Antibacterial and environmentally friendly composite plating layer and its manufacturing method, antibacterial and environmentally friendly product

Abstract

A bactericidal, environmentally friendly composite plating layer and its manufacturing method, and a bactericidal, environmentally friendly product, the bactericidal, environmentally friendly composite plating layer includes a Semi-bright nickel layer, a high sulfur nickel layer and an environmentally friendly white chrome composite bactericidal layer, the Semi-bright nickel layer is set to be located on a substrate having a bactericidal demand, the high sulfur nickel layer is disposed on a surface of the Semi-bright nickel layer away from the substrate, the environmentally friendly white chrome composite bactericidal layer is disposed on a surface of the high sulfur nickel layer away from the substrate, the environmentally friendly white chrome composite bactericidal layer has a nanoneedle structure and is formed from a composite raw material containing a bactericidal ammonium salt, and the concentration of the bactericidal ammonium salt in the composite raw material is 50g / L-100g / L.

Description

[Technical Field]

[0001] The present application relates to, but is not limited to, the field of sterilization technology, and more particularly to a sterilizing and environmentally friendly composite plating layer and a method for manufacturing the same, and a sterilizing and environmentally friendly product. [Background technology]

[0002] Currently, the surface layer materials for kitchen and bathroom hardware products on the market are primarily produced using traditional hexavalent chromium electroplating technology. However, hexavalent chromium is a common heavy metal contaminant in the electroplating industry, and its electroplating wastewater can cause long-term pollution of water sources and soil, resulting in irreparable damage to the ecological environment. Hexavalent chromium is highly toxic if swallowed or inhaled, and can cause allergies when in contact with human skin, as well as hereditary genetic defects and cancer if inhaled. Some products use the paint baking and dusting process, which involves applying a paint or powder to the substrate surface and then curing it to create a paint or powder layer. However, this process suffers from poor quality, low hardness, poor wear resistance, a lack of luxury, and environmental issues. Furthermore, the outbreak of the novel coronavirus in December 2019 has drawn global attention to the health industry, especially health products for kitchens and bathrooms.

[0003] White is a popular color for kitchen and bathroom products among many consumers. Currently, white kitchen and bathroom products can be produced using electroplating technology. However, as mentioned above, using hexavalent chromium electroplating to produce white kitchen and bathroom products is dangerous to both the environment and human health, is not environmentally friendly, and has a negative impact on the health of production line workers. In addition, industrialized white products produced using only electroplating technology cannot temporarily achieve sterilization or antibacterial functions. Researchers have added Ag composite materials to electroplating chromic acid solutions, but due to the precipitation of silver chromate, the electroplated products do not have antibacterial functions. Therefore, it is generally necessary to spray a layer of nano-Ag+-containing antibacterial material on the surface or to apply Ag+ using PVD technology. + / Cu 2+ However, it is necessary to manufacture Ag-containing composite materials.+ / Cu 2+ is easily absorbed into the pores of the human skin, and can adversely affect and damage the immune system, nervous system, reproductive system, and other organs of the human body. + or Ag + / Cu 2+ Plating with antibacterial materials is expensive. While ordinary ammonium salts are effective antibacterial materials, the ammonium salt products on the market are generally liquid and sprayed onto the surface. Once the ammonium salt liquid dries, the antibacterial effect is lost, resulting in a short antibacterial lifespan. Furthermore, the sterilization and antibacterial effects of kitchen and bathroom products on the market today are mostly explained by third-party testing reports, making visualization difficult. Summary of the Invention

[0004] The following is a summary of the subject matter described in detail in the text, which is not intended to limit the scope of protection of the present application.

[0005] The present application provides a bactericidal, environmentally friendly composite plating layer, comprising a Semi-bright nickel layer, a high-sulfur nickel layer, and an environmentally friendly white chrome composite bactericidal layer, wherein the Semi-bright nickel layer is positioned on a substrate having bactericidal needs, the high-sulfur nickel layer is disposed on a surface of the Semi-bright nickel layer facing away from the substrate, and the environmentally friendly white chrome composite bactericidal layer is disposed on a surface of the high-sulfur nickel layer facing away from the substrate, the environmentally friendly white chrome composite bactericidal layer having a nanoneedle structure and formed from a composite raw material containing a bactericidal ammonium salt, the concentration of the bactericidal ammonium salt in the composite raw material being 50g / L to 100g / L.

[0006] In embodiments of the present application, the bactericidal ammonium salt may be selected from any one or more of alkyl quaternary ammonium iodide salts and alkyl aromatic hydrocarbon group quaternary ammonium iodide salts.

[0007] In the present embodiment, the length of the carbon chain of the alkyl group in the alkyl quaternary ammonium iodide salt and the alkyl aromatic hydrocarbon group quaternary ammonium iodide salt may be 12 to 18.

[0008] In embodiments of the present application, the disinfectant ammonium salt may be selected from any one or more of dodecyldimethylbenzyl ammonium iodide, dodecyltrimethyl ammonium iodide, tetradecyldimethylbenzyl ammonium iodide, tetradecyltrimethyl ammonium iodide, hexadecyldimethylbenzyl ammonium iodide, hexadecyltrimethyl ammonium iodide, octadecyldimethylbenzyl ammonium iodide, and octadecyltrimethyl ammonium iodide.

[0009] In an embodiment of the present application, the raw materials of the environmentally friendly white chrome composite antibacterial layer may include quaternary ammonium iodide salt with a concentration of 50 g / L to 100 g / L, anhydrous citric acid crystals with a concentration of 10 g / L to 20 g / L, Trichrome ICE Salts with a concentration of 150 g / L to 400 g / L, Trichrome ICE Part 1 with a concentration of 150 ml / L to 350 ml / L, Trichrome ICE Make Up with a concentration of 10 ml / L to 25 ml / L, and Trichrome ICE WA with a concentration of 0.5 ml / L to 5 ml / L.

[0010] In an embodiment of the present application, the raw materials for the high sulfur nickel layer may include nickel sulfate having a concentration of 350 g / L to 450 g / L, nickel chloride having a concentration of 50 g / L to 100 g / L, boric acid having a concentration of 40 g / L to 60 g / L, and high sulfur nickel HAS 90 having a concentration of 2 ml / L to 4 ml / L.

[0011] In the embodiment of the present application, the raw materials of the Semi-bright nickel layer may include nickel sulfate with a concentration of 350g / L to 450g / L, nickel chloride with a concentration of 30g / L to 50g / L, boric acid with a concentration of 40g / L to 60g / L, makeup agent NIB-90 with a concentration of 5ml / L to 10ml / L, main brightener NIB-90 with a concentration of 1ml / L to 2ml / L, and wetting agent Ni-66B with a concentration of 1ml / L to 5ml / L.

[0012] In the embodiment of the present application, the thickness of the semi-bright nickel layer may be 20 μm to 50 μm, the thickness of the high sulfur nickel layer may be 20 μm to 50 μm, and the thickness of the environmentally friendly white chrome composite antibacterial layer may be greater than 0.5 μm.

[0013] The present invention further provides a method for producing the above-mentioned antibacterial and environmentally friendly composite plating layer, A first step of pre-treating the substrate, including burnishing and cleaning; a second step of electroplating said Semi-bright nickel layer onto the surface of the pretreated substrate; a third step of electroplating the high sulfur nickel layer on the surface of the semi-bright nickel layer; and and a fourth step of electroplating the environmentally friendly white chromium composite antibacterial layer on the surface of the high sulfur nickel layer.

[0014] In the embodiment of the present application, the conditions for electroplating the semi-bright nickel layer in the second step are a temperature of 50°C to 60°C, a cathode current density of 5A / dm 2 ~10A / dm 2 and the electroplating time may be 600 s to 2700 s.

[0015] In the embodiment of the present application, the conditions for electroplating the high sulfur nickel layer in the third step are a temperature of 45°C to 55°C, a voltage of 5V to 10V, and a cathode current density of 3A / dm 2 ~12A / dm 2 and the electroplating time may be 600 s to 2700 s.

[0016] In the embodiment of the present application, the conditions for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step are a temperature of 50°C to 60°C, a cathode current density of 5A / dm 2 ~10A / dm 2 and the electroplating time may be 600 s to 900 s.

[0017] The present application further provides a bactericidal, environmentally friendly product, comprising a substrate and the bactericidal, environmentally friendly composite plating layer as described above.

[0018] In the present embodiment, the substrate may be a metal substrate or a plastic substrate.

[0019] In an embodiment of the present application, the disinfecting eco-friendly product may be a disinfecting product for kitchen or toilet use.

[0020] Other features and advantages of the present application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the present application. Other advantages of the present application will be realized and obtained by the solutions set forth in the description and drawings. [Brief explanation of the drawings]

[0021] The drawings are intended to provide an understanding of the technical solution of the present application, are a part of the specification, and are used to interpret the technical solution of the present application together with the embodiments of the present application, but are not intended to limit the technical solution of the present application. [Figure 1] 1 is a front view of the structure of a bactericidal and environmentally friendly composite plating layer according to an embodiment of the present application; [Figure 2] FIG. 1 is an external view of the bactericidal and environmentally friendly product produced in Example 1 of the present application. [Figure 3] FIG. 2 is an atomic force microscope (AFM) view of the surface morphology of the environmentally friendly white chromium composite antibacterial layer of the antibacterial and environmentally friendly product according to Example 1 of the present application. [Figure 4] FIG. 2 is an atomic force microscope (AFM) view of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 1 of the present application. [Figure 5] FIG. 2 is an atomic force microscope (AFM) view of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 2 of the present application. [Figure 6] FIG. 2 is an atomic force microscope (AFM) image of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 3 of the present application. [Figure 7] FIG. 2 is an atomic force microscope (AFM) image of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 4 of the present application. [Figure 8] These are real-time visualization microscope images of a bactericidal, environmentally friendly product according to Example 1 of the present application. The left image is a visualization microscope image at the start of counting (1 s) after bacteria had been allowed to stand on the sample surface for 2 min, and the right image is a visualization microscope image at 3 s after bacteria had been allowed to stand on the sample surface for 2 min and counting had begun. [Figure 9] These are real-time visualization microscope images of an environmentally friendly product according to Comparative Example 4 of the present application. The left image is a visualization microscope image taken at 1 second after counting began after bacteria had been allowed to stand on the sample surface for 2 minutes, and the right image is a visualization microscope image taken 3 seconds after counting began after bacteria had been allowed to stand on the sample surface for 2 minutes. DETAILED DESCRIPTION OF THE INVENTION

[0022] In order to clarify the purpose, technical solution and advantages of the present application, the following detailed description of the embodiments of the present application will be given with reference to the accompanying drawings, in which the embodiments and features of the embodiments of the present application can be arbitrarily combined with each other unless they conflict.

[0023] An embodiment of the present application provides a bactericidal, environmentally friendly composite plating layer, which, as shown in FIG. 1 , comprises a Semi-bright nickel layer 10, a high sulfur nickel layer 20, and an environmentally friendly white chrome composite bactericidal layer 30, wherein the Semi-bright nickel layer 10 is positioned on a substrate 100 having a bactericidal need, the high sulfur nickel layer 20 is disposed on the surface of the Semi-bright nickel layer 10 facing away from the substrate 100, and the environmentally friendly white chrome composite bactericidal layer 30 is disposed on the surface of the high sulfur nickel layer 20 facing away from the substrate 100, the environmentally friendly white chrome composite bactericidal layer 30 having a nanoneedle structure 31 and formed from a composite raw material containing a bactericidal ammonium salt, wherein the concentration of the bactericidal ammonium salt in the composite raw material is 50 g / L to 100 g / L.

[0024] In embodiments of the present application, the bactericidal ammonium salt may be selected from any one or more of alkyl quaternary ammonium iodide salts and alkyl aromatic hydrocarbon group quaternary ammonium iodide salts.

[0025] In the present embodiment, the length of the carbon chain of the alkyl group in the alkyl quaternary ammonium iodide salt and the alkyl aromatic hydrocarbon group quaternary ammonium iodide salt may be 12 to 18.

[0026] In embodiments of the present application, the disinfectant ammonium salt may be selected from any one or more of dodecyldimethylbenzyl ammonium iodide, dodecyltrimethyl ammonium iodide, tetradecyldimethylbenzyl ammonium iodide, tetradecyltrimethyl ammonium iodide, hexadecyldimethylbenzyl ammonium iodide, hexadecyltrimethyl ammonium iodide, octadecyldimethylbenzyl ammonium iodide, and octadecyltrimethyl ammonium iodide.

[0027] In an embodiment of the present application, the raw materials of the environmentally friendly white chrome composite antibacterial layer may include quaternary ammonium iodide salt with a concentration of 50 g / L to 100 g / L, anhydrous citric acid crystals with a concentration of 10 g / L to 20 g / L, Trichrome ICE Salts with a concentration of 150 g / L to 400 g / L, Trichrome ICE Part 1 with a concentration of 150 ml / L to 350 ml / L, Trichrome ICE Make Up with a concentration of 10 ml / L to 25 ml / L, and Trichrome ICE WA with a concentration of 0.5 ml / L to 5 ml / L.

[0028] In an embodiment of the present application, the raw materials for the high sulfur nickel layer may include nickel sulfate having a concentration of 350 g / L to 450 g / L, nickel chloride having a concentration of 50 g / L to 100 g / L, boric acid having a concentration of 40 g / L to 60 g / L, and high sulfur nickel HAS 90 having a concentration of 2 ml / L to 4 ml / L.

[0029] In the embodiment of the present application, the raw materials of the Semi-bright nickel layer may include nickel sulfate with a concentration of 350g / L to 450g / L, nickel chloride with a concentration of 30g / L to 50g / L, boric acid with a concentration of 40g / L to 60g / L, makeup agent NIB-90 with a concentration of 5ml / L to 10ml / L, main brightener NIB-90 with a concentration of 1ml / L to 2ml / L, and wetting agent Ni-66B with a concentration of 1ml / L to 5ml / L.

[0030] In the description of this application, the concentration (g / L, mL / L) of a certain raw material for producing a semi-bright nickel layer, a high sulfur nickel layer, or an environmentally friendly white chrome composite antibacterial layer refers to the concentration of the raw material in a mixture consisting of all the raw materials for producing the semi-bright nickel layer, the high sulfur nickel layer, or the environmentally friendly white chrome composite antibacterial layer.

[0031] In the embodiment of the present application, the thickness of the semi-bright nickel layer may be 20 μm to 50 μm, the thickness of the high sulfur nickel layer may be 20 μm to 50 μm, and the thickness of the environmentally friendly white chrome composite antibacterial layer may be greater than 0.5 μm.

[0032] In the antibacterial, environmentally friendly composite plating layer according to the present invention, the Semi-bright nickel layer and the high-sulfur nickel layer may form a corrosion-resistant composite layer. Because the raw materials for the Semi-bright nickel layer are sulfur-free, the Semi-bright nickel layer has low stress, excellent flattening properties, and good flexibility. The raw materials for the high-sulfur nickel layer contain a large amount of sulfur. The combination of a thick (e.g., 20 μm-50 μm) Semi-bright nickel layer and a thick (e.g., 20 μm-50 μm) high-sulfur nickel layer (each with a different sulfur content) creates a potential difference, effectively reducing the corrosion rate of the substrate and improving corrosion resistance. The thickness of the environmentally friendly, white chrome antibacterial composite layer may be greater than 0.5 μm. In this case, the environmentally friendly, white chrome antibacterial composite layer, serving as a decorative appearance layer, can provide effective protection and abrasion resistance.

[0033] In the embodiment of the present application, the environmentally friendly white chrome composite antibacterial layer may have an L value of 76 to 78, an a value of -1 to +1, and a value of -1 to +1.

[0034] The present invention also provides a method for manufacturing the above-mentioned antibacterial and environmentally friendly composite plating layer, A first step of pre-treating the substrate, including burnishing and cleaning; a second step of electroplating said Semi-bright nickel layer onto the surface of the pretreated substrate; a third step of electroplating the high sulfur nickel layer on the surface of the semi-bright nickel layer; and and a fourth step of electroplating the environmentally friendly white chromium composite antibacterial layer on the surface of the high sulfur nickel layer.

[0035] In the embodiment of the present application, the cleaning treatment in the pretreatment described in the first step may include precision cleaning processes such as dewaxing, deoiling, electrolysis, and pure water cleaning.

[0036] In the embodiment of the present application, the conditions for electroplating the semi-bright nickel layer in the second step are a temperature of 50°C to 60°C, a cathode current density of 5A / dm 2 ~10A / dm 2and the electroplating time may be 600 s to 2700 s.

[0037] In the embodiment of the present application, the conditions for electroplating the high sulfur nickel layer in the third step are a temperature of 45°C to 55°C, a voltage of 5V to 10V, and a cathode current density of 3A / dm 2 ~12A / dm 2 and the electroplating time may be 600 s to 2700 s.

[0038] In the embodiment of the present application, the conditions for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step are a temperature of 50°C to 60°C, a cathode current density of 5A / dm 2 ~10A / dm 2 and the electroplating time may be 600 s to 900 s.

[0039] In the present embodiment, a semi-bright nickel layer, a high-sulfur nickel layer, and an environmentally friendly white chromium composite antibacterial layer are sequentially formed on the substrate surface by electroplating, resulting in a bactericidal, environmentally friendly composite plating layer on the substrate surface. The manufacturing process is simple and low cost. The environmentally friendly white chromium composite antibacterial layer is formed by electroplating environmentally friendly trivalent chromium material, avoiding the negative environmental impacts of traditional hexavalent chromium electroplating and the negative impact on the physical health of production line workers. The bactericidal, environmentally friendly composite plating layer exhibits a white color, a soft luster, and a beautiful appearance. Furthermore, the environmentally friendly white chromium composite antibacterial layer is formed from a composite material containing bactericidal ammonium salt and has a nanoneedle structure, which allows the bactericidal, environmentally friendly composite plating layer to have good high-speed, wide-spectrum antibacterial effect. The nano-Ag + , Cu 2+ The antibacterial effect can be directly displayed using high-resolution display technology, and the antibacterial and environmentally friendly composite plating layer according to the embodiment of the present application also has excellent corrosion resistance.

[0040] Embodiments of the present application further provide a germicidal, environmentally friendly product, which includes a substrate and a germicidal, environmentally friendly composite plating layer as described above.

[0041] In the present embodiment, the substrate may be a metal substrate or a plastic substrate, the metal substrate being, for example, an aluminum alloy, a copper alloy, a zinc alloy, a magnesium alloy, a stainless steel, a steel alloy, etc., and the plastic substrate being, for example, an ABS plastic.

[0042] In an embodiment of the present application, the disinfecting environmentally friendly product may be a disinfecting product for a kitchen or bathroom, such as a sink, cutlery, faucet, washbasin, hook, shower, shower handle, shower frame, etc.

[0043] The makeup agent NIB-90, main brightener NIB-90, and wetting agent Ni-66B used in the following examples and comparative examples were purchased from Xiamen Huahui New Materials Technology Co., Ltd.; high sulfur nickel HAS 90 solution, Trichrome ICE Salts, Trichrome ICE Part 1, Trichrome ICE Make Up, and Trichrome ICE WA were purchased from Atotech (China) Chemicals Ltd.; the model numbers of Trichrome ICE Salts are 1687212, Trichrome ICE Part 1 are 1687214, Trichrome ICE Make Up are 1687213, and Trichrome ICE WA are 1687218; and hexadecyltrimethylammonium iodide was purchased from Jinjinle Chemical Co., Ltd.

[0044] Example 1 (1) Pretreatment for electroplating The copper alloy substrate undergoes burnishing and precision cleaning (including dewaxing, deoiling, electrolysis, and pure water cleaning).

[0045] (2) Electroplating a layer of semi-bright nickel onto the surface of the pretreated substrate. The electroplating solution for forming the semi-bright nickel layer contains nickel sulfate at a concentration of 350 g / L, nickel chloride at a concentration of 40 g / L, boric acid at a concentration of 45 g / L, makeup agent NIB-90 at a concentration of 7 mL / L, main brightener NIB-90 at a concentration of 1.2 mL / L, and wetting agent Ni-66B at a concentration of 2 mL / L.

[0046] The electroplating process conditions were a temperature of 55°C and a cathode current density of 5A / dm 2 and the electroplating time is 2700 s.

[0047] (3) electroplating a high sulfur nickel layer on the surface of the semi-bright nickel layer; The electroplating solution for forming the high sulfur nickel layer contains nickel sulfate having a concentration of 380 g / L, nickel chloride having a concentration of 70 g / L, boric acid having a concentration of 45 g / L, and high sulfur nickel HAS 90 having a concentration of 3 mL / L.

[0048] The electroplating process conditions were: temperature 50°C, voltage 8V, cathode current density 5A / dm 2 and the electroplating time is 2700 s.

[0049] (4) An environmentally friendly white chromium composite antibacterial layer is electroplated on the surface of the high sulfur nickel layer.

[0050] The electroplating solution for forming the environmentally friendly white chrome composite antibacterial layer contains hexadecyltrimethylammonium iodide with a concentration of 50 g / L, anhydrous citric acid crystals with a concentration of 10 g / L, Trichrome ICE Salts with a concentration of 300 g / L, Trichrome ICE Part 1 with a concentration of 250 ml / L, Trichrome ICE Make Up with a concentration of 18 ml / L, and Trichrome ICE WA with a concentration of 1 ml / L.

[0051] The electroplating process conditions were a temperature of 55°C and a cathode current density of 5A / dm 2and the electroplating time is 900 s.

[0052] Example 2 The manufacturing method is almost the same as in Example 1, except that the concentration of hexadecyltrimethylammonium iodide in the electroplating solution used for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step is 100 g / L.

[0053] Comparative Example 1 The manufacturing method is almost the same as in Example 1, except that the concentration of hexadecyltrimethylammonium iodide in the electroplating solution used for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step is 150 g / L.

[0054] Comparative Example 2 The manufacturing method is almost the same as that of Example 1, except that the concentration of anhydrous citric acid crystals in the electroplating solution used for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step is 0 g / L.

[0055] Comparative Example 3 The manufacturing method is almost the same as in Example 1, except that the concentration of hexadecyltrimethylammonium iodide in the electroplating solution used for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step is 0 g / L.

[0056] Comparative Example 4 The manufacturing method is almost the same as that of Example 1, except that in the electroplating solution used for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step, the concentration of anhydrous citric acid crystals is 0 g / L and the concentration of hexadecyltrimethylammonium iodide is 0 g / L.

[0057] Figure 2 is an external view of the bactericidal, eco-friendly product manufactured in Example 1 of the present application (the external view of the products manufactured in Example 2 and Comparative Examples 1 to 4 is almost identical to Figure 2). As can be seen from this, the bactericidal, eco-friendly products according to the present application have a white plating layer with a soft color.

[0058] Figure 3 is an atomic force microscope (AFM) image of the surface morphology of the environmentally friendly white chrome composite bactericidal layer of the bactericidal environmentally friendly product according to Example 1 of the present application. Figure 4 is an atomic force microscope (AFM) image of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 1 of the present application. Figure 5 is an atomic force microscope (AFM) image of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 2 of the present application. Figure 6 is an atomic force microscope (AFM) image of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 3 of the present application. Figure 7 is an atomic force microscope (AFM) image of the surface morphology of the white chrome composite layer of the environmentally friendly product according to Comparative Example 4 of the present application.

[0059] As can be seen from Figure 3, the environmentally friendly white chrome composite antibacterial layer according to Example 1 of the present application certainly formed a nanoneedle structure, with the nanoneedle height being 10 nm to 40 nm, and the environmentally friendly white chrome composite antibacterial layer of the antibacterial and environmentally friendly product according to Example 2 of the present application also formed a nanoneedle structure. In contrast, the white chrome composite layers according to Comparative Examples 1 to 4 did not form a nanoneedle structure, indicating that the formation of the nanoneedle structure requires the involvement of an appropriate concentration of a quaternary ammonium salt such as hexadecyltrimethylammonium iodide and anhydrous citric acid crystals.

[0060] According to the Chinese national standard GB / T 17934.1-1999, the Lab value of the bactericidal environmentally friendly product of the example was measured, and three different height positions were selected for each product during the measurement. The measurement results showed that the L value was 76-78, the a value was -1 to +1, and the b value was -1 to +1.

[0061] According to the Chinese national standard GB / T 6461-2002, the corrosion resistance of the products of the examples and comparative examples was measured by CASS salt spray test method. The results are shown in Table 1.

[0062] According to the Chinese national standard GB / T21510-2008, the antibacterial properties of the products according to the examples and comparative examples were measured (measured using Escherichia coli), and the results are shown in Table 1.

[0063] Based on Appendix C of the Chinese national standard GB / T21510-2008, E. coli was placed on the surface of the product from the example and comparative example facing away from the substrate (the surface of the environmentally friendly white chrome composite bactericidal layer for the example product), left to stand for 2 minutes, and then the state of bacteria on the surface was observed using a double-transmission biological microscope.

[0064] Observations revealed that bacteria on the surface of the disinfectant product according to the present invention remained motionless, while bacteria on the surface of the comparative example continued to swim, with the number of swimming bacteria remaining almost constant. Figure 8 shows real-time visualization micrographs of the disinfectant, environmentally friendly product according to Example 1 of the present application. The left image shows a visualization micrograph at the start of counting (1 s) after bacteria had been allowed to stand on the sample surface for 2 minutes, and the right image shows a visualization micrograph at 3 s after the start of counting. The state observed in the micrograph 3 s after the start of counting is the same as the state observed at the start of counting (1 s). In both cases, the bacteria remained motionless, indicating that the bacteria had been killed. Figure 9 shows real-time visualization micrographs of the environmentally friendly product according to Comparative Example 4 of the present application. The left image shows a visualization micrograph at the start of counting (1 s) after bacteria had been allowed to stand on the sample surface for 2 minutes, and the right image shows a visualization micrograph at 3 s after the start of counting after bacteria had been allowed to stand on the sample surface for 2 minutes. In the left and right images, many bacteria are swimming (you can see that the position of the bacteria in the circle in the upper right corner has changed), and the number of swimming bacteria is almost the same.

[0065] [Table 1]

[0066] As can be seen from Examples 1, 2, and Comparative Example 1, when the concentration of hexadecyltrimethylammonium iodide is 50g / L to 100g / L, the environmentally friendly white chrome composite bactericidal layer of the bactericidal environmentally friendly product can form a nanoneedle structure, and the bactericidal environmentally friendly product has good bactericidal effect. When the concentration of hexadecyltrimethylammonium iodide is increased to 150g / L, the environmentally friendly white chrome composite layer of the bactericidal environmentally friendly product does not form a nanoneedle structure, and the bactericidal effect of the bactericidal environmentally friendly product against E. coli decreases to 88.1%.

[0067] As can be seen from the comparison between Examples 1 and 2 and Comparative Examples 1 to 4, the antibacterial rate of the non-nanoneedle structured hexadecyltrimethylammonium iodide composite plating layer was significantly lower than that of the nanoneedle structured hexadecyltrimethylammonium iodide composite plating layer, which indicates that the nanoneedle structure is very important for the bactericidal effect.

[0068] As described above, the bactericidal effect of the bactericidal and environmentally friendly composite plating layer according to the embodiment of the present application can be directly displayed using a double-transmission high-resolution display technology, and the bactericidal effect of the environmentally friendly product, which is an environmentally friendly white chrome composite bactericidal layer containing a nanoneedle structure, is clearly superior to that of the environmentally friendly product according to the comparative example that does not contain a nanoneedle structure. The present disclosure includes the following aspects. [Section 1] A bactericidal, environmentally friendly composite plating layer comprising a Semi-bright nickel layer, a high-sulfur nickel layer, and an environmentally friendly white chrome composite bactericidal layer, wherein the Semi-bright nickel layer is positioned on a substrate having bactericidal needs, the high-sulfur nickel layer is disposed on a surface of the Semi-bright nickel layer facing away from the substrate, and the environmentally friendly white chrome composite bactericidal layer is disposed on a surface of the high-sulfur nickel layer facing away from the substrate, the environmentally friendly white chrome composite bactericidal layer having a nanoneedle structure and formed from a composite raw material containing a bactericidal ammonium salt, wherein the concentration of the bactericidal ammonium salt in the composite raw material is 50g / L to 100g / L. [Section 2] Item 1. The bactericidal and environmentally friendly composite plating layer according to Item 1, wherein the bactericidal ammonium salt is selected from one or more of an alkyl quaternary ammonium iodide salt and an alkyl aromatic hydrocarbon group quaternary ammonium iodide salt. [Section 3] Item 3. The bactericidal and environmentally friendly composite plating layer according to Item 2, wherein the alkyl group in the alkyl quaternary ammonium iodide salt and the alkyl aromatic hydrocarbon group quaternary ammonium iodide salt has a carbon chain length of 12 to 18. [Section 4] Item 4. The bactericidal, environmentally friendly composite plating layer according to any one of Items 1 to 3, wherein the bactericidal ammonium salt is selected from one or more of dodecyldimethylbenzyl ammonium iodide, dodecyltrimethyl ammonium iodide, tetradecyldimethylbenzyl ammonium iodide, tetradecyltrimethyl ammonium iodide, hexadecyldimethylbenzyl ammonium iodide, hexadecyltrimethyl ammonium iodide, octadecyldimethylbenzyl ammonium iodide, and octadecyltrimethyl ammonium iodide. [Section 5] The raw materials of the environmentally friendly white chrome composite antibacterial layer include a quaternary ammonium iodide salt having a concentration of 50 g / L to 100 g / L, anhydrous citric acid crystals having a concentration of 10 g / L to 20 g / L, Trichrome ICE Salts having a concentration of 150 g / L to 400 g / L, Trichrome ICE Part 1 having a concentration of 150 ml / L to 350 ml / L, Trichrome ICE Make Up having a concentration of 10 ml / L to 25 ml / L, and Trichrome ICE WA having a concentration of 0.5 ml / L to 5 ml / L. [Section 6] Item 6. The bactericidal, environmentally friendly composite plating layer according to any one of Items 1 to 5, wherein raw materials for the high sulfur nickel layer include nickel sulfate having a concentration of 350 g / L to 450 g / L, nickel chloride having a concentration of 50 g / L to 100 g / L, boric acid having a concentration of 40 g / L to 60 g / L, and high sulfur nickel HAS 90 having a concentration of 2 mL / L to 4 mL / L. [Section 7] Item 7. The bactericidal, environmentally friendly composite plating layer according to any one of Items 1 to 6, wherein raw materials for the Semi-bright nickel layer include nickel sulfate having a concentration of 350 g / L to 450 g / L, nickel chloride having a concentration of 30 g / L to 50 g / L, boric acid having a concentration of 40 g / L to 60 g / L, makeup agent NIB-90 having a concentration of 5 ml / L to 10 ml / L, main brightener NIB-90 having a concentration of 1 ml / L to 2 ml / L, and wetting agent Ni-66B having a concentration of 1 ml / L to 5 ml / L. [Section 8] Item 8. The bactericidal, environmentally friendly composite plating layer according to any one of Items 1 to 7, wherein the thickness of the semi-bright nickel layer is 20 μm to 50 μm, the thickness of the high sulfur nickel layer is 20 μm to 50 μm, and the thickness of the environmentally friendly, white chromium composite bactericidal layer is greater than 0.5 μm. [Section 9] A method for producing a bactericidal, environmentally friendly composite plating layer, the bactericidal, environmentally friendly composite plating layer being the bactericidal, environmentally friendly composite plating layer described in any one of items 1 to 8, the method comprising: A first step of pre-treating the substrate, including burnishing and cleaning; a second step of electroplating said Semi-bright nickel layer onto the surface of the pretreated substrate; a third step of electroplating the high sulfur nickel layer on the surface of the semi-bright nickel layer; and a fourth step of electroplating the environmentally friendly white chromium composite antibacterial layer on the surface of the high sulfur nickel layer. [Section 10] The conditions for electroplating the semi-bright nickel layer in the second step are a temperature of 50°C to 60°C and a cathode current density of 5A / dm 2 ~10A / dm 2 Item 10. The manufacturing method according to item 9, wherein the electroplating time is 600 s to 2700 s. [Section 11] The conditions for electroplating the high sulfur nickel layer in the third step are a temperature of 45°C to 55°C, a voltage of 5V to 10V, and a cathode current density of 3A / dm 2 ~12A / dm 2 Item 11. The manufacturing method according to item 9 or 10, wherein the electroplating time is 600 seconds to 2700 seconds. [Section 12] The conditions for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step are a temperature of 50°C to 60°C and a cathode current density of 5A / dm 2 ~10A / dm 2 12. The manufacturing method according to any one of items 9 to 11, wherein the electroplating time is 600 seconds to 900 seconds. [Section 13] A bactericidal, environmentally friendly product comprising a substrate and the bactericidal, environmentally friendly composite plating layer according to any one of items 1 to 8. [Section 14] Item 14. The disinfectant, environmentally friendly product according to item 13, wherein the substrate is a metal substrate or a plastic substrate. [Section 15] Item 15. The disinfectant environmentally friendly product according to item 13 or 14, wherein the disinfectant environmentally friendly product is a disinfectant product for kitchen or toilet use.

[0069] The contents of the present disclosure are illustrative of the principles of the embodiments of the present application and do not impose any formal or essential limitations on the present application, and the present application is not limited to specific embodiments. It will be apparent to those skilled in the art that the elements, methods, and systems of the technical solutions of the embodiments of the present application may be modified, changed, altered, or transformed without departing from the principles, spirit, and scope of the embodiments and technical solutions of the present application, as defined in the claims. All such modifications, changes, alterations, and transformations are included in the same embodiments of the present application, and all such modifications are within the scope defined in the claims. The embodiments of the present application may be embodied in various forms, but only a few embodiments of the present application are described in detail herein. Furthermore, the embodiments of the present application include any possible combination of some or all of the various embodiments described herein, and are also within the scope defined in the claims. All patents, patent applications, and other cited materials mentioned anywhere in this application or any cited patents, cited patent applications, or other cited materials are incorporated by reference in their entirety.

[0070] The above disclosure is illustrative and not exhaustive. To one skilled in the art, this description will suggest many variations and alternatives. All of these alternatives and variations are included within the scope of the claims, where the term "comprising" refers to "including but not limited to."

[0071] This concludes the description of alternative embodiments of the present application. Those skilled in the art will recognize other equivalent transformations of the embodiments described herein, and these equivalent transformations are also encompassed by the appended claims.

Claims

1. A bactericidal, environmentally friendly composite plating layer comprising a Semi-bright nickel layer, a high-sulfur nickel layer, and an environmentally friendly white chrome composite bactericidal layer, wherein the Semi-bright nickel layer is configured to be located on a substrate having bactericidal needs, the high-sulfur nickel layer is disposed on a surface of the Semi-bright nickel layer facing away from the substrate, and the environmentally friendly white chrome composite bactericidal layer is disposed on a surface of the high-sulfur nickel layer facing away from the substrate, and the environmentally friendly white chrome composite bactericidal layer has a nanoneedle structure.

2. A bactericidal, environmentally friendly composite plating layer as described in claim 1, wherein the height of the nanoneedles is 10 nm to 40 nm.

3. 2. The bactericidal and environmentally friendly composite plating layer according to claim 1, wherein the thickness of the semi-bright nickel layer is 20 μm to 50 μm, the thickness of the high sulfur nickel layer is 20 μm to 50 μm, and the thickness of the environmentally friendly white chromium composite bactericidal layer is greater than 0.5 μm.

4. A method for manufacturing a bactericidal, environmentally friendly composite plating layer, the bactericidal, environmentally friendly composite plating layer being the bactericidal, environmentally friendly composite plating layer of claim 1, the manufacturing method comprising: A first step of pretreating the substrate, including burnishing and cleaning; a second step of electroplating said Semi-bright nickel layer onto the surface of the pretreated substrate; a third step of electroplating the high sulfur nickel layer on the surface of the semi-bright nickel layer; and a fourth step of electroplating the environmentally friendly white chromium composite antibacterial layer on the surface of the high sulfur nickel layer; The method for producing a bactericidal and environmentally friendly composite plating layer includes forming the environmentally friendly white chromium composite bactericidal layer from a composite raw material containing a bactericidal ammonium salt, and the concentration of the bactericidal ammonium salt in the composite raw material is 50 g / L to 100 g / L.

5. The manufacturing method described in claim 4, wherein the bactericidal ammonium salt is selected from one or more of iodine salts of alkyl quaternary ammonium and iodine salts of alkyl aromatic hydrocarbon group quaternary ammonium.

6. The manufacturing method described in claim 5, wherein the length of the carbon chain of the alkyl group in the iodine salt of the alkyl quaternary ammonium and the iodine salt of the alkyl aromatic hydrocarbon group quaternary ammonium is 12 to 18.

7. The manufacturing method described in claim 4, wherein the bactericidal ammonium salt is selected from one or more of dodecyldimethylbenzyl ammonium iodide, dodecyltrimethyl ammonium iodide, tetradecyldimethylbenzyl ammonium iodide, tetradecyltrimethyl ammonium iodide, hexadecyldimethylbenzyl ammonium iodide, hexadecyltrimethyl ammonium iodide, octadecyldimethylbenzyl ammonium iodide, and octadecyltrimethyl ammonium iodide.

8. The manufacturing method according to claim 4, wherein the raw materials of the environmentally friendly white chrome composite bactericidal layer include quaternary ammonium iodide salt having a concentration of 50 g / L to 100 g / L, anhydrous citric acid crystals having a concentration of 10 g / L to 20 g / L, Trichrome ICE Salts having a concentration of 150 g / L to 400 g / L, Trichrome ICE Part 1 having a concentration of 150 ml / L to 350 ml / L, Trichrome ICE Make Up having a concentration of 10 ml / L to 25 ml / L, and Trichrome ICE WA having a concentration of 0.5 ml / L to 5 ml / L.

9. The manufacturing method described in claim 4, wherein the raw materials for the high sulfur nickel layer include nickel sulfate having a concentration of 350 g / L to 450 g / L, nickel chloride having a concentration of 50 g / L to 100 g / L, boric acid having a concentration of 40 g / L to 60 g / L, and high sulfur nickel HAS 90 having a concentration of 2 ml / L to 4 mL / L.

10. The manufacturing method of claim 4, wherein the raw materials for the semi-bright nickel layer include nickel sulfate having a concentration of 350 g / L to 450 g / L, nickel chloride having a concentration of 30 g / L to 50 g / L, boric acid having a concentration of 40 g / L to 60 g / L, makeup agent NIB-90 having a concentration of 5 ml / L to 10 ml / L, main brightener NIB-90 having a concentration of 1 ml / L to 2 ml / L, and wetting agent Ni-66B having a concentration of 1 ml / L to 5 ml / L.

11. The conditions for electroplating the semi-bright nickel layer in the second step are a temperature of 50°C to 60°C and a cathode current density of 5 A / dm ２ ~10 A / dm ２ and the electroplating time is 600 s to 2700 s.

12. The conditions for electroplating the high sulfur nickel layer in the third step are a temperature of 45°C to 55°C, a voltage of 5V to 10V, and a cathode current density of 3A / dm ２ ~12 A / dm ２ and the electroplating time is 600 s to 2700 s.

13. The conditions for electroplating the environmentally friendly white chrome composite antibacterial layer in the fourth step are a temperature of 50°C to 60°C and a cathode current density of 5 A / dm ２ ~10 A / dm ２ and the electroplating time is 600 s to 900 s.

14. A bactericidal, environmentally friendly product comprising a substrate and the bactericidal, environmentally friendly composite plating layer of claim 1.

15. 15. The disinfectant environmentally friendly product of claim 14, wherein the substrate is a metal substrate or a plastic substrate.

16. 15. The disinfectant eco-friendly product of claim 14, wherein the disinfectant eco-friendly product is a kitchen or toilet disinfectant product.

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