating has excellent hydrophobic performance, an easy-to-clean function, friction resistance and scraping resistance, the service life of the hydrophobic layer can be further prolonged, the coating can be widely applied to kitchen and bath products, and the excellent quality and attractiveness of the products are guaranteed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electroplating, in particular to a hydrophobic layer and a preparation method thereof, a hydrophobic composite layer and an article. BACKGROUND

[0002] Kitchen and bathroom products (such as kitchen faucets, sinks, shower heads, shower heads, bathroom accessories, toilet flushing buttons, floor drains, etc.) are complex due to the humid environment, and the surface is easy to get dust, water stains, etc. during use, which is difficult to clean and affects the product quality and appearance. Therefore, it is necessary to prepare a long-acting easy-to-clean, hydrophobic functional coating on the surface of the product. Traditional hydrophobic coatings mostly use hydrophobic materials such as hydrophobic fluorosilicon composite, non-fluorosilicon high molecular solution polymer, and organic-inorganic hybrid super-hydrophobic materials with nano structure. However, such hydrophobic coatings have the disadvantages of insufficient stability and poor reliability, and the micro-nano structure on the surface is easily damaged under external stress, thereby losing the hydrophobic property. Traditional cleaning films are usually coated on the product by vacuum evaporation (PVD) of high-transparency anti-fingerprint film (AF film) or spraying of organic coating. However, the evaporation of AF film is prone to wear and tear due to the thin coating, resulting in short service life. The organic coating is not scratch-resistant on the surface of the product, which affects its service life. SUMMARY

[0003] Therefore, it is necessary to provide a hydrophobic layer and a preparation method thereof, so that the hydrophobic layer has excellent surface hydrophobic property and excellent friction resistance and scratch resistance, thereby improving the stability and service life of the hydrophobic layer.

[0004] In a first aspect, the present application provides a preparation method of a hydrophobic layer, comprising the following steps:

[0005] In the presence of a nitrogen source, a hydrophobic layer is formed on the surface of the bonding layer by direct current magnetron sputtering and radio frequency magnetron sputtering; the target material of the direct current magnetron sputtering comprises one or more of Zr, Ti, Cr, Ta and their composites; and the target material of the radio frequency magnetron sputtering comprises Si.

[0006] Optionally, the preparation method further satisfies at least one of the following (1) to (12):

[0007] (1) the material of the bonding layer comprises one or more of a metal and a nitride thereof;

[0008] (2) the Si comprises polycrystalline silicon;

[0009] Optionally, the grain size of the polycrystalline silicon is 1 μm-50 μm;

[0010] (3) the thickness of the hydrophobic layer is 1 μm-3 μm;

[0011] (4) the voltage of the direct current magnetron sputtering is 300V-500V;

[0012] (4) the current of the direct current magnetron sputtering is 1A-3A;

[0013] (5) the power of the radio frequency magnetron sputtering is 1500W-2000W;

[0014] (6) the bias voltage of the co-deposition is a negative bias voltage;

[0015] Optionally, the negative bias voltage is -200V to -500V;

[0016] (7) the time of the co-deposition is 120min-300min;

[0017] (8) the temperature of the co-deposition is 200℃-300℃;

[0018] (10) the gas pressure of the co-deposition is 8x10 -2 Pa-7x10 -1 Pa

[0019] (11) working gas is introduced during the co-deposition;

[0020] Optionally, the working gas comprises one or more of argon and helium;

[0021] Optionally, the flow rate of the working gas is 20sccm-60sccm;

[0022] (12) the nitrogen source comprises nitrogen;

[0023] Optionally, the flow rate of the nitrogen is 20sccm-60sccm.

[0024] In a second aspect, the application provides a hydrophobic layer prepared by the preparation method of the hydrophobic layer provided in the first aspect.

[0025] In a third aspect, the application provides a hydrophobic composite layer, which comprises an intermediate film layer and the hydrophobic layer provided in the second aspect formed in sequence on the surface of a substrate.

[0026] Optionally, the intermediate film layer comprises at least two film layers;

[0027] Optionally, the materials of the film layers are the same or different.

[0028] Optionally, the intermediate film layer comprises a first film layer and a second film layer formed in sequence on the surface of a substrate;

[0029] Optionally, the material of the first film layer comprises one or more of Zr, Ti, Cr, Ta and a composite thereof;

[0030] Optionally, the material of the second film layer comprises one or more of Zr, Ti, Cr, Ta and nitrides thereof;

[0031] Optionally, the thickness of the first film layer is 10 nm-50 nm;

[0032] Optionally, the thickness of the second film layer is 50 nm-100 nm.

[0033] In a fourth aspect, the application provides a method for preparing the hydrophobic composite layer of the third aspect, comprising the following steps:

[0034] depositing an intermediate film layer on the surface of the substrate by multi-arc ion plating and / or magnetron sputtering;

[0035] depositing the hydrophobic layer on the surface of the intermediate film layer by the method for preparing the hydrophobic layer of the first aspect.

[0036] Optionally, the method for preparing the intermediate film layer comprises:

[0037] forming a first film layer on the surface of the substrate by multi-arc ion plating;

[0038] forming a second film layer on the surface of the first film layer by magnetron sputtering in the presence of a nitrogen source;

[0039] Optionally, the target material for multi-arc ion plating and the target material for magnetron sputtering each independently comprises one or more of Zr, Ti, Cr, Ta and composites thereof.

[0040] Optionally, the method for preparing further satisfies at least one of the following (1)-(16):

[0041] (1) the voltage of the multi-arc ion plating is 20 V-40 V;

[0042] (2) the current of the multi-arc ion plating is 50 A-150 A;

[0043] (3) the bias voltage of the multi-arc ion plating is negative bias voltage;

[0044] Optionally, the negative bias voltage is -100 V to -300 V;

[0045] (4) the time of the multi-arc ion plating is 1 min-3 min;

[0046] (5) the temperature of the multi-arc ion plating is 50℃-150℃;

[0047] (6) the vacuum degree of the multi-arc ion plating is 8×10 -4 Pa-6×10 -3 Pa;

[0048] (7) the voltage of the magnetron sputtering is 350V-600V;

[0049] (8) the current of the magnetron sputtering is 2A-5A;

[0050] (9) the bias voltage of the magnetron sputtering is a negative bias voltage;

[0051] Optionally, the negative bias voltage is -100V to -300V;

[0052] (10) the time of the magnetron sputtering is 10min-30min;

[0053] (11) the temperature of the magnetron sputtering is 100℃-200℃;

[0054] (12) the nitrogen source comprises nitrogen gas;

[0055] Optionally, the flow rate of the nitrogen gas is 20sccm-60sccm;

[0056] (13) a working gas is introduced during the preparation of the intermediate film layer;

[0057] Optionally, the working gas comprises one or more of argon gas and helium gas;

[0058] Optionally, the flow rate of the working gas is 20sccm-60sccm;

[0059] (14) the gas pressure during the preparation of the intermediate film layer is 8x10 -2 Pa-7x10 -1 Pa;

[0060] (15) the material of the substrate comprises metal;

[0061] Optionally, the metal comprises one or more of zinc alloy, copper alloy and stainless steel;

[0062] Optionally, the substrate further comprises a substrate with a plating layer on the surface;

[0063] Further optionally, the plating layer comprises one or more of copper plating layer, nickel plating layer and chromium plating layer;

[0064] (16) the substrate further comprises a pretreatment;

[0065] Optionally, the pretreatment comprises one or more of cleaning, activation, slow pulling and drying of the substrate.

[0066] In a fifth aspect, the application further provides an article, which comprises the hydrophobic layer provided in the second aspect or the hydrophobic composite layer provided in the third aspect;

[0067] Optionally, the product comprises a kitchen and bathroom product.

[0068] Compared with the prior art, the technical scheme of the present application has the beneficial effects of:

[0069] The present application prepares a hydrophobic layer containing a special composite material by using a combination of direct current magnetron sputtering and radio frequency magnetron sputtering. In the presence of a nitrogen source, a hydrophobic layer is formed on the surface of the bonding layer by using direct current magnetron sputtering and radio frequency magnetron sputtering; the target material of the direct current magnetron sputtering comprises one or more of Zr, Ti, Cr, Ta and their composites; the target material of the radio frequency magnetron sputtering comprises Si. The hydrophobic layer prepared by the present application has excellent hydrophobic properties on the surface, and has an easy-to-clean function when applied to the surface of a workpiece. At the same time, the hydrophobic layer prepared by the present application has excellent friction resistance and scratch resistance, as well as excellent stability and durability, which can further prolong the service life of the hydrophobic layer. BRIEF DESCRIPTION OF DRAWINGS

[0070] Figure 1 Structure diagram of the hydrophobic composite layer prepared for Example 1 of the present application, in which T is the substrate, A is the first film layer, B is the second film layer, and C is the hydrophobic layer.

[0071] Figure 2 Static contact angle test diagram of the hydrophobic composite layer prepared for Example 1 of the present application.

[0072] Figure 3 Static contact angle test diagram of the hydrophobic composite layer prepared for Example 1 of the present application after 10,000 times of friction.

[0073] Figure 4 SEM surface scanning electron microscope diagram of the hydrophobic composite layer prepared for Example 1 of the present application.

[0074] Figure 5 Cross-sectional SEM scanning electron microscope diagram of the hydrophobic composite layer prepared for Example 1 of the present application.

[0075] Figure 6 EDS spectrum diagram of the hydrophobic composite layer prepared for Example 1 of the present application.

[0076] Figure 7 Line-scan element distribution diagram of the hydrophobic composite layer prepared for Example 1 of the present application.

[0077] Figure 8 Cross-sectional EDS of the hydrophobic composite layer prepared for Example 1 of the present application. DETAILED DESCRIPTION

[0078] For the purpose of promoting an understanding of the application, the application will now be described in greater detail with reference to the figures. The preferred embodiments of the application are illustrated in the figures. However, the application can be implemented in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and fully convey the scope of the application to those skilled in the art.

[0079] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0080] As used herein, "optionally", "optional", or "optional" means to choose from either of the two parallel schemes "yes" or "no". If there are multiple "options" in a technical solution, and there is no special description, and there is no contradictory relationship or mutual restriction, each "option" is independent of each other. As used herein, the term "and / or" includes any and all combinations of one or more related listed items. As used herein, "a plurality of", "a plurality of", and the like, unless otherwise limited, means greater than or equal to 2 in number, for example, "one or more" means one, two or more. The open technical features or technical solutions described herein with the words "contain", "include", "comprise" and the like, unless otherwise stated, do not exclude additional members other than the listed members, which can be regarded as providing both closed features or solutions composed of listed members and open features or solutions including additional members in addition to the listed members.

[0081] In this application, the terms "first", "second", "third", "fourth" and the like in the "first aspect", "second aspect", "third aspect", "fourth aspect" and the like are only used for description purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth" and the like only serve the purpose of non-exhaustive enumeration and description, and should be understood as not constituting a closed limitation on the quantity.

[0082] If not specifically stated, all embodiments and optional embodiments of the application can be combined with each other to form new technical solutions.

[0083] Kitchen and bathroom products (such as kitchen faucets, sinks, shower heads, shower heads, bathroom accessories, toilet flushing buttons, floor drains, etc.) due to the use of complex and humid environment, the surface is easy to get dust, oil stains, water stains, etc. during use, it is difficult to clean, affecting product quality and appearance.

[0084] Traditional hydrophobic surface treatment includes coating with inert hydrophobic fluorosilicon-based composite, non-fluorosilicon-based polymer, organic-inorganic hybrid super-hydrophobic material with nanostructure, etc. However, the hydrophobic material has poor stability, and the surface is easily damaged and quickly loses the hydrophobic function. In addition, PVD evaporation AF film or organic coating is used to coat the product, but the evaporation AF film is prone to wear due to the thin coating, resulting in short service life, and the organic coating is not resistant to scratching on the product surface, which affects the service life.

[0085] Therefore, the present application aims to provide a hydrophobic layer and a preparation method thereof to solve the technical problems of insufficient hydrophobic function of traditional hydrophobic surface, leading to difficult cleaning of workpieces, and poor durability, short service life, etc. of traditional hydrophobic surface, so as to ensure easy cleaning and aesthetics of kitchen and bathroom products and workpieces.

[0086] In a first aspect, the present application provides a preparation method of a hydrophobic layer, comprising the following steps:

[0087] In the presence of a nitrogen source, a hydrophobic layer is formed on the surface of the bonding layer by direct current magnetron sputtering and radio frequency magnetron sputtering; the target material of the direct current magnetron sputtering comprises one or more of Zr, Ti, Cr, Ta and their composites; and the target material of the radio frequency magnetron sputtering comprises Si.

[0088] The present application processes specific target materials by direct current magnetron sputtering and radio frequency magnetron sputtering to form a hydrophobic layer with a nanocrystalline composite structure, which has excellent hydrophobic performance, friction resistance, scratch resistance and cleaning agent resistance. At the same time, while taking into account the excellent hydrophobic surface performance of the hydrophobic layer, it also has excellent hardness, significantly improving the reliability of the hydrophobic layer. The hydrophobic layer prepared by the present application has long-term hydrophobic function, which significantly improves the use performance and aesthetics of the product when used on the surface of kitchen and bathroom products or other workpieces.

[0089] In some embodiments, the material of the bonding layer comprises one or more of a metal and a nitride thereof. As a non-limiting example, it comprises Zr, Ti, Cr, Ta and their composites, or is a nitride of Zr, Ti, Cr, Ta and their composites. As a non-limiting example, the composite comprises one or more of ZrTi, ZrCr, ZrTa, TiCr, TiTa, CrTa, ZrTiCr, ZrTiTa, ZrCrTa, TiCrTa and ZrTiCrTa. As a non-limiting example, the nitride comprises one or more of ZrN, TiN, CrN, TaN, ZrTiN, ZrCrN, ZrTaN, TiCrN, TiTaN, CrTaN, ZrTiCrN, ZrTiTaN, ZrCrTaN-SiN, TiCrTaN and ZrTiCrTaN.

[0090] In some embodiments, the Si comprises polycrystalline silicon. The purity of Si used in the present application is ≥ 99.999%, the grain size: 1-50 μm (uniform distribution), the density: ≥ 98% of the theoretical density (2.33 g / cm³).

[0091] In some embodiments, the thickness of the hydrophobic layer is 1-3 μm, including but not limited to 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm or a range formed by any two of the foregoing and numerical values within the range.

[0092] In some embodiments, the voltage of the DC magnetron sputtering is 300-500 V, including but not limited to 300 V, 320 V, 350 V, 380 V, 400 V, 420 V, 450 V, 480 V, 500 V or a range formed by any two of the foregoing and numerical values within the range.

[0093] In some embodiments, the current of the DC magnetron sputtering is 1-3 A, including but not limited to 1 A, 1.5 A, 2 A, 2.5 A, 3 A or a range formed by any two of the foregoing and numerical values within the range.

[0094] In some embodiments, the power of the RF magnetron sputtering is 1500-2000 W, including but not limited to 1500 W, 1600 W, 1700 W, 1800 W, 1900 W, 2000 W or a range formed by any two of the foregoing and numerical values within the range.

[0095] In some embodiments, the bias voltage of the co-deposition is a negative bias voltage.

[0096] In some embodiments, the negative bias voltage is -200 to -500 V, including but not limited to -200 V, -250 V, -300 V, -350 V, -400 V, -450 V, -500 V or a range formed by any two of the foregoing and numerical values within the range.

[0097] In some embodiments, the time of the co-deposition is 120-300 min, including but not limited to 120 min, 150 min, 180 min, 200 min, 220 min, 250 min, 280 min, 300 min or a range formed by any two of the foregoing and numerical values within the range.

[0098] In some embodiments, the temperature of the co-deposition is 200-300 °C, including but not limited to 200 °C, 220 °C, 250 °C, 280 °C, 300 °C or a range formed by any two of the foregoing and numerical values within the range.

[0099] In some embodiments, the gas pressure of the co-deposition is 8x10 -2 Pa-7x10 -1Pa, including but not limited to 8x10 -2 Pa, 9x10 -2 Pa, 1x10 -1 Pa, 2x10 -1 Pa, 3x10 -1 Pa, 4x10 -1 Pa, 5x10 -1 Pa, 6x10 -1 Pa, 7x10 -1 Pa, or a range formed by any two of the foregoing and numerical values within the range.

[0100] In some embodiments, a working gas is introduced during the co-deposition process.

[0101] In some embodiments, the working gas comprises one or more of argon and helium. The use of argon in the present application can better achieve the technical effects of the present application.

[0102] In some embodiments, the flow rate of the working gas is 20-60 seem, including but not limited to 20 seem, 25 seem, 30 seem, 35 seem, 40 seem, 45 seem, 50 seem, 55 seem, 60 seem, or a range formed by any two of the foregoing and numerical values within the range.

[0103] In some embodiments, the nitrogen source is nitrogen.

[0104] In some embodiments, the flow rate of the nitrogen is 20-60 seem, including but not limited to 20 seem, 25 seem, 30 seem, 35 seem, 40 seem, 45 seem, 50 seem, 55 seem, 60 seem, or a range formed by any two of the foregoing and numerical values within the range.

[0105] The present application combines the direct current magnetron sputtering and the radio frequency magnetron sputtering, and further controls the process parameters of the direct current magnetron sputtering and the radio frequency magnetron sputtering, thereby controlling the surface properties of the hydrophobic layer, having excellent hydrophobicity and easy-to-clean function, and at the same time having excellent friction resistance and scratch resistance, so that the hydrophobic layer has longer hydrophobicity, prolonging the service life of the hydrophobic layer.

[0106] In some embodiments, the metal nitride and silicon nitride are treated by the direct current magnetron sputtering and the radio frequency magnetron sputtering to form a nanocomposite structure of nanocrystalline metal nitride implanted in amorphous silicon nitride, which improves the hardness of the hydrophobic layer while taking into account the lubricity of the coating and effectively reducing the surface friction coefficient to improve the hydrophobic and easy-to-clean performance of the coating.

[0107] In a second aspect, the present application provides a hydrophobic layer prepared by the method for preparing a hydrophobic layer provided in the first aspect.

[0108] The hydrophobic layer of the present application has a special (X1, Si)N nanocrystalline composite structure. The (X1, Si)N represents a nitride of (X1, Si), and the X1 is a metal, including one or more of Zr, Ti, Cr, Ta and a composite thereof. As a non-limiting example, the (X1, Si)N includes one or more of ZrN-SiN, TiN-SiN, CrN-SiN, TaN-SiN, ZrTiN-SiN, ZrCrN-SiN, ZrTaN-SiN, TiCrN-SiN, TiTaN-SiN, CrTaN-SiN, ZrTiCrN-SiN, ZrTiTaN-SiN, ZrCrTaN-SiN, TiCrTaN-SiN and ZrTiCrTaN-SiN.

[0109] The hydrophobic layer of the present application realizes the hydrophobic and easy-to-clean functions of the coating without containing silane, fluorine and other organic compounds. At the same time, the prepared hydrophobic layer does not need to be modified by low surface energy substances, avoiding the volatilization of organic solvents caused by the existing preparation process, thereby being more environmentally friendly.

[0110] In a third aspect, the present application provides a hydrophobic composite layer, which includes an intermediate film layer and a hydrophobic layer provided in the second aspect formed in sequence on the surface of a substrate.

[0111] In some embodiments, the intermediate film layer includes at least two film layers.

[0112] Optionally, the materials of the film layers are the same or different.

[0113] In some embodiments, the intermediate film layer includes a first film layer and a second film layer formed in sequence on the surface of a substrate.

[0114] In some embodiments, the material of the first film layer includes one or more of Zr, Ti, Cr, Ta and a composite thereof. As a non-limiting example, the composite includes one or more of ZrTi, ZrCr, ZrTa, TiCr, TiTa, CrTa, ZrTiCr, ZrTiTa, ZrCrTa, TiCrTa and ZrTiCrTa.

[0115] In some embodiments, the material of the second film layer comprises one or more of Zr, Ti, Cr, Ta, and nitrides thereof. As non-limiting examples, the nitrides comprise one or more of ZrN, TiN, CrN, TaN, ZrTiN, ZrCrN, ZrTaN, TiCrN, TiTaN, CrTaN, ZrTiCrN, ZrTiTaN, ZrCrTaN, TiCrTaN, and ZrTiCrTaN.

[0116] In some embodiments, the thickness of the first film layer is 10 nm-50 nm, including but not limited to 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, or a range formed by any two of the foregoing and numerical values within the range.

[0117] In some embodiments, the thickness of the second film layer is 50 nm-100 nm, including but not limited to 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, or a range formed by any two of the foregoing and numerical values within the range.

[0118] The present application designs a composite structure of an intermediate film layer and a hydrophobic layer, especially uses multi-arc ion plating and magnetron sputtering to prepare a three-layer composite structure formed by a first film layer, a second film layer, and a hydrophobic layer, which has at least three layers of different materials and structures, and has excellent bonding performance and interface performance between the film layers. While the surface performance of the coating is taken into account, the hardness is excellent, and the reliability of the coating is significantly improved. The hydrophobic layer prepared by the present application has long-term hydrophobic function, which is used for the surface of kitchen and bathroom products or other workpieces to significantly improve the use performance and aesthetics of the products.

[0119] In a fourth aspect, the present application also provides a preparation method of the hydrophobic composite layer provided in the third aspect, comprising the following steps:

[0120] S10, depositing an intermediate film layer on the surface of the substrate by multi-arc ion plating and / or magnetron sputtering.

[0121] S20, depositing the hydrophobic layer on the surface of the intermediate film layer by the preparation method of the hydrophobic layer provided in the first aspect.

[0122] In some embodiments, in step S10, the intermediate film layer is deposited on the surface of the substrate by magnetron sputtering in the presence of a nitrogen source.

[0123] In some embodiments, the preparation method of the hydrophobic composite layer comprises the following steps:

[0124] S11, forming a first film layer on the surface of the substrate by multi-arc ion plating.

[0125] S12, forming a second film layer on the surface of the first film layer by magnetron sputtering in the presence of a nitrogen source.

[0126] S20, depositing the hydrophobic layer on the surface of the second film layer by the method for preparing the hydrophobic layer provided in the first aspect.

[0127] Referring to FIG. 1, Figure 1 As shown in FIG. 1, the structure of the hydrophobic composite layer prepared in the present application is A / B / C, wherein A is the first film layer, B is the second film layer, and C is the hydrophobic layer, and A, B, and C are the first film layer, the second film layer, and the hydrophobic layer deposited on the surface of the substrate T in sequence.

[0128] In some embodiments, the target material for the multi-arc ion plating and the target material for the magnetron sputtering each independently comprises one or more of Zr, Ti, Cr, Ta, and composites thereof. As non-limiting examples, the target material comprises one or more of ZrTi, ZrCr, ZrTa, TiCr, TiTa, CrTa, ZrTiCr, ZrTiTa, ZrCrTa, TiCrTa, and ZrTiCrTa.

[0129] The first film layer prepared by multi-arc ion plating in the present application has a nanoscale rough structure, which produces mechanical interlocking with the substrate material, thereby improving the interfacial bonding force of the first film layer and the substrate and enhancing the overall performance of the hydrophobic composite layer, especially the service life and reliability of the overall structure of the hydrophobic composite layer. The present application further investigates the process parameters of multi-arc ion plating, and within the range of the above-mentioned process parameters, the target deposition rate is fast, and uniformity of large-area deposition can be achieved.

[0130] The second film layer is prepared by magnetron sputtering in the present application, and the surface roughness of the second film layer is controlled by adjusting the magnetron sputtering parameters, which on the one hand can have excellent interfacial bonding performance with the first film layer, improve the hydrophobicity of the hydrophobic composite layer, and reduce the risk of coating peeling and cracking, thereby improving the reliability of the hydrophobic composite layer. At the same time, the prepared metal nitride has excellent chemical properties and dense structure, which can improve the double protection of the hydrophobic composite layer and improve the cleaning agent resistance of the hydrophobic composite layer.

[0131] In some embodiments, the voltage for multi-arc ion plating is 20V-40V, including but not limited to 20V, 25V, 30V, 35V, 40V, or a range formed by any two of the foregoing and values within the range.

[0132] In some embodiments, the current for multi-arc ion plating is 50A-150A, including but not limited to 50A, 60A, 70A, 80A, 90A, 100A, 110A, 120A, 130A, 140A, 150A, or a range formed by any two of the foregoing and values within the range.

[0133] In some embodiments, the bias voltage for the multi-arc ion plating is a negative bias voltage.

[0134] In some embodiments, the negative bias voltage is -100 V to -300 V, including but not limited to -100 V, -120 V, -150 V, -180 V, -200 V, -220 V, -250 V, -280 V, -300 V, or a range formed by any two of the foregoing and values within the range.

[0135] In some embodiments, the time for the multi-arc ion plating is 1 min to 3 min, including but not limited to 1 min, 1.2 min, 1.5 min, 1.8 min, 2 min, 2.2 min, 2.5 min, 2.8 min, 3 min, or a range formed by any two of the foregoing and values within the range.

[0136] In some embodiments, the temperature for the multi-arc ion plating is 50 °C to 150 °C, including but not limited to 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, or a range formed by any two of the foregoing and values within the range.

[0137] In some embodiments, the vacuum degree for the multi-arc ion plating is 8 x 10 -4 Pa to 6 x 10 -3 Pa, including but not limited to 8 x 10 -4 Pa, 9 x 10 -4 Pa, 1 x 10 -3 Pa, 2 x 10 -3 Pa, 3 x 10 -3 Pa, 4 x 10 -3 Pa, 5 x 10 -3 Pa, 6 x 10 -3 Pa, or a range formed by any two of the foregoing and values within the range.

[0138] In some embodiments, the voltage for the magnetron sputtering is 350 V to 600 V, including but not limited to 350 V, 400 V, 450 V, 500 V, 550 V, 600 V, or a range formed by any two of the foregoing and values within the range.

[0139] In some embodiments, the current for the magnetron sputtering is 2 A to 5 A, including but not limited to 2 A, 2.5 A, 3 A, 3.5 A, 4 A, 4.5 A, 5 A, or a range formed by any two of the foregoing and values within the range.

[0140] In some embodiments, the bias voltage for the magnetron sputtering is a negative bias voltage.

[0141] In some embodiments, the negative bias is -100 V to -300 V, including but not limited to -100 V, -120 V, -150 V, -180 V, -200 V, -220 V, -250 V, -280 V, -300 V, or a range formed by any two of the foregoing and numerical values within the range.

[0142] In some embodiments, the time for magnetron sputtering is 10 min to 30 min, including but not limited to 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min, 28 min, 30 min, or a range formed by any two of the foregoing and numerical values within the range.

[0143] In some embodiments, the temperature for magnetron sputtering is 100°C to 200°C, including but not limited to 100°C, 120°C, 150°C, 180°C, 200°C, or a range formed by any two of the foregoing and numerical values within the range.

[0144] In some embodiments, the nitrogen source introduced during the process of magnetron sputtering is nitrogen.

[0145] In some embodiments, the flow rate of the nitrogen is 20 sccm to 60 sccm, including but not limited to 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm, or a range formed by any two of the foregoing and numerical values within the range.

[0146] In some embodiments, a working gas is introduced during the preparation of the intermediate film layer.

[0147] In some embodiments, the working gas is one or more of argon and helium. The present application uses argon to better achieve the formation of the second film layer.

[0148] In some embodiments, the flow rate of the working gas is 20 sccm to 60 sccm, including but not limited to 20 sccm, 25 sccm, 30 sccm, 35 sccm, 40 sccm, 45 sccm, 50 sccm, 55 sccm, 60 sccm, or a range formed by any two of the foregoing and numerical values within the range.

[0149] In some embodiments, the gas pressure during the preparation is 8 x 10 -2 Pa to 7 x 10 -1 Pa, including but not limited to 8 x 10 -2 Pa, 9 x 10 -2 Pa, 1 x 10 -1 Pa, 2 x 10 -1 Pa, 3 x 10 -1Pa, 4x10 -1 Pa, 5x10 -1 Pa, 6x10 -1 Pa, 7x10 - 1 Pa or a range formed by any two of the foregoing and numerical values within the range.

[0150] In some embodiments, the material of the substrate comprises a metal. As non-limiting examples, the metal comprises one or more of a zinc alloy, a copper alloy, and stainless steel.

[0151] In some embodiments, the substrate further comprises a substrate provided with a plating layer. As non-limiting examples, the plating layer comprises one or more of a copper plating layer, a nickel plating layer, and a chromium plating layer.

[0152] In some embodiments, the substrate further comprises a pre-treatment;

[0153] Optionally, the pre-treatment comprises one or more of cleaning, activation, slow pull, and drying of the substrate.

[0154] In some embodiments, the cleaning comprises ultrasonic cleaning and / or running water cleaning.

[0155] In some embodiments, the activation comprises acid activation. As non-limiting examples, the activation comprises soaking with an activating dilute acid.

[0156] In a fifth aspect, the present application further provides an article, which comprises the hydrophobic layer provided in the second aspect or the hydrophobic composite layer provided in the third aspect.

[0157] In some embodiments, the article comprises a kitchen and bathroom article, including but not limited to a faucet, a sink, a shower, a shower head, a bathroom hanging accessory, a toilet and components, and a floor drain, etc.

[0158] It should be noted that, in the following embodiments of the present application, the experimental methods not specified with specific conditions are usually carried out according to the conventional conditions, or according to the conditions suggested by the manufacturers. The various common chemical reagents used in the embodiments are commercially available products, or can be prepared by the skilled person in the art according to known means.

[0159] In the specific embodiments of the present application, the polysilicon, Si, has the following related parameters: high purity: ≥99.999%, grain size: 10 μm (uniformly distributed), density: ≥98% of the theoretical density (2.33 g / cm³).

[0160] Embodiment 1

[0161] The present embodiment provides a hydrophobic composite layer and a preparation method thereof, which are as follows:

[0162] First, the workpiece surface is sequentially subjected to ultrasonic oil removal, two water washing, ultrasonic wax removal, two water washing, acid activation, four water washing, slow pulling and baking to obtain a clean workpiece surface.

[0163] Electroplating a hexavalent chromium layer on the clean workpiece surface.

[0164] Preparation of the hydrophobic composite layer Specifically as follows:

[0165] Install corresponding target materials in the PVD film coating chamber, multi-arc ion plating 1 column 2 chromium (Cr) targets, direct current sputtering plane chromium (Cr) target 1, radio frequency plane silicon (polysilicon, Si) target 1, and place the sample after pre-treatment and baking in the vacuum film coating machine to prepare corresponding film layers in the order of [A / B / C / ].

[0166] Preparation of the A film (first film layer):

[0167] Turn on the multi-arc chromium (Cr) target.

[0168] Pump down to a vacuum degree of 6×10 -3 Pa, fill in argon (Ar) at a flow rate of 30 sccm, and maintain the gas pressure at 4×10 -1 Pa. Turn on the multi-arc ion plating film power supply, the voltage is 22 V, the current is 90 A, and the film plating time is 2 min. The negative bias voltage during film plating is -200 V, the temperature in the chamber is 120℃, and the film plating thickness of A film (first film layer) is 30 nm±10 nm.

[0169] Preparation of the B film (second film layer):

[0170] Turn off the multi-arc ion plating system for preparing A film layer, and turn on the direct current plane chromium (Cr) target.

[0171] Pump down to a vacuum degree of 6×10 -3 Pa, fill in argon (Ar) at a flow rate of 30 sccm, and maintain the gas pressure at 6×10 -1 Pa. Turn on the direct current sputtering film power supply, the voltage is 450 V, the current is 1.5 A, and the film plating time is 20 min. The negative bias voltage during film plating is -200 V, the temperature in the chamber is 150℃, and the film plating thickness of B film (second film layer) is 80 nm±10 nm.

[0172] Preparation of the C film (hydrophobic layer):

[0173] Turn off the multi-arc ion plating system for preparing A film layer, and turn on the direct current plane chromium (Cr) target and the radio frequency plane silicon (polysilicon, Si) target at the same time.

[0174] Pump down to a vacuum degree of 6×10 -3Pa, the flow rate of the reaction nitrogen (N2) is 30 seem, and the gas pressure is maintained at 6x10 -1 Pa. At the same time, the direct current sputtering film power supply and the radio frequency sputtering film power supply are turned on. The voltage of the direct current sputtering film power supply is 450 V, the current of the direct current sputtering film power supply is 1.5 A, the power of the radio frequency sputtering film power supply is 1500 W, and the film plating time is 180 min. The negative bias voltage during film plating is -300 V, the temperature in the chamber is 250℃, and the plating thickness of the C film (hydrophobic layer) is 2pm±1pm.

[0175] Example 2

[0176] The present embodiment provides a hydrophobic composite layer and a preparation method thereof, which are as follows:

[0177] First, the workpiece surface is sequentially subjected to ultrasonic oil removal, two water washing, ultrasonic wax removal, two water washing, acid activation, four water washing, slow pulling, and baking to obtain a clean workpiece surface.

[0178] The workpiece surface is subjected to electroplating of a hexavalent chromium layer.

[0179] Preparation of the hydrophobic composite layer The present embodiment provides a hydrophobic composite layer and a preparation method thereof, which are as follows:

[0180] The corresponding target materials are installed in the PVD film plating chamber, one column of two titanium (Ti) targets, one direct current sputtering planar titanium (Ti) target, and one radio frequency planar silicon (polysilicon, Si) target. The sample after pre-treatment and baking is placed in the vacuum film plating machine, and the corresponding film layers are prepared in the order of [A / B / C / ].

[0181] Preparation of the A film (first film layer):

[0182] The multi-arc titanium (Ti) target is turned on.

[0183] The vacuum is pre-pumped to a degree of vacuum of 6x10 -3 Pa, and argon (Ar) is filled at a flow rate of 30 seem. The gas pressure is maintained at 4x10 -1 Pa. The multi-arc ion film plating power supply is turned on, the voltage is 22 V, the current is 90 A, and the film plating time is 2 min. The negative bias voltage during film plating is -200 V, the temperature in the chamber is 120℃, and the plating thickness of the A film (first film layer) is 30nm±10nm.

[0184] Preparation of the B film (second film layer):

[0185] The multi-arc ion film plating system for preparing the A film layer is turned off, and the direct current planar titanium (Ti) target is turned on.

[0186] The vacuum is pre-pumped to a degree of vacuum of 6x10 -3Pa, the flow rate of the reaction nitrogen (N2) is 30 seem, and the air pressure is maintained at 6x10 -1 Pa. The direct current sputtering power supply is turned on, the voltage is 450 V, the current is 1.5 A, and the film plating time is 20 min. The negative bias voltage during film plating is -200 V, the indoor temperature is 150℃, and the film plating thickness of the B film (second film layer) is 80nm±10nm.

[0187] Preparation of the C film (hydrophobic layer):

[0188] The multi-arc ion plating system for preparing the A film layer is turned off, and the direct current planar titanium (Ti) target and the radio frequency planar silicon (polysilicon, Si) target are turned on.

[0189] The vacuum is pre-pumped to a vacuum degree of 6x10 -3 Pa, the flow rate of the reaction nitrogen (N2) is 30 seem, and the air pressure is maintained at 6x10 -1 Pa. The direct current sputtering power supply and the radio frequency sputtering power supply are turned on at the same time, the voltage of the direct current sputtering power supply is 450 V, the current of the direct current sputtering power supply is 1.5 A, the power of the radio frequency sputtering power supply is 1500W, and the film plating time is 180 min. The negative bias voltage during film plating is -300 V, the indoor temperature is 250℃, and the film plating thickness of the C film (hydrophobic layer) is 2pm±1pm.

[0190] Example 3

[0191] The present embodiment provides a hydrophobic composite layer and a preparation method thereof, which are specifically as follows:

[0192] The workpiece surface is sequentially subjected to ultrasonic oil removal, two-link water washing, ultrasonic wax removal, two-link water washing, acid activation, four-link water washing, slow pulling, and baking to obtain a clean workpiece surface.

[0193] The workpiece surface is sequentially subjected to ultrasonic oil removal, two-link water washing, ultrasonic wax removal, two-link water washing, acid activation, four-link water washing, slow pulling, and baking to obtain a clean workpiece surface.

[0194] Preparation of the hydrophobic composite layer The present embodiment provides a hydrophobic composite layer and a preparation method thereof, which are specifically as follows:

[0195] The corresponding target materials are installed in the PVD film plating chamber, one column of two zirconium (Zr) targets, one direct current sputtering planar zirconium (Zr) target, and one radio frequency planar silicon (polysilicon, Si) target, the sample after pre-treatment and baking is placed in the vacuum film plating machine, and the corresponding film layers are prepared in the order of [A / B / C / ].

[0196] Preparation of the A film (first film layer):

[0197] The multi-arc zirconium (Zr) target is turned on.

[0198] Pre-evacuation, the vacuum degree is 6x10 -3 Pa, fill in argon (Ar) flow 30sccm, the gas pressure is maintained at 4x10 -1 Pa. Turn on the multi-arc ion plating power, the voltage is 22V, the current is 90A, the plating time is 2min. The negative bias is-200V during plating, the temperature in the chamber is 120℃, the plating thickness of A film (the first film layer) is 30nm±10nm.

[0199] Preparation of the B film (second film layer):

[0200] Close the multi-arc ion plating system for preparing A film layer, and open the direct current planar zirconium (Zr) target.

[0201] Pre-evacuation, the vacuum degree is 6x10 -3 Pa, fill in argon (Ar) flow 30sccm, the gas pressure is maintained at 6x10 -1 Pa. Turn on the direct current sputtering plating power, the voltage is 450V, the current is 1.5A, the plating time is 20min. The negative bias is-200V during plating, the temperature in the chamber is 150℃, the plating thickness of B film (the second film layer) is 80nm±10nm.

[0202] Preparation of the C film (hydrophobic layer):

[0203] Close the multi-arc ion plating system for preparing A film layer, and open the direct current planar zirconium (Zr) target and the radio frequency planar silicon (polysilicon, Si) target.

[0204] Pre-evacuation, the vacuum degree is 6x10 -3 Pa, fill in argon (Ar) flow 30sccm, the gas pressure is maintained at 6x10 -1 Pa. Turn on the direct current sputtering plating power and the radio frequency sputtering plating power at the same time, the voltage of the direct current sputtering plating power is 450V, the current of the direct current sputtering plating power is 1.5A, the power of the radio frequency sputtering plating power is 1500W, the plating time is 180min. The negative bias is-300V during plating, the temperature in the chamber is 250℃, the plating thickness of C film (the hydrophobic layer) is 2μm±1μm.

[0205] Example 4

[0206] The embodiment provides a hydrophobic composite layer and a preparation method thereof, and specifically as follows:

[0207] First, the workpiece surface is sequentially subjected to ultrasonic oil removal, two water washing, ultrasonic wax removal, two water washing, acid activation, four water washing, slow pulling and baking to obtain a clean workpiece surface.

[0208] Electroplating a hexavalent chromium layer on a clean workpiece surface.

[0209] Preparation of the hydrophobic composite layer Specifically as follows:

[0210] The corresponding target materials are installed in the PVD film coating chamber, two tantalum (Ta) targets are arranged in one column by multi-arc ion plating, one planar tantalum (Ta) target is arranged by direct current sputtering, and one planar silicon (polysilicon, Si) target is arranged by radio frequency, the sample after pre-treatment and baking is placed in the vacuum film coating machine, and corresponding film layers are prepared in the order of [A / B / C / ].

[0211] Preparation of the A film (first film layer):

[0212] The multi-arc tantalum (Ta) target is turned on.

[0213] The vacuum is pre-pumped to a degree of 6×10 -3 Pa, argon (Ar) gas is filled at a flow rate of 30 sccm, and the gas pressure is maintained at 4×10 -1 Pa. The multi-arc ion plating film power is turned on, the voltage is 22 V, the current is 90 A, and the film coating time is 2 min. The negative bias voltage is -200 V during film coating, the temperature in the chamber is 120℃, and the film coating thickness of the A film (the first film layer) is 30 nm±10 nm.

[0214] Preparation of the B film (second film layer):

[0215] The multi-arc ion plating film system for preparing the A film layer is turned off, and the direct current planar tantalum (Ta) target is turned on.

[0216] The vacuum is pre-pumped to a degree of 6×10 -3 Pa, argon (Ar) gas is filled at a flow rate of 30 sccm, and the gas pressure is maintained at 6×10 -1 Pa. The direct current sputtering film coating power is turned on, the voltage is 450 V, the current is 1.5 A, and the film coating time is 20 min. The negative bias voltage is -200 V during film coating, the temperature in the chamber is 150℃, and the film coating thickness of the B film (the second film layer) is 80 nm±10 nm.

[0217] Preparation of the C film (hydrophobic layer):

[0218] The multi-arc ion plating film system for preparing the A film layer is turned off, and the direct current planar tantalum (Ta) target and the radio frequency planar silicon (polysilicon, Si) target are turned on.

[0219] The vacuum is pre-pumped to a degree of 6×10 -3 Pa, argon (Ar) gas is filled at a flow rate of 30 sccm, and the gas pressure is maintained at 6×10 -1Pa. At the same time, turn on the direct current sputtering power supply and the radio frequency sputtering power supply, the voltage of the direct current sputtering power supply is 450 V, the current of the direct current sputtering power supply is 1.5 A, the power of the radio frequency sputtering power supply is 1500 W, and the film coating time is 180 min. The negative bias during film coating is -300 V, the temperature in the room is 250℃, and the thickness of the C film (hydrophobic layer) is 2 μm ± 1 μm.

[0220] Comparative Example 1

[0221] The present comparative example provides a hydrophobic composite layer and a preparation method thereof, which is different from Example 1 in that, during the preparation of the C film (hydrophobic layer), only the direct current planar chromium (Cr) target is turned on, and other process parameters during the preparation are consistent with those of Example 1.

[0222] Comparative Example 2

[0223] The present comparative example provides a hydrophobic composite layer and a preparation method thereof, which is different from Example 1 in that, during the preparation of the C film (hydrophobic layer), only the radio frequency planar silicon (polysilicon, Si) target is turned on, and other process parameters during the preparation are consistent with those of Example 1.

[0224] Test Example 1

[0225] The hydrophobic composite layers prepared in Examples 1-4 and Comparative Examples 1-2 are tested for performance, and the test indexes include hydrophobic performance, friction resistance, scratch resistance, hardness, wipeability, and cleaner resistance, and the specific test methods are as follows:

[0226] (1) Static contact angle test: use three-grade water meeting the requirements of GB / T 6682 as the reagent, the volume of the reagent for each test is 5 μL, and the test is performed according to the method in Appendix B of JC / T 2168-2013. Take 5 different positions on each piece as test points, and take the average value of the 5 test points as the contact angle value of the piece.

[0227] (2) Friction test method: use a repeated friction tester (in accordance with GB / T 9266-2009, use black pig bristles and apply a (0.45 ± 0.01) kg weight vertically on the surface of the sample for repeated friction test, the brush movement frequency is (37 ± 2) times per minute, and the distance of one-way trip is 200 mm), repeat the friction for 10,000 times, and then test the static contact angle.

[0228] (3) Mud scratch resistance test method: perform the test according to the provisions in Appendix D of QB / T 5419 2019, the mud flow rate is 3-3.5 mL / min, and the friction is 2500 cycles.

[0229] (4) Coating hardness test: measured using a Vickers hardness tester.

[0230] (5) Oil pen test: using a black oil-based marker pen in accordance with QB / T 2777 to draw a straight line on the surface of the sample with a length of 50 mm to 100 mm, and after natural drying for 1 min, using a dry dust-free cloth and applying a load of not more than 500 g to wipe the writing on the surface of the sample, checking whether the writing can be erased and recording the number of reciprocating wipes. The number of repeated wipes should not be more than 5 times, and the writing should be erased without residue.

[0231] (6) Cleaning agent resistance test: the test was carried out according to the drop method specified in GB / T 9274, and 3 drops of test liquid were added to the flat plated surface, with a volume of about 0.1 mL per drop, and kept for 16 h. After rinsing with water and wiping dry with a soft cloth, the surface was inspected under a four-fold magnifying lens. The test liquids included: 10% acetic acid, 2N sodium hydroxide, 70% ethanol, 5% sodium hypochlorite, and 1% methylene blue. The surface should have no pitting, blistering, wrinkling, cracking, peeling, corrosion or substrate exposure, and slight color change and loss of gloss were allowed.

[0232] The results obtained according to the above determination methods are shown in Table 1.

[0233] Table 1: Performance test results of the hydrophobic composite layer

[0234]

[0235] As can be seen from the data in Table 1, the A / B / C hydrophobic composite layer prepared in the present application has excellent hydrophobic effect, hardness, abrasion resistance, scratch resistance, erasability and cleaning agent resistance. When SiN is not co-deposited in the coating, the surface layer only has CrN coating without hydrophobic and easy-to-clean functions, and when CrN is not co-deposited in the composite coating, the surface layer only has SiN coating without hydrophobic and easy-to-clean functions. The performance of the coating obtained by using direct magnetic control sputtering to simultaneously deposit (Cr, Si)N and using radio frequency magnetic control sputtering to simultaneously deposit (Cr, Si)N is poorer.

[0236] Referring to Figs. 1 and 2, Figure 2 and Figs. 3 and 4, Figure 3 the static contact angle diagram and the static contact angle test diagram after 10,000 times of rubbing of the hydrophobic composite layer prepared in Example 1 of the present application show that the hydrophobic composite layer prepared in the present application has excellent hydrophobic properties, easy-to-clean and abrasion resistance.

[0237] Referring to Figs. 5 and 6, Figure 4 and Figs. 7 and 8, Figure 5 the surface SEM scanning electron microscope diagram and the cross-sectional SEM scanning electron microscope diagram of the hydrophobic composite layer prepared in Example 1 of the present application show that the hydrophobic composite layer prepared in the present application has excellent surface properties and interface properties.

[0238] See appendix Figure 6 Appendix Figure 7 and attached Figure 8 The EDS energy spectrum and cross-sectional EDS line scan elemental distribution of the hydrophobic composite layer prepared in Example 1 of this application are shown in Table 2.

[0239] Table 2: Elemental distribution of EDS line scan of hydrophobic composite layer cross section

[0240]

[0241] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0242] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A method for producing a hydrophobic layer, characterized by, The method comprises the following steps: The hydrophobic layer is formed by co-deposition on the surface of the bonding layer in the presence of a nitrogen source by means of direct current magnetron sputtering and radio frequency magnetron sputtering; the target material of the direct current magnetron sputtering comprises one or more of Zr, Ti, Cr, Ta and their composites; and the target material of the radio frequency magnetron sputtering comprises Si.

2. The method for producing a hydrophobic layer according to claim 1, characterized by, The preparation method further satisfies at least one of the following (1) to (12): (1) the material of the bonding layer comprises one or more of a metal and a nitride thereof; (2) the Si comprises polycrystalline silicon; Optionally, the grain size of the polycrystalline silicon is 1 μm to 50 μm; (3) the thickness of the hydrophobic layer is 1 μm to 3 μm; (4) the voltage of the direct current magnetron sputtering is 300 V to 500 V; (4) the current of the direct current magnetron sputtering is 1 A to 3 A; (5) the power of the radio frequency magnetron sputtering is 1500 W to 2000 W; (6) the bias voltage of the co-deposition is a negative bias voltage; Optionally, the negative bias voltage is -200 V to -500 V; (7) the co-deposition time is 120 min to 300 min; (8) the co-deposition temperature is 200 ℃ to 300 ℃; (10) The co-deposition pressure is 8 x 10 -2 Pa-7 x 10 -1 Pa (11) a working gas is introduced during the co-deposition; Optionally, the working gas comprises one or more of argon and helium; Optionally, the flow rate of the working gas is 20 sccm to 60 sccm; (12) the nitrogen source comprises nitrogen; Optionally, the flow rate of the nitrogen is 20 sccm to 60 sccm.

3. The hydrophobic layer characterized in that, The hydrophobic layer is prepared by the preparation method of claim 1 or 2.

4. Hydrophobic composite layer, characterized in that The hydrophobic composite layer comprises an intermediate film layer and the hydrophobic layer of claim 3 formed in sequence on the surface of a substrate.

5. The hydrophobic composite layer of claim 4, wherein, The intermediate film layer comprises at least two film layers; Optionally, the materials of the film layers are the same or different.

6. The hydrophobic composite layer according to claim 4 or 5, characterized in that, The intermediate film layer comprises a first film layer and a second film layer formed in sequence on the surface of a substrate; Optionally, the material of the first film layer comprises one or more of Zr, Ti, Cr, Ta and their composites; Optionally, the material of the second film layer comprises one or more of Zr, Ti, Cr, Ta and their nitrides; Optionally, the thickness of the first film layer is 10 nm to 50 nm; Optionally, the thickness of the second film layer is 50 nm to 100 nm.

7. A method of producing the hydrophobic composite layer according to any one of claims 4 to 6, characterized in that, The method comprises the following steps: The target material and / or the magnetron sputtering are used to deposit an intermediate film layer on the surface of a substrate by means of multi-arc ion plating; The hydrophobic layer is formed on the surface of the intermediate film layer by the preparation method of claim 1 or 2.

8. The method for producing a hydrophobic composite layer according to claim 7, wherein The preparation method of the intermediate film layer comprises: A first film layer is formed on the surface of the substrate by means of multi-arc ion plating; A second film layer is formed on the surface of the first film layer by means of magnetron sputtering in the presence of a nitrogen source; Optionally, the target material of the multi-arc ion plating and the target material of the magnetron sputtering each independently comprises one or more of Zr, Ti, Cr, Ta and their composites.

9. The method for producing a hydrophobic composite layer according to claim 7 or 8, characterized by, The preparation method further satisfies at least one of the following (1) to (16): (1) the voltage of the multi-arc ion plating is 20 V to 40 V; (2) the current of the multi-arc ion plating is 50 A to 150 A; (3) the bias voltage of the multi-arc ion plating is a negative bias voltage; Optionally, the negative bias voltage is -100V to -300V; (4) the time of the multi-arc ion plating is 1min-3min; (5) the temperature of the multi-arc ion plating is 50℃-150℃; (6) the vacuum degree of the multi-arc ion plating is 8 x 10 -4 Pa-6 x 10 -3 Pa; (7) the voltage of the magnetron sputtering is 350V-600V; (8) the current of the magnetron sputtering is 2A-5A; (9) the bias voltage of the magnetron sputtering is a negative bias voltage; Optionally, the negative bias voltage is -100V to -300V; (10) the time of the magnetron sputtering is 10min-30min; (11) the temperature of the magnetron sputtering is 100℃-200℃; (12) the nitrogen source comprises nitrogen gas; Optionally, the flow rate of the nitrogen gas is 20sccm-60sccm; (13) a working gas is introduced during the preparation of the intermediate film layer; Optionally, the working gas comprises one or more of argon gas and helium gas; Optionally, the flow rate of the working gas is 20sccm-60sccm; (14) The air pressure during the preparation of the intermediate film layer is 8 x 10 -2 Pa-7 x 10 -1 Pa; (15) the material of the substrate comprises metal; Optionally, the metal comprises one or more of zinc alloy, copper alloy and stainless steel; Optionally, the substrate further comprises a substrate with a plating layer on the surface; Further optionally, the plating layer comprises one or more of copper plating layer, nickel plating layer and chromium plating layer; (16) the substrate further comprises a pretreatment; Optionally, the pretreatment comprises one or more of cleaning, activation, slow pulling and drying of the substrate.

10. An article, characterized by The product comprises the hydrophobic layer of claim 3 or the hydrophobic composite layer of any one of claims 4-6; Optionally, the product comprises a kitchen and bathroom product.

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