Wear-resistant waterborne coating and method of manufacturing same, wear-resistant coating, appliance and method of manufacturing same

Abstract

The present application provides a kind of wear-resistant water-based paint and its manufacturing method, wear-resistant coating, appliance and its manufacturing method. According to the wear-resistant water-based paint provided by the embodiment of the present application, it is the dispersion liquid including core-shell emulsifier, polyaryletherketone resin and aqueous medium, the core-shell emulsifier includes inorganic particles and the long chain polymer with hydrophilic group-lipophilic chain segment grafted on the surface of the inorganic particles. The core-shell emulsifier in the wear-resistant water-based paint can prevent polyaryletherketone resin particles from agglomerating by steric hindrance and electrostatic repulsion, ensure that polyaryletherketone resin particles are uniformly dispersed in aqueous medium, and form wear-resistant water-based paint in stable dispersion state. In addition, the wear-resistant water-based paint in stable dispersion state is not easy to be affected by temperature dispersion performance, so as to reduce the defects (such as pore defects) of wear-resistant coating formed by wear-resistant water-based paint, improve wear resistance and corrosion resistance.

Description

Technical Field

[0001] This application relates to the technical field of waterborne polymer coatings, and in particular to a wear-resistant waterborne coating and its manufacturing method, wear-resistant coating, and apparatus. Background Technology

[0002] Polyaryletherketone (PEEK) resins possess excellent high-temperature resistance, mechanical strength, and chemical stability, making them valuable in the manufacture of wear-resistant coatings. As a type of polyaryletherketone resin, PEEK is typically used as a high-performance specialty engineering plastic and offers significant advantages due to its superior wear resistance.

[0003] In existing technologies, one approach is to manufacture polyetheretherketone (PEEK) resin layers via compression molding, but this method is uneconomical due to the high cost of mold manufacturing. Another approach is to form a wear-resistant coating by electrostatic spraying of PEEK resin, but this process results in low deposition efficiency and significant resin waste. To achieve the manufacture of high-performance wear-resistant coatings while controlling costs, researchers in this field have begun exploring waterborne coatings based on PEEK resin.

[0004] However, since polyetheretherketone resin itself is incompatible with water, its dispersion problem needs to be solved when applying it to water-based coating systems.

[0005] Currently, waterborne coatings of polyetheretherketone resin mainly rely on traditional small-molecule emulsifiers. However, waterborne coatings of polyetheretherketone resin containing such emulsifiers exhibit significant limitations in the storage and application process to form a wear-resistant coating. Ultimately, these coatings result in poor density of the wear-resistant layer, leading to a decrease in the hardness and strength of the wear-resistant layer, and consequently a significant reduction in its wear resistance.

[0006] Therefore, there is an urgent need to develop a wear-resistant water-based coating containing polyaryletherketone resin. Summary of the Invention

[0007] The purpose of this application is to provide a wear-resistant water-based coating and its manufacturing method, wear-resistant coating and appliance, so as to solve the technical problem that the wear-resistant coating of the appliance formed by the existing wear-resistant water-based coating has poor wear resistance due to poor density.

[0008] According to a first aspect of this application, this application provides a wear-resistant waterborne coating, wherein the wear-resistant waterborne coating is a dispersion comprising a core-shell emulsifier, a polyaryletherketone resin, and an aqueous medium, wherein the core-shell emulsifier comprises inorganic particles and polymer long chains having hydrophilic-lipophilic segments grafted onto the surface of the inorganic particles.

[0009] The wear-resistant water-based coating provided according to the embodiments of this application can form a stable dispersion due to the presence of a core-shell emulsifier. Furthermore, this stable dispersion of the wear-resistant water-based coating is not easily affected by temperature in terms of dispersion performance, thus reducing defects (e.g., pore defects) in the wear-resistant coating formed by the water-based coating, thereby improving the hardness and strength of the wear-resistant coating and ensuring its wear resistance.

[0010] According to this application, the core-shell emulsifier comprises inorganic particles and polymer long chains with hydrophilic-lipophilic segments grafted onto the surface of the inorganic particles. The inorganic particles, acting as the core, provide structural support and a functional basis, while the polymer long chains with hydrophilic-lipophilic segments disperse the individual particles of the polyaryletherketone resin. During the dispersion of the polyaryletherketone resin particles to form an abrasion-resistant waterborne coating, the inorganic particles provide significant steric hindrance, physically preventing the individual polyaryletherketone resin particles from approaching each other, greatly enhancing the stability (centrifugal and shear resistance) of the dispersed liquid abrasion-resistant waterborne coating. Furthermore, during the dispersion stage to form the abrasion-resistant waterborne coating, the lipophilic segments (e.g., long-chain alkyl chains) can be firmly adsorbed or entangled on the surface of the hydrophobic polyaryletherketone resin particles through the principle of "like dissolves like." Hydrophilic groups (e.g., quaternary ammonium salts of polyoxyethylene sulfonate) are compatible with aqueous media (e.g., water). Through electrostatic repulsion and hydration, the polyaryletherketone resin particles can be stably dispersed in water, preventing the polyaryletherketone resin from "aggregating." Furthermore, during the stage of forming the wear-resistant coating through the water-based wear-resistant coating, the core-shell emulsifier formed by the inorganic particles remains in the wear-resistant coating, acting like the "steel bars" of reinforced concrete, thus improving the hardness and density of the wear-resistant coating.

[0011] In some embodiments, the polyaryletherketone resin includes at least one of polyetherketone resin, polyetheretherketone resin, polyetherketone resin, polyetherketone resin, polyetherketone resin, and polyetherketone etherketone resin, which have superior mechanical impact resistance, hardness, and self-lubricating properties compared to fluorocarbon resins.

[0012] In some embodiments, the polyaryletherketone resin has a crystallinity of 30%-40%, making it a semi-crystalline polymer. The highly crystalline regions form hard micro-regions during friction to resist surface scratches and adhesive wear, thereby improving the wear resistance of the wear-resistant coating formed by the wear-resistant water-based coating.

[0013] In some embodiments, the glass transition temperature of the polyaryletherketone resin is in the range of 143°C to 180°C. Such a glass transition temperature can ensure that the wear-resistant coating formed therefrom can still maintain dimensional stability and hardness at high temperatures, making it suitable for appliances that need to cope with high-temperature friction environments.

[0014] In some embodiments, the polyaryletherketone resin has a coefficient of friction of 0.2-0.25, resulting in a smooth and self-lubricating surface of the wear-resistant coating formed therefrom, which reduces the possibility of other substances adhering to the surface.

[0015] In some embodiments, the hydrophilic groups and lipophilic segments grafted onto the surface of the inorganic particles are respectively hydrophilic quaternary ammonium salt groups and lipophilic alkyl chains. These hydrophilic groups and lipophilic segments can possess both good amphiphilicity and low manufacturing cost. Specifically, the hydrophilic groups are polyoxyethylene sulfonate quaternary ammonium salt groups or polyoxyethylene carboxylate groups, and the lipophilic segments are nonylphenol polyoxyethylene ether chains or long alkyl chains. These hydrophilic groups and lipophilic segments can possess both good amphiphilicity and low manufacturing cost.

[0016] In some embodiments, the HLB value of the core-shell emulsifier is 10-18. During the formation of abrasion-resistant waterborne coatings, the lipophilic segments (lipophilic ends) of this core-shell emulsifier are firmly anchored to the surface of adjacent polyaryletherketone (PAEK) resin particles. Simultaneously, its hydrophilic groups (hydrophilic ends) can form a hydrogen bond network with the aqueous medium in the abrasion-resistant waterborne coating, thereby achieving dispersion of PAEK resin particles while obtaining a highly stable dispersion resistant to centrifugation and shearing as the abrasion-resistant waterborne coating. Furthermore, during the formation of the abrasion-resistant coating using the core-shell emulsifier, the polymer melt formed by the core-shell emulsifier and PAEK resin exhibits good compatibility, effectively interacting with the PAEK molecular chains to act as an internal plasticizer and promote flow. This helps the polymer melt formed by the PAEK resin to spread and fuse better, filling crystalline defects and thus improving the density of the abrasion-resistant coating.

[0017] In some embodiments, the molecular weight of the hydrophilic group is 220 g / mol to 2200 g / mol, and the molecular weight of the lipophilic segment is 220 g / mol to 400 g / mol. Large molecular weight groups can increase the molecular weight of the core-shell emulsifier to a certain extent, preventing the core-shell emulsifier from migrating in the abrasion-resistant waterborne coating, thereby affecting the stability of the abrasion-resistant waterborne coating.

[0018] In some embodiments, the inorganic particles are selected from one or more of calcium carbonate particles, alumina particles, and titanium dioxide particles. These inorganic particles can optimize the stability and mechanical properties of the core-shell emulsifier, and are widely available and inexpensive, thereby reducing the manufacturing cost of abrasion-resistant waterborne coatings.

[0019] In some embodiments, the inorganic particles are 5nm-100nm in size. The nanoscale core layer can provide the dispersing performance of the emulsifier. If the size of the inorganic particles is too small, the prepared core-shell emulsifier is prone to agglomeration and will result in higher preparation costs and reduced emulsification and dispersion power. If the size of the inorganic particles is too large, it may cause the emulsifier molecules to settle, which will weaken the emulsification and dispersion stability of the core-shell emulsifier.

[0020] In some embodiments, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, and the aqueous medium in the dispersion is (0.7-1):(25-28):(70.85-73.5). In these embodiments, the appropriate mass ratio of the components enables the production of abrasion-resistant waterborne coatings that simultaneously possess storage stability and workability reliability.

[0021] In some embodiments, the dispersion further includes inorganic pigments, fillers, and / or thickeners. In these embodiments, by adding inorganic pigments and fillers to the components of the abrasion-resistant waterborne coating, the color of the abrasion-resistant coating formed by the coating can be guaranteed; by adding thickeners to the components of the abrasion-resistant waterborne coating, the viscosity of the coating can be guaranteed to promote reliable formation of the abrasion-resistant coating. Furthermore, the thickener can also improve the anti-sagging properties of the abrasion-resistant waterborne coating during application. Thus, the core-shell emulsifier, polyaryletherketone resin, inorganic pigments, fillers, and / or thickeners, along with the aqueous medium, work synergistically to form an abrasion-resistant waterborne coating that is stable in storage, has good application performance, and exhibits a uniform and consistent dispersion.

[0022] In some embodiments, when the dispersion further includes inorganic pigments and fillers, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, and the inorganic pigments and fillers is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5); when the dispersion further includes a thickener, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, and the thickener is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2). In these embodiments, the appropriate mass ratios of the components enable the production of abrasion-resistant waterborne coatings that simultaneously possess storage stability and application reliability.

[0023] In some embodiments, the inorganic pigments and fillers are at least one of iron oxide, carbon black, silicon carbide, titanium dioxide, and aluminum oxide, which enable the wear-resistant coating to have enhanced hardness, wear resistance, and thermal stability.

[0024] In some embodiments, the thickener is at least one of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and xanthan gum. These thickeners enable the abrasion-resistant waterborne coating to have a suitable viscosity to ensure its workability as a liquid coating.

[0025] In some embodiments, the polyaryletherketone resin has a melting point of 305°C-390°C, a characteristic that provides sufficient thermal stability safety margin for the wear-resistant coating formed by the water-based wear-resistant coating. Since the operating temperature of the appliance is much lower than the melting point of the polyaryletherketone resin, it can be ensured that the molecular structure of the wear-resistant coating formed by this water-based wear-resistant coating will not soften or flow under high-temperature operating environments, thereby maintaining the integrity, mechanical strength, and wear resistance of the coating for a long period, achieving a stable and reliable protective effect.

[0026] In some embodiments, the intrinsic viscosity of the polyaryletherketone resin is 0.60 dL / g-1.2 dL / g. Polyaryletherketone resins with intrinsic viscosities in the range of 0.60 dL / g-1.2 dL / g exhibit good melt flowability and thermal stability above their melting point. This means that during the high-temperature sintering process, the polyaryletherketone resin in the wet film formed by the wear-resistant water-based coating can fully melt, flow, and spread, forming a dense and defect-free wear-resistant coating. If the intrinsic viscosity of the polyaryletherketone resin is too low, the molecular chains are short, resulting in insufficient cohesion in the formed wear-resistant coating, which easily leads to performance degradation. If the intrinsic viscosity of the polyaryletherketone resin is too high, it will be difficult for the polyaryletherketone resin to fully flow and fuse during the sintering process, similarly affecting the density of the coating.

[0027] In some embodiments, the viscosity of the abrasion-resistant water-based coating is 80 mPa·s-150 mPa·s. Within this viscosity range, the abrasion-resistant water-based coating can have suitable application properties. If the viscosity of the abrasion-resistant water-based coating is too low, it is easy to cause sagging and insufficient film thickness. If the viscosity of the abrasion-resistant water-based coating is too high, problems such as poor atomization, orange peel, and poor leveling will occur.

[0028] In some embodiments, the dispersion further includes polysiloxane, and the mass ratio of the core-shell emulsifier, polyaryletherketone resin, aqueous medium and polysiloxane is (0.7-1):(25-28):(70.85-73.5):(0.1-0.5).

[0029] In these embodiments, by adding polysiloxane to the components of the abrasion-resistant waterborne coating comprising polyaryletherketone resin, both polyaryletherketone resin and polysiloxane serve as the main film-forming substances. The polyaryletherketone resin provides abrasion resistance, and the polysiloxane provides non-stick properties. Thus, the abrasion-resistant coating formed by the abrasion-resistant waterborne coating can have both good abrasion resistance and non-stick properties, thereby enabling the abrasion-resistant coating to have good durable non-stick performance.

[0030] According to a second aspect of this application, a method for manufacturing a wear-resistant water-based coating is provided, wherein the method comprises: mixing the above-mentioned core-shell emulsifier, polyaryletherketone resin and aqueous medium to form a dispersion, thereby obtaining a wear-resistant water-based coating.

[0031] According to the embodiments of this application, a method for manufacturing a wear-resistant waterborne coating is provided. By mixing a core-shell emulsifier, polyaryletherketone resin, and an aqueous medium, a stable dispersion can be formed as the wear-resistant waterborne coating. The core-shell emulsifier in the dispersion can prevent the agglomeration of polyaryletherketone resin particles through steric hindrance and electrostatic repulsion, thereby ensuring that the polyaryletherketone resin has long-term stable and uniform dispersion in the aqueous medium, forming a wear-resistant waterborne coating in a stable dispersion state. In addition, the wear-resistant waterborne coating in a stable dispersion state is not easily affected by temperature in terms of dispersion performance, thus reducing defects (e.g., pore defects) in the wear-resistant coating formed by the wear-resistant waterborne coating, thereby improving the hardness and strength of the wear-resistant coating and ensuring the wear resistance performance of the wear-resistant coating.

[0032] In some embodiments, the step of mixing the core-shell emulsifier, the polyaryletherketone resin, and the aqueous medium to form a dispersion includes: mixing the core-shell emulsifier and the aqueous medium to form a first mixture; and mixing the polyaryletherketone resin into the first mixture to form the dispersion.

[0033] In these embodiments, by pre-mixing the core-shell emulsifier and the aqueous medium, a first mixture in which the core-shell emulsifier is uniformly dispersed can be obtained. During this process, the core-shell emulsifier can fully expand and uniformly disperse in the aqueous medium, forming a stable dispersion system. When the polyaryletherketone resin is added to the first mixture, it can be rapidly and uniformly adsorbed by the dispersed core-shell emulsifier in the first mixture, thereby significantly improving the emulsification efficiency. At the same time, this order of addition can construct a uniform composite system with polyaryletherketone resin particles as "islands" and the emulsifier as a stable "anchor point." This uniform composite system can lay the foundation for achieving the final density, ultra-high wear resistance, and excellent adhesion of the wear-resistant coating.

[0034] In some embodiments, the polyaryletherketone resin has a particle size of 20μm-120μm. Medium-sized (20μm-120μm) polyaryletherketone resins easily form a stable suspension system in aqueous media, avoiding agglomeration problems caused by excessively small particle sizes (e.g., nanometer-scale) or sedimentation and stratification caused by excessively large particle sizes (e.g., millimeter-scale). Furthermore, the abrasion-resistant waterborne coating with medium-sized resin particles can construct a "micro-macro" multi-level abrasion-resistant structure in the formed abrasion-resistant coating: small-sized particles fill the gaps between large-sized particles, enhancing the coating's cohesion; large-sized particles act as a "skeleton" to withstand external forces, reducing coating wear.

[0035] In some embodiments, the polyaryletherketone resin is a hydroxylated modified polyaryletherketone resin. The hydroxylated modified polyaryletherketone resin will undergo a reverse crosslinking reaction with the core-shell emulsifier, thereby improving the overall density of the final wear-resistant coating.

[0036] In some embodiments, the method for manufacturing the wear-resistant waterborne coating includes the step of forming a core-shell emulsifier having hydrophilic groups and lipophilic segments, wherein the core-shell emulsifier is amphiphilic and can stabilize the oil-water interface in the dispersed wear-resistant waterborne coating, thereby solving the problems of poor dispersibility and single function of traditional emulsifiers.

[0037] In some embodiments, the step of forming the core-shell emulsifier includes: providing inorganic particles; grafting hydroxyl groups onto the surface of the inorganic particles; grafting hydrophilic groups onto the hydroxyl groups on the surface of the inorganic particles by silanization coupling treatment; and grafting lipophilic segments onto the hydrophilic groups on the surface of the inorganic particles by ion exchange, thereby obtaining the core-shell emulsifier having hydrophilic groups and lipophilic segments.

[0038] In these embodiments, by hydroxylating the surface of inorganic particles, performing silanization coupling treatment, and performing ion exchange treatment, a core-shell emulsifier with a core-shell structure and possessing hydrophilic groups and lipophilic segments can be manufactured. This allows the amphiphilic nature of the core-shell emulsifier to stabilize the oil-water interface in abrasion-resistant waterborne coatings, thereby solving the problems of poor dispersibility and limited functionality of traditional emulsifiers.

[0039] According to a third aspect of this application, a wear-resistant coating is provided, wherein the wear-resistant coating comprises a polyaryletherketone resin layer and particulate matter dispersed in the polyaryletherketone resin layer, the particulate matter comprising the aforementioned core-shell emulsifier.

[0040] In some embodiments, the wear-resistant coating is dense, which avoids affecting the hardness and strength of the wear-resistant coating due to poor density, thereby ensuring the wear resistance performance of the wear-resistant coating. As an example, the wear-resistant coating has a porosity of no more than 0.1% and a pore size of no more than 10 μm.

[0041] In some embodiments, the Vickers hardness of the wear-resistant coating is 35HV-45HV, which can further improve the wear resistance of the wear-resistant coating.

[0042] In some embodiments, the coefficient of friction of the wear-resistant coating is 0.1-0.2, which can further improve the wear resistance of the wear-resistant coating.

[0043] In some embodiments, the thickness of the wear-resistant coating is 30μm-200μm, which is suitable as an intermediate layer for various types of appliances and a base layer for grafted non-adhesive molecules.

[0044] In some embodiments, the polyaryletherketone resin layer and the core-shell emulsifier are chemically bonded at the contact interface. Specifically, the product is a crosslinking product of the surface groups of the hydroxylated polyaryletherketone and the core-shell emulsifier. In this way, the density of the bonding interface inside the wear-resistant coating can be further optimized due to crosslinking.

[0045] In some embodiments, the mass of the polyaryletherketone resin layer is 96%-99% of the total mass of the wear-resistant coating, with the balance being a core-shell emulsifier. The appropriate mass proportions of each component balance the overall performance of the wear-resistant coating, including its wear resistance and strength.

[0046] In some embodiments, the particulate matter further includes pigment and filler particles, the mass of the polyaryletherketone resin layer is 95%-98% of the total mass of the wear-resistant coating, the mass of the core-shell emulsifier is 1%-4% of the total mass of the wear-resistant coating, and the balance is the pigment and filler particles. The appropriate mass proportions of each component balance the overall performance of the wear-resistant coating, including its wear resistance and strength.

[0047] According to a fourth aspect of this application, an apparatus is provided, wherein the apparatus includes an apparatus substrate and an abrasion-resistant coating formed on the apparatus substrate, wherein the abrasion-resistant coating includes the abrasion-resistant coating described above.

[0048] In some embodiments, the utensil includes frying pans, rice cooker inner pots, cups, kettles, or knives, and is applicable to a wide variety of types, thus forming multiple types of utensils.

[0049] In some embodiments, the appliance further includes a non-stick layer formed on the wear-resistant coating. Using the wear-resistant coating of this application as the base for forming the non-stick layer, it has a relatively large bonding surface compared to an intermediate layer of the same size formed directly by polyaryletherketone resin, an intermediate layer formed by a small molecule emulsifier and polyaryletherketone resin, or an intermediate layer formed by a metal material. In this way, the bonding force with the non-stick layer disposed thereon can be guaranteed, thereby greatly improving the overall wear resistance and non-stick performance of the appliance due to its resistance to peeling.

[0050] According to a fifth aspect of this application, a method for manufacturing an appliance is provided, wherein the method comprises: providing the above-described abrasion-resistant water-based coating or an abrasion-resistant water-based coating manufactured by the method thereof; applying the abrasion-resistant water-based coating onto an appliance substrate to form an initial abrasion-resistant layer; and sintering the initial abrasion-resistant layer at a sintering temperature not lower than the melting point of the polyaryletherketone resin in the initial abrasion-resistant layer to obtain an abrasion-resistant coating in which at least a core-shell emulsifier is dispersed in the polyaryletherketone resin layer, thereby manufacturing the appliance. Attached Figure Description

[0051] The above and other aspects, features, and other advantages of this application will become clearer and more readily understood from the following detailed description of exemplary embodiments in conjunction with the accompanying drawings, in which:

[0052] Figure 1 A schematic diagram illustrating the formation principle of a wear-resistant coating provided according to an exemplary embodiment of this application is shown;

[0053] Figure 2 A photograph is shown of the abrasion-resistant water-based coating provided according to Example 1 of this application after standing for 7 days;

[0054] Figure 3 SEM images of the surface of the wear-resistant coating provided according to Embodiment 9 of this application are shown;

[0055] Figure 4 An SEM image of a cross section of the wear-resistant coating provided according to Embodiment 9 of this application is shown;

[0056] Figure 5 Photographs of the surface of the wear-resistant coating provided according to Embodiment 9 of this application before and after 200,000 wear cycles are shown.

[0057] Figure 6 A comparison graph showing the thickness of the wear-resistant coating provided according to Embodiment 9 of this application before and after 200,000 wear cycles is shown.

[0058] Figure 7 The results of a cross-cut adhesion test of the abrasion-resistant coating provided according to Example 9 of this application are shown. Detailed Implementation

[0059] The following will combine Figures 1 to 7 This application describes the wear-resistant water-based coatings and their manufacturing methods, wear-resistant coatings, and appliances and their manufacturing methods provided in the embodiments of this application.

[0060] The inventors of this application have discovered that traditional water-based coatings containing polyaryletherketones mainly rely on small-molecule emulsifiers, which exhibit significant limitations in storage, transportation, and application.

[0061] Specifically, this water-based coating exhibits poor stability, easily demulsifying under shear and centrifugal forces. This leads to instability during storage and transportation, and makes it difficult to guarantee the reliability of the spraying process. More critically, during the film formation and high-temperature sintering process to create the wear-resistant layer, small-molecule emulsifiers can migrate, aggregate, and remain within the wear-resistant coating due to heat, or create large pores and defects, forming structural weaknesses (microscopic defects and hydrophilic channels). This severely weakens the overall performance (wear resistance, strength, and corrosion resistance) of the wear-resistant coating. Consequently, the coating's density decreases, its hardness and wear resistance differ significantly from the properties of PEEK material itself, and its water resistance is also significantly reduced. Therefore, it cannot meet the requirements for cookware coatings used in long-term, frequent friction and high-temperature, high-humidity environments.

[0062] Based on this, this application proposes to use core-shell emulsifiers and polyaryletherketone resins to form a wear-resistant waterborne coating with good shear resistance and centrifugal resistance, thereby fundamentally solving the inherent defects of small molecule emulsifier-based polyaryletherketone waterborne coatings.

[0063] According to a first aspect of this application, a method for manufacturing a wear-resistant water-based coating is provided. This wear-resistant water-based coating is used to manufacture wear-resistant coatings for frying pans, rice cooker inner pots, cups, kettles, or knives, particularly for manufacturing wear-resistant coatings for frying pans to meet the friction requirements of hard objects such as iron spatulas used in Chinese cooking. In this application, the method for manufacturing the wear-resistant water-based coating includes mixing a core-shell emulsifier, a polyaryletherketone resin, and an aqueous medium to form a dispersion, thereby obtaining the wear-resistant water-based coating.

[0064] According to the embodiments of this application, a method for manufacturing a wear-resistant waterborne coating is provided. By mixing a core-shell emulsifier, polyaryletherketone resin, and an aqueous medium, a stable dispersion can be formed as the wear-resistant waterborne coating. The core-shell emulsifier in the dispersion can prevent the agglomeration of polyaryletherketone resin particles through steric hindrance and electrostatic repulsion, thereby ensuring that the polyaryletherketone resin has long-term stable and uniform dispersion in the aqueous medium, forming a wear-resistant waterborne coating in a stable dispersion state. In addition, the wear-resistant waterborne coating in a stable dispersion state is not easily affected by temperature in terms of dispersion performance, thus reducing defects (e.g., pore defects) in the wear-resistant coating formed by the wear-resistant waterborne coating, thereby improving the hardness and strength of the wear-resistant coating and ensuring the wear resistance performance of the wear-resistant coating. Furthermore, the wear-resistant waterborne coating manufactured in this way can make full use of the polyaryletherketone resin, which has a significant cost reduction advantage.

[0065] In this application, the abrasion-resistant waterborne coating exhibits excellent shear resistance, centrifugal resistance, and heat resistance, is resistant to demulsification, is suitable for atomized spraying processes, and provides a feasible path for high-viscosity non-stick materials. As an example, the abrasion-resistant waterborne coating is suitable as a carrier for polysiloxane, a non-stick material, thereby broadening the applicability of polysiloxane as a non-stick material.

[0066] The following describes a method for manufacturing abrasion-resistant waterborne coatings according to this application, with reference to specific embodiments.

[0067] Provide core-shell emulsifiers

[0068] According to this application, the core-shell emulsifier, as an emulsifying aid in abrasion-resistant waterborne coatings, has a core-shell structure and can form a dispersion system together with polyaryletherketone resin and aqueous medium. This emulsifier not only efficiently and stably disperses polyaryletherketone resin particles but also acts as a functional filler in the final abrasion-resistant coating, significantly improving the coating's abrasion resistance, density, and impact resistance.

[0069] Specifically, core-shell emulsifiers play a dispersing role in the dispersion stage of manufacturing wear-resistant waterborne coatings. By providing steric hindrance, they physically prevent the individual particles of polyaryletherketone resin from approaching each other, ensuring that the particles are uniformly dispersed in the aqueous medium and preventing agglomeration. This results in a stable and dispersed wear-resistant waterborne coating whose stability is not easily compromised by external forces, temperature, or time, demonstrating excellent dispersibility. Furthermore, during the surface drying process of the initial wear-resistant layer, core-shell emulsifiers prevent the agglomeration of dispersed polyaryletherketone resin particles through steric hindrance and electrostatic repulsion, ensuring uniform dispersion of all components within the initial wear-resistant layer. In addition, during the sintering process of the wear-resistant coating, core-shell emulsifiers promote the flow of the polyaryletherketone resin melt, filling crystalline defects and forming a dense coating. Moreover, they can act as a reinforcing phase in the polyaryletherketone resin layer, thereby enhancing the impact resistance and hardness of the wear-resistant coating.

[0070] In some embodiments, the core-shell emulsifier is a core-shell macromolecular emulsifier with a core-shell structure, i.e., having a core layer and a shell layer surrounding the core layer. In this case, inorganic particles serve as the core layer, and organic molecules serve as the shell layer. The shell layer (outer layer, grafted layer) can be chemically grafted onto the surface of the inorganic particles, thereby forming a stable structure with a "rigid core-flexible chain". The core layer acts as an attachment, and the shell layer is an amphiphilic polymer, serving as a functional layer capable of achieving emulsification and dispersion performance. As an example, the core-shell emulsifier includes inorganic particles and long polymer chains with hydrophilic-lipophilic segments grafted onto the surface of the inorganic particles. In these embodiments, the core-shell emulsifier consists of inorganic particles and long polymer chains with hydrophilic-lipophilic segments. The inorganic particles serve as the core, providing structural support and a functional basis, while the long polymer chains with hydrophilic-lipophilic segments disperse the individual particles of the polyaryletherketone resin. In the stage of dispersing polyaryletherketone resin particles to form abrasion-resistant waterborne coatings, inorganic particles provide significant steric hindrance, physically preventing the individual polyaryletherketone resin particles from approaching each other, greatly enhancing the stability (centrifugal and shear resistance) of the dispersed liquid abrasion-resistant waterborne coating. Furthermore, during the dispersion stage of the abrasion-resistant waterborne coating, lipophilic segments (e.g., long-chain alkyl chains) can firmly adsorb or entangle on the surface of the hydrophobic polyaryletherketone resin particles through the principle of "like dissolves like." Hydrophilic groups (e.g., quaternary ammonium polyoxyethylene sulfonate) are compatible with aqueous media (e.g., water), allowing the polyaryletherketone resin particles to be stably dispersed in water through electrostatic repulsion and hydration, preventing the polyaryletherketone resin from "aggregating." Moreover, during the stage of forming the abrasion-resistant coating through the abrasion-resistant waterborne coating, the core-shell emulsifier formed by the inorganic particles is retained in the abrasion-resistant coating, acting like the "steel bars" of reinforced concrete, enhancing the hardness and density of the abrasion-resistant coating.

[0071] In some embodiments, the core-shell emulsifier is a macromolecular emulsifier, and the inorganic particles are nanoscale in size, specifically 5nm-100nm. The nanoscale core layer can provide the emulsifier with dispersion performance. If the size of the inorganic particles is too small, the prepared core-shell emulsifier is prone to agglomeration and will result in higher preparation costs and reduced emulsification and dispersion power. If the size of the inorganic particles is too large, it may cause the emulsifier molecules to settle, which will weaken the emulsification and dispersion stability of the core-shell emulsifier.

[0072] In some embodiments, the molecular weight of the hydrophilic group is 220 g / mol to 2200 g / mol, and the molecular weight of the lipophilic segment is 220 g / mol, which can increase the molecular weight of the core-shell emulsifier to a certain extent, preventing it from migrating in the wear-resistant waterborne coating and thus affecting the stability of the wear-resistant waterborne coating.

[0073] In some embodiments, when hydrophilic groups and lipophilic segments are grafted onto inorganic particles, the surface-grafted hydrophilic groups are polyoxyethylene sulfonate quaternary ammonium salts, and the lipophilic segments are long-chain alkyl chains. These hydrophilic groups and lipophilic segments can have both good amphiphilicity and low manufacturing cost.

[0074] In some embodiments, the inorganic particles are selected from one or more of calcium carbonate, alumina, and titanium dioxide. These inorganic particles can be selected to optimize the stability and mechanical properties of the core-shell emulsifier, and are widely available and inexpensive, thereby reducing the manufacturing cost of abrasion-resistant waterborne coatings.

[0075] According to this application, the core-shell emulsifier is an amphiphilic emulsifier. In an exemplary embodiment, the HLB value (hydrophilic-lipophilic balance value) of the core-shell emulsifier is 10-18. During the formation of abrasion-resistant waterborne coatings, the lipophilic segments (lipophilic ends) of this core-shell emulsifier can firmly anchor to the surface of adjacent particles of polyaryletherketone resin. For example, the lipophilic segments can form a dense coating layer on the surface of each polyaryletherketone resin particle, preventing direct contact between particles and reducing agglomeration. Simultaneously, its hydrophilic groups (hydrophilic ends) can form a hydrogen bond network with the aqueous medium in the abrasion-resistant waterborne coating, thereby achieving dispersion of the polyaryletherketone resin particles while obtaining an ultra-stable dispersion resistant to centrifugation and shear as an abrasion-resistant waterborne coating. In addition, during the formation of abrasion-resistant coatings in abrasion-resistant water-based coatings containing this core-shell emulsifier, the polymer melt formed by the core-shell emulsifier and polyaryletherketone resin has good compatibility and can effectively interact with the PAEK molecular chains, playing a role in internal plasticization and promoting flow. This helps the polymer melt formed by the polyaryletherketone resin to spread and fuse better, fill crystal defects, and thus improve the density of the abrasion-resistant coating.

[0076] In exemplary embodiments, when the lipophilic segments of the core-shell emulsifier are long-chain alkyl groups, aromatic rings, or fluorinated groups, they can be adsorbed onto the surface of polyaryletherketone resins via van der Waals forces, π-π stacked hydrogen bonds, or chemical bonding (such as ester bonds or amide bonds). Additionally, when the hydrophilic groups are carboxylates, sulfonates, or polyoxyethylene chains, they can dissociate or hydrogen-bond in water to form a hydration layer (approximately 0.5-2 nm thick), enabling stable dispersion of PAEK particles in water.

[0077] According to some embodiments of this application, the core-shell emulsifier is manufactured using a combination of surface grafting and ion exchange methods. Specifically, through a two-step reaction, hydrophilic groups and lipophilic segments are sequentially introduced onto inorganic particles, thereby producing a macromolecular emulsifier with a core-shell structure.

[0078] As an exemplary embodiment, a method for manufacturing a core-shell emulsifier is provided, specifically including the following steps.

[0079] Step S101: Provide inorganic particles.

[0080] Step S102: Graft hydroxyl groups onto the surface of the inorganic particles.

[0081] Step S103: Hydrophilic groups are grafted onto the hydroxyl groups on the surface of the inorganic particles by silanization coupling treatment.

[0082] Step S104 involves grafting lipophilic segments onto the hydrophilic groups on the surface of the inorganic particles via ion exchange, thereby obtaining the core-shell emulsifier having hydrophilic groups and lipophilic segments. In other words, lipophilic segments are introduced into the hydrophilic groups on the surface of the inorganic particles through ion exchange, thereby obtaining the core-shell emulsifier according to this application.

[0083] In step S101, the inorganic particles include one or more of calcium carbonate particles, alumina particles, and titanium dioxide particles. The particle size of the inorganic particles can be controlled at the nanoscale to enhance specific surface area and reactivity. As an example, the particle size of the inorganic particles can be in the range of 5 nm to 100 nm.

[0084] In step S102, grafting hydroxyl groups onto the surface of the inorganic particles constitutes hydroxylation treatment of the particle surface. This step increases the reactive sites on the particle surface, providing more anchoring sites for subsequent silanization coupling. As a specific example, ammonia can be used to disperse and hydroxylate the inorganic particles, and the pH of the suspension can be adjusted to a suitable range (e.g., alkaline conditions) to improve the dispersibility of the suspension and prevent the aggregation of individual inorganic particles.

[0085] In step S103, a silanization coupling treatment allows hydrophilic groups to be grafted onto the hydroxyl groups of hydroxyl-grafted inorganic particles. As a specific example, inorganic particles with hydroxyl groups on their surface can undergo a coupling reaction with an organosilicon quaternary ammonium salt (whose molecule contains a siloxane group at one end and a quaternary ammonium salt cationic hydrophilic group at the other end). The siloxane group in the organosilicon quaternary ammonium salt molecule can undergo a condensation-hydrolysis-condensation reaction (e.g., silanization) with the hydroxyl groups on the surface of the inorganic particles, forming a strong Si-O-covalent bond. This grafts the quaternary ammonium salt cationic hydrophilic group onto the surface of the inorganic particles, forming a strong covalently bonded shell on the surface of the inorganic particles. Furthermore, the quaternary ammonium salt group imparts hydrophilicity to the inorganic particles and lays the foundation for ion exchange.

[0086] In step S104, inorganic particles with surface-grafted hydrophilic groups can be reacted with sodium nonylphenol polyoxyethylene ether sulfonate (an anionic surfactant whose lipophilic portion is a nonylphenol chain, with a degree of polymerization controllable between 5 and 50). Through ion exchange, the anions in the quaternary ammonium salt groups (such as Cl-) are... -The ions are replaced by sulfonate anions, thereby introducing a lipophilic segment (nonylphenol chain).

[0087] In these embodiments, by hydroxylating the surface of inorganic particles, performing silanization coupling treatment, and performing ion exchange treatment, a core-shell emulsifier with a core-shell structure and possessing hydrophilic groups and lipophilic segments can be manufactured. This allows the amphiphilic nature of the core-shell emulsifier to stabilize the oil-water interface in abrasion-resistant waterborne coatings, thereby solving the problems of poor dispersibility and limited functionality of traditional emulsifiers.

[0088] According to this application, by selecting sodium nonylphenol polyoxyethylene ether sulfonate with different degrees of polymerization (e.g., polyoxyethylene chain segment number n=5~50), the ratio of hydrophilic groups (quaternary ammonium salt) and lipophilic segments (nonylphenol chains) on the surface of inorganic particles can be balanced, thereby controlling the HLB value of the core-shell emulsifier within the range of 10-18. By obtaining a core-shell emulsifier with the target HLB value, the interaction between the core-shell emulsifier and polyaryletherketone (PAEK) resin and aqueous media can be controlled at the molecular level, thereby optimizing the stability of the wear-resistant waterborne coating. It should be noted that the grafted hydrophilic groups and lipophilic segments may possess certain chemical activity, such as hydroxyl groups, which can then bond with the hydroxylated polyaryletherketone, forming a molecular bridge at the interface between the two, further promoting the densification and wear resistance of the wear-resistant coating.

[0089] Provide polyaryletherketone resin

[0090] According to this application, the molecular backbone of polyaryletherketone resin is composed of alternating benzene rings, ether bonds (—O—), and ketone bonds (—CO—). As the main film-forming substance in wear-resistant waterborne coatings, the rigid structure of the benzene rings endows the polyaryletherketone resin with high modulus and high compressive strength, making it less prone to plastic deformation during friction, thereby reducing wear. The ether bonds endow the polyaryletherketone resin with flexibility, forming a "rigid-flexible" balanced structure, making the polyaryletherketone resin both resistant to deformation and less prone to brittleness during friction.

[0091] In some embodiments, the polyaryletherketone resin (PAEK) includes at least one of polyetherketone resin (PEK), polyetheretherketone resin (PEEK), polyetherketone resin (PEKK), polyetheretherketone resin (PEEKK), and polyetherketone etherketone resin (PEKEKK). These polyaryletherketones exhibit superior resistance to mechanical impact, hardness, and self-lubricating properties compared to fluorocarbon resins. In some embodiments, the polyaryletherketone resin has a crystallinity of 30%-40%, making it a semi-crystalline polymer. The highly crystalline regions form "hard micro-regions" during friction to resist surface scratches and adhesive wear, thereby improving the wear resistance of the wear-resistant coating formed by the wear-resistant water-based coating. In some embodiments, the degree of polymerization of the polyaryletherketone resin is 100-300, which has a medium degree of polymerization. When polyaryletherketones with this degree of polymerization are selected, the molecular chains have formed a sufficient number of entanglement points (about 10-30 entanglement points per chain), which can significantly improve the melt viscosity and melt strength of the wear-resistant coating formed by the wear-resistant water-based coating during the sintering process, avoid melt cracking or drooling during sintering, and have good tensile strength, heat resistance and corrosion resistance.

[0092] In some embodiments, the glass transition temperature (Tg) of polyaryletherketone resin is in the range of 143°C-180°C. As specific examples, the glass transition temperature of polyetherketone resin (PEK) is 155°C-165°C, that of polyetheretherketone resin (PEEK) is 143°C-155°C, that of polyetherketoneketone resin (PEKK) is 162°C-165°C, that of polyetheretherketoneketone resin (PEEKK) is 165°C-175°C, and that of polyetherketoneetherketoneketone resin (PEKEKK) is 170°C-180°C. Below Tg, polyaryletherketone resin exhibits rigidity; above Tg, it exhibits increased toughness due to chain segment movement, softening only near its melting point. This glass transition temperature ensures that the resulting wear-resistant coating maintains dimensional stability and hardness at high temperatures, making it suitable for appliances requiring high-temperature friction environments.

[0093] In some embodiments, polyaryletherketone resins have a low coefficient of friction. For example, the coefficient of friction of polyaryletherketone resins is 0.2-0.25, so the wear-resistant coating formed therefrom has a smooth surface and good self-lubricating properties, which can reduce the possibility of other substances adhering to the surface.

[0094] In the appliances involved in this application, the normal operating temperature is generally no higher than 280°C. According to this application, the polyaryletherketone resin in the abrasion-resistant water-based coating has a melting point of 305°C-390°C. This characteristic provides sufficient thermal stability safety margin for the abrasion-resistant coating formed by the abrasion-resistant water-based coating. Since the operating temperature of the appliance is much lower than the melting point of the polyaryletherketone resin, it can be ensured that the molecular structure of the abrasion-resistant coating formed by this abrasion-resistant water-based coating will not soften or flow under high-temperature working environments, thereby maintaining the integrity, mechanical strength, and abrasion resistance of the coating for a long time, achieving a stable and reliable protective effect.

[0095] In some embodiments, the intrinsic viscosity of the polyaryletherketone resin is 0.60 dL / g-1.2 dL / g. Polyaryletherketone resins with intrinsic viscosities in this range exhibit good melt flowability and thermal stability above their melting point. This means that during the high-temperature sintering process, the polyaryletherketone resin in the wet film formed by the abrasion-resistant water-based coating can fully melt, flow, and spread, forming a dense and defect-free abrasion-resistant coating. If the intrinsic viscosity of the polyaryletherketone resin is too low, the molecular chains are short, resulting in insufficient cohesion in the formed abrasion-resistant coating, which easily leads to performance degradation. If the intrinsic viscosity of the polyaryletherketone resin is too high, it will be difficult for the polyaryletherketone resin to fully flow and fuse during sintering, similarly affecting the density of the coating. Here, intrinsic viscosity is used to characterize the specific viscosity limit of the polyaryletherketone resin polymer chain when infinitely diluted in a specific solvent, and can be determined using specialized instruments and methods. For example, the intrinsic viscosity of polyetheretherketone (PEEK) can be determined by extrapolation using an automated Ubbelohde viscometer. The testing process typically involves dissolving the PAEK sample in 96% concentrated sulfuric acid, measuring the flow time of the solution at a specific temperature of 30.0 ± 0.1°C, and then calculating the intrinsic viscosity value.

[0096] According to the manufacturing method of the wear-resistant waterborne coating of this application, the particle size range of the selected polyaryletherketone resin can be narrow or wide. In some embodiments, the particle size of the polyaryletherketone resin is 20μm-120μm. Polyaryletherketone resin with a medium particle size (20μm-120μm) easily forms a stable suspension system in an aqueous medium, which can avoid the agglomeration problem caused by excessively small particle size (such as nanometers) or the sedimentation and stratification caused by excessively large particle size (such as millimeters). Furthermore, the wear-resistant waterborne coating with medium-sized resin particles can construct a "micro-macro" multi-level wear-resistant structure in the formed wear-resistant coating: small-sized particles fill the gaps between large-sized particles, enhancing the cohesion of the coating; large-sized particles act as a "skeleton" to withstand external forces, reducing coating wear.

[0097] According to this application, the polyetheretherketone (PEEK) resin can be selected from either unmodified raw resin or hydroxylated PEEK resin. The hydroxylation modification of the PEEK resin can be achieved by plasma treatment. The resulting polyetheretherketone resin possesses reactive groups capable of reverse crosslinking with the core-shell emulsifier, thereby improving the overall density of the final wear-resistant coating. Specifically, the plasma treatment can use oxygen (O2), argon (Ar), or a mixture thereof to form the plasma. The treatment power can be 300W-500W, the treatment time can be 5 minutes-30 minutes, and the gas flow rate can be 60mL / min-200mL / min. Furthermore, the plasma treatment of the PEEK resin can be performed under low vacuum conditions.

[0098] Provide water-based media

[0099] According to this application, the aqueous medium can be water, or it can be an organic solvent containing water that does not dissolve polyarylether ketone, wherein the organic solvent can be, for example, methanol, ethanol, isopropanol, etc.

[0100] Manufacturing abrasion-resistant water-based coatings

[0101] According to this application, a core-shell emulsifier, polyaryletherketone resin, and an aqueous medium are mixed to form a stable dispersion, thereby obtaining a wear-resistant waterborne coating. The resulting wear-resistant waterborne coating has good stability and dispersibility, which is beneficial for storage and subsequent formation of a wear-resistant coating.

[0102] In some embodiments, the step of mixing the core-shell emulsifier, polyaryletherketone resin, and aqueous medium to form a dispersion includes mixing the core-shell emulsifier and aqueous medium to form a first mixture, and then mixing the polyaryletherketone resin into the first mixture, thereby obtaining a wear-resistant aqueous coating in dispersion form. In these embodiments, by pre-mixing the core-shell emulsifier and aqueous medium, a first mixture in which the core-shell emulsifier is uniformly dispersed can be obtained. During this process, the core-shell emulsifier can fully expand and uniformly disperse in the aqueous medium, forming a stable dispersion system. When the polyaryletherketone resin is added to the first mixture, it can be rapidly and uniformly adsorbed by the dispersed core-shell emulsifier in the first mixture, thereby significantly improving emulsification efficiency. At the same time, this order of addition can construct a uniform composite system with polyaryletherketone resin particles as "islands" and the emulsifier as a stable "anchor point." This uniform composite system can lay the foundation for achieving the final density, ultra-high wear resistance, and excellent adhesion of the wear-resistant coating.

[0103] It should be noted that the above describes one possible composition of the wear-resistant waterborne coating. In some other embodiments of this application, the dispersion may include inorganic pigments and fillers and / or thickeners in addition to the core-shell emulsifier, polyaryletherketone resin, and aqueous medium. When the dispersion also includes inorganic pigments and fillers, the mass ratio of the core-shell emulsifier, polyaryletherketone resin, aqueous medium, and inorganic pigments and fillers is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5). When the dispersion also includes a thickener, the mass ratio of the core-shell emulsifier, polyaryletherketone resin, aqueous medium, and inorganic pigments and fillers is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5). The mass ratio of ether ketone resin, aqueous medium and thickener is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2). When the dispersion also includes inorganic pigments and fillers and thickener, the mass ratio of core-shell emulsifier, polyarylether ketone resin, aqueous medium, inorganic pigments and fillers and thickener is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5):(0.15-0.2).

[0104] In these embodiments, by adding inorganic pigments and fillers to the components of the abrasion-resistant waterborne coating, the color of the abrasion-resistant coating formed by the coating can be guaranteed. By adding thickeners to the components of the abrasion-resistant waterborne coating, the viscosity of the coating can be guaranteed, thereby promoting the reliable formation of the abrasion-resistant coating. Furthermore, the thickener can also improve the anti-sagging properties of the abrasion-resistant waterborne coating during application. Thus, the core-shell emulsifier, polyaryletherketone resin, inorganic pigments and fillers and / or thickeners, and the aqueous medium work synergistically to form an abrasion-resistant waterborne coating that is stable in storage, has good application performance, and exhibits a uniform and consistent dispersion of the coating.

[0105] In some embodiments, the inorganic pigments and fillers are carbon black or iron oxide black, and the thickener is at least one selected from ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and xanthan gum. These inorganic pigments and fillers, along with the thickener, offer advantages in both food safety and low cost while maintaining inherent performance. Correspondingly, the manufacturing method of the abrasion-resistant waterborne coating includes the steps of: adding a core-shell emulsifier to deionized water and stirring to obtain a first premix; then, adding inorganic pigments and fillers to the obtained first premix and stirring to obtain a second premix; next, adding polyetheretherketone resin to the second premix and stirring to obtain a third premix; and finally, adding a thickener to the third premix and stirring to obtain the abrasion-resistant waterborne coating. In these embodiments, the subsequent addition of the thickener can improve the sprayability of the abrasion-resistant waterborne coating while locking in dispersion performance.

[0106] In some other embodiments of this application, the dispersion includes a polysiloxane in addition to the core-shell emulsifier, polyaryletherketone resin, and aqueous medium. As an example, the mass ratio of the core-shell emulsifier, polyaryletherketone resin, aqueous medium, and polysiloxane is (0.7-1):(25-28):(70.85-73.5):(0.1-0.5).

[0107] As a specific example, the polysiloxane is polydimethylsiloxane, specifically a low-polymer polydimethylsiloxane (silicone oil). In these embodiments, by adding polysiloxane to the components of the abrasion-resistant waterborne coating comprising polyaryletherketone resin, both the polyaryletherketone resin and the polysiloxane serve as the main film-forming substances. The polyaryletherketone resin provides abrasion resistance, and the polysiloxane provides non-stick properties. Therefore, the abrasion-resistant coating formed by the abrasion-resistant waterborne coating can possess both good abrasion resistance and non-stick properties, thereby enabling the abrasion-resistant coating to have good durable non-stick performance.

[0108] According to a second aspect of this application, a water-based abrasion-resistant coating is provided, wherein the water-based abrasion-resistant coating is a liquid coating and has fluidity, wherein, as... Figure 1 As shown, the wear-resistant waterborne coating is a dispersion comprising a core-shell emulsifier, a polyaryletherketone resin, and an aqueous medium.

[0109] The wear-resistant water-based coating provided according to the embodiments of this application can form a stable dispersion due to the presence of a core-shell emulsifier. Furthermore, this stable dispersion of the wear-resistant water-based coating is not easily affected by temperature in terms of dispersion performance, thus reducing defects (e.g., pore defects) in the wear-resistant coating formed by the water-based coating, thereby improving the hardness and strength of the wear-resistant coating and ensuring its wear resistance.

[0110] According to this application, in the dispersion, the mass ratio of core-shell emulsifier, polyaryletherketone resin, and aqueous medium is (0.7-1):(25-28):(70.85-73.5). In these embodiments, the appropriate mass ratio of each component enables the production of abrasion-resistant waterborne coatings that simultaneously possess storage stability and application reliability.

[0111] In some embodiments, the dispersion includes, in addition to the core-shell emulsifier, polyaryletherketone resin, and aqueous medium, inorganic pigments, fillers, and / or thickeners. In these embodiments, by adding inorganic pigments and fillers to the components of the abrasion-resistant waterborne coating, the color of the abrasion-resistant coating formed by the coating can be guaranteed; by adding thickeners to the components of the abrasion-resistant waterborne coating, the viscosity of the coating can be guaranteed to promote reliable formation of the abrasion-resistant coating. Furthermore, the thickener can also improve the anti-sagging properties of the abrasion-resistant waterborne coating during application. Thus, the core-shell emulsifier, polyaryletherketone resin, inorganic pigments, fillers, and / or thickeners, along with the aqueous medium, work synergistically to form an abrasion-resistant waterborne coating that is stable in storage, has good application performance, and exhibits a uniform and consistent dispersion.

[0112] In some embodiments, the mass ratio of core-shell emulsifier, polyaryletherketone resin, aqueous medium, and inorganic pigments and fillers is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5); when the dispersion also includes a thickener, the mass ratio of core-shell emulsifier, polyaryletherketone resin, aqueous medium, and thickener is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2). In these embodiments, the appropriate mass ratio of each component enables the production of abrasion-resistant waterborne coatings that simultaneously possess storage stability and application reliability.

[0113] In a preferred embodiment, the wear-resistant waterborne coating is a dispersion composed of a core-shell emulsifier, polyaryletherketone resin, an aqueous medium, inorganic pigments and fillers, and a thickener. The mass ratio of the core-shell emulsifier, polyaryletherketone resin, aqueous medium, inorganic pigments and fillers, and thickener is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5):(0.15-0.2). Converted to mass percentages, the core-shell emulsifier accounts for 0.7%-1%, the polyaryletherketone resin accounts for 25%-28%, the aqueous medium accounts for 70.85%-73.5%, the inorganic pigments and fillers account for 0.3%-0.5%, and the thickener accounts for 0.15%-0.2%.

[0114] In some embodiments, the inorganic pigments and fillers include at least one selected from iron oxide (e.g., iron oxide red, iron oxide yellow, iron oxide black), carbon black, silicon carbide, titanium dioxide, and aluminum oxide. These pigments and fillers enable the wear-resistant coating to possess enhanced hardness, wear resistance, and thermal stability. In a preferred embodiment, the pigments and fillers have nanoscale dimensions. Nanoscale pigments and fillers have numerous bonding sites, thereby ensuring the adhesion between the wear-resistant coating and the appliance substrate. As an example, the particle size of the pigments and fillers is 15 nanometers to 20 nanometers.

[0115] In some embodiments, the thickener is at least one of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and xanthan gum. These thickeners enable the abrasion-resistant waterborne coating to have a suitable viscosity to ensure its workability as a liquid coating.

[0116] As an exemplary embodiment, the viscosity of the abrasion-resistant water-based coating is 80 mPa·s-150 mPa·s. The viscosity of the abrasion-resistant water-based coating measured by the Forecast-4 cup is between 20 seconds and 40 seconds (corresponding to an apparent viscosity of 80 mPa·s-150 mPa·s). Within this viscosity range, the abrasion-resistant water-based coating can have suitable application performance. If the viscosity of the abrasion-resistant water-based coating is too low, it is easy to cause sagging and insufficient film thickness; if the viscosity of the abrasion-resistant water-based coating is too high, problems such as poor atomization, orange peel, and poor leveling will occur.

[0117] According to a third aspect of this application, a wear-resistant coating is provided, wherein the wear-resistant coating is obtained by curing a wear-resistant water-based coating. Specifically, the wear-resistant coating comprises a polyaryletherketone resin layer and particulate matter dispersed in the polyaryletherketone resin layer, wherein the particulate matter comprises a core-shell emulsifier.

[0118] It should be noted that the core-shell emulsifier in the wear-resistant coating can be the same as or slightly different from the wear-resistant coating in the wear-resistant water-based coating. This is because, during the process of forming the wear-resistant coating by sintering the film formed by the wear-resistant water-based coating, some of the active groups of the core-shell emulsifier may react. For example, at high temperatures, the carbonyl group may be oxidized to a carboxyl group (-COOH) or further decarboxylated to generate carbon dioxide (CO2), resulting in a decrease in the molecular weight of the emulsifier. However, this only changes some groups or molecular weight of the core-shell emulsifier and does not destroy the core-shell structure of the core-shell emulsifier.

[0119] According to the embodiments of this application, the wear-resistant coating includes a polyaryletherketone resin layer and a core-shell emulsifier dispersed in the polyaryletherketone resin layer. The core-shell emulsifier can reinforce the polyaryletherketone resin layer, thereby improving the overall hardness and density of the wear-resistant coating, solving the problem of poor density affecting the hardness and strength of the wear-resistant coating, and thus ensuring the wear resistance performance of the wear-resistant coating.

[0120] In some embodiments, the wear-resistant coating is dense, which avoids affecting the hardness and strength of the wear-resistant coating due to poor density, thereby ensuring the wear resistance performance of the wear-resistant coating. As an example, the wear-resistant coating has a porosity of no more than 0.1% and a pore size of no more than 10 μm. The Vickers hardness of the wear-resistant coating is 35HV-45HV, which further enhances the wear resistance performance. The coefficient of friction of the wear-resistant coating is 0.1-0.2, which further enhances the wear resistance performance.

[0121] In some embodiments, the polyaryletherketone resin layer and the core-shell emulsifier are chemically bonded at the contact interface. Specifically, the product is a crosslinking product of the surface groups of the hydroxylated polyaryletherketone and the core-shell emulsifier. In this way, the density of the bonding interface inside the wear-resistant coating can be further optimized due to crosslinking.

[0122] In some embodiments, the wear-resistant coating uses a polyaryletherketone resin layer as the continuous phase (main body) and a core-shell emulsifier as the dispersed phase (added in small amounts). This balances the overall performance of the wear-resistant coating, including its wear resistance and strength. For example, the polyaryletherketone resin layer constitutes 96%-99% of the total mass of the wear-resistant coating, with the balance being the core-shell emulsifier. The appropriate mass proportions of each component ensure a balanced overall performance of the wear-resistant coating, including its wear resistance and strength.

[0123] In some embodiments, the particulate matter further includes pigment and filler particles, thereby enabling the wear-resistant coating to possess reliable color and strength. As a specific example, the mass of the polyaryletherketone resin layer is 95%-98% of the total mass of the wear-resistant coating, the mass of the core-shell emulsifier is 1%-4% of the total mass of the wear-resistant coating, and the balance is the pigment and filler particles. The appropriate mass proportions of each component balance the overall performance of the wear-resistant coating, including its wear resistance and strength.

[0124] In this application, the surface and interior of the wear-resistant coating are both formed into a dense structure, which can give full play to the advantages of polyaryletherketone resin, thereby improving the wear resistance of the wear-resistant coating formed by the wear-resistant water-based coating including polyaryletherketone resin.

[0125] According to a fourth aspect of this application, an apparatus is provided, wherein the apparatus includes an apparatus substrate and an abrasion-resistant coating formed on the apparatus substrate, wherein the abrasion-resistant coating includes the abrasion-resistant coating of the above embodiments.

[0126] In some embodiments, the utensil includes frying pans, rice cooker inner pots, cups, kettles, or knives, and is applicable to a wide variety of types, thus forming multiple types of utensils.

[0127] According to a fifth aspect of this application, a method for manufacturing an appliance is provided. The method includes: step S201, providing an appliance substrate; step S202, providing a wear-resistant water-based coating, wherein the wear-resistant water-based coating is a dispersion comprising a core-shell emulsifier, a polyaryletherketone resin, and an aqueous medium; step S203, applying the wear-resistant water-based coating onto the appliance substrate to form an initial wear-resistant layer; and step S204, sintering the initial wear-resistant layer at a sintering temperature not lower than the melting point of the polyaryletherketone resin in the initial wear-resistant layer to obtain a wear-resistant coating in which the core-shell emulsifier is dispersed in the polyaryletherketone resin layer, thereby manufacturing the appliance.

[0128] In the embodiments of this application, coating refers to the method of uniformly covering the surface of the appliance substrate with a wear-resistant water-based coating (liquid coating) by means of brushing, spraying, rolling, dipping, etc.

[0129] According to the manufacturing method of the device provided in the embodiments of this application, under the influence of sintering temperature, the wear-resistant waterborne coating, which includes a core-shell emulsifier, polyaryletherketone resin, and an aqueous medium in the form of a dispersion, exhibits stability. The core-shell emulsifier, unlike small-molecule emulsifiers, does not volatilize, escape, or agglomerate; instead, it directly integrates into the polyaryletherketone resin melt and serves as part of the wear-resistant coating, playing a reinforcing role. This effectively avoids microscopic defects (e.g., pore defects) caused by volatile matter escape or agglomeration, ensuring the high density of the wear-resistant coating and providing its hardness and strength. Simultaneously, sintering the initial wear-resistant layer at a temperature not lower than the melting point of the polyaryletherketone resin in the initial wear-resistant layer effectively promotes the melt flow of the polyaryletherketone resin, sealing the internal pores of the initial wear-resistant layer and optimizing the microstructure of the coating, resulting in a more uniform and dense wear-resistant coating. On the other hand, this temperature condition ensures that the molten polyaryletherketone resin forms a tight contact with the matrix and a strong mechanical interlocking effect, thereby further improving the wear resistance of the wear-resistant coating.

[0130] The following describes the manufacturing method of the appliance according to this application, with specific steps.

[0131] Provide appliance base

[0132] According to the present invention, the appliance substrate has a substrate structure comprising a receiving cavity formed by stretching or spinning a metallic material. As examples, the metallic material includes magnesium, aluminum, iron, or titanium.

[0133] In some embodiments, the thickness of the appliance substrate is 1.0 mm to 2.0 mm, which can reduce the weight of the final manufactured appliance.

[0134] According to some embodiments of this application, the bonding surface between the utensil substrate and the wear-resistant coating has a micron-level roughness. The wear-resistant coating is conformally disposed on the utensil substrate. Thus, the rough surface of the utensil substrate allows the wear-resistant coating to possess a nano-level uneven surface, enriching the oil-retaining structure or protecting the non-stick layer, thereby further improving the utensil's long-lasting non-stick properties. According to other embodiments of this application, the bonding surface between the utensil substrate and the wear-resistant coating has an uneven structure composed of protrusions and grooves. The wear-resistant coating fills the grooves of the uneven structure to create a patterned non-stick pan, thereby meeting the usage needs of different users.

[0135] Preheating (optional)

[0136] According to this application, the method for manufacturing the appliance may further include a step of preheating the appliance substrate. As an example, the preheating temperature may be 50°C-70°C, and the preset time may be 5 min-10 min. Preheating allows the water-based abrasion-resistant coating to evaporate moisture quickly when it comes into contact with the preheated appliance substrate, which is beneficial for the rapid formation of a wet film.

[0137] Formation of initial wear-resistant layer

[0138] According to this application, a wet film with a thickness of 31μm-202μm is formed by atomizing and spraying a water-based abrasion-resistant coating. Specifically, the nozzle diameter of the atomizing spray gun is 1.0mm-1.5mm, the atomizing pressure is 2.5Bar-3.0Bar, the distance is 20cm-35cm, and the time is 2 seconds-5 seconds.

[0139] In some embodiments, the wet film obtained by atomized spraying is surface-dried to obtain an initial wear-resistant layer. As an example, the surface-drying temperature is 120°C-200°C, and the surface-drying time is 3 min-5 min.

[0140] Sintering to form a wear-resistant coating

[0141] According to this application, after obtaining the initial wear-resistant layer, sintering is performed to solidify the initial wear-resistant layer and form a wear-resistant and dense wear-resistant coating. In this application, the initial wear-resistant layer is sintered at a temperature not lower than the melting point of the polyaryletherketone resin in the initial wear-resistant layer. This allows the polyaryletherketone resin to fully melt and solidify, while maintaining the core-shell emulsifier uniformly dispersed in the polyaryletherketone resin matrix, forming a wear-resistant coating with polyaryletherketone resin as the continuous phase and core-shell emulsifier as the dispersed phase, ultimately resulting in an appliance with significantly improved surface wear resistance. Furthermore, because the wear-resistant coating is relatively dense and has numerous connection points with the appliance substrate, it also exhibits good bonding performance with the appliance substrate.

[0142] In a preferred embodiment, the sintering temperature is 50°C-100°C higher than the melting point of the polyaryletherketone resin in the initial wear-resistant layer. As an example, the sintering temperature is 380°C-420°C, and the curing time is 5 min-20 min. Performing sintering at this temperature and time allows the initial wear-resistant layer to be completely cured, forming a dense wear-resistant coating after natural cooling, thereby manufacturing the appliance.

[0143] In some embodiments, the thickness of the wear-resistant coating is 30μm-200μm, which is suitable as an intermediate layer for various types of appliances and as a base layer for grafted non-adhesive molecules.

[0144] According to this application, non-stick molecules can be added to abrasion-resistant water-based coatings, so that the abrasion-resistant coating formed by the abrasion-resistant water-based coating can itself have both abrasion resistance and non-stick properties to meet the usage requirements of appliances (e.g., cookware). Alternatively, a non-stick layer can be rearranged on top of the abrasion-resistant coating after it has been formed.

[0145] Spraying a non-stick material to create a non-stick layer on top of the abrasion-resistant coating.

[0146] In some embodiments, the appliance further includes a non-stick layer formed on the abrasion-resistant coating. Correspondingly, the method of manufacturing the appliance includes coating or applying a non-stick material over the abrasion-resistant coating to form a non-stick layer on the abrasion-resistant coating, wherein the abrasion-resistant coating serves as an intermediate layer. As a specific example, the non-stick material may be a liquid fluorine coating, a liquid ceramic coating, or a solid non-stick material as known in the art.

[0147] In these embodiments, the wear-resistant coating of this application has a relatively large bonding surface compared to an intermediate layer of the same size formed directly by polyaryletherketone resin, an intermediate layer formed by a small molecule emulsifier and polyaryletherketone resin, or an intermediate layer formed by a metal material. This ensures the bonding force with the non-stick layer disposed thereon, thereby greatly improving the overall wear resistance and non-stick properties of the appliance due to its resistance to peeling.

[0148] In a preferred embodiment, when a non-stick material is coated or applied over the wear-resistant coating, the surface of the wear-resistant coating is made into a viscous flow state, which combines with the coated or applied non-stick material, thereby greatly improving the bonding performance between the wear-resistant coating and the non-stick layer.

[0149] In addition, the surface of the wear-resistant coating of this application may contain active groups such as hydroxyl (-OH) and amino (-NH2). Therefore, in some embodiments, a non-stick material that can chemically bond or hydrogen bond with the wear-resistant coating can also be used to further improve the bonding performance between the wear-resistant coating and the non-stick layer by chemically bonding the wear-resistant coating and the non-stick layer.

[0150] According to this application, the appliance obtained through the above steps includes an appliance substrate and a wear-resistant coating formed on the surface of the appliance substrate.

[0151] The beneficial effects of the present invention will be described below with reference to specific examples.

[0152] Example 1

[0153] The abrasion-resistant waterborne coating of Example 1 was formed by the following method.

[0154] Step S301: Provide polyaryletherketone resin, core-shell emulsifier, and water. The selected polyaryletherketone resin has a particle size D50 of 20μm-120μm. The core-shell emulsifier has a structure with inorganic particles as the core layer and polymer long chains as the shell layer. In this embodiment, the core-shell emulsifier uses calcium carbonate with a particle size of 20nm-60nm as inorganic particles and polymer long chains with hydrophilic and lipophilic segments as polymer long chains. The hydrophilic group is a polyoxyethylene (molecular weight 990g / mol) sulfonic acid quaternary ammonium salt group, the lipophilic segment is a nonylphenol chain, and the HLB value of the core-shell emulsifier is 13.

[0155] In step S302, the polyaryletherketone resin and the core-shell emulsifier are dispersed in water (aqueous medium) and stirred to form a wear-resistant waterborne coating in the form of a dispersion, wherein the weight ratio of the core-shell emulsifier, the polyaryletherketone resin and water is 0.8:26:72, thereby enabling the manufacture of the wear-resistant waterborne coating according to Example 1.

[0156] Example 2

[0157] Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a wear-resistant waterborne coating (the polyaryletherketone resin of Example 2 is a polyetherketone resin), the wear-resistant waterborne coating of Example 2 according to this application is formed using the same method as in Example 1.

[0158] Example 3

[0159] Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a wear-resistant waterborne coating (the polyaryletherketone resin of Example 3 is a polyetherketone resin), the wear-resistant waterborne coating of Example 3 according to this application is formed using the same method as in Example 1.

[0160] Example 4

[0161] Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a wear-resistant waterborne coating (the polyaryletherketone resin of Example 4 is a polyetheretherketone resin), the wear-resistant waterborne coating of Example 4 according to this application is formed by the same method as in Example 1.

[0162] Example 5

[0163] Except for using a different polyaryletherketone resin to replace the polyaryletherketone resin of Example 1 to form a wear-resistant waterborne coating (the polyaryletherketone resin of Example 5 is a polyetherketone etherketone resin), the wear-resistant waterborne coating of Example 5 according to this application is formed by the same method as in Example 1.

[0164] Example 6

[0165] Except for using different core-shell emulsifiers to replace the core-shell emulsifier of Example 1 to form a wear-resistant waterborne coating (the core-shell emulsifier of Example 6 uses titanium dioxide with a particle size of 20nm-60nm as inorganic particles and polymer long chains with hydrophilic groups and lipophilic segments as polymer long chains, wherein the hydrophilic groups are polyoxyethylene (molecular weight 990g / mol) sulfonic acid quaternary ammonium salt groups, the lipophilic segments are nonylphenol chains, and the HLB value of the core-shell emulsifier is 10), the wear-resistant waterborne coating of Example 6 according to this application is formed by the same method as in Example 1.

[0166] Example 7

[0167] Except for using a different core-shell emulsifier to replace the core-shell emulsifier of Example 1 to form a wear-resistant waterborne coating (the core-shell emulsifier of this example uses calcium carbonate with a particle size of 20nm-60nm as inorganic particles and a polymer long chain with hydrophilic and lipophilic segments as polymer long chains, wherein the hydrophilic group is a polyoxyethylene (molecular weight 2200g / mol) sulfonic acid quaternary ammonium salt group, the lipophilic segment is a nonylphenol chain, and the HLB value of the core-shell emulsifier is 18), the wear-resistant waterborne coating of Example 7 according to this application is formed by the same method as in Example 1.

[0168] Example 8

[0169] Except for using a different core-shell emulsifier to replace the core-shell emulsifier of Example 1 to form a wear-resistant waterborne coating (the core-shell emulsifier of this example uses calcium carbonate with a particle size of 20nm-60nm as inorganic particles and a polymer long chain with hydrophilic and lipophilic segments as polymer long chains, wherein the hydrophilic group is a polyoxyethylene (molecular weight 220g / mol) sulfonic acid quaternary ammonium salt group, the lipophilic segment is a nonylphenol chain, and the HLB value of the core-shell emulsifier is 18), the wear-resistant waterborne coating of Example 8 according to this application is formed by the same method as in Example 1.

[0170] Example 9

[0171] Except for using different components to form the abrasion-resistant waterborne coating (the components for forming the abrasion-resistant waterborne coating in Example 8 include not only the components of Example 1, but also polydimethylsiloxane, wherein the weight ratio of core-shell emulsifier, polyaryletherketone resin, water and polydimethylsiloxane is 0.8:26:72:0.1), the abrasion-resistant waterborne coating of Example 9 according to this application is formed using the same method as in Example 1.

[0172] Comparative Example 1

[0173] Except for omitting the core-shell emulsifier in Example 1, the sample of Comparative Example 1 was prepared using the same method as in Example 1. This sample was a suspension and was not uniformly dispersed.

[0174] Comparative Example 2

[0175] Except that the core-shell emulsifier in Example 1 was replaced with an equal amount of a small molecule emulsifier (sodium dodecyl sulfonate), the sample of Comparative Example 2 was prepared using the same method as in Example 1. This sample was a dispersion.

[0176] Comparative Example 3

[0177] Except that the core-shell emulsifier in Example 1 was replaced with an equal amount of a small molecule emulsifier (Tween 20), the sample of Comparative Example 3 was prepared using the same method as in Example 1. This sample was a dispersion.

[0178] Comparative Example 4

[0179] Except that the core-shell emulsifier in Example 1 was replaced with an equal amount of a small molecule emulsifier (Tween 40), the sample of Comparative Example 4 was prepared using the same method as in Example 1. This sample was a dispersion.

[0180] Comparative Example 5

[0181] Except that the core-shell emulsifier in Example 1 was replaced with an equal amount of a small molecule emulsifier (Tween 60), the sample of Comparative Example 5 was prepared using the same method as in Example 1. This sample was a dispersion.

[0182] The performance of the abrasion-resistant waterborne coatings of Examples 1-9 and the samples of Comparative Examples 1-5 was tested and the results are recorded in Table 1 below.

[0183] (1) High stability test: Specifically, the characterization was carried out by the storage stability test method: The test coating was sealed and placed in a constant temperature and humidity chamber (25℃±2℃, 50%RH±5%), and the appearance, sedimentation rate and viscosity stability were checked periodically (e.g., every 1 month, every 3 months). The test coating was the wear-resistant water-based coating of Examples 1-8 and the samples of Comparative Examples 1-5 (the same below).

[0184] Test standard: No layering, no sedimentation, or no significant viscosity change indicates good stability of the tested coating; layering, sedimentation, or significant viscosity change indicates poor stability of the tested coating.

[0185] (2) Shear resistance test: at a constant 1000 s-1 The shear resistance test is performed continuously at a high shear rate for 20 minutes. After shearing, it is necessary to observe whether delamination, agglomeration, or demulsification occurs. If delamination or precipitation occurs, the shear resistance test is considered NG (not acceptable). If no delamination or precipitation occurs, the shear resistance test is considered OK.

[0186] (3) Centrifugal resistance test: Specifically, the test coating is centrifuged for 60 minutes at a speed of 15000 r / min using an enhanced centrifugation test method. After the test, the coating is observed to see if it separates into layers or precipitates. If it separates into layers or precipitates, the centrifugal resistance test is NG. If it does not separate into layers or precipitates, the centrifugal resistance test is OK.

[0187] (4) Demulsibility test: The time required for demulsification is measured by the static method. Specifically, the test coating is placed in a constant temperature environment and the time required for the corresponding test coating to reach demulsification is recorded.

[0188] (5) High emulsifying performance test: The emulsifying ability is specifically characterized by a shaking test. After shaking under specific conditions (e.g., using a vortex shaker at 2500 rpm at 25°C, mixing the emulsifier solution and the oil phase at a weight ratio of 9:1 and shaking continuously for 15 minutes), the emulsion formation rate and stability are observed. Standard: The smaller the emulsion particle size and the more uniform the distribution, the stronger the emulsifying performance.

[0189] Table 1 Performance Test Record Table

[0190]

[0191] As can be seen from Table 1 above, the wear-resistant water-based coatings of the various embodiments of this application, compared with the comparative examples, possess excellent shear resistance and centrifugal resistance. This ensures that the wear-resistant water-based coating is not damaged by the shear force generated by the spraying airflow during the formation of the wear-resistant coating, nor is it damaged by centrifugal force when sprayed onto a high-speed rotating substrate, thus guaranteeing the structural integrity of the wear-resistant coating.

[0192] Figure 2 A photograph is shown of the abrasion-resistant water-based coating provided according to Example 1 of this application after standing for 7 days. Figure 2 As shown, the wear-resistant water-based coating of Example 1 has no obvious layering and no sedimentation.

[0193] Furthermore, the other embodiments of this application, excluding Embodiment 1, were tested in the same way as Embodiment 1. It can be seen that the wear-resistant water-based coatings of the other embodiments of this application, excluding Embodiment 1, can remain uniform and stable even after being placed for a long time, and do not separate into layers. This is sufficient to demonstrate that the wear-resistant water-based coatings provided in the embodiments of this application have high stability.

[0194] The cookware of the embodiment is formed by the following method.

[0195] Example 9

[0196] The cookware of Example 9 is formed by the following method.

[0197] Step S401: Provide a cookware base with a thickness of 2 mm and made of aluminum, and preset the cookware base to 60°C.

[0198] Step S402: The wear-resistant water-based coating of Example 1 is atomized and sprayed onto the cookware substrate (the spray gun diameter for atomization is 1.3 mm, the atomization pressure is 3.0 Bar, the atomization distance is 30 cm, and the atomization time is 3 seconds). After surface drying at 150°C for 5 min, an initial wear-resistant layer is obtained. Then, the cookware with the initial wear-resistant layer is placed in a sintering furnace and sintered at 380°C for 15 min, thereby forming a wear-resistant coating with a thickness of 150 micrometers on the cookware substrate to obtain the cookware provided according to Example 1 of this application.

[0199] Example 10

[0200] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 2, the cookware of Example 10 was manufactured using the same method as that of Example 9.

[0201] Example 11

[0202] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 3, the cookware of Example 11 was manufactured using the same method as in Example 9.

[0203] Example 12

[0204] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 4, the cookware of Example 12 was manufactured using the same method as in Example 9.

[0205] Example 13

[0206] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 5, the cookware of Example 13 was manufactured using the same method as in Example 9.

[0207] Example 14

[0208] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 6, the cookware of Example 14 was manufactured using the same method as in Example 9.

[0209] Example 15

[0210] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 7, the cookware of Example 15 was manufactured using the same method as that of Example 9.

[0211] Example 16

[0212] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 8, the cookware of Example 16 was manufactured using the same method as that of Example 9.

[0213] Example 17

[0214] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the abrasion-resistant water-based coating of Example 9, the cookware of Example 17 was manufactured using the same method as in Example 9.

[0215] Example 18

[0216] After step S402, step S403 is added, in which a non-stick layer with a thickness of 45 μm is formed on the wear-resistant coating by using liquid ceramic coating, and the cookware of Example 18 is manufactured by the same method as in Example 9.

[0217] Example 19

[0218] Between steps S402 and S403, the surface of the wear-resistant coating is heated to a viscous state at 385°C, and then a liquid ceramic coating is applied in this state. The cookware of Example 19 is then manufactured using the same method as in Example 18.

[0219] Comparative Example 6

[0220] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the sample of Comparative Example 1, the cookware of Comparative Example 6 was manufactured using the same method as in Example 9.

[0221] Comparative Example 7

[0222] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the sample of Comparative Example 2, the cookware of Comparative Example 7 was manufactured using the same method as in Example 9.

[0223] Comparative Example 8

[0224] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the sample of Comparative Example 3, the cookware of Comparative Example 8 was manufactured using the same method as in Example 9.

[0225] Comparative Example 9

[0226] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the sample of Comparative Example 4, the cookware of Comparative Example 9 was manufactured using the same method as that of Example 9.

[0227] Comparative Example 10

[0228] Except that the abrasion-resistant water-based coating of Example 9 was replaced with the sample of Comparative Example 5, the cookware of Comparative Example 10 was manufactured using the same method as in Example 9.

[0229] The performance of the cookware in Examples 9-19 and Comparative Examples 6-10 was tested, and the test results are shown in the table.

[0230] 1. Vickers Hardness Test Method for Coatings: The standard Vickers hardness test method is adopted. A diamond indenter with a 136° angle between its two opposing faces is vertically pressed into the coating surface of the specimen under a specified test force. After maintaining the pressure for a specified time, the test force is removed, and the lengths of the two diagonals of the residual indentation on the specimen surface are measured. The Vickers hardness value is obtained by calculating the test force per unit area of ​​the indentation. The coating of the specimen refers to the coating of the spatula in the examples and comparative examples (hereinafter the same).

[0231] 2. Initial Non-stick Test Method: Following the test method in GB / T 32095.2-2015, heat the central area of ​​the inner coating surface of the cookware to a temperature between 150℃ and 170℃. Using a plastic spatula, stir-fry and remove the egg in an oil-free state. Before testing, the cookware must be cleaned according to the standard requirements. After testing, based on the residue of the fried egg on the cookware, the non-stick properties are classified into three progressively lower grades: Grade I, Grade II, and Grade III.

[0232] 3. Mechanical tensile strength test: Start the program to stretch at a constant rate of 5 mm / min. During the process, observe and record the fracture location. After the tested product breaks, the equipment will automatically record the maximum tensile force and elongation. This process needs to be repeated for all valid samples. The arithmetic mean of the final samples is recorded as the final tensile strength value.

[0233] 4. Corrosion Resistance Test Method: Prepare a 5% sodium chloride solution. Add the solution to the pot being tested, filling it to 1 / 3 of the pot's volume. Cover and maintain a gentle boil. Observe the surface of the pot for rust every half hour until obvious rust appears, then stop the experiment. For the corrosion resistance test, it is expected that the tested product will have a corrosion resistance of over 100 hours.

[0234] 5. Cross-cut adhesion test method: The cross-cut adhesion test shall be conducted according to the method specified in GB / T 9286-2021 standard. The number of cross-cuts detached from 100 squares of the tested product shall be measured, and the retention rate shall be calculated. Level 1 is a retention rate >95%, Level 2 is a retention rate of 85%-95%, Level 3 is a retention rate of 65%-85%, Level 4 is a retention rate of 35%-65%, and Level 5 is a retention rate <35%. The higher the retention rate, the better the adhesion. This project requires a retention rate of Level 1.

[0235] II. The test results are shown in the table below.

[0236] Table 2 Performance Test Record Table

[0237]

[0238] As can be seen from Table 2 above, the composite coatings of the various embodiments of this application exhibit high coating hardness, good wear resistance, high tensile strength, and strong corrosion resistance. These data indirectly demonstrate that the composite coatings have few internal defects, are dense, and are corrosion-resistant. For Comparative Examples 6-10, the instability of the small-molecule emulsifier leads to numerous structural defects in the coatings during processing due to the shearing action of the spray gun nozzle, the centrifugal force of the substrate's high-speed rotation, and the thermal migration and decomposition during high-temperature sintering. Ultimately, the coatings of Comparative Examples 6-10 exhibit poor film formation, severe cracking, and numerous porosity defects, failing to form an effective protective layer on the sprayed substrate. This indirectly illustrates the advantages of the large-molecule core-shell emulsifier in the PEEK waterborne spraying process of this application.

[0239] Figure 3 SEM images of the surface of the wear-resistant coating provided according to Embodiment 9 of this application are shown; Figure 4 SEM images of a cross-section of the wear-resistant coating provided according to Embodiment 9 of this application are shown. Figure 3 and Figure 4 It can be seen that the surface and interior of the wear-resistant coating of Embodiment 9 of this application are both formed into a dense structure.

[0240] Figure 5 Photographs of the surface of the wear-resistant coating provided according to Embodiment 9 of this application before and after 200,000 wear cycles are shown. Figure 5 As can be seen, before wear, the wear-resistant coating of Example 9 of this application has a smooth surface, dense structure, and no obvious defects or pores. This indicates that the initial wear-resistant coating has uniform quality and meets the relevant requirements for high wear resistance. After 200,000 cycles of friction, the surface of the wear-resistant coating of Example 9 can still maintain its overall integrity without peeling, cracking, or severe deformation. Only slight wear marks are present in local areas. This also demonstrates that the wear-resistant coating of Example 9 of this application has strong adhesion to the tool substrate and excellent fatigue resistance.

[0241] Figure 6A comparison graph showing the thickness of the wear-resistant coating provided according to Embodiment 9 of this application before and after 200,000 wear cycles is shown. Figure 6 It can be seen that the wear-resistant coating of Example 9 loses no more than 20 μm in thickness after being rubbed 200,000 times in the wear-resistant testing machine.

[0242] Conventional wear-resistant materials (such as ordinary metal coatings) can experience wear loss of 50-100 μm / 200,000 cycles, while the wear-resistant coating of this application, after being rubbed 200,000 times in a wear-resistant testing machine, shows a coating thickness loss of no more than 20 μm. This demonstrates that the wear loss of the wear-resistant coating of this application is far lower than that of conventional wear-resistant materials, exhibiting excellent wear resistance.

[0243] Figure 7 The results of a cross-cut adhesion test for the abrasion-resistant coating provided according to Example 9 of this application are shown. From Figure 7 As can be seen, after the cross-cut adhesion test, the wear-resistant coating of Example 9 showed no coating peeling at the cut intersections, and the grid edges were smooth without lifting. This directly proves that the wear-resistant coating of Example 9 has good adhesion to the tool substrate and can resist mechanical cutting and peeling.

[0244] In addition, all the tests described above were performed on other embodiments of this application besides Embodiment 9. The tests showed that the wear-resistant coatings of other embodiments of this application besides Embodiment 9 also possess all the excellent properties similar to those of Embodiment 9 (e.g., good density, good adhesion, and fewer defects).

[0245] According to this application, by using a core-shell emulsifier with a specific structure, it is possible to successfully achieve high stability of abrasion-resistant waterborne coatings and good abrasion resistance of abrasion-resistant coatings. Specifically, the abrasion-resistant waterborne coatings have excellent shear resistance, centrifugal resistance, and thermal stability. After spraying, surface drying, and sintering, an abrasion-resistant coating (polyaryletherketone resin layer) with ultra-dense abrasion resistance (coating thickness loss ≤50μm after 200,000 cycles of friction in a plane abrasion tester) and excellent adhesion (level 1 in cross-cut adhesion test) can be obtained. This provides a solution related to waterborne coatings for the abrasion resistance of appliance coatings.

Claims

1. A wear-resistant water-based coating, characterized in that, The wear-resistant waterborne coating is a dispersion comprising a core-shell emulsifier, a polyaryletherketone resin, and an aqueous medium. The core-shell emulsifier comprises inorganic particles and polymer long chains with hydrophilic-lipophilic segments grafted onto the surface of the inorganic particles. The hydrophilic groups are polyoxyethylene sulfonate quaternary ammonium salt groups. The inorganic particles have a size of 5 nm-100 nm. The steps for forming the core-shell emulsifier include: grafting hydroxyl groups onto the surface of the inorganic particles; grafting quaternary ammonium salt hydrophilic groups onto the hydroxyl groups on the surface of the inorganic particles through silanization coupling treatment; and grafting lipophilic segments onto the quaternary ammonium salt hydrophilic groups on the surface of the inorganic particles through ion exchange, thereby obtaining the core-shell emulsifier with hydrophilic-lipophilic segments.

2. The wear-resistant water-based coating according to claim 1, characterized in that, The polyaryletherketone resin includes at least one of polyetherketone resin, polyetheretherketone resin, polyetherketone-ketone resin, polyetheretherketone-ketone resin, and polyetherketone-etherketone-ketone resin; and / or, the crystallinity of the polyaryletherketone resin is 30%-40%; and / or, the glass transition temperature of the polyaryletherketone resin is in the range of 143℃-180℃; and / or, the coefficient of friction of the polyaryletherketone resin is 0.2-0.

25.

3. The wear-resistant water-based coating according to claim 1, characterized in that, The lipophilic segments grafted onto the surface of the inorganic particles are lipophilic alkyl chains; and / or, the HLB value of the core-shell emulsifier is 10-18.

4. The wear-resistant water-based coating according to claim 1, characterized in that, The lipophilic segment is a nonylphenol chain or a long alkyl chain; and / or, The hydrophilic group has a molecular weight of 220 g / mol to 2200 g / mol, and the lipophilic segment has a molecular weight of 220 g / mol to 400 g / mol; and / or, The inorganic particles are selected from one or more of calcium carbonate particles, alumina particles, and titanium dioxide particles.

5. The wear-resistant water-based coating according to claim 1, characterized in that, In the dispersion, the mass ratio of the core-shell emulsifier, the polyarylether ketone resin, and the aqueous medium is (0.7-1):(25-28):(70.85-73.5).

6. The wear-resistant water-based coating according to claim 1, characterized in that, The dispersion also includes inorganic pigments, fillers, and / or thickeners.

7. The wear-resistant water-based coating according to claim 6, characterized in that, When the dispersion further includes inorganic pigments and fillers, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, and the inorganic pigments and fillers is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5); when the dispersion further includes a thickener, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, and the thickener is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2).

8. The wear-resistant water-based coating according to claim 6, characterized in that, The inorganic pigments and fillers are at least one of iron oxide, carbon black, silicon carbide, titanium dioxide, and aluminum oxide; the thickener is at least one of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and xanthan gum.

9. The wear-resistant water-based coating according to claim 1, characterized in that, The melting point of the polyaryletherketone resin is 305℃-380℃; and / or, the intrinsic viscosity of the polyaryletherketone resin is 0.60dL / g-1.2dL / g; and / or, the viscosity of the wear-resistant water-based coating is 80mPa·s-150mPa·s.

10. The abrasion-resistant waterborne coating according to any one of claims 1 to 9, characterized in that, The dispersion further includes polysiloxane, and the mass ratio of the core-shell emulsifier, polyaryletherketone resin, aqueous medium and polysiloxane is (0.7-1):(25-28):(70.85-73.5):(0.1-0.5).

11. A method for manufacturing a wear-resistant water-based coating, characterized in that, The method for manufacturing the wear-resistant water-based coating includes: Grafting hydroxyl groups onto the surface of inorganic particles; Quaternary ammonium salt hydrophilic groups are grafted onto the hydroxyl groups on the surface of the inorganic particles by silanization coupling treatment; By grafting lipophilic segments onto the quaternary ammonium salt hydrophilic groups on the surface of the inorganic particles via ion exchange, a core-shell emulsifier having hydrophilic groups and lipophilic segments is obtained. A core-shell emulsifier, polyaryletherketone resin, and an aqueous medium are mixed to form a dispersion, thereby obtaining a wear-resistant waterborne coating. The core-shell emulsifier comprises inorganic particles and polymer long chains with hydrophilic-lipophilic segments grafted onto the surface of the inorganic particles. The hydrophilic groups are polyoxyethylene sulfonate quaternary ammonium salt groups, and the size of the inorganic particles is 5 nm-100 nm.

12. The method for manufacturing the wear-resistant water-based coating according to claim 11, characterized in that, The step of mixing the core-shell emulsifier, polyaryletherketone resin, and aqueous medium to form a dispersion: The core-shell emulsifier and the aqueous medium are mixed to form a first mixture; The polyaryletherketone resin is mixed into the first mixture to form the dispersion.

13. The method for manufacturing the wear-resistant water-based coating according to claim 11, characterized in that, The polyaryletherketone resin has a particle size of 20μm-120μm; and / or, the polyaryletherketone resin is a hydroxylated modified polyaryletherketone resin.

14. The method for manufacturing the wear-resistant water-based coating according to claim 11, characterized in that, The step of grafting lipophilic segments onto the quaternary ammonium salt hydrophilic groups on the surface of the inorganic particles via ion exchange includes: The step of reacting inorganic particles with quaternary ammonium salt hydrophilic groups grafted on their surface with sodium nonylphenol polyoxyethylene ether sulfonate.

15. A wear-resistant coating, characterized in that, The wear-resistant coating comprises a polyaryletherketone resin layer and particulate matter dispersed in the polyaryletherketone resin layer. The particulate matter comprises a core-shell emulsifier, wherein the core-shell emulsifier comprises inorganic particles and polymer long chains with hydrophilic-lipophilic segments grafted onto the surface of the inorganic particles. The hydrophilic group is a polyoxyethylene sulfonate quaternary ammonium salt group. The size of the inorganic particles is 5 nm-100 nm. The step of forming the core-shell emulsifier comprises: grafting hydroxyl groups onto the surface of the inorganic particles; grafting quaternary ammonium salt hydrophilic groups onto the hydroxyl groups on the surface of the inorganic particles by silanization coupling treatment; and grafting lipophilic segments onto the quaternary ammonium salt hydrophilic groups on the surface of the inorganic particles by ion exchange, thereby obtaining the core-shell emulsifier with hydrophilic-lipophilic segments.

16. The wear-resistant coating according to claim 15, characterized in that, The wear-resistant coating has a porosity of no more than 0.1% and a pore size of no more than 10 μm; and / or, the wear-resistant coating has a Vickers hardness of 35 HV-45 HV; and / or, the wear-resistant coating has a coefficient of friction of 0.1-0.2; and / or, the wear-resistant coating has a thickness of 30 μm-200 μm.

17. The wear-resistant coating according to claim 15, characterized in that, The polyaryletherketone resin layer and the core-shell emulsifier are chemically bonded at the contact interface; and / or, the mass of the polyaryletherketone resin layer is 96%-99% of the total mass of the wear-resistant coating, with the remainder being the core-shell emulsifier.

18. The wear-resistant coating according to claim 15, characterized in that, The particulate matter also includes pigment and filler particles. The mass of the polyaryletherketone resin layer is 95%-98% of the total mass of the wear-resistant coating, the mass of the core-shell emulsifier is 1%-4% of the total mass of the wear-resistant coating, and the remainder is the pigment and filler particles.

19. The wear-resistant coating according to claim 15, characterized in that, The lipophilic segments grafted onto the surface of the inorganic particles are lipophilic alkyl chains; and / or, the HLB value of the core-shell emulsifier is 10-18.

20. The wear-resistant coating according to claim 15, characterized in that, The lipophilic segment is a nonylphenol chain or a long alkyl chain; and / or, The hydrophilic group has a molecular weight of 220 g / mol to 2200 g / mol, and the lipophilic segment has a molecular weight of 220 g / mol to 400 g / mol; and / or, The inorganic particles are selected from one or more of calcium carbonate particles, alumina particles, and titanium dioxide particles.

21. An appliance, characterized in that, The appliance includes an appliance substrate and a wear-resistant coating formed on the appliance substrate; Wherein, the wear-resistant coating comprises the wear-resistant coating according to any one of claims 15 to 20; or, the wear-resistant coating is a wear-resistant water-based coating formed by a wear-resistant water-based coating, and the wear-resistant water-based coating is a wear-resistant water-based coating manufactured by the manufacturing method of the wear-resistant water-based coating according to any one of claims 1 to 10 or the wear-resistant water-based coating according to any one of claims 11 to 14.

22. The appliance according to claim 21, characterized in that, The appliance includes a frying pan, a rice cooker inner pot, a cup, a kettle, or a knife; and / or, the appliance further includes a non-stick layer formed on the wear-resistant coating.

23. A method for manufacturing an appliance, characterized in that, The method for manufacturing the device includes: Provides a water-based abrasion-resistant coating manufactured by any one of claims 1 to 10 or by any one of claims 11 to 14; The wear-resistant water-based coating is applied to the appliance substrate to form an initial wear-resistant layer; The initial wear-resistant layer is sintered at a sintering temperature not lower than the melting point of the polyaryletherketone resin in the initial wear-resistant layer to obtain a wear-resistant coating in which at least the core-shell emulsifier is dispersed in the polyaryletherketone resin layer, thereby manufacturing an appliance.

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