CN115926502A - Non-stick material, preparation method thereof and non-stick coating - Google Patents
Non-stick material, preparation method thereof and non-stick coating Download PDFInfo
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Abstract
A non-stick material, a preparation method thereof and a non-stick coating are provided. The non-stick material includes modified fatty acid metal salt particles, wherein the modified fatty acid metal salt particles are composed of fatty acid metal salt particles and nano-silica particles, and in the modified fatty acid metal salt particles, the nano-silica particles are attached to the surface of the fatty acid metal salt particles to at least partially coat the fatty acid metal salt particles. The non-stick material can have good non-stick properties and paint compatibility, and can have a self-protective function.
Description
Technical Field
The invention relates to the field of materials for cookers, in particular to a non-stick material, a preparation method thereof and a non-stick coating.
Background
At present, non-stick materials for cookers mainly comprise fluorine coatings, and the non-stick materials are mainly sprayed and sintered to form non-stick coatings on the inner surfaces of the cookers so as to achieve the purpose of non-sticking.
The fluorine paint mainly comprises PTFE (polytetrafluoroethylene), PFA (copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene), FEP (fluorinated ethylene propylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer) and the like, and the non-stick principle of the fluorine paint is that the fluorine polymer has extremely low surface energy. However, non-stick coatings formed from fluorine paints suffer from the significant drawback of not being abrasion resistant. Therefore, cookware that is non-stick with a fluorine paint non-stick coating cannot be cooked with an iron spatula, and cannot be cleaned with steel wire balls, scouring pads, and the like. In addition, the fluorine paint non-stick coating has the problem of not being resistant to high temperature, and has the problem of more serious non-stick property reduction even if undergoing daily wear.
Therefore, there is still a need to develop other new non-stick materials.
Disclosure of Invention
Embodiments of the inventive concept provide a novel non-stick material that can have good non-stick properties and paint compatibility, and can have a self-protective function.
Embodiments of the inventive concept provide a method for preparing the aforementioned non-stick material.
Embodiments of the inventive concept provide a non-stick paint including the aforementioned non-stick material to have improved paint properties.
Embodiments of the inventive concept provide a non-stick coating formed from the aforementioned non-stick coating and having good non-stick properties and a "pan stick" prevention function.
According to an embodiment of the inventive concept, there is provided a non-stick material including modified fatty acid metal salt particles, wherein the modified fatty acid metal salt particles are composed of fatty acid metal salt particles and nano-silica particles, and in the modified fatty acid metal salt particles, the nano-silica particles are adhered to the surfaces of the fatty acid metal salt particles to at least partially coat the fatty acid metal salt particles.
In an embodiment, the fatty acid used to form the fatty acid metal salt particles may be selected from stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid, and linolenic acid.
In an embodiment, the metal used to form the fatty acid metal salt particles may be selected from sodium, potassium, calcium, magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, tin, and titanium.
In an embodiment, the particle size of the fatty acid metal salt particles may be in the range of 800 mesh to 1500 mesh.
In an embodiment, the particle size of the nano-silica particles may be in the range of 300nm to 800 nm.
According to an embodiment of the inventive concept, there is provided a method of preparing the above non-stick material, the method comprising the steps of: adding fatty acid metal salt powder into silica sol, and heating and stirring to obtain wet gel; and drying the wet gel to obtain the non-stick material, wherein the fatty acid metal salt powder comprises fatty acid metal salt particles and the silica sol comprises nano silica particles.
In an embodiment, the heating and stirring may be performed at a temperature of 50 ℃ to 80 ℃.
In an embodiment, the drying may be performed at a temperature of 200 ℃ to 280 ℃.
In embodiments, the weight ratio of fatty acid metal salt powder to silica sol may be in the range of 1 to 1.
According to an embodiment of the inventive concept, there is provided a non-stick paint including an aqueous curing agent and the above non-stick material, wherein the aqueous curing agent includes an alkaline silica sol and an acid assistant, and the acid assistant is used to subject the alkaline silica sol to a sol-gel reaction.
In an embodiment, the non-stick coating may comprise: 50 to 70 parts by weight of an alkaline silica sol, 3 to 8 parts by weight of an acid assistant, and 10 to 15 parts by weight of a non-stick material.
In an embodiment, the non-stick coating may further comprise a siloxane, wherein the siloxane may comprise dimethyl siloxane, methyltrimethoxysilane, or ethyl orthosilicate.
In embodiments, the amount of silicone in the non-stick coating may be from 10 parts by weight to 20 parts by weight.
In an embodiment, the acid adjuvant may include a low melting point fatty acid, acetic acid, or hydrochloric acid, wherein the low melting point fatty acid may be a fatty acid having a melting point below 40 ℃.
In an embodiment, the low melting point fatty acid may include at least one of oleic acid, linoleic acid, and linolenic acid.
Drawings
The foregoing and/or other features and aspects of the present inventive concept will become apparent and readily appreciated from the following description of the exemplary embodiments, taken in conjunction with the accompanying drawings.
Fig. 1 is a schematic view illustrating modified fatty acid metal salt particles according to an embodiment of the inventive concept.
Fig. 2 is a flow chart illustrating a method of making a non-stick material according to an embodiment of the present inventive concept.
Fig. 3 is a flow chart illustrating a method of manufacturing a non-stick coating according to an embodiment of the inventive concept.
Detailed Description
Example embodiments of the inventive concept will be described in more detail below. While example embodiments of the inventive concept are described below, it should be understood that the inventive concept may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the inventive concept to those skilled in the art.
The cooker (taking a 'pot' as an example) can generate a 'sticking' phenomenon in the process of cooking food. "clay pot" foods can be largely classified into starch and protein types. During cooking, the starch that causes the "clay pot" undergoes processes of water absorption, swelling, gelatinization and final carbonization, while the protein that causes the "clay pot" undergoes processes of dissociation denaturation, hydrolytic inactivation and final dehydration and carbonization. In the above process, the food appears "pot-sticking" from the combination of starch gel and protein gel produced therefrom with the surface of the cookware, and peaks in the adhesion with the cookware after the carbonization of the contact surface thereof. The explanation of the cause of the "sticking" phenomenon mainly includes a mechanical binding theory, an adsorption theory and a chemical bond theory.
Mechanical bonding theory states that the adhesion between food and cookware is mainly due to mechanical interlocking (e.g., mechanical forces such as engagement, anchoring, hooking, wedging, etc.) between the food and the surface of the cookware. However, the inventors have found that this mechanical bond is not the primary cause of the "pot sticking" phenomenon.
Adsorption theory states that the adhesion force between food and cookware is mainly due to, for example, hydrogen bonds and van der waals forces generated by molecular contact and interfacial forces between food and cookware. In this regard, the inventors have found that the adhesive force generated via hydrogen bonds and van der waals forces dominates at the gel stage.
Chemical bond theory indicates that the adhesion between food and cookware is mainly due to the chemical bond formed at the atomic level between food and cookware. In this regard, the inventors have found that the adhesion force via chemical bonds dominates in the "pot sticking" phenomenon (especially during and after carbonization of starch and protein).
Many studies have been made to solve the "sticking" phenomenon. For example, from the theory of mechanical bonding, the mechanical bonding between the food and the cooker may be reduced by improving the surface roughness of the cooker, or by forming the surface of the cooker to have a microscopic concavo-convex structure similar to the lotus leaf surface microstructure. For another example, from the surface adsorption theory, the adsorption of food to the cooker can be reduced by using pore oil storage by forming the surface of the cooker to have a micro-pore structure.
Accordingly, aspects of the inventive concept are to provide a novel non-stick material and a method of preparing the same, a non-stick coating including the non-stick material, a non-stick coating formed of the non-stick coating and a method of manufacturing the same, and a non-stick cooker having the non-stick coating, starting from a chemical bond theory.
Hereinafter, embodiments according to the inventive concept will be described in more detail with reference to the accompanying drawings.
The non-stick material according to an embodiment of the inventive concept includes modified fatty acid metal salt particles, wherein the modified fatty acid metal salt particles are composed of fatty acid metal salt particles and nano silica particles. In the modified fatty acid metal salt particles, nano-silica particles are attached to the surface of the fatty acid metal salt particles to at least partially coat the fatty acid metal salt particles.
Fig. 1 is a schematic view illustrating modified fatty acid metal salt particles according to an embodiment of the inventive concept. For reference, fig. 1 shows a single modified fatty acid metal salt particle.
As shown in fig. 1, the modified fatty acid metal salt particles may be composed of the fatty acid metal salt particles AM located at the center and the nano silica particles NS surrounding the fatty acid metal salt particles AM. The nano-silica particles NS surrounding the fatty acid metal salt particles AM may be attached to the surface (e.g., outer surface) of the fatty acid metal salt particles AM, and accordingly cover the fatty acid metal salt particles AM. For example, the nanosilica may be physically adsorbed on the surface of the fatty acid metal salt particles AM. The nano-silica particles NS may be physically adsorbed on the surface of the fatty acid metal salt particles AM by, for example, intermolecular forces or the like. Although not specifically shown in fig. 1, a plurality of nano silica particles NS may be attached to the surface of the individual fatty acid-metal salt particles AM to form a coating layer at the periphery of the fatty acid-metal salt particles AM, thereby forming modified fatty acid-metal salt particles.
As shown in fig. 1, the coating layer formed of the nano silica particles NS may partially coat the surface of the fatty acid metal salt particles AM. In an embodiment, unlike that shown in fig. 1, the coating layer formed of nano silica particles may coat the surface of the fatty acid metal salt particles more or less. That is, the surface of the modified fatty acid metal salt particles may be exposed differently from that shown in fig. 1. Further, since the modified fatty acid metal salt particles are formed by coating the fatty acid metal salt particles AM with the nano silica particles NS, the modified fatty acid metal salt particles may be spheroidal as a whole, but the outer surfaces thereof may be non-smooth. This may be due to a physisorption/coating mechanism, but the inventive concept is not so limited.
According to an embodiment of the inventive concept, the particle size of the fatty acid metal salt particles AM may be greater than that of the nano-silica particles NS. As such, the nano silica particles NS (e.g., a plurality of nano silica particles NS) may be attached on the surface of the fatty acid metal salt particle AM and form a coating layer. In an embodiment, the fatty acid metal salt particles AM may have a particle size of a micrometer scale, and the nano-silica particles NS may have a particle size of a nanometer scale. As such, the modified fatty acid metal salt particle structure of the nano silica particle NS-coated fatty acid metal salt particle AM as shown in fig. 1 can be formed more efficiently. For example, the particle diameter of the fatty acid metal salt particles AM may be in the range of 800 mesh to 1500 mesh. For example, the particle size of the nano silica particles NS may be in the range of 300nm to 800 nm.
According to an embodiment of the inventive concept, the fatty acid metal salt particles AM may be particles of a fatty acid metal salt formed of a fatty acid and a metal. In an embodiment, the fatty acid used to form the fatty acid metal salt particles AM may be selected from stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid, and linolenic acid. In an embodiment, the metal used to form fatty acid metal salt particles AM may be selected from sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), aluminum (Al), tin (Sn), and titanium (Ti). The fatty acid metal salt particles AM may be formed of the corresponding fatty acid and the corresponding metal, and may be, for example, particles of sodium stearate, iron stearate, aluminum palmitate, potassium oleate, manganese oleate, iron oleate, copper linoleate, zinc laurate, calcium linolenate, cobalt linolenate, and the like. It is to be understood that the examples herein are shown only for the convenience of understanding the combination of "fatty acid metal salts (particles) formed from the respective fatty acids and the respective metals", and that fatty acid metal salts (particles) formed via other fatty acid/metal combinations within the range of the above-described fatty acids and metals are possible in the embodiments of the inventive concept.
As described above, the non-stick material according to the embodiment of the inventive concept includes the modified fatty acid metal salt particles formed by coating the fatty acid metal salt particles with the nano-silica particles (for example, may be a powder material including the modified fatty acid metal salt particles or composed of the modified fatty acid metal salt particles). The non-stick material can provide long chain hydrocarbon groups on the one hand by its fatty acid groups and excellent coating compatibility on the other hand by nanosilica. Therefore, the non-stick material can solve the phenomenon of food sticking from the theory of chemical bonds, and is suitable for the non-stick coating of the cooker. This will be described in detail later.
Next, a method of preparing a non-stick material according to an embodiment of the inventive concept will be described with reference to fig. 2.
Fig. 2 is a flow chart illustrating a method of making a non-stick material according to an embodiment of the present inventive concept.
Referring to fig. 2, in step S100, a silica sol may be prepared, and a fatty acid metal salt powder may be prepared. The fatty acid metal salt powder includes fatty acid metal salt particles. The silica sol comprises nano silica particles.
Silica sol as used herein refers to a colloidal solution in which nano-sized silica (particles) form colloidal fine particles in an aqueous solvent (e.g., water) and are stably dispersed. As the silica sol prepared herein, a commercially available silica sol can be used as it is. Further, the solid content of the silica sol prepared herein may be in the range of 15% to 25%. Further, the particle diameter of the nano silica particles dispersed in the prepared silica sol may be in the range of 300nm to 800 nm.
The fatty acid metal salt powder prepared herein may include one or more single fatty acid metal salt powders. When a plurality of single fatty acid metal salt powders are used, the fatty acid metal salt powder prepared herein may be formed by blending them. The particle diameter of the fatty acid metal salt particles included in the prepared fatty acid metal salt powder may be in the range of 800 mesh to 1500 mesh. In the embodiment, the single fatty acid metal salt powder included in or constituting the fatty acid metal salt powder may be formed of one fatty acid selected from stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid, and linolenic acid and one metal selected from Na, K, ca, mg, cr, mn, fe, co, ni, cu, zn, al, sn, and Ti.
In an embodiment, the single fatty acid metal salt powder described above may be prepared by synthesis. For example, a single fatty acid metal salt powder may be prepared by a liquid phase chemical process as follows: preparing commercially available corresponding metal alkoxide powder, adding the metal alkoxide powder to an organic solvent (e.g., ethanol), adding a corresponding fatty acid to the resulting mixture, heating to raise the temperature to allow the metal alkoxide to sufficiently react with the fatty acid, and finally drying to obtain corresponding fatty acid metal salt powder. Optionally, the resulting fatty acid metal salt may also be subjected to a process such as ball milling to eliminate or reduce agglomeration of the fatty acid metal salt and/or to obtain a desired particle size and particle size distribution. The metal alkoxide described herein refers to a metal organic compound obtained by substituting hydrogen of a hydroxyl group of an aliphatic alcohol molecule (R-OH) with a metal, and its molecular formula may be represented as M (OR) n Wherein n corresponds to the valence of the metal M forming the metal alkoxide, and R is a long-chain hydrocarbon group. However, the inventive concept is not limited thereto, and for example, the above-mentioned single fatty acid metal salt powder may be prepared by other suitable methods in the art, and a commercially available fatty acid metal salt powder may be directly used.
Referring to fig. 2, in step S110, the prepared fatty acid metal salt powder may be added to the prepared silica sol, and then heated and stirred to obtain a wet gel.
In the examples, the fatty acid metal salt powder may be added to the silica sol in a weight part ratio in the range of 1. In an embodiment, the step of heating with stirring may be performed at a temperature of 50 ℃ to 80 ℃. Further, in the embodiment, the stirring rate used in the step of heating and stirring may be in the range of 20 revolutions (r)/min to 40 r/min.
During the heating and stirring process, as the solvent of the silica sol is evaporated, the nano silica gel in the silica sol gradually aggregates into a network structure, and a large amount of liquid phase containing fatty acid metal salt particles is wrapped in the gradually formed solid-phase skeleton of the silica gel. As the heating and stirring are continued, the viscosity of the silica sol continues to increase and eventually loses fluidity, thereby forming a wet gel in which the silica gel surrounds the fatty acid metal salt particles. At this time, the nano silica particles provided from the silica sol are adsorbed on the surface of the fatty acid metal salt particles, and at least partially coat the fatty acid metal salt particles as the core.
Thereafter, with continued reference to fig. 2, in step S120, the wet gel may be dried to obtain a non-stick material according to the inventive concept. The wet gel obtained through step S110 may be dried by being placed at a temperature of 200 to 280 ℃. In an embodiment, the step of drying may end with the wet gel completely losing the solvent (e.g., water) therein. After the wet gel has dried to lose moisture completely, the wet gel can resume the state of a powder charge, and thus a non-stick material according to the inventive concept can be obtained.
The non-stick material prepared via the above method may include modified fatty acid metal salt particles. Specifically, referring to fig. 1 together, the modified fatty acid-metal salt particles may be composed of fatty acid-metal salt particles AM and nano-silica particles NS, and in the modified fatty acid-metal salt particles, the nano-silica particles NS are attached to the surface of the fatty acid-metal salt particles AM to at least partially coat the fatty acid-metal salt particles AM. The non-stick material obtained here and the modified fatty acid metal salt particles comprised therein are the same as the non-stick material and the modified fatty acid metal salt particles comprised therein described in detail above with reference to fig. 1 alone, and therefore, redundant description thereof is omitted. Furthermore, it is to be understood that due to the nature of the process and/or physical adsorption, individual fatty acid metal salt particles and/or individual nanosilica particles may be present in small amounts in the non-stick material prepared by the above-described method, but such individual fatty acid metal salt particles and/or nanosilica particles do not affect the bulk properties of the non-stick material.
As described above, the non-stick material including modified fatty acid metal salt particles according to the present inventive concept can be prepared by mixing the silica sol and the fatty acid metal salt powder with heating under stirring and drying at a moderate temperature. Therefore, the method has the advantages of simple process, low process cost and the like. Meanwhile, since the above-described processes are each performed at a relatively low temperature (e.g., a temperature lower than the thermal decomposition temperature of the fatty acid metal salt), the fatty acid groups in the modified fatty acid metal salt particles can be maintained to the maximum extent, which can cause the non-tackiness of the non-tacky material to be maintained. In addition, the fatty acid metal salt particles are coated by the nano silicon dioxide particles, so that the fatty acid metal salt particles can be better protected from being damaged by external factors in a subsequent coating/coating process, and the non-stickiness of the non-stick material can be further maintained.
Next, a method of manufacturing the non-stick coating according to an embodiment of the inventive concept will be described in detail with reference to fig. 3.
Fig. 3 is a flow chart illustrating a method of manufacturing a non-stick coating according to an embodiment of the inventive concept.
Referring to fig. 3, in step S200, a non-stick paint may be prepared.
Non-stick coatings according to the present concepts may include an aqueous curing agent and a non-stick material as described above. In an embodiment, the aqueous curing agent may include a basic silica sol and an acid adjuvant.
As used herein, an alkaline silica sol refers to a silica sol prepared by any known silica sol preparation method in an alkaline colloidal system, which can undergo a sol-gel reaction under the action of an acid promoter to cure into a film. The solid content of the alkaline silica sol used herein may not be particularly limited, and may have various solid contents commonly used as long as it can satisfy requirements of a coating layer formed accordingly (e.g., coating thickness, coating hardness, coating workability, etc.); in addition, the same is true of the nano-silica particles dispersed in the basic silica sol used herein. As described above, the non-stick material according to the embodiment of the inventive concept includes the modified fatty acid metal salt particles formed by coating the nano-silica particles with the fatty acid metal salt particles, and thus, the fatty acid groups of the non-stick material, which provide non-stick properties, may be protected by the nano-silica. Therefore, the restrictions on the alkaline silica sol such as alkalinity, solid content, amount, etc., can be significantly reduced, and thus a non-stick coating having excellent coating properties can be prepared within an expanded selection range of the alkaline silica sol.
The acid assistant used herein can cause the alkaline silica sol to undergo a sol-gel reaction, thereby promoting the alkaline silica sol to cure to form a film. In embodiments, the acid adjuvant may include a low melting point fatty acid, acetic acid, or hydrochloric acid. By low melting fatty acid is meant a fatty acid having a melting point below 40 ℃. For example, the low melting fatty acid may include at least one of oleic acid, linoleic acid, and linolenic acid. In embodiments, each of the low melting point fatty acid, acetic acid, and hydrochloric acid may have their usual reagent morphology, and may have any suitable content/concentration range that enables the alkaline silica sol to undergo a sol-gel reaction. Preferably, the specific concentration and amount of the acid adjuvant can be determined according to the pH value of the system of the non-stick coating material adjusted to 4.8-5.5. When the pH of the non-stick coating system is within the aforementioned range, the reaction rate of the sol-gel reaction of the alkaline silica sol can be controlled within a desired range. Therefore, on one hand, the method is favorable for the curing of alkaline silica sol to form a film, and on the other hand, the method is favorable for the stability of a material system of the non-stick coating.
In some embodiments, the non-stick coating may include 50 to 70 parts by weight of the alkaline silica sol, 3 to 8 parts by weight of the acid adjuvant, and 10 to 15 parts by weight of the non-stick material described above.
In some embodiments, the non-stick coating may also include silicone to assist in promoting non-stick properties of a non-stick coating formed via the non-stick coating, although the inventive concept is not so limited. For example, examples of the siloxane used herein may include dimethylsiloxane, methyltrimethoxysilane, and tetraethoxysilane. When the non-stick coating includes silicone, the amount of silicone can range from 10 parts by weight to 20 parts by weight.
As described above, the non-stick coating according to embodiments of the inventive concept may include the above-described non-stick material, an alkaline silica sol, an acid assistant, and optionally a siloxane. Thus, step S200 may include: respectively preparing a non-stick material, alkaline silica sol, an acid assistant and optional siloxane; adding a non-stick material and optional siloxane into an alkaline silica sol and uniformly mixing to form a mixed solution; and adding an acid assistant into the mixed solution, and uniformly mixing to form the non-stick coating. The non-stick material used herein may be prepared according to the method of preparation of the non-stick material described in connection with fig. 2. The alkaline silica sol used herein can be prepared by using a commercially available alkaline silica sol. The acid adjuvant used herein may be prepared by using commercially available low melting point fatty acid, acetic acid or hydrochloric acid. The silicone used herein can be prepared by using commercially available silicones.
With continued reference to fig. 3, after the non-stick coating is prepared, in step S210, the prepared non-stick coating may be laid on the surface of the substrate to form a preliminary non-stick coating.
Here, the base material refers to a body of the cooker. In particular, the base material of the cooker is used to provide a receiving space for an operation of the cooker such as cooking. The base material may be made of, for example, a metal material, and may be manufactured to have various suitable shapes according to the type of cooker. In an embodiment, the metal material forming the substrate may include at least one of iron, aluminum, an aluminum alloy, copper, tin, titanium, a titanium alloy, stainless steel, antibacterial stainless steel, and cast iron, and may have a single-layer or multi-layer structure.
In embodiments, application of the non-stick coating may be performed by various suitable means known in the art. For example, the non-stick coating can be applied to the surface of the substrate by an air spray process. In this case, the application of the non-stick paint may comprise: the substrate is preheated to 50 ℃ to 60 ℃, and then the non-stick coating is sprayed on the surface of the substrate by utilizing an air spraying process. In an embodiment, the process parameters of the air spraying process may be: the caliber of the spray gun is 0.8 to 1.5mm; the spraying distance is 200mm to 250mm; air pressure is 0.2MPa to 0.4MPa. However, embodiments of the inventive concept are not limited thereto.
With continued reference to fig. 3, after the formation of the preliminary non-stick coating, the preliminary non-stick coating may be sintered to form the non-stick coating in step S220. For example, the preliminary non-stick coating can be sintered at a temperature of 200 ℃ to 300 ℃ for 3min to 8min to cure the preliminary non-stick coating and ultimately form the non-stick coating. According to the embodiments of the present inventive concept, since the aqueous curing agent including the basic silica sol and the acid assistant is used, the sintering temperature required to form the non-stick coating layer can be significantly reduced, for example, the sintering temperature can be lowered below the thermal decomposition temperature of the fatty acid metal salt contained in the non-stick coating material. Therefore, the long-chain hydrocarbon groups provided via the fatty acid groups contained in the non-stick material can be retained to the maximum extent, so that the non-stick property of the formed non-stick coating can be sufficiently retained. In addition, since the non-stick material forming the non-stick paint includes the modified fatty acid metal salt particles as described above, the non-stick material can have better compatibility with the aqueous curing agent, and the fatty acid metal salt particles as the core can be protected from being damaged by external factors by the nano silica particles during physical stirring, physical application, and sintering (i.e., can have a self-protection function in a subsequent paint/coating process), which can also sufficiently ensure non-stick property and non-stick uniformity of the formed non-stick coating. In addition, since the nanosilica of the modified fatty acid metal salt particles can react with the nano-scale silica in the alkaline silica sol in the coating sintering process to form together with the latter a silica skeleton of the non-stick coating, the stability of the fatty acid metal salt particles in the non-stick coating can be improved.
By the above method, the non-stick coating according to the present inventive concept can be formed on the surface of the base material of the cooker. In embodiments, the non-stick coating may be formed to a thickness in the range of 20 μm to 30 μm. If the coating is too thin (e.g., less than 20 μm), coating leaks or coating weaknesses can easily occur due to spray non-uniformity, affecting the overall non-stick properties and service life of the coating. If the coating is too thick (e.g., greater than 30 μm), the non-stick coating tends to sag, affecting the appearance and utility of the coating, and resulting in a costly coating.
When the non-stick coating according to the present inventive concept is formed on the surface of the base material of the cookware, the non-stick coating replaces the surface of the base material to provide a surface for contact with food when cooking. When cooking is performed using a cooker having the non-stick coating, the long-chain hydrocarbon groups provided by the fatty acid groups contained in the non-stick coating can form a thin oil film on the surface of the non-stick coating, and thus the original chemical bond bonding between food and metal atoms of the substrate can be changed into the contact of food and the oil film, and thus the formation of chemical bonds between food and the cooker can be avoided. Furthermore, the long-chain hydrocarbon groups provided by the fatty acid groups contained in the non-stick coating can have a good affinity for external fats and oils (e.g., cooking oil used in cooking, fats and oils spilled from food via cooking, etc.) and can therefore adsorb the external fats and oils on the surface of the non-stick coating to form a thicker oil film, thereby spacing the non-stick coating from the food, and thus can avoid adhesion of starch and/or protein gels of the food to the non-stick coating. Furthermore, because of the reversibility of the adsorption of the outer fat by the long chain hydrocarbon groups, the adsorbed outer fat can also be reversibly released to encapsulate the starch and/or protein gel to isolate the food-released "clay pot" substance from the cookware. Thus, the non-stick coating according to the inventive concept may have an excellent "stick pan" prevention effect.
Hereinafter, a non-stick material, a non-stick paint, a non-stick coating and a non-stick cooker according to the inventive concept will be described with reference to specific examples, reference examples and comparative examples.
Examples, reference examples and comparative examples
Example 1
Step 1) preparation of non-stick Material
15 parts by weight of silica sol (commercially available, with a solid content of 20%) and 1 part by weight of iron oleate powder (commercially available, with a particle size of 800 mesh) were prepared. Wherein the nano silica particles contained in the silica sol have a particle size in the range of 300nm to 800 nm.
Adding the prepared iron oleate powder into the prepared silica sol, and then stirring and mixing at a temperature of 50-80 ℃ and a stirring speed of 20-40r/min until the mixture loses fluidity, thereby obtaining wet gel.
The wet gel is dried at a temperature of 200-280 ℃ to obtain a non-stick material.
Step 2) preparation of non-stick coating
13 parts by weight of the above non-stick material, 60 parts by weight of an alkaline silica sol (commercially available) and 4 parts by weight of oleic acid (commercially available) were prepared.
The prepared non-stick material is added into the prepared alkaline silica sol, and is stirred and mixed uniformly, so that a mixed solution is obtained.
And adding the prepared oleic acid into the mixed solution, and uniformly mixing to obtain the non-stick coating. Wherein the system pH of the non-stick coating obtained is about 5.2.
Step 3) manufacture of non-stick cookware
Preparing a stainless steel pot blank, cleaning the surface of the stainless steel pot blank, and drying.
Heating the stainless steel pot blank to 50 ℃, and then spraying the non-stick coating on the surface of the stainless steel pot blank by utilizing an air spraying process so as to form a preliminary non-stick coating on the surface of the stainless steel pot blank. The air spraying process used here had the following process parameters: the caliber of the spray gun is 0.8mm; the spraying distance is 200mm; the air pressure was 0.2MPa.
The preliminary non-stick coating is then sintered at a temperature of 250 ℃ for 5min to form the non-stick coating. Wherein the thickness of the formed non-stick coating is 20 μm.
By the above-described process, the non-stick cooker of the present example in which the non-stick coating was formed on the surface of the stainless steel pan blank was obtained.
Example 2
The present embodiment is different from embodiment 1 in that: in step 1, the particle size of the iron oleate powder is 1000 mesh.
Example 3
The present embodiment is different from embodiment 1 in that: in step 1, the particle size of the iron oleate powder is 1500 mesh.
Example 4
The present embodiment is different from embodiment 1 in that: in step 1, the amount of silica sol used was 20 parts by weight, and the solid content of silica sol was 25%.
Example 5
The present embodiment is different from embodiment 1 in that: in step 1, the amount of silica sol used was 10 parts by weight, and the solid content of silica sol was 15%.
Example 6
The present embodiment is different from embodiment 1 in that: in step 1, aluminum stearate powder is used instead of ferric oleate powder.
Example 7
The present embodiment is different from embodiment 1 in that: in step 1, copper linoleate powder was used in place of iron oleate powder.
Example 8
The present embodiment is different from embodiment 1 in that: in step 1, zinc laurate was used in place of iron oleate.
Example 9
The present embodiment is different from embodiment 1 in that: in step 2, the non-stick material is used in an amount of 10 parts by weight and the alkaline silica sol is used in an amount of 70 parts by weight.
Example 10
The present embodiment is different from embodiment 1 in that: in step 2, the nonstick material is used in an amount of 15 parts by weight and the alkaline silica sol is used in an amount of 50 parts by weight.
Reference example 1
The reference example differs from example 10 in that: step 1 was not performed and the same iron oleate powder as that of example 1 was used directly as the non-stick material of step 2.
Reference example 2
The reference example differs from example 1 in that: step 1 was not performed, the same iron oleate powder as that of example 1 was directly used as the non-stick material of step 2, and in step 2, the non-stick material was used in an amount of 10 parts by weight, and the alkaline silica sol was used in an amount of 70 parts by weight.
Comparative example 1
This comparative example used a commercially available cookware with a PTFE coating.
Non-tackiness and non-tackiness durability test and evaluation
The cookers of the above examples 1 to 10, reference examples 1 to 2 and comparative example 1 were subjected to the "fried egg non-tackiness" test and evaluation. The "fried egg non-tackiness" test and evaluation performed herein differs only from the test and evaluation specified in "5.1.1 fried egg non-tackiness" in GB/T32095.2-2015 "in that: the cooking utensil is pretreated by boiling before egg frying operation, namely: pouring 20mL of edible oil into a cooker, shaking the cooker until the edible oil uniformly covers the bottom in the cooker, then placing the cooker on a cooker, heating until slight oil smoke is generated, turning off the fire, cooling to room temperature, and then cleaning the cooker.
Thereafter, the cookers of examples 1 to 10, reference examples 1 to 2 and comparative example 1 were tested and evaluated for non-stick durability according to the test and evaluation method specified in "5.6.9 permanent non-stick" in GB/T32388-2015.
The evaluation results of the non-tackiness and non-tackiness durability of the cookers of examples 1 to 10, reference examples 1 to 2, and comparative example 1 are recorded in the following table 1.
[ Table 1]
| Sample (I) | Non-tackiness | Lasting non-stick property (second time) |
| Example 1 | I | 25000 |
| Example 2 | I | 25000 |
| Example 3 | I | 25000 |
| Example 4 | I | 25000 |
| Example 5 | I | 25000 |
| Example 6 | I | 25000 |
| Example 7 | I | 25000 |
| Example 8 | I | 25000 |
| Example 9 | I | 20000 |
| Example 10 | I | 28000 |
| Reference example 1 | I | 3000 |
| Reference example 2 | I | 1000 |
| Comparative example 1 | I | 8000 |
As can be seen from the test results in table 1, the non-stick coatings of the cookers of examples 1-10 exhibited non-stick properties comparable to those of the fluororesin non-stick coating of comparative example 1. Meanwhile, the non-stick coatings of the cookers of examples 1-10 also exhibited a longer-lasting non-stick property that was better than that of the fluororesin non-stick coating of comparative example 1. Therefore, the nonstick material, the nonstick paint and the nonstick coating according to the present inventive concept can satisfy the nonstick requirement of the cooker.
In addition, the non-stick coatings of the cookers of examples 1-10 exhibited a longer lasting non-stick property that was better than that of reference examples 1-2. This may be because the non-stick coating of the cookware of examples 1-10 was made by a non-stick coating comprising modified fatty acid metal salt particles according to the inventive concept. For example, the non-stick material including modified fatty acid metal salt particles according to the present inventive concept, in which fatty acid metal salt particles as a core are coated with nano silica particles, can improve the compatibility of the non-stick material with an aqueous curing agent on the one hand, thereby improving the non-stick uniformity of the formed non-stick coating; on the other hand, the fatty acid groups of the fatty acid metal salt particles can be protected from external factors (e.g., acidic paint environment, physical agitation, physical application and/or sintering, etc.) by the nano-silica particles in the paint preparation process and coating manufacturing process (i.e., self-protection of the non-stick material can be achieved), thereby sufficiently retaining the non-stick properties of the non-stick coating provided by the fatty acid groups of the fatty acid metal salt particles.
Paint workability test and evaluation
Preparing three sets of air spraying equipment with the same model, thoroughly cleaning the spray gun and the coating runner, and then adjusting the states of all the equipment to be basically consistent.
A quantity of non-stick coating was prepared for continuous manufacture according to steps 1 and 2 of example 10, reference 1 and reference 2, respectively. Then, using the previously prepared air spraying apparatus, cookware was continuously manufactured in accordance with each of step 3 of example 10, reference example 1 and reference example 2 in the same environment without cleaning the spray gun all the time, and then the number of cookware manufactured until the spray gun was clogged was observed and recorded. The results recorded are shown in table 2 below.
[ Table 2]
| Sample (I) | Number of cookers manufactured continuously |
| Example 10 | 9000 |
| Reference example 1 | 80 |
| Reference example 2 | 230 |
It can be seen from the results in table 2 that example 10 can provide good continuous workability of coating with a larger amount of non-stick material and a smaller amount of aqueous curing agent than the non-stick coating of reference examples 1-2 formed by directly using fatty acid metal salt powder and aqueous curing agent. This may be because the non-stick material including modified fatty acid metal salt particles according to the present inventive concept has better compatibility with the aqueous curing agent, thereby improving the uniformity of the formed non-stick coating, and further reducing the probability of gun blockage during continuous construction.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims and their equivalents. The embodiments should be considered in descriptive sense only and not for purposes of limitation. Therefore, the scope of the invention is defined not by the detailed description of the invention but by the appended claims, and all differences within the scope will be construed as being included in the present invention.
Claims (13)
1. A non-stick material, characterized in that the non-stick material comprises modified fatty acid metal salt particles,
wherein the modified fatty acid metal salt particles are composed of fatty acid metal salt particles and nano-silica particles, and
in the modified fatty acid metal salt particles, the nano-silica particles are attached to the surface of the fatty acid metal salt particles to at least partially coat the fatty acid metal salt particles.
2. The non-stick material of claim 1 wherein the fatty acid used to form said fatty acid metal salt particles is selected from the group consisting of stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid, and linolenic acid.
3. The non-stick material of claim 1 wherein the metal used to form the fatty acid metal salt particles is selected from the group consisting of sodium, potassium, calcium, magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, tin, and titanium.
4. The non-stick material of claim 1 wherein the fatty acid metal salt particles have a particle size in the range of 800 mesh to 1500 mesh.
5. The non-stick material of claim 1 wherein the nanosilica particles have a particle size in the range of 300nm to 800 nm.
6. Method for the preparation of a non-stick material according to any of claims 1 to 5, characterized in that it comprises the following steps:
adding fatty acid metal salt powder into silica sol, and heating and stirring to obtain wet gel; and
drying the wet gel to obtain the non-stick material,
wherein the fatty acid metal salt powder comprises the fatty acid metal salt particles and the silica sol comprises the nano silica particles.
7. The production method according to claim 6, wherein the heating stirring is performed at a temperature of 50 ℃ to 80 ℃.
8. The production method according to claim 6, wherein the drying is performed at a temperature of 200 ℃ to 280 ℃.
9. The production method according to claim 6, characterized in that the weight ratio of the fatty acid metal salt powder to the silica sol is in the range of 1,
wherein the silica sol has a solid content in the range of 15% to 25%.
10. Non-stick coating, characterized in that it comprises an aqueous curing agent and a non-stick material according to any of claims 1 to 5,
wherein the aqueous curing agent comprises an alkaline silica sol and an acid assistant, and
wherein the acid auxiliary agent is used for carrying out sol-gel reaction on the alkaline silica sol.
11. The non-stick coating of claim 10, characterized in that it comprises: 50 to 70 parts by weight of the alkaline silica sol, 3 to 8 parts by weight of the acid adjuvant, and 10 to 15 parts by weight of the non-stick material.
12. The non-stick coating of claim 10 or 11 in which the acid adjuvant comprises a low melting point fatty acid, acetic acid or hydrochloric acid,
wherein the low melting point fatty acid is a fatty acid having a melting point of less than 40 ℃.
13. The non-stick coating of claim 12 wherein said low melting point fatty acid comprises at least one of oleic acid, linoleic acid and linolenic acid.
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| JPS62109865A (en) * | 1985-11-06 | 1987-05-21 | Kouto Gijutsu Kenkyusho:Kk | Anti-adhesion agent for paint |
| CN102449077A (en) * | 2009-06-02 | 2012-05-09 | 阿克佐诺贝尔国际涂料股份有限公司 | Waterborne coating composition comprising a polyester and a metal salt of a fatty acid |
| CN103894120A (en) * | 2012-12-26 | 2014-07-02 | 富士施乐株式会社 | Method for manufacturing fatty acid metal salt particle, and fatty acid metal salt particle |
| CN111713983A (en) * | 2020-07-10 | 2020-09-29 | 阳江市惠尔特新材料科技有限公司 | Preparation method of acidic silica sol for non-stick pan |
| CN114729125A (en) * | 2019-12-02 | 2022-07-08 | 美国陶氏有机硅公司 | Composition for preparing release coating |
| CN115260799A (en) * | 2022-07-25 | 2022-11-01 | 万华化学集团股份有限公司 | Anti-sticking coating material, coating method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS62109865A (en) * | 1985-11-06 | 1987-05-21 | Kouto Gijutsu Kenkyusho:Kk | Anti-adhesion agent for paint |
| CN102449077A (en) * | 2009-06-02 | 2012-05-09 | 阿克佐诺贝尔国际涂料股份有限公司 | Waterborne coating composition comprising a polyester and a metal salt of a fatty acid |
| CN103894120A (en) * | 2012-12-26 | 2014-07-02 | 富士施乐株式会社 | Method for manufacturing fatty acid metal salt particle, and fatty acid metal salt particle |
| CN114729125A (en) * | 2019-12-02 | 2022-07-08 | 美国陶氏有机硅公司 | Composition for preparing release coating |
| CN111713983A (en) * | 2020-07-10 | 2020-09-29 | 阳江市惠尔特新材料科技有限公司 | Preparation method of acidic silica sol for non-stick pan |
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