Non-stick coating material, preparation method thereof, non-stick coating and cooking utensil

Abstract

The invention discloses a non-stick coating material and a preparation method thereof, a non-stick coating and a cooking utensil. A main chain of the non-stick coating material comprises a silicon-oxygen bond, and a side chain of the non-stick coating material comprises an active group and a low surface energy group; the low surface energy group comprises a silyl group; the active group comprises at least one of-NH2,-SH,-Cl,-Br, an epoxy group, a glycidyl group and a glycidoxy group. Therefore, the bond angle of Si-O in the main chain of the non-stick coating material is large, so that the non-stick coating material has better flexibility. Low-surface-energy groups in the non-stick coating material can migrate to the surface of the coating under a heated condition, so that the coating has relatively good anti-sticking performance; active groups in the non-stick coating material can be combined with other structures in the coating in the form of chemical bonds, the problem of loss of the high-temperature evaporation material is avoided, and the non-stick coating has lasting non-stick performance. In addition, the non-stick coating material does not harm human health and has the advantage of high safety.

Description

Technical Field

[0001] The invention belongs to the technical field of materials, and in particular relates to a non-stick coating material and a preparation method thereof, a non-stick coating and a cooking utensil. Background Art

[0002] The mainstream non-stick pans on the market currently rely on spraying a layer of non-stick coating on the surface of the pan, relying on its strong hydrophobicity and low friction coefficient to achieve non-stick food. However, the existing non-stick coatings have problems such as poor coating strength, easy to fall off and damage, poor non-stick performance, and short service life.

[0003] Therefore, it is necessary to improve the non-stick coating. Summary of the invention

[0004] The present invention aims to improve at least one of the above technical problems at least to some extent.

[0005] The present invention provides a non-stick coating material, wherein the main chain of the non-stick coating material includes a silicon-oxygen bond, and the side chain of the non-stick coating material has an active group and a low surface energy group; the low surface energy group includes a silane group; the active group includes at least one of -NH2, -SH, -Cl, -Br, an epoxy group, a glycidyl group, and a glycidyloxy group. Therefore, the non-stick coating material of the present invention has a plurality of Si-O bonds, and the plurality of Si-O bonds form a cross-linked network structure, and the bond angle of Si-O is large, which can make the non-stick coating material have good flexibility. The low surface energy group in the non-stick coating material can make the coating have good anti-stick properties; the active group R in the non-stick coating material can be combined with other structures in the coating in the form of a chemical bond, which effectively avoids the problem of material loss due to high-temperature evaporation, and is conducive to making the non-stick coating have a lasting non-stick property.

[0006] According to an embodiment of the present invention, the structural formula of the low surface energy group is: -(Si(CH3)2O) b Si(CH3)3, wherein b is a positive integer greater than 1.

[0007] According to an embodiment of the present invention, the structural formula of the non-stick coating material is shown in Formula I:

[0008]

[0009] Wherein, a, f, and n are independently selected from positive integers greater than 1, e is 0 or a positive integer, R3 is H or an alkyl group, R1 and R2 are independently selected from alkyl groups, L does not exist or is an -alkyl-ester group, and R is the active group.

[0010] The present invention also provides a method for preparing the non-stick coating material described above, the method comprising: mixing a first silane coupling agent represented by formula II, a second silane coupling agent represented by formula III, water, and a first solvent, and performing a first reaction to obtain an intermediate; mixing the intermediate with tetramethylcyclotetrasiloxane, a compound represented by formula IV, a vinyl silicone oil represented by formula V, a second solvent, and a platinum catalyst, and performing a second reaction to obtain the non-stick coating material represented by formula I;

[0011]

[0012] Formula V: H2C=CH(CH2) a (Si(CH3)2O) b Si(CH3)3. Thus, the non-stick coating material prepared by this method has all the characteristics and advantages of the non-stick coating material described above, which will not be repeated here. In addition, this method also has the advantages of simple operation and low production cost.

[0013] According to an embodiment of the present invention, the content of the first silane coupling agent is 10 to 50 parts by weight, the content of the second silane coupling agent is 10 to 50 parts by weight, the content of the water is 0.5 to 3 parts by weight, and the content of the first solvent is 40 to 80 parts by weight; the content of the tetramethylcyclotetrasiloxane is 30 to 40 parts by weight, the content of the compound of formula IV is 7 to 15 parts by weight, the content of the intermediate is 6 to 12 parts by weight, the content of the vinyl silicone oil is 15 to 30 parts by weight, the content of the second solvent is 30 to 60 parts by weight, and the content of the platinum catalyst is 0.001 to 0.01 parts by weight.

[0014] According to an embodiment of the present invention, the method satisfies at least one of the following conditions: the first silane coupling agent includes at least one of vinyl trimethoxy silane, vinyl triethoxy silane, methacryloxypropyl trimethoxy silane, and methacryloxypropyl triethoxy silane; the second silane coupling agent includes at least one of aminopropyl trimethoxy silane, aminopropyl triethoxy silane, mercaptopropyl trimethoxy silane, mercaptopropyl triethoxy silane, glycidoxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, chloropropyl trimethoxy silane, and chloropropyl triethoxy silane; the molecular weight of the vinyl silicone oil is 3000-5000; the first solvent and the second solvent include at least one of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol butyl ether, isopropyl alcohol, and isobutyl alcohol; when performing the first reaction, a catalyst is also added to the reaction; the catalyst includes an acid; the content of the catalyst is 0.5-3 parts by weight.

[0015] According to an embodiment of the present invention, the method satisfies at least one of the following conditions: the temperature of the first reaction is 40 to 100°C; the time of the first reaction is 8 to 48 hours; the particle size of the intermediate is 5 to 50 nm; the second reaction is carried out under the protection of an inert gas; the temperature of the second reaction is 60 to 120°C, and the time of the second reaction is 6 to 12 hours.

[0016] The present invention also provides a non-stick coating, the non-stick coating comprising a first sub-coating, a second sub-coating, and a third sub-coating arranged in layers, the material forming the second sub-coating comprising the non-stick coating material described above or comprising the non-stick coating material prepared by the method described above. Therefore, the non-stick coating has all the features and advantages of the non-stick coating material described above, which will not be described in detail here.

[0017] According to an embodiment of the present invention, the material forming the first sub-coating layer includes at least one of polyethersulfone, polyetheretherketone, and polyphenylene sulfide; and the material forming the third sub-coating layer includes nano-silicon dioxide.

[0018] According to an embodiment of the present invention, the thickness of the first sub-coating layer is 10-30 μm, the thickness of the second sub-coating layer is 15-25 μm, and the thickness of the third sub-coating layer is 10-25 μm.

[0019] The present invention also provides a cooking utensil, the cooking utensil comprising the non-stick coating as described above, and a substrate, wherein the first sub-coating in the non-stick coating is disposed on the surface of the substrate. Thus, the cooking utensil has all the features and advantages of the non-stick coating as described above, which will not be described in detail here.

[0020] According to an embodiment of the present invention, the material forming the substrate includes at least one of aluminum, aluminum alloy, iron, and stainless steel.

[0021] According to an embodiment of the present invention, the cooking utensil includes at least one of an electric rice cooker, a frying pan, a wok, a stew pot, a pressure cooker, and a wall breaking machine. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a flow chart of a method for preparing a non-stick coating material in one embodiment of the present invention;

[0023] Figure 2 is a schematic structural diagram of a non-stick coating in one embodiment of the present invention;

[0024] Figure 3 is a schematic structural diagram of a cooking utensil in one embodiment of the present invention;

[0025] Figure 4 is a structural schematic diagram of a cooking utensil in another embodiment of the present invention;

[0026] Description of Reference Numerals

[0027] 100 - non-stick coating, 110 - first sub-coating, 120 - second sub-coating, 130 - third sub-coating, 200 - substrate. DETAILED DESCRIPTION

[0028] The present invention will be described below by specific examples, and it will be appreciated by those skilled in the art that the following specific examples are only for illustrative purposes, and do not limit the scope of the present invention in any way. In addition, in the following examples, unless otherwise specified, the specific techniques or conditions not specified in the examples are carried out according to the techniques or conditions described in the document in this area or according to the product specification. Reagents used or instruments not specified by the manufacturer are conventional products that can be obtained commercially.

[0029] Currently, non-stick pan coatings on the market include fluorine-containing coatings and ceramic coatings. However, polyfluororesin coatings have poor strength and are easy to fall off and damage. In addition, they soften during cooking and can only be used with wooden spatulas, and cannot cook harder foods. In addition, polyfluororesin compounds will decompose at high temperatures (greater than 410°C), causing the polyfluororesin coating to gradually damage. Once the polyfluororesin coating on the inner surface of the pan is damaged, the non-stick pan will lose its non-stick function. In addition, there has always been controversy over whether polyfluororesin-coated non-stick pans are harmful to human health during use. Ceramic non-stick coatings form an inorganic layer through sol-gel, have excellent heat resistance, high hardness, and a pencil hardness of more than 6H. They do not contain fluorine-containing compounds that are harmful to human health, but ceramic non-stick coatings also have some disadvantages. For example, compared with polyfluororesin organic non-stick coatings, ceramic non-stick coatings have fewer polar bonds in their molecular chemical bonds, very small molecular van der Waals forces, and insufficient affinity for metal substrates, resulting in poor adhesion to metal substrates and easy detachment after long-term use. In addition, due to the molecular structure, the coating has high hardness but high brittleness, and is very poor in toughness compared to organic coatings, and is easy to break. In addition, ceramic coatings are susceptible to acid corrosion; in addition, ceramic coatings also have the problems of poor long-term non-stick properties and short service life. The inventors found that the reason for the poor long-term non-stick properties of ceramic coatings is that the non-stick additives of existing ceramic coatings are usually silicone oil. During long-term use, as the silicone oil slowly evaporates and is consumed (the consumption is accelerated when used at high temperatures), the ceramic coating will gradually lose its non-stick properties, resulting in poor long-term non-stick properties and short service life of the non-stick coating.

[0030] In order to improve the above technical problems, the present invention provides a non-stick coating material, wherein the main chain of the non-stick coating material includes a silicon-oxygen bond, and the side chain of the non-stick coating material has an active group and a low surface energy group; the low surface energy group includes a silane group; the active group includes at least one of -NH2, -SH, -Cl, -Br, an epoxy group, a glycidyl group, and a glycidyloxy group. Therefore, since the main chain of the non-stick coating material includes a silicon-oxygen bond, the bond angle of Si-O is large, and the non-stick coating material can have good flexibility. Moreover, the low surface energy group in the non-stick coating material will migrate to the coating surface under heating conditions, which can make the coating have good anti-stick properties; the active group in the non-stick coating material can be combined with other structures in the coating in the form of a chemical bond, effectively avoiding the problem of high-temperature evaporation material loss, which is conducive to making the non-stick coating have a lasting non-stick property. In addition, the non-stick coating material of the present invention has outstanding thermal oxidation stability, does not release toxic substances at high temperatures, and almost does not harm human health, and has the advantages of being environmentally friendly and highly safe. In addition, the non-stick coating material of the present invention also has excellent moisture-proof, waterproof, rust-proof, cold-resistant and corrosion-resistant properties.

[0031] It should be noted that the silyl group refers to a group formed by introducing an alkyl group onto a silicon atom, and the structural formula of the silyl group is -SiR4R5R6, and at least one of R4, R5, and R6 is an alkyl group. Specifically, one of R4, R5, and R6 is an alkyl group, and the other two groups are H, or two of R4, R5, and R6 are the same or different and are independently selected from alkyl groups, and the other group is H, or three of R4, R5, and R6 are the same or different and are independently selected from alkyl groups.

[0032] According to an embodiment of the present invention, the structural formula of the low surface energy group is: -(Si(CH3)2O) b Si(CH3)3, where b is a positive integer greater than 1. Long-chain silyl methyl groups have low surface energy, and under heating conditions, low surface energy groups will migrate to the coating surface, giving the coating better anti-stick properties.

[0033] According to an embodiment of the present invention, the structural formula of the non-stick coating material is shown in Formula I:

[0034]

[0035] Wherein, a, f, and n are the same or different and are independently selected from a positive integer greater than 1, e is 0 or a positive integer, R3 is H or an alkyl group, R1 and R2 are the same or different and are independently selected from an alkyl group, L does not exist or is an -alkyl-ester group, and R is the active group, specifically, R includes at least one of -NH2, -SH, -Cl, -Br, epoxy, glycidyl, and glycidyloxy.

[0036] Unless otherwise defined, all technical terms herein have the same meaning as those generally understood by a person skilled in the art to which the subject matter of the claims belongs. The numerical ranges recorded in the specification and claims of this application, when the numerical range is defined as "integer", should be understood as recording the two endpoints of the range and each integer in the range. For example, "an integer of 0 to 10" should be understood as recording each integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. When the numerical range is defined as "number", it should be understood as recording the two endpoints of the range, each integer in the range and each decimal in the range. For example, "a number of 0 to 10" should be understood as recording not only each integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10, but also at least recording the sum of each integer with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively. It should be noted that -alkyl-ester group refers to: -alkyl-COO, and the term "alkyl" should be understood to preferably represent a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 40 carbon atoms, preferably C 1-10 Alkyl. "C 1-10 “Alkyl” is to be understood as meaning preferably a linear or branched, saturated, monovalent hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl radical is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl etc. or their isomers. In particular, the radical has 1, 2, 3, 4, 5, 6 carbon atoms (“C 1-6 alkyl), for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly, the radical having 1, 2 or 3 carbon atoms (“C 1-3 alkyl"), for example methyl, ethyl, n-propyl or isopropyl.

[0037] The non-stick coating material of the present invention can be used in high temperature resistant adhesives and can also be used in fluororesin non-stick coatings to improve the bonding strength between the non-stick coating and the substrate.

[0038] The present invention also provides a method for preparing the non-stick coating material as described above, referring to Figure 1 , the method comprising:

[0039] S100, mixing a first silane coupling agent represented by formula II, a second silane coupling agent represented by formula III, water, and a first solvent, and performing a first reaction to obtain an intermediate;

[0040]

[0041] Through step S100, the first silane coupling agent and the second silane coupling agent can be hydrolyzed, and the hydrolyzed molecules are condensed to obtain an intermediate.

[0042] According to some embodiments of the present invention, the content of the first silane coupling agent is 10 to 50 parts by weight, the content of the second silane coupling agent is 10 to 50 parts by weight, the content of water is 0.5 to 3 parts by weight, and the content of the first solvent is 40 to 80 parts by weight. When the content of each component is within the above range, an intermediate can be obtained with high yield.

[0043] According to some embodiments of the present invention, the first silane coupling agent includes at least one of vinyl trimethoxy silane, vinyl triethoxy silane, methacryloxypropyl trimethoxy silane, and methacryloxypropyl triethoxy silane.

[0044] According to some embodiments of the present invention, the second silane coupling agent includes at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, chloropropyltrimethoxysilane, and chloropropyltriethoxysilane.

[0045] According to some embodiments of the present invention, during the first reaction, a catalyst may be added to the reaction, wherein the content of the catalyst is 0.5 to 3 parts by weight, and the catalyst includes an acid, for example, the acid may be hydrochloric acid.

[0046] According to some embodiments of the present invention, the first solvent includes at least one of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol butyl ether, isopropyl alcohol and isobutyl alcohol.

[0047] According to some embodiments of the present invention, the temperature of the first reaction is 40-100° C. and the time of the first reaction is 8-48 hours. Under the above reaction conditions, the first reaction can be fully carried out and the intermediate can be obtained with high yield.

[0048] According to an embodiment of the present invention, the particle size of the intermediate is 5 to 50 nm.

[0049] According to an embodiment of the present invention, after the first reaction is completed, the method further includes the step of spin-drying water and the first solvent, and then adding the first solvent to dilute the intermediate to a solid content of 50%. By spin-drying water, water can be prevented from affecting the next reaction. The intermediate is relatively viscous and it is inconvenient to add materials. After the water and solvent are spin-dried, the first solvent is added to facilitate the addition of materials, and the intermediate with a solid content of 50% can be directly used in the next reaction.

[0050] S200, mixing the intermediate with tetramethylcyclotetrasiloxane, a compound of formula IV, a vinyl silicone oil of formula V, a second solvent, and a platinum catalyst, and performing a second reaction to obtain a non-stick coating material of formula I;

[0051]

[0052] Formula V: H2C=CH(CH2) a (Si(CH3)2O) b Si(CH3)3.

[0053] It should be noted that the single-terminated vinyl silicone oil in the embodiment of the present invention refers to the vinyl silicone oil represented by Formula V.

[0054] According to some embodiments of the present invention, the second solvent includes at least one of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol butyl ether, isopropyl alcohol and isobutyl alcohol.

[0055] According to some embodiments of the present invention, the content of tetramethylcyclotetrasiloxane is 30 to 40 parts by weight, the content of the compound of formula IV is 7 to 15 parts by weight, the content of the intermediate is 6 to 12 parts by weight, the content of the vinyl silicone oil is 15 to 30 parts by weight, the content of the second solvent is 30 to 60 parts by weight, and the content of the platinum catalyst is 0.001 to 0.01 parts by weight. When the content of each component is within the above range, it is conducive to the occurrence of hydrosilylation reaction, and the non-stick coating material shown in formula I is prepared with high yield.

[0056] According to some embodiments of the present invention, the molecular weight of the vinyl silicone oil is 3000 to 5000. If the molecular weight of the vinyl silicone oil is too small, the non-stick performance will be poor; if the molecular weight of the vinyl silicone oil is too large, the hardness of the coating will be reduced, and if the molecular weight of the vinyl silicone oil is too large, the final product will be too viscous, and when sprayed into a film, the surface flatness of the coating will be poor, affecting the appearance effect.

[0057] According to some embodiments of the present invention, the second reaction is carried out under the protection of an inert gas; the temperature of the second reaction is 60 to 120° C., and the time of the second reaction is 6 to 12 hours. Under the above conditions, it is conducive to fully carrying out the hydrosilylation reaction, and the non-stick coating material shown in Formula I is prepared with a high yield.

[0058] In general, the above method for preparing a non-stick coating material has the advantages of being simple, convenient, and easy to implement, can obtain a non-stick coating material with a high yield, and also has industrial application prospects.

[0059] The present invention also provides a non-stick coating, referring to Figure 2 The non-stick coating 100 includes a first sub-coating 110, a second sub-coating 120, and a third sub-coating 130 which are stacked. The material forming the second sub-coating 120 includes the non-stick coating material described above or includes the non-stick coating material prepared by the method described above. Therefore, the non-stick coating 100 has all the characteristics and advantages of the non-stick coating material described above, which will not be repeated here. In general, the non-stick coating 100 has better non-stick performance, greater hardness, wear resistance, scratch resistance, corrosion resistance, longer service life, and high temperature resistance. It will not release toxic substances at high temperatures, and will hardly damage human health. It is relatively friendly to the environment and has higher safety. In addition, the non-stick coating of the present invention also has excellent moisture-proof, waterproof, rust-proof, and cold-resistant properties.

[0060] According to an embodiment of the present invention, the material forming the first sub-coating 110 includes at least one of polyethersulfone, polyetheretherketone, and polyphenylene sulfide. These materials have the advantages of being cheap, easily available, resistant to high temperatures, and having strong adhesion, so that the first sub-coating 110 has strong bonding strength and toughness with the metal substrate and is not easy to fall off.

[0061] According to an embodiment of the present invention, the material forming the third sub-coating layer 130 includes nano-silicon dioxide, thereby enabling the surface of the non-stick coating layer to have excellent hardness.

[0062] The active group R in the second sub-coating 120 of the present invention can react with the ether bond in the first sub-coating 110 and the compound in the third sub-coating 130 , so that the first sub-coating 110 and the third sub-coating 130 are firmly combined together through the second sub-coating 120 .

[0063] According to an embodiment of the present invention, the thickness of the first sub-coating 110 is 10 to 30 μm, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm. Thus, the first sub-coating 110 can be firmly attached to the substrate 200. If the thickness of the first sub-coating 110 is too small, the adhesion may be too small. If the thickness of the first sub-coating 110 is too large, the first sub-coating 110 will be easily cracked, shortening the service life.

[0064] According to an embodiment of the present invention, the thickness of the second sub-coating 120 is 15 to 25 μm, for example, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, and 25 μm. Thus, the second sub-coating 120 within this thickness range as a transition layer can provide good bonding between the first sub-coating 110 and the third sub-coating 130, and can also make the non-stick coating have a better non-stick effect. If the thickness of the second sub-coating 120 is too small, the non-stick effect of the non-stick coating cannot be significantly improved, and the bonding between the first sub-coating 110 and the third sub-coating 130 will be poor. If the thickness of the second sub-coating 120 is too large, the second sub-coating 120 will be easy to crack, shortening the service life, and in addition, increasing the production cost.

[0065] According to an embodiment of the present invention, the thickness of the third sub-coating 130 is 10 to 25 μm, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm. Thus, the surface of the non-stick coating can have excellent hardness, and the first sub-coating 110 and the second sub-coating 120 can also be effectively protected. If the thickness of the third sub-coating 130 is too small, the hardness of the surface of the non-stick coating will be small and the corrosion resistance will be poor; if the thickness of the third sub-coating 130 is too large, the coating will easily crack, which will shorten the service life.

[0066] The first sub-coating 110, the second sub-coating 120, and the third sub-coating 130 within the above-mentioned thickness range cooperate with each other to enable the non-stick coating 100 to have a durable non-stick property and better corrosion resistance.

[0067] The present invention also provides a cooking utensil, referring to Figure 3 and Figure 4, the cooking utensil includes the non-stick coating 100 described above, and a substrate 200, and the first sub-coating 110 in the non-stick coating 100 is arranged on the surface of the substrate 200. Therefore, the cooking utensil includes all the features and advantages of the non-stick coating described above, which will not be repeated here. In general, the non-stick performance of the cooking utensil is better. During the use of the cooking utensil of the present invention, the food will not stick to the pot, which can improve the appearance and taste of the food. Moreover, the cooking utensil has a large hardness, is wear-resistant, scratch-resistant, corrosion-resistant, has a long service life, and is resistant to high temperatures. The cooking utensil will not release toxic substances at high temperatures, and will hardly damage human health. It is relatively friendly to the environment and has high safety. In addition, the cooking utensil also has the advantages of excellent moisture-proof, waterproof, rust-proof, cold-resistant, and corrosion-resistant.

[0068] It should be noted that the substrate refers to a part of the main structure of the cooking utensil, and the non-stick coating is provided on the inner surface of the cooking utensil, that is, the side that is in direct contact with food when the cooking utensil is in use.

[0069] According to an embodiment of the present invention, the material forming the substrate includes a metal, and the metal includes at least one of aluminum, aluminum alloy, iron, and stainless steel, and these materials have the advantages of being cheap and readily available. The present invention does not limit the shape of the substrate, and the substrate can have various shapes according to the type and / or usage scenario of the cooking utensil. For example, when the cooking utensil is a non-stick pan, the substrate can have a common pot body shape, for example, the shape of the substrate can be a kettle shape, a frying pan shape, a round bottom pan shape, etc. According to some embodiments of the present invention, before spraying to form a non-stick coating, the surface of the substrate can also be pre-treated by polishing, micro-engraving, cleaning, etc. to improve the surface properties of the substrate. The present invention does not limit the specific size of the substrate, and those skilled in the art can adjust it according to the type and / or usage scenario of the cooking utensil.

[0070] According to an embodiment of the present invention, the cooking utensil includes at least one of an electric rice cooker, a frying pan, a wok, a stew pot, a soup pot, a pressure cooker, a wall breaking machine, a bread maker, and a grilling machine.

[0071] According to some embodiments of the present invention, when preparing cooking utensils, the substrate can be preheated to 50-60°C, and then the first sub-coating material is sprayed on the substrate to form a first sub-coating, and then the second sub-coating material is sprayed on the first sub-coating to form a second sub-coating, and then the third sub-coating material is sprayed on the second sub-coating to form a third sub-coating. After the three layers of sub-coating are sprayed, they are baked at 150°C for 10 minutes to remove the solvent in the three layers of sub-coatings, and then the temperature is raised to 300°C and baked for 15 minutes to sinter and solidify, so that the second sub-coating reacts with the groups in the first sub-coating and the third sub-coating at high temperature, so that the first sub-coating and the third sub-coating are firmly bonded through the second sub-coating.

[0072] It should be noted that, in addition to the structures described above, the cooking utensil may also include structures that a conventional cooking utensil should have. For example, the cooking utensil may also include other structures such as a heating element, a pot cover, and a handle.

[0073] The present invention is described below with reference to specific embodiments. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0074] Example 1

[0075] Preparation of non-stick coating materials

[0076] (1) Add 25 g of vinyl trimethoxysilane, 25 g of glycidyloxypropyl trimethoxysilane, 0.5 g of hydrochloric acid, 2 g of deionized water, and 50 g of isopropanol into a flask, stir at 60° C. for 48 hours, then spin dry the water and solvent, and then add solvent to dilute the intermediate to a solid content of 50%.

[0077] (2) Add 34 g of tetramethylcyclotetrasiloxane, 10 g of tetraethylenetetramethylcyclotetrasiloxane, 6 g of the intermediate, 20 g of single-end vinyl silicone oil (molecular weight 3500), 35 g of solvent, and 0.005 g of platinum catalyst into a flask, and react at 80° C. for 8 h under nitrogen protection to obtain a non-stick coating material.

[0078] Preparing non-stick coatings

[0079] The substrate of the cooking utensil is preheated to 50-60° C., and then a first sub-coating material is sprayed on the substrate, the first sub-coating material is a polyethersulfone emulsion, to form a first sub-coating, the thickness of the first sub-coating is 20 μm, and then the non-stick coating material prepared in Example 1 is sprayed on the first sub-coating to form a second sub-coating, the thickness of the second sub-coating is 15 μm, and then nano-silicon dioxide is sprayed on the second sub-coating to form a third sub-coating, the thickness of the third sub-coating is 15 μm, and after the three layers of sub-coating are sprayed, they are baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0080] Example 2

[0081] Preparation of non-stick coating materials

[0082] (1) Add 25 g of vinyltrimethoxysilane, 25 g of mercaptopropyltrimethoxysilane, 0.5 g of hydrochloric acid, 2 g of deionized water, and 50 g of isopropanol into a flask, stir at 60° C. for 48 hours, then spin dry the water and solvent, and then add solvent to dilute the intermediate to a solid content of 50%.

[0083] (2) Add 34 g of tetramethylcyclotetrasiloxane, 10 g of tetraethylenetetramethylcyclotetrasiloxane, 6 g of the intermediate, 20 g of single-end vinyl silicone oil (molecular weight 3500), 35 g of solvent, and 0.005 g of platinum catalyst into a flask, and react at 80° C. for 8 h under nitrogen protection to obtain a non-stick coating material.

[0084] Preparing non-stick coatings

[0085] The substrate of the cooking utensil is preheated to 50-60° C., and then a first sub-coating material is sprayed on the substrate, the first sub-coating material is a polyethersulfone emulsion, to form a first sub-coating, the thickness of the first sub-coating is 20 μm, and then the non-stick coating material prepared in Example 2 is sprayed on the first sub-coating to form a second sub-coating, the thickness of the second sub-coating is 15 μm, and then nano-silicon dioxide is sprayed on the second sub-coating to form a third sub-coating, the thickness of the third sub-coating is 15 μm, and after the three layers of sub-coating are sprayed, they are baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0086] Example 3

[0087] Preparation of non-stick coating materials

[0088] (1) Add 25 g of vinyl trimethoxysilane, 25 g of aminopropyl trimethoxysilane, 2 g of deionized water, and 50 g of isopropanol into a flask, stir at 60° C. for 48 hours, then spin dry the water and solvent, and then add solvent to dilute the intermediate to a solid content of 50%.

[0089] (2) Add 34 g of tetramethylcyclotetrasiloxane, 10 g of tetraethylenetetramethylcyclotetrasiloxane, 6 g of the intermediate, 20 g of single-end vinyl silicone oil (molecular weight 3500), 35 g of solvent, and 0.005 g of platinum catalyst into a flask, and react at 80° C. for 8 h under nitrogen protection to obtain a non-stick coating material.

[0090] Preparing non-stick coatings

[0091] The substrate of the cooking utensil is preheated to 50-60° C., and then a first sub-coating material is sprayed on the substrate, the first sub-coating material is a polyethersulfone emulsion, to form a first sub-coating, the thickness of the first sub-coating is 20 μm, and then the non-stick coating material prepared in Example 3 is sprayed on the first sub-coating to form a second sub-coating, the thickness of the second sub-coating is 15 μm, and then nano-silicon dioxide is sprayed on the second sub-coating to form a third sub-coating, the thickness of the third sub-coating is 15 μm, and after the three layers of sub-coating are sprayed, they are baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0092] Example 4

[0093] Preparation of non-stick coating materials

[0094] (1) Add 25 g of vinyltrimethoxysilane, 25 g of chloropropyltrimethoxysilane, 0.5 g of hydrochloric acid, 2 g of deionized water, and 50 g of isopropanol into a flask, stir at 60° C. for 48 hours, then spin dry the water and solvent, and then add solvent to dilute the intermediate to a solid content of 50%.

[0095] (2) Add 34 g of tetramethylcyclotetrasiloxane, 10 g of tetraethylenetetramethylcyclotetrasiloxane, 6 g of the intermediate, 20 g of single-end vinyl silicone oil (molecular weight 3500), 35 g of solvent, and 0.005 g of platinum catalyst into a flask, and react at 80° C. for 8 h under nitrogen protection to obtain a non-stick coating material.

[0096] Preparing non-stick coatings

[0097] The substrate of the cooking utensil is preheated to 50-60° C., and then a first sub-coating material is sprayed on the substrate, the first sub-coating material is a polyethersulfone emulsion, to form a first sub-coating, the thickness of the first sub-coating is 20 μm, and then the non-stick coating material prepared in Example 4 is sprayed on the first sub-coating to form a second sub-coating, the thickness of the second sub-coating is 15 μm, and then nano-silicon dioxide is sprayed on the second sub-coating to form a third sub-coating, the thickness of the third sub-coating is 15 μm, and after the three layers of sub-coating are sprayed, they are baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0098] Example 5

[0099] Preparation of non-stick coating materials

[0100] (1) Add 25 g of vinyl trimethoxysilane, 25 g of glycidyloxypropyl trimethoxysilane, 0.5 g of hydrochloric acid, 2 g of deionized water, and 50 g of isopropanol into a flask, stir at 60° C. for 48 hours, then spin dry the water and solvent, and then add solvent to dilute the intermediate to a solid content of 50%.

[0101] (2) Add 34 g of tetramethylcyclotetrasiloxane, 10 g of tetraethylenetetramethylcyclotetrasiloxane, 6 g of the intermediate, 20 g of single-end vinyl silicone oil (molecular weight of 5000), 35 g of solvent, and 0.005 g of platinum catalyst into a flask, and react at 80° C. for 8 h under nitrogen protection to obtain a non-stick coating material.

[0102] Preparing non-stick coatings

[0103] The substrate of the cooking utensil is preheated to 50-60° C., and then a first sub-coating material is sprayed on the substrate, the first sub-coating material is a polyethersulfone emulsion, to form a first sub-coating, the thickness of the first sub-coating is 20 μm, and then the non-stick coating material prepared in Example 5 is sprayed on the first sub-coating to form a second sub-coating, the thickness of the second sub-coating is 15 μm, and then nano-silicon dioxide is sprayed on the second sub-coating to form a third sub-coating, the thickness of the third sub-coating is 15 μm, and after the three layers of sub-coating are sprayed, they are baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0104] Comparative Example 1

[0105] Preparation of non-stick coating materials

[0106] (1) Add 25 g of vinyltrimethoxysilane, 0.5 g of hydrochloric acid, 2 g of deionized water, and 50 g of isopropanol into a flask, stir at 60° C. for 48 hours, then spin dry the water and solvent, and then add solvent to dilute the intermediate to a solid content of 50%.

[0107] (2) Add 34 g of tetramethylcyclotetrasiloxane, 10 g of tetraethylenetetramethylcyclotetrasiloxane, 6 g of the intermediate, 20 g of single-end vinyl silicone oil (molecular weight 3500), 35 g of solvent, and 0.005 g of platinum catalyst into a flask, and react at 80° C. for 8 h under nitrogen protection to obtain a non-stick coating material.

[0108] Preparing non-stick coatings

[0109] The substrate of the cooking utensil is preheated to 50-60° C., and then a first sub-coating material is sprayed on the substrate, the first sub-coating material is a polyethersulfone emulsion, to form a first sub-coating, the thickness of the first sub-coating is 20 μm, and then the non-stick coating material prepared in Comparative Example 1 is sprayed on the first sub-coating to form a second sub-coating, the thickness of the second sub-coating is 15 μm, and then nano-silicon dioxide is sprayed on the second sub-coating to form a third sub-coating, the thickness of the third sub-coating is 15 μm, and after the three layers of sub-coating are sprayed, they are baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0110] Comparative Example 2

[0111] Preparation of non-stick coating materials

[0112] (1) Add 25 g of vinyl trimethoxysilane, 25 g of glycidyloxypropyl trimethoxysilane, 20 g of hydroxy silicone oil (molecular weight 3500), 0.5 g of hydrochloric acid, 2 g of deionized water, and 50 g of isopropanol into a flask, stir at 60° C. for 48 hours, then spin dry the water and solvent, and then add solvent to dilute the intermediate to a solid content of 50%.

[0113] (2) 34 g of tetramethylcyclotetrasiloxane, 10 g of tetraethylenetetramethylcyclotetrasiloxane, 6 g of the intermediate, 35 g of the solvent, and 0.005 g of the platinum catalyst were added to a flask, and the reaction was carried out at 80° C. under nitrogen protection for 8 h, and then the reaction was terminated to obtain a non-stick coating material.

[0114] Preparing non-stick coatings

[0115] The substrate of the cooking utensil is preheated to 50-60° C., and then a first sub-coating material is sprayed on the substrate, the first sub-coating material is a polyethersulfone emulsion, to form a first sub-coating, the thickness of the first sub-coating is 20 μm, and then the non-stick coating material prepared in Comparative Example 2 is sprayed on the first sub-coating to form a second sub-coating, the thickness of the second sub-coating is 15 μm, and then nano-silicon dioxide is sprayed on the second sub-coating to form a third sub-coating, the thickness of the third sub-coating is 15 μm, and after the three layers of sub-coating are sprayed, they are baked at 150° C. for 10 min, and then the temperature is increased to 300° C. and baked for 15 min to obtain a cooking utensil with a non-stick coating.

[0116] The non-stick coatings of Examples 1-5 and Comparative Examples 1-2 were subjected to the following performance tests:

[0117] 1. Boil salt water test

[0118] The test method is as follows: put an equal amount of 5% salt water by mass into each cooking utensil of Examples 1-5 and Comparative Examples 1-2, boil the salt water for 8 hours and then keep it warm for 16 hours, which is regarded as one cycle. Observe and record the number of cycles required for the non-stick coating of each cooking utensil to start bubbling or falling off.

[0119] 2. High temperature resistance test

[0120] Experimental method: The cooking utensils of Examples 1-5 and Comparative Examples 1-2 were placed under a heating condition of 400°C for 4 hours, and after cooling, 250g of rice (brand: Golden Dragon Fish) was added, and the rice was cooked at a power of 500W. After cooking, it was observed and recorded whether the rice could be poured directly from the cooking utensils without any rice residue.

[0121] 3. Wear resistance test

[0122] Test method: Use detergent to prepare 5% concentration of washing water, 3M (7447C) scouring pad, load 2.5kg, swing left and right as one stroke, replace the scouring pad every 250 strokes, check whether the non-stick coating is exposed to the substrate every 250 strokes, if the substrate is exposed, terminate the test; if the substrate is not exposed, continue the wear resistance test, record the number of strokes that meet the wear resistance requirements, which is the number of wear resistance tests.

[0123] The test results are shown in Table 1.

[0124] Table 1

[0125]

[0126]

[0127] The side chains of the non-stick coating materials prepared in Examples 1-5 have active groups and low surface energy groups. Comparative Example 1 did not add the second silane coupling agent, and the non-stick coating materials prepared did not have active groups. The steps of preparing the intermediate in Comparative Example 2 are different from those of preparing the intermediate in Examples 1-5. In Comparative Example 2, hydroxy silicone oil is added in the steps of preparing the intermediate. As shown in Table 1, the number of cycles, high temperature resistance, and wear resistance of the cooking utensils in Examples 1-5 in the boiling salt water test are better than those of the cooking utensils in Comparative Examples 1-2, indicating that the non-stick coating prepared by the method of the present invention has lasting non-stickiness, high temperature resistance, and strong wear resistance. That is to say, when the main chain of the non-stick coating material includes a silicon-oxygen bond, the side chain of the non-stick coating material has an active group and a low surface energy group, and the low surface energy group includes a silane group, and the active group includes at least one of -NH2, -SH, -Cl, -Br, epoxy, glycidyl, and glycidyloxy, it is beneficial for the non-stick coating to have lasting non-stickiness, high temperature resistance, and strong wear resistance.

[0128] The embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, and these simple modifications all belong to the protection scope of the present invention. It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction.

[0129] In the description of the present invention, it is to be understood that the terms “center”, “longitudinal”, “lateral”, “length”, “width”, “thickness”, “up”, “down”, “front”, “back”, “left”, “right”, “vertical”, “horizontal”, “top”, “bottom”, “inside”, “outside”, “clockwise”, “counterclockwise”, “axial”, “radial”, “circumferential”, etc., indicating orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0130] It should be noted that in this specification, the terms "first" and "second" are only used for description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. The orientation or position relationship indicated by the terms "upper" and "lower" is based on the orientation or position relationship shown in the drawings, which is only for the convenience of describing the present invention and does not require that the present invention must be constructed and operated in a specific orientation, and cannot be understood as limiting the present invention. In the present invention, unless otherwise clearly specified and limited, the first feature "upper" or "lower" of the second feature may be that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. Moreover, the first feature "above", "above" and "above" of the second feature may be that the first feature is directly above or obliquely above the second feature, or simply indicates that the first feature is higher in level than the second feature. The first feature "below", "below" and "below" of the second feature may be that the first feature is directly below or obliquely below the second feature, or simply indicates that the first feature is lower in level than the second feature. In the description of the present invention, the meaning of "multiple" is two or more, unless otherwise clearly and specifically limited. In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0131] In the description of this specification, the description with reference to the terms "embodiment", "one embodiment", "another embodiment", "some specific embodiments", "some specific embodiments", "other specific embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, unless they are contradictory.

[0132] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A non-stick coating material, It is characterized in that The main chain of the non-stick coating material includes a silicon-oxygen bond, and the side chain of the non-stick coating material has an active group and a low surface energy group; The low surface energy groups include silane groups; The active groups include -NH 2 , -SH, -Cl, -Br, epoxy, glycidyl, and glycidyloxy.

2. The non-stick coating material according to claim 1, It is characterized in that The structural formula of the low surface energy group is: -(Si(CH 3 ) 2 O) b Si(CH 3 ) 3 , where b is a positive integer greater than 1.

3. The non-stick coating material according to claim 2, It is characterized in that The structural formula of the non-stick coating material is shown in Formula I: Wherein, a, f, and n are independently selected from positive integers greater than 1, e is 0 or a positive integer, R 3 is H or alkyl, R 1 , R 2 are independently selected from alkyl groups, L is absent or is an -alkyl-ester group, and R is the active group.

4. A method for preparing the non-stick coating material according to any one of claims 1 to 3, the method include: Mixing a first silane coupling agent represented by formula II, a second silane coupling agent represented by formula III, water, and a first solvent, and performing a first reaction to obtain an intermediate; The intermediate is mixed with tetramethylcyclotetrasiloxane, a compound of formula IV, a vinyl silicone oil of formula V, a second solvent, and a platinum catalyst to carry out a second reaction to obtain a non-stick coating material of formula I; Formula II: Formula III: Formula IV: Formula V: H 2 C=CH(CH 2 ) a (Si(CH 3 ) 2 O) b Si(CH 3 ) 3 .

5. The method according to claim 4, It is characterized in that The content of the first silane coupling agent is 10 to 50 parts by weight, the content of the second silane coupling agent is 10 to 50 parts by weight, the content of water is 0.5 to 3 parts by weight, and the content of the first solvent is 40 to 80 parts by weight; The content of the tetramethylcyclotetrasiloxane is 30 to 40 parts by weight, the content of the compound of formula IV is 7 to 15 parts by weight, the content of the intermediate is 6 to 12 parts by weight, the content of the vinyl silicone oil is 15 to 30 parts by weight, the content of the second solvent is 30 to 60 parts by weight, and the content of the platinum catalyst is 0.001 to 0.01 parts by weight.

6. The method according to claim 4, It is characterized in that The method satisfies at least one of the following conditions: The first silane coupling agent includes at least one of vinyl trimethoxy silane, vinyl triethoxy silane, methacryloxypropyl trimethoxy silane, and methacryloxypropyl triethoxy silane; The second silane coupling agent includes at least one of aminopropyl trimethoxy silane, aminopropyl triethoxy silane, mercaptopropyl trimethoxy silane, mercaptopropyl triethoxy silane, glycidoxypropyl trimethoxy silane, glycidoxypropyl triethoxy silane, chloropropyl trimethoxy silane and chloropropyl triethoxy silane; The molecular weight of the vinyl silicone oil is 3000 to 5000; The first solvent and the second solvent include at least one of propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol butyl ether, isopropyl alcohol and isobutyl alcohol; When performing the first reaction, a catalyst is also added to the reaction; The catalyst comprises an acid; The content of the catalyst is 0.5 to 3 parts by weight.

7. The method according to claim 4, It is characterized in that The method satisfies at least one of the following conditions: The temperature of the first reaction is 40-100°C; The first reaction time is 8 to 48 hours; The particle size of the intermediate is 5 to 50 nm; The second reaction is carried out under the protection of an inert gas; The temperature of the second reaction is 60-120°C; The second reaction time is 6 to 12 hours.

8. A non-stick coating, It is characterized in that The non-stick coating comprises a first sub-coating, a second sub-coating, and a third sub-coating which are stacked, and the material forming the second sub-coating comprises the non-stick coating material according to any one of claims 1 to 3 or comprises the non-stick coating material prepared by the method according to any one of claims 4 to 7.

9. The non-stick coating according to claim 8, It is characterized in that The material forming the first sub-coating layer includes at least one of polyethersulfone, polyetheretherketone, and polyphenylene sulfide; The material forming the third sub-coating layer includes nano-silicon dioxide.

10. The non-stick coating according to claim 8, It is characterized in that The thickness of the first sub-coating layer is 10-30 μm, the thickness of the second sub-coating layer is 15-25 μm, and the thickness of the third sub-coating layer is 10-25 μm.

11. A cooking utensil, It is characterized in that The cooking utensil comprises the non-stick coating according to any one of claims 8 to 10, and a substrate, wherein the first sub-coating in the non-stick coating is disposed on the surface of the substrate.

12. The cooking appliance according to claim 11, It is characterized in that The material forming the substrate includes at least one of aluminum, aluminum alloy, iron, and stainless steel.

13. The cooking appliance according to claim 11, It is characterized in that The cooking utensil comprises at least one of an electric rice cooker, a frying pan, a wok, a stew pot, a pressure cooker and a wall breaking machine.

Images