Wear-resistant water-based paint and manufacturing method thereof, wear-resistant coating, appliance and manufacturing method thereof

Abstract

The invention provides a wear-resistant water-based paint and a manufacturing method thereof, a wear-resistant coating, an appliance and a manufacturing method thereof. The wear-resistant water-based paint provided by the embodiment of the invention is dispersion liquid comprising a core-shell emulsifier, polyaryletherketone resin and a water-based medium, wherein the core-shell emulsifier comprises inorganic particles and polymer long chains which are grafted on the surfaces of the inorganic particles and have hydrophilic group-oleophylic chain segments. The core-shell emulsifier in the wear-resistant water-based paint can prevent aggregation of polyaryletherketone resin particles through steric hindrance and electrostatic repulsion, so that the polyaryletherketone resin particles are uniformly dispersed in a water-based medium, and the wear-resistant water-based paint in a stable dispersion state is formed. Besides, the dispersion performance of the wear-resistant water-based paint in the stable dispersion state is not easily influenced by the temperature, so that the defects (such as pore defects) of a wear-resistant coating formed by the wear-resistant water-based paint can be reduced, and the wear resistance and the corrosion resistance are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-based polymer coatings, and particularly relates to a wear-resistant water-based coating, a manufacturing method thereof, a wear-resistant coating layer and an appliance. BACKGROUND

[0002] Polyaryletherketone resin has excellent high-temperature resistance, mechanical strength and chemical stability, and thus has important value in manufacturing wear-resistant coating layers. As a kind of polyaryletherketone resin, polyether ether ketone resin is usually used as a high-performance special engineering plastic and has relatively high advantages due to its excellent wear-resistant properties.

[0003] In the prior art, one method is to manufacture a polyether ether ketone resin layer through a mold forming process, but this method lacks economic efficiency due to high mold manufacturing cost. Another method is to form a wear-resistant coating layer by electrostatic spraying of polyether ether ketone resin, but this process causes low deposition efficiency of the polyether ether ketone resin and serious resin waste. In order to achieve the manufacturing of high-performance wear-resistant coating layers under the premise of cost control, researchers in the field have begun to explore water-based coatings of polyether ether ketone resin.

[0004] However, since polyether ether ketone resin itself is not compatible with water, its dispersion problem needs to be solved when it is applied to a water-based coating system.

[0005] At present, water-based coatings of polyether ether ketone resin mainly rely on traditional small-molecule emulsifiers, and water-based coatings of polyether ether ketone resin with such emulsifiers show obvious limitations in storage and the process of forming wear-resistant coating layers, which ultimately leads to poor compactness of the formed wear-resistant layer, thereby causing the hardness and strength of the wear-resistant layer to decrease, and the wear-resistant performance of the wear-resistant layer to decrease significantly.

[0006] Therefore, it is urgent to develop a wear-resistant water-based coating containing polyaryletherketone resin. SUMMARY

[0007] The present application aims to provide a wear-resistant water-based coating, a manufacturing method thereof, a wear-resistant coating layer and an appliance, so as to solve the technical problem that the wear-resistant coating layer of the appliance formed by the existing wear-resistant water-based coating has poor wear-resistant performance due to poor compactness.

[0008] According to a first aspect of the present application, the present application provides a wear-resistant water-based coating, wherein the wear-resistant water-based coating is a dispersion liquid comprising a core-shell emulsifier, polyaryletherketone resin and a water-based medium, the core-shell emulsifier comprises inorganic particles and a long-chain polymer with a hydrophilic group-lipophilic chain segment grafted on the surface of the inorganic particles.

[0009] According to the embodiments of the present application, the wear-resistant water-based paint can form a wear-resistant water-based paint in a stable dispersion state due to the core-shell emulsifier. In addition, the wear-resistant water-based paint in a stable dispersion state is not easily affected by temperature, so that the defects (for example, pore defects) of the wear-resistant coating layer formed by the wear-resistant water-based paint can be reduced, thereby improving the hardness and strength of the wear-resistant coating layer and ensuring the wear-resistant performance of the wear-resistant coating layer.

[0010] According to the present application, the core-shell emulsifier includes inorganic particles and long polymer chains with hydrophilic groups-lipophilic segments grafted on the surface of the inorganic particles. The inorganic particles serve as the core, providing structural support and functional basis, and the long polymer chains with hydrophilic groups-lipophilic segments are used to disperse the individual particles of the polyaryletherketone resin. During the stage of dispersing the particles of the polyaryletherketone resin to form the wear-resistant water-based paint, the inorganic particles can provide a large steric hindrance, physically preventing the individual particles of the polyaryletherketone resin from approaching each other, greatly enhancing the stability (anti-centrifugal, anti-shearing) of the dispersion of the wear-resistant water-based paint. In addition, during the stage of dispersing to form the wear-resistant water-based paint, the lipophilic segments (for example, long alkyl chains) can firmly adsorb or entangle on the surface of the hydrophobic polyaryletherketone resin particles through the "like dissolves like" principle. The hydrophilic groups (for example, polyoxyethylene quaternary ammonium sulfonate) are compatible with the aqueous medium (for example, water), allowing the particles of the polyaryletherketone resin to be stably dispersed in water through electrostatic repulsion and hydration, preventing the polyaryletherketone resin from "agglomeration". Furthermore, during the stage of forming the wear-resistant coating layer by the wear-resistant water-based paint, the core-shell emulsifier formed by the inorganic particles remains in the wear-resistant coating layer, which can act as a reinforcing agent like the "steel bars" in reinforced concrete, improving the hardness and compactness of the wear-resistant coating layer.

[0011] In some embodiments, the polyaryletherketone resin includes at least one of polyetherketone resin, polyetheretherketone resin, polyetherketoneketone resin, polyetheretherketoneketone resin, and polyetherketoneetherketoneketone resin, which have more excellent 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%, being a semi-crystalline polymer, and a high crystallinity region forms a hard micro-region when rubbed to resist surface scratches and adhesive wear, thereby improving the wear-resistant performance of the wear-resistant coating layer formed by the wear-resistant water-based paint.

[0013] In some embodiments, the polyaryletherketone resin has a glass transition temperature in the range of 143°C-180°C, which can ensure that the wear-resistant coating layer formed thereby maintains dimensional stability and hardness at high temperatures, and is suitable for use in instruments that need to cope with high-temperature friction environments.

[0014] In some embodiments, the polyaryletherketone resin has a friction coefficient of 0.2-0.25, so that the surface of the wear-resistant coating formed therefrom is smooth and has good self-lubricating property, and the possibility of surface adhesion of other substances is reduced.

[0015] In some embodiments, the hydrophilic groups and the lipophilic segments grafted on the surface of the inorganic particles are hydrophilic quaternary ammonium salt groups and lipophilic alkyl chains, respectively, which have good amphiphilicity and low manufacturing cost.

[0016] In some embodiments, the core-shell emulsifier has an HLB value of 10-18. In the process of forming the wear-resistant water-based paint, the lipophilic segments (lipophilic ends) of the core-shell emulsifier can be firmly anchored on the surface of adjacent particles of the polyaryletherketone resin. At the same time, the hydrophilic groups (hydrophilic ends) thereof can form a hydrogen bond network with the aqueous medium in the wear-resistant water-based paint, so as to obtain an ultra-stable dispersion liquid against centrifugal force and shear as the wear-resistant water-based paint on the premise of dispersing the particles of the polyaryletherketone resin. In addition, in the process of forming the wear-resistant coating by the wear-resistant water-based paint with the core-shell emulsifier, the polymer melt formed by the core-shell emulsifier and the polyaryletherketone resin has good compatibility, can effectively interact with the PAEK molecular chain, and plays a role of internal plasticization and flow promotion, so as to help the polymer melt formed by the polyaryletherketone resin to spread and fuse better, fill the crystal defects, and thus improve the compactness of the wear-resistant coating.

[0017] In some embodiments, the molecular weight of the hydrophilic groups is 220 g / mol-2200 g / mol, and the molecular weight of the lipophilic segments is 220 g / mol-400 g / mol. The macromolecular weight of the groups can increase the molecular weight of the core-shell emulsifier to a certain extent, so as to avoid the migration of the core-shell emulsifier in the wear-resistant water-based paint, thereby affecting the stability of the wear-resistant water-based paint.

[0018] In some embodiments, the inorganic particles are selected from one or more of calcium carbonate particles, alumina particles, and titanium dioxide particles, which can be selected to optimize the stability and mechanical properties of the core-shell emulsifier, and are widely available and low in price, thereby reducing the manufacturing cost of the wear-resistant water-based paint.

[0019] In some embodiments, the size of the inorganic particles is 5-100 nm. 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 the preparation cost is high, and the emulsifying dispersing force is reduced. If the size of the inorganic particles is too large, the emulsifier molecules can be precipitated, which can weaken the emulsifying dispersing 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 components have a suitable mass ratio, and a wear-resistant water-based paint with both storage stability and reliable construction performance can be obtained.

[0021] In some embodiments, the dispersion further comprises an inorganic pigment and / or a thickening agent. In these embodiments, by adding the inorganic pigment to the components of the wear-resistant water-based paint, the color of the wear-resistant coating formed by the wear-resistant water-based paint can be ensured. By adding the thickening agent to the components of the wear-resistant water-based paint, the viscosity of the wear-resistant water-based paint can be ensured to facilitate the reliable formation of the wear-resistant coating. In addition, the thickening agent can also improve the sag resistance of the wear-resistant water-based paint during construction. In this way, the core-shell emulsifier, the polyaryletherketone resin, the inorganic pigment and / or the thickening agent, and the aqueous medium synergistically act to form a wear-resistant water-based paint with storage stability, good construction performance, and uniform and consistent dispersion of the coating.

[0022] In some embodiments, when the dispersion further comprises an inorganic pigment, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium and the inorganic pigment is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5). When the dispersion further comprises a thickening agent, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium and the thickening agent is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2). In these embodiments, the components have a suitable mass ratio, and a wear-resistant water-based paint with both storage stability and reliable construction performance can be obtained.

[0023] In some embodiments, the inorganic pigment is at least one of iron oxide, carbon black, silicon carbide, titanium dioxide and aluminum oxide. These pigments can make the wear-resistant coating have enhanced hardness, wear resistance and thermal stability.

[0024] In some embodiments, the thickening agent is at least one of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and xanthan gum, which can provide the abrasion-resistant water-based paint with suitable viscosity to ensure the workability as a liquid paint.

[0025] In some embodiments, the polyaryletherketone resin has a melting point of 305-390°C, which can provide sufficient safety margin for the thermal stability of the abrasion-resistant coating layer formed by the abrasion-resistant water-based paint. Since the service temperature of the appliance is much lower than the melting point of the polyaryletherketone resin, the molecular structure of the abrasion-resistant coating layer formed by the abrasion-resistant water-based paint will not soften or flow in a high-temperature working environment, thereby ensuring the integrity, mechanical strength, and abrasion resistance of the coating layer for a long time, and achieving stable and reliable protection.

[0026] In some embodiments, the polyaryletherketone resin has an intrinsic viscosity of 0.60-1.2 dL / g, which means that the polyaryletherketone resin with an intrinsic viscosity of 0.60-1.2 dL / g has good melt flowability and thermal stability above the melting point, which means that the polyaryletherketone resin in the wet film formed by the abrasion-resistant water-based paint can fully melt, flow, and spread during the high-temperature sintering process to form a dense and defect-free abrasion-resistant coating layer. If the intrinsic viscosity of the polyaryletherketone resin is too low, the molecular chain is short, the cohesion of the abrasion-resistant coating layer formed is insufficient, and performance degradation is likely to occur. If the intrinsic viscosity of the polyaryletherketone resin is too high, the polyaryletherketone resin will be difficult to fully flow and fuse during the sintering process, which will also affect the denseness of the coating layer.

[0027] In some embodiments, the abrasion-resistant water-based paint has a viscosity of 80-150 mPa·s, which can provide the abrasion-resistant water-based paint with suitable workability. If the viscosity of the abrasion-resistant water-based paint is too low, it is likely to cause sagging, insufficient film thickness, and other problems. If the viscosity of the abrasion-resistant water-based paint is too high, it is likely to cause poor atomization, orange peel, poor leveling, and other problems.

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

[0029] In these embodiments, by additionally adding polysiloxane to the components of the abrasion-resistant water-based paint including the polyaryletherketone resin, both the polyaryletherketone resin and the polysiloxane serve as the main film-forming substances, the polyaryletherketone resin is used to provide abrasion resistance, and the polysiloxane is used to provide non-stickiness, so that the abrasion-resistant coating layer formed by the abrasion-resistant water-based paint has good abrasion resistance and non-stickiness, thereby enabling the abrasion-resistant coating layer to have better long-lasting non-stickiness.

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

[0031] According to the method for manufacturing a wear-resistant water-based paint provided by the embodiments of the present application, by mixing the core-shell emulsifier, the polyaryletherketone resin and the water-based medium, a stable dispersion liquid can be formed as the wear-resistant water-based paint. The core-shell emulsifier in the dispersion liquid can prevent the polyaryletherketone resin from agglomerating by the effects of steric hindrance and electrostatic repulsion, thereby ensuring that the polyaryletherketone resin has long-term stable uniform dispersibility in the water-based medium, and forming the wear-resistant water-based paint in a stable dispersion state. In addition, the wear-resistant water-based paint in the stable dispersion state is less affected by temperature in terms of dispersion performance, thereby reducing defects (e.g., pore defects) of the wear-resistant coating layer formed by the wear-resistant water-based paint, and improving the hardness and strength of the wear-resistant coating layer, and ensuring the wear-resistant performance of the wear-resistant coating layer.

[0032] In some embodiments, the step of mixing the core-shell emulsifier, the polyaryletherketone resin and the water-based medium to form a dispersion liquid comprises: mixing the core-shell emulsifier and the water-based medium to form a first mixed liquid; and mixing the polyaryletherketone resin in the first mixed liquid to form the dispersion liquid.

[0033] In these embodiments, by pre-mixing the core-shell emulsifier and the water-based medium, a first mixed liquid with uniformly dispersed core-shell emulsifier can be obtained. In this process, the core-shell emulsifier can be fully stretched and uniformly dispersed in the water-based medium to form a stable dispersion system. When the polyaryletherketone resin is added to the first mixed liquid, it can be quickly and uniformly adsorbed by the dispersed core-shell emulsifier in the first mixed liquid, thereby significantly improving the emulsification efficiency. At the same time, such a feeding sequence can construct a uniform composite system with the particles of the polyaryletherketone resin as “islands” and the emulsifier as stable “anchor points”, which can lay the foundation for realizing the final compactness, ultra-high wear resistance and excellent adhesion of the wear-resistant coating layer.

[0034] In some embodiments, the polyaryletherketone resin has a particle size of 20 μm-120 μm. The polyaryletherketone resin with a medium particle size (20 μm-120 μm) can form a stable suspension system in the water-based medium, thereby avoiding agglomeration problems caused by too small particle size (e.g., nanoscale) or sedimentation and stratification caused by too large particle size (e.g., millimeter scale). In addition, the wear-resistant water-based paint with the medium particle size resin particles can construct a “micro-macro” multi-level wear-resistant structure in the formed wear-resistant coating: small particle size particles fill the gaps between large particle size particles to enhance the cohesion of the coating; and large particle size particles act as “skeleton” to bear external force and reduce the wear of the coating.

[0035] In some embodiments, the polyaryletherketone resin is a hydroxyl-modified polyaryletherketone resin, which is capable of cross-linking with the core-shell emulsifier, thereby improving the overall compactness of the final wear-resistant coating.

[0036] In some embodiments, the method for manufacturing the wear-resistant water-based coating comprises a step of forming a core-shell emulsifier having a hydrophilic group-lipophilic segment, which is capable of having amphiphilicity, thereby stabilizing the oil-water interface in the dispersed wear-resistant water-based coating, and thereby solving the problems of poor dispersibility and single function of conventional emulsifiers.

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

[0038] In these embodiments, by hydroxylating the surface of the inorganic particles and performing silane coupling treatment and ion exchange treatment, the core-shell emulsifier having a core-shell structure and having a hydrophilic group and a lipophilic segment can be manufactured, thereby stabilizing the oil-water interface in the wear-resistant water-based coating due to the amphiphilicity of the core-shell emulsifier, and thereby solving the problems of poor dispersibility and single function of conventional emulsifiers.

[0039] According to a third aspect of the present application, a wear-resistant coating is provided, wherein the wear-resistant coating comprises a polyaryletherketone resin layer and particles dispersed in the polyaryletherketone resin layer, the particles comprising the above-mentioned core-shell emulsifier.

[0040] In some embodiments, the wear-resistant coating is compact, which can avoid affecting the hardness and strength of the wear-resistant coating due to poor compactness, thereby ensuring the wear-resistant performance of the wear-resistant coating. As an example, the wear-resistant coating has a porosity of not more than 0.1% and a pore size of not more than 10 μm.

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

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

[0043] In some embodiments, the wear-resistant coating has a thickness of 30-200 microns, which is suitable as an intermediate layer for various types of utensils and as a base layer for grafting non-stick molecules.

[0044] In some embodiments, the polyaryletherketone resin layer and the core-shell emulsifier are chemically bonded at the contact interface, and the specific product is a cross-linked product of the surface groups of the hydroxyl-modified polyaryletherketone and the core-shell emulsifier, which can further optimize the compactness of the bonding interface within the wear-resistant coating due to cross-linking.

[0045] In some embodiments, the polyaryletherketone resin layer has a mass of 96-99% of the total mass of the wear-resistant coating, and the balance is the core-shell emulsifier. With appropriate mass proportions of each component, the comprehensive performance of the wear-resistant coating in terms of wear resistance, strength, and other aspects can be balanced.

[0046] In some embodiments, the particulate matter further includes color filler particles, the polyaryletherketone resin layer has a mass of 95-98% of the total mass of the wear-resistant coating, the core-shell emulsifier has a mass of 1-4% of the total mass of the wear-resistant coating, and the balance is the color filler particles. With appropriate mass proportions of each component, the comprehensive performance of the wear-resistant coating in terms of wear resistance, strength, and other aspects can be balanced.

[0047] According to a fourth aspect of the present application, a utensil is provided, wherein the utensil includes a utensil base and a wear-resistant coating formed on the utensil base, and the wear-resistant coating includes the wear-resistant coating described above.

[0048] In some embodiments, the utensil includes a wok, a rice cooker liner, a cup, a kettle, or a knife, and is suitable for various types of utensils, which can form multiple types of utensils.

[0049] In some embodiments, the utensil further includes a non-stick layer formed on the wear-resistant coating. The wear-resistant coating of the present application serves as a base for forming a non-stick layer, and has a relatively large bonding surface compared to an intermediate layer formed directly by a polyaryletherketone resin, an intermediate layer formed by a small molecule emulsifier and a polyaryletherketone resin, or an intermediate layer formed by a metal material of the same size, which can ensure the bonding force with the non-stick layer arranged thereon, thereby greatly improving the wear resistance and non-stick performance of the utensil as a whole due to the difficulty of falling off.

[0050] According to a fifth aspect of the present application, a manufacturing method of an appliance is provided, wherein the manufacturing method of the appliance comprises: providing the wear-resistant water-based paint or the wear-resistant water-based paint manufactured by the manufacturing method of the wear-resistant water-based paint; coating the wear-resistant water-based paint on an appliance substrate to form an initial wear-resistant layer; and performing a sintering treatment on the initial wear-resistant layer under a condition that a sintering temperature is not lower than a melting point of the polyaryletherketone resin in the initial wear-resistant layer, to obtain a wear-resistant coating layer in which at least the core-shell emulsifier is dispersed in the polyaryletherketone resin layer, thereby manufacturing the appliance. BRIEF DESCRIPTION OF DRAWINGS

[0051] The above and other aspects, features and other advantages of the present application will become more apparent and more readily appreciated from the following detailed description, taken in conjunction with the accompanying drawings, in which: Figure 1 A schematic diagram showing the forming principle of the wear-resistant coating layer according to the exemplary embodiments of the present application is shown; Figure 2 A photo showing the wear-resistant water-based paint according to Embodiment 1 of the present application after standing for 7 days is shown; Figure 3 A SEM photo showing the surface of the wear-resistant coating layer according to Embodiment 9 of the present application is shown; Figure 4 A SEM photo showing the cross section of the wear-resistant coating layer according to Embodiment 9 of the present application is shown; Figure 5 Photos showing the surface of the wear-resistant coating layer according to Embodiment 9 of the present application before and after 200,000 times of abrasion are shown; Figure 6 A comparison chart showing the thickness test of the wear-resistant coating layer according to Embodiment 9 of the present application before and after 200,000 times of abrasion is shown; Figure 7 A result of the grid adhesion test of the wear-resistant coating layer according to Embodiment 9 of the present application is shown. DETAILED DESCRIPTION

[0052] The embodiments of the present application will be described below in conjunction with Figures 1 to 7 the wear-resistant water-based paint and the manufacturing method thereof, the wear-resistant coating layer and the manufacturing method of the appliance.

[0053] The inventors of the present application have found that the conventional water-based paint with polyaryletherketone mainly relies on small molecule emulsifiers, which exhibit obvious limitations in storage, transportation and construction process.

[0054] Specifically, the water-based paint has poor stability, is easily affected by shearing force and centrifugal force, and is prone to demulsification, which can cause the water-based paint to be unstable during storage or transportation and can make it difficult to ensure the reliability of the spraying process. Meanwhile, more importantly, during the process of forming a wear-resistant layer by using the water-based paint to form a film and sintering at high temperature, the small molecule emulsifier can migrate, agglomerate and remain inside the wear-resistant coating or form large pore defects inside the wear-resistant coating structure due to the influence of heat, etc., forming a structural weak point (forming micro defects and hydrophilic channels) of the wear-resistant layer, which can seriously weaken the comprehensive performance (wear resistance, strength and corrosion resistance) of the wear-resistant coating. This can cause the compactness of the coating to decrease, the hardness and wear resistance to be greatly different from the properties of the PEEK material itself, and the water resistance to be significantly reduced, so the coating cannot meet the use requirements of the cookware in a long-term frequent rubbing and high-temperature and high-humidity environment.

[0055] Therefore, the present application proposes to use a core-shell emulsifier and a polyaryletherketone resin to form a wear-resistant water-based paint, which has good shear resistance and centrifugal resistance, so as to fundamentally solve the inherent defects of the small molecule emulsifier type polyaryletherketone water-based paint.

[0056] According to a first aspect of the present application, a manufacturing method of a wear-resistant water-based paint is provided, wherein the wear-resistant water-based paint is used to manufacture a wear-resistant coating of a frying pan, a rice cooker liner, a cup, a kettle or a knife, and is particularly used to manufacture a wear-resistant coating of a frying pan to meet the rubbing requirements of hard objects such as iron spatulas in Chinese cooking. In the present application, the manufacturing method of the wear-resistant water-based paint comprises mixing a core-shell emulsifier, a polyaryletherketone resin and a water-based medium, and forming a dispersion liquid, so as to obtain the wear-resistant water-based paint.

[0057] According to the manufacturing method of the wear-resistant water-based paint provided by the embodiments of the present application, by mixing the core-shell emulsifier, the polyaryletherketone resin and the water-based medium, a stable dispersion liquid can be formed as the wear-resistant water-based paint. The core-shell emulsifier in the dispersion liquid can prevent the polyaryletherketone resin from agglomerating by the action of steric hindrance and electrostatic repulsion, so as to ensure that the polyaryletherketone resin has long-term stable uniform dispersibility in the water-based medium, and the wear-resistant water-based paint is in a stable dispersion state. In addition, the wear-resistant water-based paint in the stable dispersion state is not easily affected by temperature to affect the dispersion performance, so as to reduce the defects (for example, pore defects) of the wear-resistant coating formed by the wear-resistant water-based paint, so as to improve the hardness and strength of the wear-resistant coating and ensure the wear resistance of the wear-resistant coating. Furthermore, the wear-resistant water-based paint manufactured in this way can fully utilize the polyaryletherketone resin therein and has obvious cost reduction advantages.

[0058] In the present application, the abrasion-resistant waterborne coating can exhibit excellent shear resistance, centrifugal resistance and heat resistance, is difficult to demulsify, is suitable for atomization spraying process, and can provide an implementable path for non-stick materials with high viscosity. As an example, the abrasion-resistant waterborne coating can be suitable as a carrier for polysiloxane, a non-stick material, thereby expanding the applicability of polysiloxane as a non-stick material.

[0059] Hereinafter, a method for manufacturing the abrasion-resistant waterborne coating according to the present application will be described in connection with specific examples.

[0060] Providing a core-shell emulsifier According to the present application, the core-shell emulsifier, as an emulsifying aid in the abrasion-resistant waterborne coating, has a core-shell structure, which can form a dispersion system together with the polyaryletherketone resin and the aqueous medium. The emulsifier not only can stably disperse the particles of the polyaryletherketone resin with high efficiency, but also can significantly improve the abrasion resistance, compactness and impact resistance of the coating as a functional filler in the final abrasion-resistant coating.

[0061] Specifically, the core-shell emulsifier can play a dispersing role in the dispersion stage of manufacturing the abrasion-resistant waterborne coating, physically prevent the particles of the polyaryletherketone resin from approaching each other by providing steric hindrance, so that the particles of the polyaryletherketone resin can be uniformly dispersed in the aqueous medium and avoid agglomeration, thereby forming a stably dispersed abrasion-resistant waterborne coating with good dispersing performance, and the stability of which is not easily destroyed by external force, temperature or time. Moreover, the core-shell emulsifier can prevent the particles of the dispersed polyaryletherketone resin from agglomerating by steric hindrance and electrostatic repulsion during the surface drying process of forming the initial abrasion-resistant layer, and ensure that each component can be uniformly dispersed in the initial abrasion-resistant layer. In addition, the core-shell emulsifier can promote the flow of the melt of the polyaryletherketone resin, fill the crystal defects, and thus form a compact coating during the sintering process of forming the abrasion-resistant coating. In addition, it can act as a reinforcing phase in the polyaryletherketone resin layer, thereby enhancing the impact resistance and hardness of the abrasion-resistant coating.

[0062] In some embodiments, the core-shell emulsifier is a core-shell macromolecular emulsifier, which has a core-shell structure, i.e., has a core layer and a shell layer wrapped outside the core layer, wherein the inorganic particles are as the core layer, the organic molecules are as the shell layer, and the shell layer (outer layer, grafted layer) can be fixed on the surface of the inorganic particles by chemical grafting, thereby forming a stable structure with "rigid core-flexible chain". Among them, the core layer is as the adherend, the shell layer is an amphiphilic polymer, and is a functional layer capable of realizing emulsification and dispersion performance. As an example, the core-shell emulsifier includes inorganic particles and polymer long chains with hydrophilic groups-lipophilic segments grafted on the surface of the inorganic particles. In these embodiments, the core-shell emulsifier is composed of inorganic particles and polymer long chains with hydrophilic groups-lipophilic segments, the inorganic particles are as the core, which can provide structural support and functional basis, and the polymer long chains with hydrophilic groups-lipophilic segments are used to disperse each particle of the polyaryletherketone resin. At the stage of dispersing the particles of the polyaryletherketone resin to form the wear-resistant water-based paint, the inorganic particles can provide a huge steric hindrance, physically prevent each particle of the polyaryletherketone resin from approaching each other, and greatly enhance the stability (anti-centrifugal, anti-shearing) of the dispersion liquid wear-resistant water-based paint. In addition, at the stage of dispersing to form the wear-resistant water-based paint, the lipophilic segments (for example, long-chain alkyl chains) can be firmly adsorbed or wrapped on the surface of the hydrophobic polyaryletherketone resin particles through the "like dissolves like" principle. The hydrophilic groups (for example, polyoxyethylene quaternary ammonium sulfonate) can be compatible with the aqueous medium (for example, water), and through electrostatic repulsion and hydration, the particles of the polyaryletherketone resin can be stably dispersed in water, preventing the polyaryletherketone resin from "agglomeration". Furthermore, at the stage of forming the wear-resistant coating by the wear-resistant water-based paint, the core-shell emulsifier formed by the inorganic particles will remain in the wear-resistant coating, which can play a reinforcing role like the "steel bars" of reinforced concrete, improving the hardness and compactness of the wear-resistant coating.

[0063] In some embodiments, the core-shell emulsifier is a macromolecular emulsifier, and the size of the inorganic particles is nanoscale, specifically 5 nm-100 nm. The nanoscale core layer can provide the dispersion 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 increase the preparation cost, and reduce the emulsification and dispersion force. If the size of the inorganic particles is too large, the emulsifier molecules may be precipitated, which will weaken the emulsification and dispersion stability of the core-shell emulsifier.

[0064] In some embodiments, the molecular weight of the hydrophilic groups is 220 g / mol-2200 g / mol, and the molecular weight of the lipophilic segments is 220 g / mol, which can increase the molecular weight of the core-shell emulsifier to a certain extent, avoid its migration in the wear-resistant water-based paint, and thus affect the stability of the wear-resistant water-based paint.

[0065] In some embodiments, in the case that the inorganic particles are grafted with hydrophilic groups and lipophilic segments, the surface-grafted hydrophilic groups are polyoxyethylene quaternary ammonium sulfonate, and the lipophilic segments are long-chain alkyl chains. These hydrophilic groups and lipophilic segments can have good amphiphilicity and low manufacturing cost.

[0066] In some embodiments, the inorganic particles are selected from one or more of calcium carbonate, aluminum oxide, 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 low in cost, thereby reducing the manufacturing cost of the wear-resistant water-based paint.

[0067] According to the present application, the core-shell emulsifier is an amphiphilic emulsifier. In exemplary embodiments, the core-shell emulsifier has an HLB value (hydrophilic-lipophilic balance value) of 10-18. In the process of forming the wear-resistant water-based paint, the lipophilic segments (lipophilic end) of the core-shell emulsifier can be firmly anchored to the surface of adjacent particles of the polyaryletherketone resin. For example, the lipophilic segments can form a dense coating layer on the surface of each particle of the polyaryletherketone resin, preventing direct contact between the particles and reducing agglomeration. At the same time, the hydrophilic groups (hydrophilic end) can form a hydrogen bond network with the aqueous medium in the wear-resistant water-based paint, thereby achieving a super-stable dispersion of the particles of the polyaryletherketone resin while achieving anti-centrifugal and anti-shearing properties. In addition, in the process of forming the wear-resistant coating layer from the wear-resistant water-based paint, the polymer melt formed by the core-shell emulsifier and the polyaryletherketone resin has good compatibility, can effectively interact with the PAEK molecular chain, and can play the role of internal plasticization and flow promotion, thereby helping the polymer melt formed by the polyaryletherketone resin to spread and fuse better, filling the crystal defects, and thereby improving the compactness of the wear-resistant coating layer.

[0068] In exemplary embodiments, in the case that the lipophilic segments of the core-shell emulsifier are long-chain alkyl groups, aromatic rings, or fluorine-containing groups, they can be adsorbed on the surface of the polyaryletherketone resin through van der Waals forces, π-π stacking hydrogen bonds, or chemical bonding (such as ester bonds, amide bonds). In addition, in the case that the hydrophilic groups are carboxylate, sulfonate, or polyoxyethylene chains, they can dissociate or hydrogen bond in water to form a hydration layer (thickness of about 0.5-2 nm), thereby stably dispersing the PAEK particles in water.

[0069] According to some embodiments of the present application, the core-shell emulsifier is manufactured by a combination of surface grafting and ion exchange. Specifically, a hydrophilic group and a lipophilic segment are introduced onto the inorganic particles in sequence through a two-step reaction, thereby manufacturing a macromolecular emulsifier with a core-shell structure.

[0070] As an exemplary embodiment, a method for manufacturing a core-shell emulsifier is provided, which specifically includes the following steps.

[0071] Step S101, providing inorganic particles.

[0072] Step S102, grafting hydroxyl groups on the surface of the inorganic particles.

[0073] Step S103, grafting hydrophilic groups on the hydroxyl groups on the surface of the inorganic particles through silane coupling treatment.

[0074] Step S104, grafting lipophilic segments on the hydrophilic groups on the surface of the inorganic particles through ion exchange, thereby obtaining the core-shell emulsifier with hydrophilic group-lipophilic segment. In other words, through ion exchange, lipophilic segments are introduced into the hydrophilic groups on the surface of the inorganic particles, thereby obtaining the core-shell emulsifier according to the present application.

[0075] In step S101, the inorganic particles include one or more of calcium carbonate particles, aluminum oxide particles, and titanium dioxide particles. The particle size of the inorganic particles can be controlled at the nanoscale to enhance the specific surface area and reactivity. As an example, the particle size of the inorganic particles can be in the range of 5-100 nm.

[0076] In step S102, grafting hydroxyl groups on the surface of the inorganic particles is to hydroxylate the surface of the inorganic particles. Through this step, the reactive sites on the surface of the particles can be increased to provide more anchor points for subsequent silane coupling. As a specific example, the inorganic particles can be dispersed and hydroxylated using ammonia water, and the pH of the suspension is adjusted to an appropriate range (such as alkaline conditions) to improve the dispersibility of the suspension and prevent agglomeration of individual inorganic particles.

[0077] In step S103, through silane coupling treatment, hydrophilic groups can be grafted on the hydroxyl groups of the inorganic particles grafted with hydroxyl groups. As a specific example, the inorganic particles with hydroxyl groups on the surface can be subjected to a coupling reaction with organosilicon quaternary ammonium salt (which contains a siloxane group at one end of the molecule and a quaternary ammonium salt cationic hydrophilic group at the other end). The siloxane group in the organosilicon quaternary ammonium salt molecule can undergo condensation-hydrolysis-condensation reaction (such as silanization reaction) with the hydroxyl groups on the surface of the inorganic particles, forming a strong Si-O-covalent bond, thereby grafting the quaternary ammonium salt cationic hydrophilic group to the surface of the inorganic particles to form a strong shell layer through covalent bonding on the surface of the inorganic particles. In addition, the quaternary ammonium salt group can impart hydrophilicity to the inorganic particles and lay the foundation for ion exchange.

[0078] In step S104, the inorganic particles grafted with hydrophilic groups on the surface can be reacted with sodium nonylphenol polyoxyethylene ether sulfate (which belongs to anionic surfactants, with nonylphenol chain as the lipophilic part, and the degree of polymerization can be controlled at 5-50). Through ion exchange, the anion (such as Cl -) are substituted by sulfonate anions, thereby introducing lipophilic segments (nonylphenol chains).

[0079] In these embodiments, by hydroxylating the surface of the inorganic particles, and performing silanization coupling treatment and ion exchange treatment, a core-shell emulsifier with core-shell structure and provided with hydrophilic groups and lipophilic segments can be manufactured, thereby stabilizing the oil-water interface in the wear-resistant water-based paint due to the amphiphilicity of the core-shell emulsifier, and thereby solving the problems of poor dispersibility and single function of traditional emulsifiers.

[0080] According to the present application, by selecting nonylphenol polyoxyethylene ether sodium sulfate with different polymerization degrees (for example, the number of polyoxyethylene chain n = 5-50), the ratio of the hydrophilic groups (quaternary ammonium salt) and the lipophilic segments (nonylphenol chain) on the surface of the inorganic particles can be balanced, thereby controlling the HLB value of the core-shell emulsifier within the range of 10-18. By obtaining the core-shell emulsifier with the target HLB value, the interaction between the core-shell emulsifier and the polyaryletherketone (PAEK) resin and the aqueous medium can be regulated at the molecular level, and thereby the optimization of the stability of the wear-resistant water-based paint can be achieved. It should be noted that the grafted hydrophilic groups and lipophilic segments may have certain chemical activity, for example, have hydroxyl groups, thereby being able to bond with the hydroxyl groups of the polyaryletherketone modified by hydroxylation treatment, and thereby crosslinking at the connecting interface of the two to form molecular connecting bridges, to further promote the densification and wear resistance of the wear-resistant coating.

[0081] Providing a polyaryletherketone resin According to the present application, the molecular main chain of the polyaryletherketone resin is alternately composed of benzene rings, ether bonds (—O—) and ketone bonds (—CO—), and as the main film-forming material of the wear-resistant water-based paint, the rigid structure of the benzene ring can give the polyaryletherketone resin high modulus and high compressive strength, so that it is not easy to deform plastically during friction, thereby reducing wear. The ether bond can give the polyaryletherketone resin flexibility, forming a "rigid-flexible" balanced structure, so that the polyaryletherketone resin is resistant to deformation and brittle fracture during friction.

[0082] In some embodiments, the polyaryletherketone resin (PAEK) includes at least one of polyetherketone resin (PEK), polyether-etherketone resin (PEEK), polyetherketoneketone resin (PEKK), polyether-ether-ketone-ketone resin (PEEKK), and polyether-ketone-ether-ketone-ketone resin (PEKEKK), which have more excellent mechanical impact resistance, hardness, and self-lubricating properties compared to fluorocarbon resins. In some embodiments, the polyaryletherketone resin has a crystallinity of 30-40%, which is a semi-crystalline polymer, and a high crystallinity region forms a "hard microzone" when rubbed to resist surface scratches and adhesive wear, thereby improving the wear resistance of the wear-resistant coating formed by the wear-resistant water-based paint. In some embodiments, the polyaryletherketone resin has a degree of polymerization of 100-300, which has a moderate degree of polymerization. The polyaryletherketone resin with such a degree of polymerization has a sufficient number of entanglement points (about 10-30 entanglement points per chain) in the molecular chain, which can significantly improve the melt viscosity and melt strength of the wear-resistant coating formed by the wear-resistant water-based paint during the sintering process, avoid melt rupture or drooling during sintering, and have good tensile strength, heat resistance, and corrosion resistance.

[0083] In some embodiments, the polyaryletherketone resin has a glass transition temperature (Tg) in the range of 143-180°C. As specific examples, the polyetherketone resin (PEK) has a glass transition temperature of 155-165°C, the polyether-ether-ketone resin (PEEK) has a glass transition temperature of 143-155°C, the polyether-ketone-ketone resin (PEKK) has a glass transition temperature of 162-165°C, the polyether-ether-ketone-ketone resin (PEEKK) has a glass transition temperature of 165-175°C, and the polyether-ketone-ether-ketone-ketone resin (PEKEKK) has a glass transition temperature of 170-180°C. The polyaryletherketone resin behaves as a rigid solid below Tg, and behaves as a toughened material above Tg due to chain segment motion, and softens only near the melting point. Such a glass transition temperature ensures that the wear-resistant coating formed thereby maintains dimensional stability and hardness at high temperatures, and is suitable for use in instruments that need to cope with high-temperature friction environments.

[0084] In some embodiments, the polyaryletherketone resin has a low friction coefficient, for example, the polyaryletherketone resin has a friction coefficient of 0.2-0.25, so that the surface of the wear-resistant coating formed thereby is smooth and has good self-lubricating properties, which can reduce the possibility of surface adhesion to other substances.

[0085] In the appliances involved in the present application, the normal use temperature is usually not higher than 280°C. According to the present application, the melting point of the polyaryletherketone resin in the wear-resistant water-based paint is 305°C-390°C, and this property can provide sufficient thermal stability safety margin for the wear-resistant coating formed by the wear-resistant water-based paint. Since the use temperature of the appliance is much lower than the melting point of the polyaryletherketone resin, the molecular structure of the wear-resistant coating formed by the wear-resistant water-based paint will not soften or flow in a high-temperature working environment, thereby ensuring that the integrity, mechanical strength and wear resistance of the coating can be maintained for a long time, and achieving stable and reliable protection.

[0086] In some embodiments, the intrinsic viscosity of the polyaryletherketone resin is 0.60 dL / g-1.2 dL / g. The polyaryletherketone resin with an intrinsic viscosity of 0.60 dL / g-1.2 dL / g has good melt flowability and thermal stability above the melting point, which means that during the high-temperature sintering process of the wet film formed by the wear-resistant water-based paint, the polyaryletherketone resin can fully melt, flow and spread to form a dense and defect-free wear-resistant coating. If the intrinsic viscosity of the polyaryletherketone resin is too low, the molecular chain is short, the cohesion of the wear-resistant coating formed is insufficient, and performance degradation is easy to occur; if the intrinsic viscosity of the polyaryletherketone resin is too high, the polyaryletherketone resin will be difficult to fully flow and fuse during sintering, which will also affect the density of the coating. Here, the intrinsic viscosity is used to represent the specific concentration viscosity limit value of the high molecular chain of the polyaryletherketone resin when it is infinitely diluted in a specific solvent, which can be measured by a special instrument and method. For example, the intrinsic viscosity of polyether ether ketone (PEEK) can be measured by an automatic Ubbelohde viscometer through extrapolation method. The test process usually requires dissolving the PAEK sample in 96% concentrated sulfuric acid, then measuring the flow time of the solution at a specific temperature of 30.0±0.1°C, and calculating the intrinsic viscosity value.

[0087] According to the manufacturing method of the wear-resistant water-based paint of the present 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 20-120 μm. The polyaryletherketone resin with a medium particle size (20-120 μm) can form a stable suspension system in the aqueous medium, which can avoid the agglomeration problem caused by too small particle size (such as nanoscale) or the sedimentation and stratification caused by too large particle size (such as millimeter scale). Moreover, the wear-resistant water-based paint with medium particle size resin particles can construct a "micro-macro" multi-level wear-resistant structure in the formed wear-resistant coating: small particle size particles fill the voids between large particle size particles, enhancing the cohesion of the coating; large particle size particles act as "skeleton" to bear external force, reducing coating wear.

[0088] According to the present application, the polyether ether ketone resin can be selected to use the original resin without any modification treatment, or can be selected to use the polyether ether ketone resin subjected to hydroxylation modification treatment. Among them, the way of hydroxylation modification treatment of the polyether ether ketone resin can be realized by plasma treatment of the polyether ether ketone resin, and the polyaryl ether ketone resin thus obtained has reactive groups and can react with the core-shell emulsifier to form a cross-linked reaction, 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 a plasma, and the treatment power can be 300W-500W, the treatment time can be 5-30 minutes, and the gas flow rate can be 60-200 mL / min. At the same time, the plasma treatment of the polyether ether ketone resin can be carried out in a low vacuum state.

[0089] Providing an aqueous medium According to the present application, the aqueous medium can be water, or can be an organic solvent containing water and not dissolving polyaryl ether ketone, wherein the organic solvent can be, for example, methanol, ethanol, isopropanol, etc.

[0090] Manufacturing a wear-resistant aqueous coating According to the present application, the core-shell emulsifier, the polyaryl ether ketone resin and the aqueous medium are mixed to form a stable dispersion liquid, thereby obtaining a wear-resistant water-based paint. The wear-resistant water-based paint thus obtained has good stability and dispersibility, thereby facilitating storage and subsequent formation of a wear-resistant coating.

[0091] In some embodiments, the step of mixing the core-shell emulsifier, the polyaryl ether ketone resin and the aqueous medium to form a dispersion liquid includes mixing the core-shell emulsifier and the aqueous medium to form a first mixture, and then mixing the polyaryl ether ketone resin in the first mixture, thereby obtaining a wear-resistant water-based paint in the form of a dispersion liquid. In these embodiments, by pre-mixing the core-shell emulsifier and the aqueous medium, a first mixture with uniformly dispersed core-shell emulsifier can be obtained. In this process, the core-shell emulsifier can be fully stretched and uniformly dispersed in the aqueous medium to form a stable dispersion system. When the polyaryl ether ketone resin is added to the first mixture, it can be quickly and uniformly adsorbed by the dispersed core-shell emulsifier in the first mixture, thereby significantly improving the emulsification efficiency. At the same time, such a feeding sequence can build a uniform composite system with the particles of the polyaryl ether ketone resin as "islands" and the emulsifier as stable "anchor points", which can lay the foundation for realizing the final density, ultra-high wear resistance and excellent adhesion of the wear-resistant coating, etc.

[0092] It is to be noted that the above shows one possible component of the abrasion-resistant water-based paint. In some embodiments of the present application, the dispersion liquid can further include inorganic pigments and / or thickening agents in addition to the core-shell emulsifier, the polyaryletherketone resin and the water-based medium. In the case where the dispersion liquid further includes inorganic pigments, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the water-based medium and the inorganic pigments is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5). In the case where the dispersion liquid further includes thickening agents, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the water-based medium and the thickening agents is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2). In the case where the dispersion liquid further includes both inorganic pigments and thickening agents, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the water-based medium, the inorganic pigments and the thickening agents is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5):(0.15-0.2).

[0093] In these embodiments, the addition of inorganic pigments to the components of the abrasion-resistant water-based paint can ensure the color of the abrasion-resistant coating formed by the abrasion-resistant water-based paint, and the addition of thickening agents to the components of the abrasion-resistant water-based paint can ensure the viscosity of the abrasion-resistant water-based paint to facilitate the reliable formation of the abrasion-resistant coating. Furthermore, the thickening agents can also improve the sag resistance of the abrasion-resistant water-based paint during application. Thus, the core-shell emulsifier, the polyaryletherketone resin, the inorganic pigments and / or the thickening agents and the water-based medium can synergistically form an abrasion-resistant water-based paint that is storage-stable, has good application performance and forms a uniform and consistent coating.

[0094] In some embodiments, the inorganic pigments are carbon black or iron oxide black, and the thickening agents are at least one of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and xanthan gum. These inorganic pigments and thickening agents can ensure inherent performance while having the advantages of food safety and low cost. Correspondingly, the method for manufacturing the abrasion-resistant water-based paint includes the steps of adding the core-shell emulsifier to deionized water, stirring to obtain a first premix, then adding inorganic pigments to the obtained first premix, stirring to obtain a second premix, then adding the polyaryletherketone resin to the second premix, stirring to obtain a third premix, and finally adding the thickening agents to the third premix, stirring to obtain the abrasion-resistant water-based paint. In these embodiments, the addition of the thickening agents at the end can improve the sprayability of the abrasion-resistant water-based paint while locking the dispersion performance.

[0095] In yet some embodiments of the present application, the dispersion further comprises a polysiloxane in addition to the core-shell emulsifier, the polyaryletherketone resin and the aqueous medium. As an example, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium and the polysiloxane is (0.7-1):(25-28):(70.85-73.5):(0.1-0.5).

[0096] As a specific example, the polysiloxane is a polydimethylsiloxane, in particular, an oligomerized polydimethylsiloxane (silicone oil). In these embodiments, by additionally adding the polysiloxane in the components of the wear-resistant aqueous coating comprising the polyaryletherketone resin, both the polyaryletherketone resin and the polysiloxane serve as the main film-forming substance, the polyaryletherketone resin serves to provide wear resistance, and the polysiloxane serves to provide non-stickiness, so that the wear-resistant coating layer formed by the wear-resistant aqueous coating can have both good wear resistance and non-stickiness, thereby enabling the wear-resistant coating layer to have better long-lasting non-stickiness.

[0097] According to a second aspect of the present application, there is provided a wear-resistant aqueous coating, wherein the wear-resistant aqueous coating is a liquid coating having flowability, and wherein, as shown in Figure 1 the wear-resistant aqueous coating is a dispersion comprising a core-shell emulsifier, a polyaryletherketone resin and an aqueous medium.

[0098] According to the embodiments of the present application, the wear-resistant aqueous coating can be formed in a stable dispersion state due to the presence of the core-shell emulsifier. In addition, the wear-resistant aqueous coating in the stable dispersion state is less susceptible to temperature affecting the dispersion performance, so that the wear-resistant coating layer formed by the wear-resistant aqueous coating can have reduced defects (e.g., pore defects), thereby improving the hardness and strength of the wear-resistant coating layer and ensuring the wear-resistant performance of the wear-resistant coating layer.

[0099] According to the present application, in the dispersion, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin and the aqueous medium is (0.7-1):(25-28):(70.85-73.5). In these embodiments, each component has a suitable mass ratio, so that the wear-resistant aqueous coating can have both storage stability and reliable workability.

[0100] In some embodiments, the dispersion further comprises inorganic pigments and / or thickening agents in addition to the core-shell emulsifier, the polyaryletherketone resin, and the aqueous medium. In these embodiments, the inorganic pigments are added to the components of the wear-resistant water-based paint to ensure the color of the wear-resistant coating formed by the wear-resistant water-based paint, and the thickening agents are added to the components of the wear-resistant water-based paint to ensure the viscosity of the wear-resistant water-based paint to facilitate the reliable formation of the wear-resistant coating. Moreover, the thickening agents can also improve the anti-sagging property of the wear-resistant water-based paint during application. Thus, the core-shell emulsifier, the polyaryletherketone resin, the inorganic pigments and / or the thickening agents, and the aqueous medium synergistically act to form a wear-resistant water-based paint that is storage-stable, has good application performance, and forms a uniform and consistent wear-resistant coating.

[0101] In some embodiments, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, and the inorganic pigments is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5), and when the dispersion further comprises a thickening agent, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, and the thickening agent is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2). In these embodiments, the respective components have suitable mass ratios to obtain a wear-resistant water-based paint that is both storage-stable and reliable to apply.

[0102] In preferred embodiments, the wear-resistant water-based paint is a dispersion composed of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, the inorganic pigments, and the thickening agent, wherein the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the aqueous medium, the inorganic pigments, and the thickening agent is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5):(0.15-0.2), and the mass percentage of the core-shell emulsifier is 0.7%-1%, the mass percentage of the polyaryletherketone resin is 25%-28%, the mass percentage of the aqueous medium is 70.85%-73.5%, the mass percentage of the inorganic pigments is 0.3%-0.5%, and the mass percentage of the thickening agent is 0.15%-0.2%.

[0103] In some embodiments, the inorganic pigments include at least one of iron oxide (e.g., red iron oxide, yellow iron oxide, black iron oxide), carbon black, silicon carbide, titanium dioxide, and aluminum oxide, which can endow the wear-resistant coating with enhanced hardness, wear resistance, and thermal stability. In preferred embodiments, the pigments have a nanoscale size, and the combination of pigments with a nanoscale size has a large number of combination sites, thereby ensuring the bonding force between the wear-resistant coating and the substrate of the appliance. As an example, the particle size of the pigments is 15-20 nanometers.

[0104] In some embodiments, the thickening agent is at least one of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and xanthan gum. These thickening agents can provide the abrasion-resistant waterborne coating with a suitable viscosity to ensure the workability as a liquid coating.

[0105] As an example, the abrasion-resistant waterborne coating has a viscosity of 80 mPa s-150 mPa s, and the abrasion-resistant waterborne coating has a viscosity of 20 s-40 s (corresponding to a viscosity of 80 mPa s-150 mPa s) as measured by the 4-cup method. In this viscosity range, the abrasion-resistant waterborne coating can have suitable workability. If the viscosity of the abrasion-resistant waterborne coating is too low, it can easily lead to sagging, insufficient film thickness. If the viscosity of the abrasion-resistant waterborne coating is too high, it can cause poor atomization, orange peel, poor leveling, and other problems.

[0106] According to a third aspect of the present application, an abrasion-resistant coating is provided, wherein the abrasion-resistant coating is obtained by curing the abrasion-resistant waterborne coating. Specifically, the abrasion-resistant coating includes a polyaryletherketone resin layer and particles dispersed in the polyaryletherketone resin layer, wherein the particles include a core-shell emulsifier.

[0107] It should be noted that the core-shell emulsifier in the abrasion-resistant coating can be the same as or slightly different from the core-shell emulsifier in the abrasion-resistant waterborne coating. This is because, during the process of forming the film from the abrasion-resistant waterborne coating and sintering to form the abrasion-resistant coating, some active groups of the core-shell emulsifier can react. For example, at high temperatures, the carbonyl group can be oxidized to carboxyl (-COOH) or further decarboxylated to 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.

[0108] According to the abrasion-resistant coating of the embodiments of the present application, the abrasion-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 abrasion-resistant coating, solving the problem of poor density affecting the hardness and strength of the abrasion-resistant coating, and thereby ensuring the abrasion-resistant performance of the abrasion-resistant coating.

[0109] In some embodiments, the abrasion-resistant coating is dense, which can avoid the problem of poor density affecting the hardness and strength of the abrasion-resistant coating, thereby ensuring the abrasion-resistant performance of the abrasion-resistant coating. As an example, the abrasion-resistant coating has a porosity of not more than 0.1% and a pore size of not more than 10 μm. The Vickers hardness of the abrasion-resistant coating is 35 HV-45 HV, which can further improve the abrasion-resistant performance of the abrasion-resistant coating. The friction coefficient of the abrasion-resistant coating is 0.1-0.2, which can further improve the abrasion-resistant performance of the abrasion-resistant coating.

[0110] In some embodiments, the polyaryletherketone resin layer and the core-shell emulsifier are chemically bonded at the contact interface, and the specific product is a cross-linking product of the hydroxyl-modified polyaryletherketone and the surface groups of the core-shell emulsifier, so that the compactness of the bonding interface inside the wear-resistant coating can be further optimized due to cross-linking.

[0111] In some embodiments, the wear-resistant coating is formed with the polyaryletherketone resin layer as the continuous phase (main body) and the core-shell emulsifier as the dispersed phase (small amount of addition), so that the comprehensive performance of the wear-resistant coating in terms of wear resistance, strength and other aspects can be balanced. As an example, the mass of the polyaryletherketone resin layer is 96%-99% of the total mass of the wear-resistant coating, and the balance is the core-shell emulsifier. With appropriate mass proportions of each component, the comprehensive performance of the wear-resistant coating in terms of wear resistance, strength and other aspects can be balanced.

[0112] In some embodiments, the particulate matter further includes color filler particles, so that the wear-resistant coating has 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 color filler particles. With appropriate mass proportions of each component, the comprehensive performance of the wear-resistant coating in terms of wear resistance, strength and other aspects can be balanced.

[0113] In this application, the surface and the interior of the wear-resistant coating are formed into a compact structure, which can fully utilize the advantages of the polyaryletherketone resin, thereby improving the wear-resistant performance of the wear-resistant coating formed by the wear-resistant water-based paint including the polyaryletherketone resin.

[0114] According to a fourth aspect of the present application, an appliance is provided, wherein the appliance includes an appliance base and a wear-resistant coating formed on the appliance base, and the wear-resistant coating includes the wear-resistant coating of the above-mentioned embodiments.

[0115] In some embodiments, the appliance includes a frying pan, a rice cooker liner, a cup, a kettle or a knife, and is suitable for a variety of types of appliances.

[0116] According to a fifth aspect of the present application, a manufacturing method of an appliance is provided. The manufacturing method of the appliance includes: step S201, providing an appliance base. Step S202, providing a wear-resistant water-based paint, wherein the wear-resistant water-based paint is a dispersion liquid including a core-shell emulsifier, a polyaryletherketone resin and a water-based medium. Step S203, applying the wear-resistant water-based paint on the appliance base to form an initial wear-resistant layer. Step S204, performing sintering treatment on the initial wear-resistant layer under the condition that the sintering temperature is not lower than the melting point of the polyaryletherketone resin in the initial wear-resistant layer, thereby obtaining a wear-resistant coating with the core-shell emulsifier dispersed in the polyaryletherketone resin layer, to manufacture the appliance.

[0117] In the embodiments of the present application, coating refers to a method of uniformly covering the wear-resistant water-based paint (liquid paint) on the surface of the utensil base by brushing, spraying, rolling, dipping, or the like.

[0118] According to the manufacturing method of the utensil provided by the embodiments of the present application, under the influence of the sintering temperature, the wear-resistant water-based paint containing the core-shell emulsifier, the polyaryletherketone resin, and the water-based medium and existing in the form of a dispersion liquid has stability. The core-shell emulsifier will not volatilize and escape or agglomerate like a small molecule emulsifier, but directly melt into the polyaryletherketone resin melt and serve as part of the wear-resistant coating, thereby playing a reinforcing role, effectively avoiding the micro defects (for example, pore defects) caused by volatilized components escaping or agglomerating, ensuring the high density of the wear-resistant coating, and providing the hardness and strength of the wear-resistant coating. At the same time, 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. On the one hand, this temperature condition can fully promote the melting flow of the polyaryletherketone resin, and can close the pores in the interior of the initial wear-resistant layer, thereby optimizing the microstructure of the coating and making the wear-resistant coating more uniform and dense. On the other hand, this temperature condition can ensure that the molten polyaryletherketone resin forms close contact and strong mechanical interlocking with the base, thereby further improving the wear resistance of the wear-resistant coating.

[0119] In the following, the manufacturing method of the utensil according to the present application will be introduced in combination with specific steps.

[0120] Providing a substrate for an implement According to the present application, the utensil base has a base structure formed by using a metal material through stretching or spinning to form a containing cavity. As an example, the metal material includes magnesium, aluminum, iron, or titanium.

[0121] In some embodiments, the thickness of the utensil base is 1.0 mm-2.0 mm, and such thickness can reduce the weight of the utensil finally manufactured.

[0122] According to some embodiments of the present application, the combination surface of the utensil base and the wear-resistant coating is a micron-level rough surface, and the wear-resistant coating is conformally arranged on the utensil base. In this way, the micron-level concave-convex surface of the wear-resistant coating can be utilized to enrich the oil storage structure or protect the non-stick layer by using the rough surface of the utensil base, so as to further improve the persistent non-stickiness of the utensil. According to other embodiments of the present application, the combination surface of the utensil base and the wear-resistant coating has a concave-convex structure composed of protrusions and grooves, and the wear-resistant coating is filled in the grooves of the concave-convex structure to manufacture a patterned non-stick pot, thereby being able to meet the use requirements of different users.

[0123] Pre-heating (optional) According to the present application, the manufacturing method of the appliance can further comprise a step of preheating the appliance base body. As an example, the preheating temperature can be 50-70°C, and the preheating time can be 5-10 minutes. The preheating can make the water in the wear-resistant water-based paint evaporate quickly when the wear-resistant water-based paint is in contact with the preheated appliance base body, which is conducive to the rapid formation of a wet film.

[0124] Forming an initial wear-resistant layer According to the present application, the wet film with a thickness of 31-202 μm is formed by atomizing and spraying the wear-resistant water-based paint. Specifically, the spray gun aperture of the atomizing and spraying is 1.0-1.5 mm, the pressure of the atomizing and spraying is 2.5-3.0 Bar, the distance is 20-35 cm, and the time is 2-5 seconds.

[0125] In some embodiments, the wet film obtained by atomizing and spraying is subjected to surface drying to obtain an initial wear-resistant layer. As an example, the surface drying temperature is 120-200°C, and the surface drying time is 3-5 minutes.

[0126] Sintering to form a wear-resistant coating According to the present application, after obtaining the initial wear-resistant layer, sintering is performed to make the initial wear-resistant layer sintered and solidified, and form a wear-resistant and dense wear-resistant coating layer. In the present application, the initial wear-resistant layer is subjected to sintering treatment under the condition that the sintering temperature is not lower than the melting point of the polyaryletherketone resin in the initial wear-resistant layer. In this way, the polyaryletherketone resin can be fully melted and solidified, while the core-shell emulsifier is uniformly dispersed in the polyaryletherketone resin matrix, forming a wear-resistant coating layer with the polyaryletherketone resin as the continuous phase and the core-shell emulsifier as the dispersed phase, and finally obtaining an appliance with significantly improved surface wear resistance. In addition, since the wear-resistant coating layer is relatively dense and has more connection sites with the appliance base body, it also has good bonding performance with the appliance base body.

[0127] In preferred embodiments, the sintering temperature is 50-100°C higher than the melting point of the polyaryletherketone resin in the initial wear-resistant layer. As an example, the sintering temperature is 380-420°C, and the solidification time is 5-20 minutes. With this temperature and time, the initial wear-resistant layer can be completely solidified, and a dense wear-resistant coating layer can be formed after natural cooling, thereby manufacturing the appliance.

[0128] In some embodiments, the thickness of the wear-resistant coating layer is 30-200 μm. With this thickness, it can be suitable as an intermediate layer and a base layer for grafting non-stick molecules for various types of appliances.

[0129] According to the present application, the non-stick molecules can be added in the wear-resistant water-based paint, so that the wear-resistant coating formed by the wear-resistant water-based paint can have both wear-resistant performance and non-stick performance, and the non-stick layer can be arranged on the wear-resistant coating.

[0130] Spraying a non-stick material to build a non-stick layer on the wear-resistant coating In some embodiments, the utensil further comprises a non-stick layer formed on the wear-resistant coating, and correspondingly, the manufacturing method of the utensil comprises coating or applying a non-stick material on the wear-resistant coating, so as to form a non-stick layer on the wear-resistant coating, wherein the wear-resistant coating serves as an intermediate layer. As a specific example, the non-stick material can be a liquid fluorine coating, a liquid ceramic coating or a solid non-stick material in the prior art.

[0131] In these embodiments, the wear-resistant coating of the present application has a relatively large bonding surface relative to an intermediate layer formed by a polyaryletherketone resin directly, an intermediate layer formed by a small molecule emulsifier and a polyaryletherketone resin together, or an intermediate layer formed by a metal material, so that the bonding force with the non-stick layer arranged thereon can be ensured, thereby greatly improving the wear-resistant performance and non-stick performance of the utensil as a whole.

[0132] In preferred embodiments, when the non-stick material is coated or applied on the wear-resistant coating, the surface of the wear-resistant coating is formed into a viscous flow state and combined with the coated or applied non-stick material, so that the bonding performance of the wear-resistant coating and the non-stick layer can be greatly improved.

[0133] In addition, the surface of the wear-resistant coating of the present application can contain active groups such as hydroxyl (-OH) and amino (-NH2), and therefore, in some embodiments, a non-stick material capable of chemical bonding or hydrogen bonding with the wear-resistant coating can be used to chemically bond the wear-resistant coating and the non-stick layer, so as to further improve the bonding performance between the wear-resistant coating and the non-stick layer.

[0134] According to the present application, the utensil obtained by the above steps comprises a utensil base body and a wear-resistant coating formed on the surface of the utensil base body.

[0135] In the following, the beneficial effects of the inventive concept will be described in combination with specific examples.

[0136] Example 1 The wear-resistant water-based paint of Example 1 is formed by the following method.

[0137] Step S301, providing polyaryletherketone resin, core-shell emulsifier and water, wherein the particle size D50 of the selected polyaryletherketone resin is 20-120 μm polyether ether ketone resin, the core-shell emulsifier has a structure with inorganic particles as the core layer and polymer long chain as the shell layer, wherein the core-shell emulsifier of the present embodiment is calcium carbonate with a particle size of 20-60 nm as the inorganic particles, and the polymer long chain with hydrophilic group-oleophilic segment as the polymer long chain, wherein the hydrophilic group is polyoxyethylene group (molecular weight 990 g / mol) sulfonic acid quaternary ammonium salt group, the oleophilic segment is nonylphenol chain, and the HLB value of the core-shell emulsifier is 13.

[0138] Step S302, dispersing the polyaryletherketone resin and the core-shell emulsifier in water (aqueous medium), stirring and dispersing, so as to form a wear-resistant water-based paint in the form of a dispersion liquid, wherein the weight ratio of the core-shell emulsifier, the polyaryletherketone resin and the water is 0.8:26:72, so as to obtain the wear-resistant water-based paint according to Embodiment 1.

[0139] Example 2 In addition to using different polyaryletherketone resins to replace the polyaryletherketone resin of Embodiment 1 to form a wear-resistant water-based paint (the polyaryletherketone resin of the present embodiment 2 is polyether ketone resin), the same method as Embodiment 1 is used to form the wear-resistant water-based paint according to Embodiment 2 of the present application.

[0140] Example 3 In addition to using different polyaryletherketone resins to replace the polyaryletherketone resin of Embodiment 1 to form a wear-resistant water-based paint (the polyaryletherketone resin of the present embodiment 3 is polyether ketone ketone resin), the same method as Embodiment 1 is used to form the wear-resistant water-based paint according to Embodiment 3 of the present application.

[0141] Example 4 In addition to using different polyaryletherketone resins to replace the polyaryletherketone resin of Embodiment 1 to form a wear-resistant water-based paint (the polyaryletherketone resin of the present embodiment 4 is polyether ether ketone ketone resin), the same method as Embodiment 1 is used to form the wear-resistant water-based paint according to Embodiment 4 of the present application.

[0142] Example 5 In addition to using different polyaryletherketone resins to replace the polyaryletherketone resin of Embodiment 1 to form a wear-resistant water-based paint (the polyaryletherketone resin of the present embodiment 5 is polyether ketone ether ketone ketone resin), the same method as Embodiment 1 is used to form the wear-resistant water-based paint according to Embodiment 5 of the present application.

[0143] Example 6 A wear-resistant water-based paint according to the present application was prepared in the same manner as in Example 1, except that a different core-shell emulsifier was used instead of the core-shell emulsifier of Example 1 (the core-shell emulsifier of this example was a polymer long chain having a hydrophilic group-oleophilic segment, in which the hydrophilic group was a polyoxyethylene group (molecular weight 990 g / mol) sulfonic acid quaternary ammonium salt group, and the oleophilic segment was a nonylphenol chain, and the HLB value of the core-shell emulsifier was 10, and the inorganic particles were titanium dioxide having a particle diameter of 20 nm to 60 nm).

[0144] Example 7 A wear-resistant water-based paint according to the present application was prepared in the same manner as in Example 1, except that a different core-shell emulsifier was used instead of the core-shell emulsifier of Example 1 (the core-shell emulsifier of this example was a polymer long chain having a hydrophilic group-oleophilic segment, in which the hydrophilic group was a polyoxyethylene group (molecular weight 2200 g / mol) sulfonic acid quaternary ammonium salt group, and the oleophilic segment was a nonylphenol chain, and the HLB value of the core-shell emulsifier was 18, and the inorganic particles were calcium carbonate having a particle diameter of 20 nm to 60 nm).

[0145] Example 8 A wear-resistant water-based paint according to the present application was prepared in the same manner as in Example 1, except that a different core-shell emulsifier was used instead of the core-shell emulsifier of Example 1 (the core-shell emulsifier of this example was a polymer long chain having a hydrophilic group-oleophilic segment, in which the hydrophilic group was a polyoxyethylene group (molecular weight 220 g / mol) sulfonic acid quaternary ammonium salt group, and the oleophilic segment was a nonylphenol chain, and the HLB value of the core-shell emulsifier was 18, and the inorganic particles were calcium carbonate having a particle diameter of 20 nm to 60 nm).

[0146] Example 9 A wear-resistant water-based paint according to the present application was prepared in the same manner as in Example 1, except that a different component was used (the component used in this example was polydimethylsiloxane, in addition to the components used in Example 1, and the weight ratio of the core-shell emulsifier, the polyaryletherketone resin, the water, and the polydimethylsiloxane was 0.8:26:72:0.1).

[0147] Comparative Example 1 A sample of Comparative Example 1 was prepared in the same manner as in Example 1, except that the core-shell emulsifier of Example 1 was omitted. This sample was a suspension, and was not uniformly dispersed.

[0148] Comparative Example 2 Example 2 was prepared by the same method as Example 1 except that the core-shell emulsifier of Example 1 was replaced by the same amount of a small molecule emulsifier (sodium dodecyl sulfonate). The sample was a dispersion.

[0149] Comparative Example 3 Example 3 was prepared by the same method as Example 1 except that the core-shell emulsifier of Example 1 was replaced by the same amount of a small molecule emulsifier (Tween 20). The sample was a dispersion.

[0150] Comparative Example 4 Example 4 was prepared by the same method as Example 1 except that the core-shell emulsifier of Example 1 was replaced by the same amount of a small molecule emulsifier (Tween 40). The sample was a dispersion.

[0151] Comparative Example 5 Example 5 was prepared by the same method as Example 1 except that the core-shell emulsifier of Example 1 was replaced by the same amount of a small molecule emulsifier (Tween 60). The sample was a dispersion.

[0152] The properties of the abrasion-resistant water-based paints of Examples 1-9 and the samples of Comparative Examples 1-5 were tested, and the results are recorded in Table 1 below.

[0153] (1) High stability test: Specifically characterized by the storage stability test method: Specifically, the test paint was placed in a constant temperature and humidity chamber (25°C ± 2°C, 50% RH ± 5%) after sealing, and the appearance, sedimentation rate and viscosity stability were checked regularly (e.g., 1 month, 3 months), wherein the test paint was the abrasion-resistant water-based paint of Examples 1-8 and the samples of Comparative Examples 1-5 (the same below).

[0154] Test standard: No delamination, no precipitation or no significant change in viscosity indicates that the test paint has good stability performance, and delamination, precipitation or significant change in viscosity indicates that the test paint has poor stability performance.

[0155] (2) Shear resistance test: Sheared continuously at a constant high shear rate of 1000 s -1 for 20 minutes, and delamination, coalescence or demulsification was observed after shearing. If delamination or precipitation occurs, the shear resistance test is NG, and if delamination or precipitation does not occur, the shear resistance test is OK.

[0156] (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.

[0157] (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.

[0158] (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.

[0159] Table 1 Performance Test Record Table

[0160] 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.

[0161] 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.

[0162] 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.

[0163] The cookware of the embodiment is formed by the following method.

[0164] Example 9 The cookware of Example 9 is formed by the following method.

[0165] Step S401, providing a pot body with a thickness of 2 mm and made of aluminum, and presetting the pot body to 60℃.

[0166] Step S402, spraying the abrasion-resistant water-based paint of Example 1 on the pot body by atomization (the spraying gun aperture of atomization is 1.3 mm, the pressure of atomization is 3.0 Bar, the distance of atomization is 30 cm, and the time of atomization is 3 seconds), and then, after the initial abrasion-resistant layer obtained after 5 min of surface drying at 150℃, the pot with the initial abrasion-resistant layer is placed in a sintering furnace for sintering at 380℃ for 15 min, so as to form an abrasion-resistant coating layer with a thickness of 150 microns on the pot body, thereby obtaining the pot provided by Example 1 of the present application.

[0167] Example 10 Example 10 is manufactured by the same method as Example 9, except that the abrasion-resistant water-based paint of Example 9 is replaced by the abrasion-resistant water-based paint of Example 2.

[0168] Example 11 Example 11 is manufactured by the same method as Example 9, except that the abrasion-resistant water-based paint of Example 9 is replaced by the abrasion-resistant water-based paint of Example 3.

[0169] Example 12 Example 12 is manufactured by the same method as Example 9, except that the abrasion-resistant water-based paint of Example 9 is replaced by the abrasion-resistant water-based paint of Example 4.

[0170] Example 13 Example 13 is manufactured by the same method as Example 9, except that the abrasion-resistant water-based paint of Example 9 is replaced by the abrasion-resistant water-based paint of Example 5.

[0171] Example 14 Example 14 is manufactured by the same method as Example 9, except that the abrasion-resistant water-based paint of Example 9 is replaced by the abrasion-resistant water-based paint of Example 6.

[0172] Example 15 Example 15 is manufactured by the same method as Example 9, except that the abrasion-resistant water-based paint of Example 9 is replaced by the abrasion-resistant water-based paint of Example 7.

[0173] Example 16 Example 16 is manufactured by the same method as Example 9, except that the abrasion-resistant water-based paint of Example 9 is replaced by the abrasion-resistant water-based paint of Example 8.

[0174] Example 17 The pot of Example 17 was manufactured in the same manner as Example 9 except that the wear-resistant water-based paint of Example 9 was replaced with the wear-resistant water-based paint of Example 9.

[0175] Example 18 The pot of Example 18 was manufactured in the same manner as Example 9 except that, after Step S402, a liquid ceramic paint was applied to the wear-resistant coating to form a non-stick layer having a thickness of 45 μm in addition to Step S403.

[0176] Example 19 The pot of Example 19 was manufactured in the same manner as Example 18 except that, between Step S402 and Step S403, the surface of the wear-resistant coating was heated to a viscous flow state at a temperature of 385°C, and then a liquid ceramic paint was applied in this state in addition to Step S403.

[0177] Comparative Example 6 The pot of Comparative Example 6 was manufactured in the same manner as Example 9 except that the wear-resistant water-based paint of Example 9 was replaced with the sample of Comparative Example 1.

[0178] Comparative Example 7 The pot of Comparative Example 7 was manufactured in the same manner as Example 9 except that the wear-resistant water-based paint of Example 9 was replaced with the sample of Comparative Example 2.

[0179] Comparative Example 8 The pot of Comparative Example 8 was manufactured in the same manner as Example 9 except that the wear-resistant water-based paint of Example 9 was replaced with the sample of Comparative Example 3.

[0180] Comparative Example 9 The pot of Comparative Example 9 was manufactured in the same manner as Example 9 except that the wear-resistant water-based paint of Example 9 was replaced with the sample of Comparative Example 4.

[0181] Comparative Example 10 The pot of Comparative Example 10 was manufactured in the same manner as Example 9 except that the wear-resistant water-based paint of Example 9 was replaced with the sample of Comparative Example 5.

[0182] The pots of Examples 9-19 and Comparative Examples 6-10 were tested for performance, and the results are shown in the table.

[0183] 1. Coating Vickers Hardness Test Method: The standard Vickers hardness test method is used. A right tetragonal pyramid diamond indenter with an included angle of 136° between opposite faces is used to vertically press into the coating surface of the sample under a specified test force. After maintaining for a specified time, the test force is removed, and the lengths of two opposite angles of the residual indentation on the sample surface are measured. The Vickers hardness value is obtained by calculating the test force per unit area of the indentation. The coating of the sample refers to the coating of the shovel of the examples and the comparative examples (the same below).

[0184] 2. Initial Non-stick Test Method: According to GB / T 32095.2-2015 test method, the center area of the inner coating surface of the pot is heated to the range of 150℃ to 170℃, and the egg is flipped and taken out using a plastic shovel in an oil-free state. Before testing, the pot needs to be cleaned according to the standard requirements. After testing, according to the residual situation of the fried egg on the pot, the non-stick property is divided into three levels of grade I, grade II and grade III in descending order.

[0185] 3. Mechanical Tensile Strength Test: Start the program to stretch at a constant rate, the stretching rate is 5 mm / min, and the fracture position needs to be observed and recorded during the process. After the measured product is broken, the equipment automatically records the maximum tension and elongation. This process needs to be repeated for all valid samples, and the final tensile strength value is recorded as the final tensile strength value.

[0186] 4. Corrosion Resistance Test Method: A 5% sodium chloride solution is prepared, and the sodium chloride solution is added to the pot of the measured product to 1 / 3 of the volume of the pot. Cover and keep it slightly boiling. Observe the rusting of the pot surface every half hour until obvious rust appears. For corrosion resistance testing, the measured product is expected to have a corrosion resistance of more than 100h.

[0187] 5. Cross-hatch Test Method: According to the standard method specified in GB / T 9286-2021, the number of squares peeled off from 100 squares of the measured product is determined, and the retention rate is calculated. First level is retention rate > 95%, second level is retention rate 85%-95%, third level is retention rate 65%-85%, fourth level is retention rate 35%-65%, and fifth level is retention rate < 35%. The higher the retention rate, the better the adhesion. This project requires a retention rate of level one.

[0188] II. Test Results are shown in the table below.

[0189] Table 2 Performance Test Record

[0190] From the above Table 2, it can be seen that the composite coating of each embodiment of the present application has high coating hardness, good wear resistance, high tensile strength and strong corrosion resistance. These data can indirectly indicate that the composite coating has few internal defects, is dense and corrosion resistant. For Comparative Examples 6-10, the instability of the small molecule emulsifier leads to a large number of structural defects in the coating during processing due to the influence of the shearing action of the spray gun nozzle, the high-speed rotation centrifugal action of the substrate and the thermal migration and thermal decomposition of high-temperature sintering, and finally the coating of Comparative Examples 6-10 has poor film forming effect, serious cracking and many pore defects, and cannot form an effective protective layer on the sprayed substrate, which indirectly indicates the advantages of the macromolecular core-shell emulsifier in the process of forming a PEEK water-based spray coating according to the present application.

[0191] Figure 3 An SEM photo of the surface of the wear-resistant coating provided by Embodiment 9 of the present application is shown; Figure 4 An SEM photo of the cross-section of the wear-resistant coating provided by Embodiment 9 of the present application is shown, from Figure 3 and Figure 4 It can be seen that the surface and the interior of the wear-resistant coating of Embodiment 9 of the present application are both formed into a dense structure.

[0192] Figure 5 A surface photo of the wear-resistant coating provided by Embodiment 9 of the present application before and after 200,000 times of wear is shown. From Figure 5 It can be seen that before wear, the surface of the wear-resistant coating of Embodiment 9 of the present application is flat, the structure is dense, and there are no obvious defects or pores, which indicates that the initial wear-resistant coating is uniform in quality and meets the relevant requirements of high wear resistance. After 200,000 times of friction, the surface of the wear-resistant coating of Embodiment 9 can still maintain the integrity as a whole, and there is no peeling, cracking or severe deformation, only a slight scratch in a local area, which also indicates that the wear-resistant coating of Embodiment 9 of the present application has strong adhesion to the substrate of the appliance and excellent fatigue resistance.

[0193] Figure 6 A thickness test comparison chart of the wear-resistant coating provided by Embodiment 9 of the present application before and after 200,000 times of wear is shown. From Figure 6 It can be seen that the thickness loss of the wear-resistant coating of Embodiment 9 is not greater than 20 μm before and after 200,000 times of friction on the wear tester.

[0194] The wear loss of conventional wear-resistant materials (such as ordinary metal coatings) can reach 50-100 μm / 200,000 times, while the thickness loss of the wear-resistant coating of the present application is not greater than 20 μm after 200,000 times of friction on the wear tester, which shows that the wear loss of the wear-resistant coating of the present application is much lower than that of conventional wear-resistant materials, and the wear-resistant coating has good wear resistance.

[0195] Figure 7The cross-hatch adhesion test results of the wear-resistant coating provided by Embodiment 9 of the present application are shown. From Figure 7 It can be seen that the wear-resistant coating of Embodiment 9 has no coating peeling at the cutting intersection and the grid edge is smooth without lifting after the cross-hatch adhesion test. This can directly prove that the wear-resistant coating of Embodiment 9 has good bonding force with the instrument substrate and can resist mechanical cutting and peeling.

[0196] In addition, all the above tests identical to Embodiment 9 are performed on other embodiments of the present application except for Embodiment 9. It can be seen from the tests that the wear-resistant coatings according to other embodiments of the present application except for Embodiment 9 also have all the excellent properties similar to Embodiment 9 (for example, good compactness, good bonding force, and less defects).

[0197] According to the present application, by using the core-shell emulsifier with a specific structure, the high stability of the wear-resistant water-based paint and the good wear-resistant performance of the wear-resistant coating can be successfully achieved. Specifically, the wear-resistant water-based paint has excellent shear resistance, centrifugal resistance, and heat resistance. After spraying, surface drying, and sintering, the wear-resistant coating has an ultra-compact wear-resistant coating (polyaryletherketone resin layer) with excellent wear resistance (the coating thickness loss is ≤50 μm after 200,000 times of friction by the flat abrasion tester) and excellent adhesion (cross-hatch test 1st level), thereby providing a water-based paint-related solution for the wear resistance of the instrument coating.

Claims

1. A wear resistant waterborne coating, characterized in that, The wear-resistant water-based paint is a dispersion liquid comprising a core-shell emulsifier, a polyaryletherketone resin and a water-based medium, wherein the core-shell emulsifier comprises inorganic particles and long chains of polymers with hydrophilic groups-lipophilic chain segments grafted on the surface of the inorganic particles.

2. The abrasion-resistant waterborne coating of claim 1, wherein, The polyaryletherketone resin comprises at least one of polyetherketone resin, polyetheretherketone resin, polyetherketoneketone resin, polyetheretherketoneketone resin and polyetherketoneetherketoneketone 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 friction coefficient of the polyaryletherketone resin is 0.2-0.

25.

3. The abrasion-resistant waterborne coating of claim 1, wherein, The hydrophilic groups and the lipophilic chain segments grafted on the surface of the inorganic particles are hydrophilic quaternary ammonium salt groups and lipophilic alkyl chains respectively; and / or, the HLB value of the core-shell emulsifier is 10-18.

4. The abrasion-resistant waterborne coating of claim 1, wherein, The hydrophilic groups are polyoxyethylene quaternary ammonium salt groups or polyoxyethylene carboxylate groups, and the lipophilic chain segments are nonylphenol chains or long alkyl chains; and / or, The molecular weight of the hydrophilic groups is 220g / mol-2200g / mol, and the molecular weight of the lipophilic chain segments is 220g / mol-400g / mol; and / or, The inorganic particles are selected from one or more of calcium carbonate particles, aluminum oxide particles and titanium dioxide particles; and / or, The size of the inorganic particles is 5nm-100nm.

5. The abrasion resistant waterborne coating of claim 1, wherein, In the dispersion liquid, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin and the water-based medium is (0.7-1):(25-28):(70.85-73.5).

6. The abrasion-resistant waterborne coating of claim 1, wherein, The dispersion liquid further comprises inorganic color fillers and / or thickening agents.

7. The abrasion-resistant waterborne coating according to claim 6, characterized in that, In the case that the dispersion liquid further comprises inorganic color fillers, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the water-based medium and the inorganic color fillers is (0.7-1):(25-28):(70.85-73.5):(0.3-0.5); in the case that the dispersion liquid further comprises thickening agents, the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the water-based medium and the thickening agents is (0.7-1):(25-28):(70.85-73.5):(0.15-0.2).

8. The abrasion resistant waterborne coating of claim 6, wherein, The inorganic color fillers are at least one of iron oxide, carbon black, silicon carbide, titanium dioxide and aluminum oxide; the thickening agents are at least one of ethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose and xanthan gum.

9. The abrasion-resistant waterborne coating of claim 1, wherein, 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 paint 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 liquid further comprises polysiloxane, and the mass ratio of the core-shell emulsifier, the polyaryletherketone resin, the water-based medium and the polysiloxane is (0.7-1):(25-28):(70.85-73.5):(0.1-0.5).

11. A method for producing a wear-resistant water-based paint, characterized by, The manufacturing method of the wear-resistant water-based paint comprises: Mixing a core-shell emulsifier, a polyaryletherketone resin and an aqueous medium, and forming a dispersion liquid, thereby obtaining a wear-resistant water-based paint, wherein the core-shell emulsifier comprises inorganic particles and polymer long chains with hydrophilic group-lipophilic chain segment grafted on the surface of the inorganic particles.

12. The method for producing a wear-resistant water-based paint according to claim 11, characterized by, The step of mixing the core-shell emulsifier and the aqueous medium to form a first mixed liquid; Mixing the core-shell emulsifier and the aqueous medium to form a first mixed liquid; Mixing the polyaryletherketone resin in the first mixed liquid to form the dispersion liquid.

13. The method of claim 11, wherein the abrasion-resistant waterborne coating is prepared by the steps of: The polyaryletherketone resin has a particle size of 20 μm-120 μm; and / or, the polyaryletherketone resin is a hydroxyl-modified polyaryletherketone resin.

14. The method for manufacturing the wear-resistant water-based coating according to claim 11, characterized in that, The method for manufacturing the wear-resistant water-based paint further comprises the step of forming a core-shell emulsifier with hydrophilic group-lipophilic chain segment.

15. The method of claim 14, wherein the abrasion-resistant waterborne coating is prepared by the steps of: The step of forming the core-shell emulsifier comprises: Providing inorganic particles; Grafting hydroxyl groups on the surface of the inorganic particles; Grafting hydrophilic groups on the hydroxyl groups on the surface of the inorganic particles through silanization coupling treatment; Grafting lipophilic chain segments on the hydrophilic groups on the surface of the inorganic particles through ion exchange, thereby obtaining the core-shell emulsifier with hydrophilic group-lipophilic chain segment.

16. A wear resistant coating characterized in that, The wear-resistant coating comprises a polyaryletherketone resin layer and particulates dispersed in the polyaryletherketone resin layer, the particulates comprising a core-shell emulsifier, wherein the core-shell emulsifier comprises inorganic particles and polymer long chains with hydrophilic group-lipophilic chain segment grafted on the surface of the inorganic particles.

17. The wear-resistant coating of claim 16, wherein, The wear-resistant coating has a porosity of not more than 0.1% and a pore size of not 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 friction coefficient of 0.1-0.2; and / or, the wear-resistant coating has a thickness of 30 μm-200 μm.

18. The wear-resistant coating of claim 16, wherein, 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 accounts for 96%-99% of the total mass of the wear-resistant coating, and the balance is the core-shell emulsifier.

19. The wear-resistant coating of claim 16, wherein, The particulates further comprise color filler particles, the mass of the polyaryletherketone resin layer accounts for 95%-98% of the total mass of the wear-resistant coating, the mass of the core-shell emulsifier accounts for 1%-4% of the total mass of the wear-resistant coating, and the balance is the color filler particles.

20. The wear-resistant coating of claim 16, wherein, The hydrophilic group and the lipophilic chain segment grafted on the surface of the inorganic particles are hydrophilic quaternary ammonium salt group and lipophilic alkyl chain, respectively; and / or, the HLB value of the core-shell emulsifier is 10-18.

21. The wear-resistant coating of claim 16, wherein, The hydrophilic group is polyoxyethylene quaternary ammonium salt group or polyoxyethylene carboxylate group, and the lipophilic chain segment is nonylphenol chain or long alkyl chain; and / or, The molecular weight of the hydrophilic group is 220 g / mol-2200 g / mol, and the molecular weight of the lipophilic chain segment is 220 g / mol-400 g / mol; and / or, The inorganic particles are selected from one or more of calcium carbonate particles, alumina particles and titanium dioxide particles; and / or, The size of the inorganic particles is 5 nm-100 nm.

22. An appliance characterized in that The utensil comprises a utensil base and a wear-resistant coating layer formed on the utensil base; The wear-resistant coating layer comprises the wear-resistant coating layer according to any one of claims 16 to 21; or the wear-resistant coating layer is a wear-resistant coating layer formed by a wear-resistant water-based paint, and the wear-resistant water-based paint is the wear-resistant water-based paint according to any one of claims 1 to 10 or the wear-resistant water-based paint obtained by the manufacturing method of the wear-resistant water-based paint according to any one of claims 11 to 15.

23. An appliance as claimed in claim 22, characterised in that The utensil comprises a wok, a rice cooker liner, a cup, a kettle or a knife; and / or the utensil further comprises a non-stick layer formed on the wear-resistant coating layer.

24. A method of manufacturing an appliance, characterized by, The manufacturing method of the utensil comprises: providing the wear-resistant water-based paint according to any one of claims 1 to 10 or the wear-resistant water-based paint obtained by the manufacturing method of the wear-resistant water-based paint according to any one of claims 11 to 15; coating the wear-resistant water-based paint on a utensil base to form an initial wear-resistant layer; sintering the initial wear-resistant layer under the condition that the sintering temperature is not lower than the melting point of the polyaryletherketone resin in the initial wear-resistant layer to obtain a wear-resistant coating layer in which at least the core-shell emulsifier is dispersed in the polyaryletherketone resin layer, thereby obtaining the utensil.

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