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WO2021203504A1 - 一种具有凹凸结构的物理不粘锅及其制备方法 - Google Patents

一种具有凹凸结构的物理不粘锅及其制备方法 Download PDF

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Publication number
WO2021203504A1
WO2021203504A1 PCT/CN2020/089170 CN2020089170W WO2021203504A1 WO 2021203504 A1 WO2021203504 A1 WO 2021203504A1 CN 2020089170 W CN2020089170 W CN 2020089170W WO 2021203504 A1 WO2021203504 A1 WO 2021203504A1
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WO
WIPO (PCT)
Prior art keywords
concave
stick
convex structure
pot body
layer
Prior art date
Application number
PCT/CN2020/089170
Other languages
English (en)
French (fr)
Inventor
王科
Original Assignee
浙江巴赫厨具有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN202010322008.5A external-priority patent/CN111387795B/zh
Application filed by 浙江巴赫厨具有限公司 filed Critical 浙江巴赫厨具有限公司
Priority to DE112020000451.1T priority Critical patent/DE112020000451B4/de
Priority to US18/277,390 priority patent/US12303057B2/en
Publication of WO2021203504A1 publication Critical patent/WO2021203504A1/zh

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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J27/00—Cooking-vessels
    • A47J27/02—Cooking-vessels with enlarged heating surfaces
    • A47J27/022—Cooking-vessels with enlarged heating surfaces with enlarged bottom
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • A47J36/025—Vessels with non-stick features, e.g. coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D51/00—Making hollow objects
    • B21D51/16—Making hollow objects characterised by the use of the objects
    • B21D51/18—Making hollow objects characterised by the use of the objects vessels, e.g. tubs, vats, tanks, sinks, or the like
    • B21D51/22—Making hollow objects characterised by the use of the objects vessels, e.g. tubs, vats, tanks, sinks, or the like pots, e.g. for cooking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
    • B23P2700/00—Indexing scheme relating to the articles being treated, e.g. manufactured, repaired, assembled, connected or other operations covered in the subgroups
    • B23P2700/05—Cooking vessels

Definitions

  • the invention belongs to the field of kitchen supplies, and specifically relates to a physical non-stick pan with a concave-convex structure and a preparation method thereof.
  • non-stick pans need to be sprayed with a chemical non-stick coating on the inner surface of the pan.
  • This chemical non-stick coating is prone to decomposition and failure at high temperatures, and the coating will quickly be destroyed under the use of a metal shovel.
  • CN201020591079.7 represents a solution in which multiple grooves are arranged on the top surface of the bottom of the pot to form lines, and a Teflon material non-stick layer is arranged in the grooves.
  • CN201310455227.0 which has deepened the design of the groove pattern setting, clarified the length, width, height of the groove pattern, and the size and height of the bump. On this basis, spray non-stick coatings, and then through further The process of polishing the surface of the pot body becomes the final product.
  • non-stick pans give up the solution of setting up a chemical non-stick layer to achieve the non-stick effect, and move to the direction of physical non-stick to achieve the non-stick effect.
  • the design of the non-stick layer based on the principle of the lotus leaf effect is particularly prominent; the lotus leaf effect is also called the self-cleaning effect.
  • the upper surface is covered with a lot of papillae, with an average size of about 53-57 microns. They are also composed of 6-13 microns in size. The surface of these papillae is covered with more and smaller papillae.
  • the average size of the papillae is about 6-8 microns, the average height is about 11-13 microns, and the average spacing is about 19-21 microns.
  • the physical non-stick solution can be further optimized, which can more effectively combine the characteristics of the non-stick cooking environment, and design a non-stick non-stick cooking system in a physically non-stick way.
  • the purpose of the present invention is to provide a device that can protect the physical non-stick layer from being damaged, and make the pot body achieve a lasting non-stick effect.
  • the main technical solution of the present invention is to provide a physical non-stick pot with a concave-convex structure, including a pot body, characterized in that the inner surface of the pot body forms a uniformly distributed concave-convex structure, and the concave-convex structure includes The convex ribs protruding on the inner surface of the pot and the concave area surrounded by the convex ribs, and the physical non-stick layer is arranged at least on the inner surface of the pot in the concave area.
  • the physical non-stick layer is at least arranged on the inner surface of the pot body in the recessed area, and the raised edge has a height difference from the recessed area, when the spatula is repeatedly scraped, it can only be located on the surface of the raised edge
  • the physical non-stick layer includes the lotus leaf in the principle of the lotus leaf effect mentioned in the background art Surface structure.
  • the side wall of the convex edge of the recessed area also has a physical non-stick layer; adding this structure can ensure the non-stick effect under the concave-convex structure. If it is not provided, the side wall may be stuck.
  • the physical non-stick layer includes a rough surface of at least a micron level, and an oxide film with a nano-scale rough porous structure is further formed on the rough surface; Oil storage and oil lock function, so as to realize the physical non-stick function; the pore size of the oxide film can shrink and expand with the change of heating temperature.
  • the pore size of the oxide film varies with The pot body expands when the temperature of the pot body rises, and shrinks as the pot body temperature decreases; further explain that when the user heats the pot body, the pore size of the oxide film expands to facilitate the access of grease; when the pot body stops heating, The temperature of the pot body is gradually cooled, and the aperture of the oxide film shrinks, and the grease entering the hole is locked in, thereby realizing the oil locking function.
  • the rough surface is composed of several papillae that are at least micron-sized, wherein at least micron-scale should be interpreted as micron-scale or nano-scale.
  • At least the hardness of the surface layer of the rough surface is HV400-1100; on the one hand, it is to minimize the scraping and abrasion of the spatula on the pot body during non-stick cooking, and on the other hand, it is to prevent steel balls from being washed.
  • the rough surface of the pot tool is worn when brushing the pot.
  • the area of the recessed area accounts for 80% to 95% of the area of the entire uneven structure, and the ribs account for 5% to 20% of the area of the entire uneven structure.
  • the ribs protect the physical non-stick layer in the recessed area from being shoveled or worn away; but the top of the ribs is not provided with a non-stick layer. Therefore, it is very important to rationally lay out the percentage of the convex ribs and recessed areas in the entire concave-convex structure area.
  • the convex ribs occupy a larger area, the effect of non-stick pan will be reduced; if the concave area takes up a large area, the convex ribs will be The protection of the recessed area is reduced, especially in the process of brushing the pot with the steel wire ball all the year round, it will gradually damage the physical non-stick layer in the recessed area.
  • the layout of this part ensures that the rib arrangement can protect the physical non-stick layer without affecting the non-stick effect.
  • the depression depth of the recessed area is 0.01 to 0.13 mm. If the depression depth is too deep, during the cooking process, the greater depression depth may result in viscous food materials (such as eggs).
  • the area has a deeper depression, forming a higher gap with the food on the convex edge, which separates the food; some of the food remains in the depression and cannot be shoveled out.
  • the pot body has a single-layer or multi-layer composite structure.
  • Concave-convex structure treatment chemically etched or mechanically pressed a uniformly distributed concavo-convex structure on the surface of the metal plate;
  • Sandblasting process Select abrasives, use compressed air as power to spray the abrasives on the surface of the pot body, so that the surface of the pot body forms at least a micron-level rough surface.
  • (2) Sandblasting process select 36-130 mesh abrasives, use 0.4-0.8MPa compressed air as the power, and use high-speed jet equipment to spray the abrasives on the inner surface of the pot body, and make the surface of the pot body form multiple At least a rough surface composed of micron-sized papillae.
  • it further includes: (4) Surface treatment: hardening and oxidizing the surface of the pot body to further form an oxide film with a nano-scale rough porous structure on the rough surface.
  • (4) surface treatment further includes:
  • the (4.1) hardening step before the heat treatment, the pot body is cleaned, and then placed in a heat treatment furnace, and heat treated in an environment of 400 to 650 degrees Celsius for 0.5 to 24 hours, so that the surface of the pot body A hardened layer with a hardness of HV400 to 1100 and a thickness of 3 to 35 microns is formed.
  • the (4.2) oxidation step put the pot body forming the hardened layer into a treatment furnace filled with liquid or gas, and oxidize it in an environment of 400-500 degrees Celsius for 0.5-2 hours.
  • it further includes: (5) Polishing process: mechanically polish the preset area of the inner surface of the pot body, remove the rough surface at the convex edge in the concave-convex structure, and retain the roughness on the concave area in the concave-convex structure Noodles, and then get the body of the non-stick pan.
  • a concave-convex structure is provided, and the convex edge protects the non-stick layer arranged in the recessed area, reduces the direct friction between the spatula and the non-stick layer, and prolongs the non-stick effect of the pot body.
  • the microscopic rough oxide film can store tiny air to achieve the hydrophobic effect.
  • the oxide film of the non-stick pan can realize the oil-locking function, and the inner surface of the pan after raising the pan, even if it is cleaned with a neutral detergent, still has a hydrophobicity similar to that of a lotus leaf. Sexual and physical non-stick function.
  • Fig. 1 is a schematic structural diagram of an embodiment of the present invention
  • FIG. 2 is a schematic diagram of the structure of the uneven structure combined with the rough surface of the embodiment of FIG. 1,
  • Fig. 3 is a schematic diagram of the nano-scale rough structure on the mastoid in the embodiment of Fig. 1,
  • Fig. 4 is a schematic diagram of the pot body in the embodiment of Fig. 1 having a multilayer structure
  • the pot body 1 the concave-convex structure 11, the convex rib 111, the concave area 112, the inner working layer 12, the middle heat conducting layer 13, the outer heating layer 14, the mastoid 2, the nano-level roughness a.
  • the term “a” should be understood as “at least one” or “one or more”, that is, in one embodiment, the number of an element may be one, and in another embodiment, the number of the element The number can be multiple, and the term “one” cannot be understood as a restriction on the number.
  • the non-stick pan includes a pan body 1.
  • the pan body 1 can be a single layer or multiple layers.
  • the material can be iron or stainless steel.
  • the alloying elements in the stainless steel are Cr, Ni, Ti, Mn, N, Nb, Mo, Si, Cu and other elements, and the main alloying element is Cr.
  • the pot body 1 is a single layer, including an inner working layer 12.
  • the material can be iron, stainless steel or composite material, but at least the inner surface of the pot body 1 is made of iron or stainless steel regardless of single layer or multiple layers.
  • the pot body 1 is multi-layer
  • the surface material of the pot body 1 cannot be made of aluminum.
  • the inner surface of the pot body 1 has a physical non-stick layer
  • the physical non-stick layer includes a rough surface of at least a micrometer level, at least a micrometer level should be interpreted as a micrometer or nanometer level
  • the rough surface further forms a nanometer level
  • the oxide film with rough porous structure, the micro and nano micro rough film layer has the function of oil storage and oil lock in actual cooking, so as to realize the physical non-stick function; it needs to be explained that the nano-level roughness formed by the oxide film is mainly caused by the oxidation process. ⁇ particles are generated.
  • the pore size of the oxide film can shrink and expand with the change of heating temperature, because the oxide film is formed by the base metal Yes, it is integrated with the base metal and is firmly bonded to the base.
  • the oxide film has excellent heat resistance.
  • the rough surface is composed of several papillae 2 of at least micron level, the hardness of at least the surface layer of the rough surface reaches HV400-1100, and the inner surface of the pot body 1 forms a uniformly distributed uneven structure 11,
  • the concave-convex structure 11 includes a convex rib 111 protruding from the inner surface of the bottom wall of the pot body and a recessed area 112 surrounded by the convex ribs 111, and the physical non-stick layer is at least disposed on the inner surface of the pot body of the recessed area 112
  • a physical non-stick layer is also provided on the side wall of the convex rib 111 of the recessed area 112, which increases the effect of the structure to ensure non-stick under the concave-convex structure.
  • the side wall may be stuck; the convex rib 111
  • the setting is to protect the physical non-stick layer on the inner surface of the pot body in the recessed area 112, because if there is no rib 111, the spatula will directly and repeatedly perform contact friction on the physical non-stick layer during cooking, and this work will be done for a long time. , The rough surface will be worn, and the effect of non-sticking will not continue.
  • the area of the recessed area 112 accounts for 80%-95% of the area of the entire concave-convex structure 11, and the convex rib 111 accounts for the area of the entire concave-convex structure 11 5% to 20%, the depression depth of the depression area 112 is 0.01 to 0.13 mm.
  • the preferred depression depth is 0.05 to 0.06 mm.
  • the deep recession may lead to viscous food materials (such as eggs), and some areas are deep recessed, forming a higher gap with the food materials on the convex edges, which separates the food; some food materials remain in the recessed area and cannot be Shovel out; in a word, under this scheme, because the physical non-stick layer is provided at least on the inner surface of the pot body in the recessed area, and there is a height difference between the convex edge and the recessed area, then when the spatula repeatedly scrapes, it can only It is located on the surface of the protruding edge, thereby realizing the use of the protruding edge to protect the non-stick layer in the recessed area, avoiding the physical non-stick layer from being worn, and helping to achieve a long-term non-stick effect.
  • the pore size of the oxide film expands as the temperature of the pot body rises, and shrinks as the temperature of the pot body 1 decreases;
  • the pore size of the oxide film expands to facilitate the access of grease;
  • the temperature of the pot body 1 gradually cools, the pore size of the oxide film shrinks, and the grease entering the hole is locked in Inside, and then realize the oil lock function.
  • a manufacturing method of the non-stick pan described in the first embodiment including the following steps:
  • Polishing process mechanically polish the predetermined area of the inner surface of the pot body 1 to remove the rough surface at the convex rib 111 in the concave-convex structure 11, and retain the rough surface on the concave area 112 in the concave-convex structure 11, and then The body 1 of the non-stick pan is obtained; since the top of the rib is not provided with a non-stick layer, it is explained that the layout of this part ensures that the rib is arranged to protect the physical layer without affecting the effect of the non-stick pan.
  • the pot body 1 is ultrasonically polished and waxed, and then cleaned with deionized hot water, and the handle is riveted to package the finished product.
  • the production of the pot body 1 further includes:
  • Concave-convex structure 11 treatment chemically etched or mechanically pressed a uniformly distributed concavo-convex structure 11 on the surface of the iron or stainless steel plate; the concave depth is 0.01 to 0.13 mm, and the preferred concave depth is 0.05 to 0.06 mm. If the depth is too deep, during the cooking process, the food may remain in the recessed area 112 and cannot be shoveled out; the cross section of the rib 111 of the concave-convex structure 11 can be semi-circular or rectangular; in the iron plate or stainless steel The surface of the board is chemically etched or engraved or rolled to form the uneven structure 11. The engraving includes cutting engraving and laser engraving.
  • the thickness of the pot body 1 is 0.3-8 mm.
  • the thickness of the pot body 1 is 0.6-5 mm.
  • (2) Sandblasting process select 36-130 mesh abrasives, use 0.4-0.8MPa compressed air as power, and use high-speed spray equipment (such as spray guns) to spray the abrasives on the inner surface of the pot body 1 Impurities on the inner surface are completely removed, and the surface of the pot body 1 is formed with a plurality of rough surfaces composed of at least micron-level papillae, and the abrasive is brown corundum or white corundum.
  • (3) surface treatment further includes:
  • Hardening process clean the pot body 1 after the sandblasting process is completed, and put the cleaned pot body 1 into a gas or liquid heat treatment furnace, heat treatment in an environment of 400-650 degrees Celsius for 0.5-24 hours, so A hardened layer with a hardness of HV400-1100 and a thickness of 3-35 microns is formed on the surface of the body 1;
  • Oxidation process Oxidize the pot body 1 that meets the hardening standard, that is, put the pot body 1 that forms the hardened layer into a treatment furnace filled with liquid or gas, and oxidize it in an environment of 400-500 degrees Celsius for 0.5- After 2 hours, an oxide film with a nano-scale rough porous structure is further formed on the rough surface of the pot body 1.
  • the two steps of the hardening process and the oxidation process can be completed in the same treatment furnace, or the two processes can be completed separately; in addition, after the hardening process and the oxidation process are completed, the surface of the pot body 1 can be observed under a microscope It can be seen that the inner surface of the pot is formed with a micron-level rough surface with a thickness of 3-35 microns and a hardness of HV400-1100, and an oxide film with a nano-scale rough porous structure is further formed on the rough surface, and the surface structure becomes non-sticky.
  • the physical non-stick layer, and the surface of the rib 111 at this time also has a rough surface and an oxide film with a nano-scale rough porous structure.
  • the step (4) polishing process in the manufacturing method of the non-stick pan is specifically: in order not to damage the micro-nano structure of the inner surface of the pan, the inner surface of the pan is A soft cloth wheel is used for polishing, and then the rough surface of the rib 111 is polished, so that the surface of the rib 111 becomes relatively smooth; while the outer surface of the pot is polished with a 60-320 mesh nylon wheel, which can effectively prevent the pot body 1 Slipping on the gas stove.
  • the pot body 1 After the pot body 1 is hardened and oxidized by heat treatment, its color is dark gray or black, which is favored by general consumers; however, general metal base pots are easy to stick to the pot when used. Therefore, this application further provides a hardening treatment on the inner surface of the pot.
  • the physical non-stick layer of micron or nano-scale rough surface After consumers use pork or animal fat or oil to heat the pot for the first time, the temperature of the pot body 1 rises, and the pore size of the nano-scale rough oxide film expands with the temperature. , Pork or animal fat or oil enters from the hole.
  • the temperature of the pot body 1 gradually cools down, and the pore size of the nano-scale rough oxide film shrinks with the temperature, which locks the grease inside, thereby producing
  • the oil storage function when the cooking body 1 needs to be heated next time, the oil will enter and exit again.
  • the rough surface of the micron or nanometer structure combines with the oil-locking effect to avoid the phenomenon that the cooking sticks to the pot and realize the physical non-stick effect.
  • the inner surface of the pot even if it is cleaned with neutral detergent, still has the hydrophobicity and physical non-stick function similar to that of a lotus leaf.
  • the present invention is based on the bionic principle of the lotus leaf effect, combined with the characteristics of the use environment of the pot body 1 for overall design, by forming a micron-level or nano-scale rough structure on the inner surface of the pot body 1 and combining it on the rough surface to further form a nanometer Grade-grade rough porous structure with oil-locking oxide film, which makes it non-sticky without spraying chemical coatings. It also changes the long-term view that the bottom of the pot can be as smooth as possible to be non-sticky. It has been expected.
  • the inadequate non-stick effect effectively solves the problem that the industry has long relied on chemical coating to improve the non-stick effect and cannot solve the problem of non-stick performance failure or easy fall off during high-temperature cooking, making people's diet healthier.
  • the present invention forms sub-millimeter, micron, and/or nano-scale multiple rough structures on the inner surface of the pot body 1, so that it has no need for
  • the combination of process parameters in the sandblasting, heat treatment, and oxidation processes mentioned in the present invention is an important factor to ensure the best non-stick effect.
  • the combination of process parameters is also the invention point of the present invention. one.
  • the formation of surface micron-level and nano-level rough surfaces and the formation of hardened layers require strict control of various process parameters such as sandblasting and heat treatment in order to achieve the ideal non-stick performance.
  • the present invention is not limited to the above-mentioned best embodiment. Under the enlightenment of the present invention, anyone can derive other products in various forms, but regardless of any changes in its shape or structure, all products that are the same or similar to those of the present application Approximate technical solutions fall within the protection scope of the present invention.

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Abstract

一种具有凹凸结构的物理不粘锅及其制备方法。其中物理不粘锅包括锅身（1），锅身（1）内表面形成凹凸结构（11），凹凸结构（11）包括凸起于锅内表面的凸棱（111）以及由凸棱（111）围合构成的凹陷区（112）。物理不粘层至少设置在凹陷区（112）的锅体内表面上。通过设置凹凸结构（11），凸棱（111）保护设置在凹陷区（112）的不粘层，减少锅铲直接与不粘层摩擦，延长锅身（1）不粘效果。

Description

一种具有凹凸结构的物理不粘锅及其制备方法 技术领域
本发明属于厨房用品领域，具体涉及一种具有凹凸结构的物理不粘锅及其制备方法。
背景技术
目前常规的不粘锅，需要在锅的内表面喷涂化学不粘涂层，这种化学不粘涂层在高温下容易分解失效，而且涂层在金属铲的使用下会很快破坏。为了使不粘锅具有不易粘、易清洗、快速平均的受热等特点，目前市面上有多种解决方案。比如CN201020591079.7为代表的在锅底部的顶面上布设多个凹槽形成纹路，并在凹槽中设置铁氟龙材质不粘层的解决方案。还有CN201310455227.0，对凹槽纹路的设置进行了深化设计，明确了凹槽条纹的长度、宽度、高度以及凸点的大小和高度，在此基础上喷涂不粘涂料，然后通过进一步的将锅身表面打磨等工艺成为最终产品。
以上解决方案虽然在一定程度上达到不粘的效果，但是存在同样的问题，都使用了化学材质的不粘涂层。众所周知，不粘锅的化学不粘涂层容易在高温烧菜时不粘性能失效或易脱落，从而导致炒菜食物粘锅和误食化学涂层等问题。
因此，生产不粘锅的厂商放弃以设置化学不粘层的方案来达到不粘的效果，而往物理不粘的方向来实现不粘的效果。以荷叶效应为原理来设计不粘层尤为突出；荷叶效应也叫作自清洁效应，主要应用在物体表面，可以实现防水防油的效果，具体而言，荷叶效应原理在于荷叶的上表面布满非常多乳突，平均大小约为53-57微米，它们也是由6-13微米大小的微型突起聚在一起构成，而这些乳突表面布满更多的体型更小的乳突，乳突的平均大小约为6-8微米，平均高度约为11-13微米，平均间距约19-21微米，乳突的顶端均呈扁平状且中央略微凹陷。这种乳突结构用肉眼以及普通显微镜是很难察觉的，通常被称作多重纳米和微米级的超微结构。这些大大小小的乳突和突起在荷叶表面上犹如一个挨一个隆起的“小山包”，“小山包”之间的凹陷部分充满空气，这样就在紧贴叶面上形成一层极薄，只有纳米级厚的空气层。水滴最小直径为1-2毫米(1毫米＝1000微米)，这相比荷叶表面上的乳突要大得多，因此雨水落到叶面上后，隔着一层极薄的空气，只能同叶面上“小山包”的顶端形成几个点的接触，从而不能浸润到荷叶表面上。水滴在自身的表面张力作用下形成球状体，水球在滚动中吸附灰尘，并滚出叶面，从而达到清洁叶面的效果。
而光将该结构应用于不粘锅表面，形成物理不粘层是远远不够的。因为，荷叶处于常温的环境中，会形成极薄的空气层，且滴落到荷叶上的水滴也是常温状态下或甚至温度偏 低情况下打落到荷叶上，但是不粘锅需要进一步的加热，其锅体的温度会不断上升甚至到达250多度以上，所以，将该结构应用于不粘锅上还无法完全达到不粘的效果。
因此，在荷叶效应原理的基础上进一步优化其物理不粘的方案，能够更有效地结合不粘锅使用环境特点，设计出一款以物理不粘方式的不粘锅。
此外，如果单单将以物理不粘方式设置在锅身表面还不足长久持续的不粘，因为每次进行作业时，锅铲需要多次反复与锅表面摩擦，那么长时间摩擦则磨损物理不粘层，进而无法达到长久不粘的效果，该问题也亟待解决。
发明内容
本发明的目的在于提供了一种具有保护物理不粘层不被破坏,而使锅体达到持久不粘效果。
为达上述目的，本发明的主要技术解决手段是提供一种具有凹凸结构的物理不粘锅，包括锅身，其特征在于，所述锅身内表面形成均匀分布的凹凸结构，所述凹凸结构包括凸起于锅内表面的凸棱以及由凸棱围合构成的凹陷区，所述物理不粘层至少设置在所述凹陷区的锅体内表面上。该方案下，由于物理不粘层至少设置在所述凹陷区的锅体内表面，而凸棱又与凹陷区有个高度落差，那么当锅铲反复进行刮擦时，只能位于凸棱表面上；采用凸棱保护凹陷区内的物理不粘层，避免物理不粘层被磨损，有利于实现长久的不粘效果，所述物理不粘层包括背景技术提到的荷叶效应原理中荷叶表面结构。
在一些实施例中，所述凹陷区的凸棱侧壁上也具有物理不粘层；增加该结构，在凹凸结构下保证不粘的效果，如果不设置，可能存在侧壁粘连的情况。
在一些实施例中，所述物理不粘层包括至少为微米级的粗糙面，所述粗糙面上进一步形成纳米级粗糙多孔结构的氧化膜；微米和纳米微观粗糙膜层在实际烹调使用时具有蓄油锁油作用，从而实现物理不粘功能；所述氧化膜的孔径能够随受热温度的改变而缩张，使用时用猪肉或动物油脂或油加热养锅后，所述氧化膜的孔径随着锅体温度上升而扩张，随着锅身温度下降而收缩；进一步说明，当使用者对锅身进行加热时，氧化膜的孔径扩张，便于油脂的出入；当停止对锅身进行加热时，锅身温度逐渐冷却，氧化膜的孔径收缩，进入孔内油脂就被锁入在内，进而实现锁油功能。
背景技术中已经说明了现有物理不粘原理在加热状态下的不足之处；而本方案在荷叶物理不粘基础上，结合锁油状态后的疏水效果；达到真正意义上的物理不粘。
在一些实施例中，所述粗糙面由数个至少为微米级的乳突构成，其中，至少为微米级应解释为微米级或纳米级。
在一些实施例中，所述粗糙面至少其表层的硬度为HV400～1100；一方面是不粘锅作业时，尽可能减低锅铲对锅身刮擦磨损，另一方面是防止钢丝球等洗锅工具刷锅时磨损粗糙面。
在一些实施例中，所述凹陷区面积占比整个凹凸结构的面积为80％～95％，为凸棱的占比整个凹凸结构的面积为5％～20％。虽然凸棱保护凹陷区内的物理不粘层不会铲掉或磨损掉；但是凸棱顶部未设置不粘层。故合理布局凸棱和凹陷区所占整个凹凸结构面积的百分比十分重要，如果凸棱占用面积较大，则会导致不粘锅效果降低；如凹陷区占用面积较大，则会导致凸棱对于凹陷区的保护降低，尤其是在钢丝球常年刷锅过程中，会逐渐损坏凹陷区内的物理不粘层。该部分布局即保证了凸棱设置能够保护物理不粘层，同时不影响不粘锅效果。
在一些实施例中，所述凹陷区的下凹深度为0.01～0.13毫米，下凹深度如果过于深的话，在炒菜过程中，下凹深度较大可能导致粘稠状食材(如鸡蛋)，部分区域下凹较深，与凸棱上的食材形成较高落差，而使食物分离；部分食材残留在凹陷区内，无法被铲出。
在一些实施例中，所述锅身为单层或多层复合结构。
还提供了一种具有凹凸结构的物理不粘锅的制作方法，包括如下步骤：
(1)凹凸结构处理：在金属材质的板材表面通过化学蚀刻或机械压制出均匀分布的凹凸结构；
(2)拉伸工序：利用设备将形成凹凸结构的板材制成锅身；
(3)喷砂工序：选用磨料，以压缩空气为动力，将磨料喷向锅身表面，使得锅身表面形成至少微米级的粗糙面。
在一些实施例中，(2)喷砂工序：选用36～130目的磨料，以0.4～0.8MPa压缩空气为动力，采用高速喷射设备将磨料喷向锅身内表面，并使得锅身表面形成多个至少为微米级的乳突构成的粗糙面。
在一些实施例中，还包括：(4)表面处理：对锅身表面进行硬化、氧化处理，在粗糙面上进一步形成纳米级粗糙的多孔结构的氧化膜。
在一些实施例中，(4)表面处理进一步包括：
(4.1)硬化工序：将锅身进行加热处理，锅身表面硬度达到HV400～1100；
(4.2)氧化工序：对达到硬化标准的锅身进行氧化处理，锅身的粗糙面上进一步形成纳米级粗糙的多孔结构的氧化膜。
在一些实施例中，所述(4.1)硬化工序：在进行热处理前，将锅身进行清洗，再放 入热处理炉内，在400～650摄氏度的环境内热处理0.5～24小时，使得锅身表面形成硬度为HV400～1100、厚度为3～35微米的硬化层。
在一些实施例中，所述(4.2)氧化工序：将形成硬化层的锅身放入装有液体或气体的处理炉内，并在400～500摄氏度的环境内氧化0.5～2小时。
在一些实施例中，还包括：(5)抛光工序：对锅身内表面的预设区域进行机械抛光，将凹凸结构中的凸棱处的粗糙面去除，保留凹凸结构中的凹陷区上的粗糙面，进而得到不粘锅的锅身。
本发明的有益效果是：
1.设置凹凸结构，凸棱保护设置在凹陷区的不粘层，减少锅铲直接与不粘层摩擦，延长锅身不粘效果。
2.仿荷叶的表面结构，结合了不粘锅所处的环境，在微观粗糙的氧化膜具有储存微小空气从而达到疏水效果。
3.对不粘锅进行养锅时，不粘锅的氧化膜可以实现锁油功能，并且养锅之后的锅体内表面，即使用中性洗涤剂清洗，仍具有类似荷叶不沾水的疏水性和物理不粘功能。
4.取消了化学不沾涂层的设置，使得不粘锅在使用时更为健康和卫生。
附图说明
图1是本发明一实施例的结构示意图，
图2是图1实施例的凹凸结构结合粗糙面的结构示意图，
图3是图1实施例的乳突上的纳米级粗糙的结构示意图，
图4是图1实施例的锅身为多层结构示意图，
图中：锅身1、凹凸结构11、凸棱111、凹陷区112、内层作业层12、中间导热层13、外层受热层14、乳突2、纳米级粗糙a。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本发明保护的范围。
本领域技术人员应理解的是，在本发明的揭露中，术语“纵向”、“横向”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”“内”、“外”等指示的方位或位置关系是基于附图所示的方位或位置关系，其仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此 上述术语不能理解为对本发明的限制。
可以理解的是，术语“一”应理解为“至少一”或“一个或多个”，即在一个实施例中，一个元件的数量可以为一个，而在另外的实施例中，该元件的数量可以为多个，术语“一”不能理解为对数量的限制。
实施例一：
参考本发明说明书附图之图1至图4所示，根据本发明一优选实施的一种具有凹凸结构的物理不粘锅被阐明，所述不粘锅的种类包括煮锅、煎锅、炒锅、奶锅等，本实施例以炒锅为例，其不粘锅包括锅身1，所述锅身1可以为单层或多层，锅身1为单层时材料可采用铁或不锈钢，所述不锈钢中的合金元素是Cr、Ni、Ti、Mn、N、Nb、Mo、Si、Cu等元素，其中主要合金元素是Cr。例如图1和图2，锅身1为单层，包括内层作业层12。锅身1为多层时材料可采用铁或不锈钢或复合材质，但无论单层还是多层至少其锅身1的内表面材质为铁或不锈钢，例如图3所述，锅身1为多层结构，从内到外依次包括内层作业层12、中间导热层13以及外层受热层14，那么至少内层作业层12的表面材料采用铁或不锈钢，此外，锅身1表面材质不能采用铝合金；所述锅身1内表面具有物理不粘层，物理不粘层包括至少为微米级的粗糙面，至少为微米级应解释为微米级或纳米级；所述粗糙面上进一步形成纳米级粗糙多孔结构的氧化膜，微米和纳米微观粗糙膜层在实际烹调使用时具有蓄油锁油作用，从而实现物理不粘功能；需要说明氧化膜形成的纳米级粗糙主要是由氧化工序产生的氧化物颗粒生成。如铁锅的氧化物(氧化铁)，不锈钢的氧化膜(主要成分为三氧化二铬等)，所述氧化膜的孔径能够随受热温度的改变而缩张，因为氧化膜是由基体金属生成的，与基体金属结成为一个整体，与基体结合牢固，此外，氧化膜耐热性能优良。
具体而言，所述粗糙面由数个至少为微米级的乳突2构成，所述粗糙面至少其表层的硬度达到HV400～1100，所述锅身1内表面形成均匀分布的凹凸结构11，所述凹凸结构11包括凸起于锅体底壁内表面的凸棱111以及由凸棱111围合构成的凹陷区112，所述物理不粘层至少设置在所述凹陷区112的锅体内表面上，所述凹陷区112的凸棱111侧壁上也设有物理不粘层，增加该结构在凹凸结构下保证不粘的效果，如果不设置，可能存在侧壁粘连的情况；凸棱111的设置是为了保护凹陷区112的锅体内表面上的物理不粘层，因为如果没有凸棱111的话，在炒菜时，锅铲将直接反复在物理不粘层进行接触摩擦，长时间这样的工作，将磨损粗糙面，进而无法继续有不粘的效果，所述凹陷区112面积占比整个凹凸结构11的面积为80％～95％，为凸棱111的占比整个凹凸结构11的面积为5％～20％，所述凹陷区112的下凹深度为0.01～0.13毫米，在本实施例中，优选的下凹深度为0.05～0.06毫米， 下凹深度如果过于深的话，在炒菜过程中，下凹深度较大可能导致粘稠状食材(如鸡蛋)，部分区域下凹较深，与凸棱上的食材形成较高落差，而使食物分离；部分食材残留在凹陷区内，无法被铲出；总而言之，该方案下，由于物理不粘层至少设置在所述凹陷区的锅体内表面，而凸棱又与凹陷区有个高度落差，那么当锅铲反复进行刮擦时，只能位于凸棱表面上，进而实现了利用凸棱保护凹陷区内的不粘层，避免物理不粘层被磨损，有利于实现长久的不粘效果。
当使用者初次使用时用猪肉或动物油脂或油加热养锅后，所述氧化膜的孔径随着锅体温度上升而扩张，随着锅身1温度下降而收缩；进一步说明，当使用者对锅身1进行加热时，氧化膜的孔径扩张，便于油脂的出入；当停止对锅身1进行加热时，锅身1温度逐渐冷却，氧化膜的孔径收缩，进入孔内油脂就被锁入在内，进而实现锁油功能。背景技术中已经说明了现有物理不粘原理在加热状态下的不足之处；而本方案在荷叶物理不粘基础上，结合锁油状态后的油脂拒水效果；达到真正意义上的物理不粘。
需要特别指出，目前的实验中发现，采用上述结构下；铁锅和不锈钢锅能够实现上述锁油；但在铝锅上尝试无法实现，铝锅上采用硬质阳极氧化，能产生微米级和纳米级粗糙表面，但不粘效果差；从而只能通过涂层实现不粘。
实施例二：
一种实施例一所述不粘锅的制作方法被阐述，包括如下步骤：
(1)锅身1制作：利用将板材制成锅身1；
(2)喷砂工序：选用磨料，以压缩空气为动力，将磨料喷向锅身1表面，使得锅身1表面形成至少微米级的粗糙面；
(3)表面处理：对锅身1表面进行硬化、氧化处理，在粗糙面上进一步形成纳米级粗糙多孔结构的氧化膜。
(4)打磨工序：对锅身1内表面的预设区域进行机械打磨，将凹凸结构11中的凸棱111处的粗糙面去除，保留凹凸结构11中的凹陷区112上的粗糙面，进而得到不粘锅的锅身1；由于凸棱顶部未设置不粘层；说明该部分布局即保证了凸棱设置能够保护物理不占层，同时不影响不粘锅效果。
(5)清洗和包装工序：将锅身1用超声波去抛光蜡，再用去离子热水清洗干净后，铆接手柄包装成品。
具体而言，在本实施例中，(1)锅身1制作进一步包括：
(1.1)凹凸结构11处理：在铁或不锈钢的板材表面通过化学蚀刻或机械压制出均匀分布的凹 凸结构11；下凹深度0.01～0.13毫米，优选的下凹深度为0.05～0.06毫米，下凹深度如果过于深的话，在炒菜过程中，食物可能会残留在凹陷区112内，而无法被铲出；凹凸结构11的凸棱111的横截面可以为半圆形或矩形；在铁板或不锈钢板表面通过化学蚀刻或雕刻或滚压方法形成凹凸结构11，雕刻包括切削雕刻和激光雕刻，其中，机械压制使用范围广，激光雕刻，可以制作更加精密的花纹；当化学蚀刻或机械压制工序后，以达到凸棱111占比整个凹凸结构11的面积为5％～20％，凹陷区112面积占比整个凹凸结构11的面积为80％～95％，上述两个面积占比范围只是本实施方式所产生的情况，总体来说只需要尽量减少凸棱111占比范围，增大凹陷区112面积的占比范围即可；烹调时金属铲使用，并不会破坏下凹处坚硬的物理不粘层，以达到锅能提供长期的物理不粘效果。
(1.2)拉伸工序：利用拉伸机将形成凹凸结构11的铁板材或不锈钢板材拉伸制成锅身1，并将锅边沿修整圆滑，所述锅身1的厚度为0.3～8毫米，优选锅身1厚度为0.6～5毫米。
在本实施例中，(2)喷砂工序：选用36～130目的磨料，以0.4～0.8MPa压缩空气为动力，采用高速喷射设备(例如喷枪等)将磨料喷向锅身1内表面，将其内表面杂质彻底清除，并使得锅身1表面形成多个至少为微米级的乳突构成的粗糙面，所述磨料采用棕刚玉或白刚玉等。
在本实施例中，(3)表面处理进一步包括：
(3.1)硬化工序：将喷砂工序完成后的锅身1进行清洗，清洗干净锅身1放入装有气体或液体热处理炉，在400～650摄氏度的环境内热处理0.5～24小时，使得锅身1表面形成硬度为HV400～1100、厚度为3～35微米的硬化层；
(3.2)氧化工序：对达到硬化标准的锅身1进行氧化处理，即将形成硬化层的锅身1放入装有液体或气体的处理炉内，并在400～500摄氏度的环境内氧化0.5～2小时，进而锅身1的粗糙面上进一步形成纳米级粗糙多孔结构的氧化膜。
进一步需要说明，硬化工序和氧化工序这两个步骤可以放置在同一个处理炉里完成，也可以分开完成两步工序；此外，完成硬化工序和氧化工序后，锅身1表面在通过显微镜观察下，可见锅内表面形成了具有3-35微米厚度和硬度为HV400～1100的微米级粗糙面，粗糙面上进一步形成有纳米级粗糙多孔结构的氧化膜，由此该表面结构成为具有不粘特性的物理不粘层，而此时的凸棱111表面上也存在粗糙面以及纳米级粗糙多孔结构的氧化膜。
在本实施例中，为了去除凸棱111上的粗糙面，所述不粘锅的制作方法中的步骤(4)抛光工序工序具体是：为了不破坏锅内表面的微纳结构，锅内表面采用软布轮进行抛光，进 而打磨掉凸棱111出的粗糙面，使得凸棱111表面变得相对光滑；而锅外表面的打磨采用60～320目尼龙轮对其抛光，可有效防止锅身1在燃气灶上打滑。
综述：
从上述的实施例一以及实施例二，可以看出，本发明上述的实施例实现了如下技术效果：
锅身1经热处理硬化和氧化后，其颜色为深灰色或黑色，为一般消费者所青睐；但是一般金属基材锅具使用容易粘锅，因此本申请进一步在锅内表面设置了硬化处理的微米级或纳米级粗糙面的物理不粘层，经消费者初次使用时用猪肉或动物油脂或油加热养锅后，锅身1温度上升，其纳米级粗糙的氧化膜的孔径随温度而扩张，猪肉或动物油脂或油从孔进入，当停止对锅身1进行加热时，锅身1温度逐渐冷却，其纳米级粗糙氧化膜的孔径随温度而收缩，将油脂锁入在内，进而产生蓄油作用，当下次需要对锅身1加热炒菜时，油脂再次出入，微米或纳米结构的粗糙面结合锁油效果进而避免炒菜粘锅的现象，实现物理不粘的效果。养锅之后的锅体内表面，即使用中性洗涤剂清洗，仍具有类似荷叶不沾水的疏水性和物理不粘功能。
本发明依据在荷叶效应的仿生原理的基础上，再结合锅身1使用环境的特点进行总体设计，通过在锅身1内表面形成微米级或纳米级粗糙结构结合在粗糙面上进一步形成纳米级粗糙多孔结构的具有锁油功能的氧化膜，使其具有无需喷涂化学涂料也能达到不粘的效果，也改变了长期以来业界认为锅底尽可能的平滑才能不粘的观点，获得了预料不到的不粘效果，有效解决了业界长久以来依赖化学涂层提升不粘效果而无法解决高温烧菜时不粘性能失效或易脱落的问题，使人们的饮食更加健康。需要特别指出的是，本发明除了创造性的提出了依据荷叶不沾水的仿生原理，通过在锅身1内表面形成亚毫米级、微米级和/或纳米级多元粗糙结构，使其具有无需喷涂化学涂料即具有不粘的效果之外，本发明提及的喷砂、热处理及氧化等工序的工艺参数组合是保障最佳不粘效果的重要因素，工艺参数的组合也是本发明的发明点之一。表面微米级和纳米级粗糙面的形成以及硬化层的形成都需要严格控制喷砂、热处理等工作的各项工艺参数才能达到理想的不粘性能，本发明提出的工艺参数是发明人经过大量的实验，反复的校正才摸索出来的，不是本领域技术人员凭想象或者简单的推理就能得到的。要达到最佳的效果，还需要使用本发明的工艺参数组合。
本发明不局限于上述最佳实施方式，任何人在本发明的启示下都可得出其他各种形式的产品，但不论在其形状或结构上作任何变化，凡是具有与本申请相同或相近似的技术方案，均落在本发明的保护范围之内。

Claims (15)

  1. 一种具有凹凸结构的物理不粘锅，包括锅身，其特征在于，所述锅身内表面形成均匀分布的凹凸结构，所述凹凸结构包括凸起于锅内表面的凸棱以及由凸棱围合构成的凹陷区，所述物理不粘层至少设置在所述凹陷区的锅体内表面上。
  2. 根据权利要求1所述的具有凹凸结构的物理不粘锅，其特征在于，所述凸棱侧壁上也设有物理不粘层。
  3. 根据权利要求1所述的具有凹凸结构的物理不粘锅，其特征在于，所述物理不粘层包括至少为微米级的粗糙面，所述粗糙面上进一步形成纳米级粗糙多孔结构的氧化膜；微米和纳米微观粗糙膜层在实际烹调使用时具有蓄油锁油作用，从而实现物理不粘功能。
  4. 根据权利要求3所述的具有凹凸结构的物理不粘锅，其特征在于，所述粗糙面由数个至少为微米级的乳突构成。
  5. 根据权利要求3所述的具有凹凸结构的物理不粘锅，其特征在于，所述粗糙面至少其表层的硬度为HV400～1100。
  6. 根据权利要求1所述的具有凹凸结构的物理不粘锅，其特征在于，所述凹陷区面积占比整个凹凸结构的面积为80％～95％，凸棱的占比整个凹凸结构面积的5％～20％左右。
  7. 根据权利要求1所述的具有凹凸结构的物理不粘锅，其特征在于，所述凹陷区的下凹深度为0.01～0.13毫米。
  8. 根据权利要求1所述的具有凹凸结构的物理不粘锅，其特征在于，所述锅身为单层或多层复合结构。
  9. 一种具有凹凸结构的物理不粘锅的制备方法，其特征在于，包括如下步骤：
    (1)凹凸结构处理：在金属材质的板材表面通过化学蚀刻或机械压制出均匀的凹凸结构；
    (2)拉伸工序：利用设备将形成凹凸结构的板材制成锅身；
    (3)喷砂工序：选用磨料，以压缩空气为动力，将磨料喷向锅身表面，使得锅身表面形成至少微米级的粗糙面。
  10. 根据权利要求9所述的具有凹凸结构的物理不粘锅的制备方法，其特征在于，(2)喷砂工序：选用36～130目的磨料，以0.4～0.8MPa压缩空气为动力，采用高速喷射设备将磨料喷向锅身内表面，并使得锅身表面形成多个至少为微米级的乳突构成的粗糙面。
  11. 根据权利要求9所述的具有凹凸结构的物理不粘锅的制备方法，其特征在于，还包括：
    (4)表面处理：对锅身表面进行硬化、氧化处理，在粗糙面上进一步形成纳米级粗糙多孔结构的氧化膜。
  12. 根据权利要求11所述的具有凹凸结构的物理不粘锅的制备方法，其特征在于，(4)表 面处理进一步包括：
    (4.1)硬化工序：将锅身进行热处理，锅身表面硬度达到HV400～1100；
    (4.2)氧化工序：对达到硬化标准的锅身进行氧化处理，锅身的粗糙面上进一步形成纳米级粗糙多孔结构的氧化膜。
  13. 根据权利要求12所述的具有凹凸结构的物理不粘锅的制备方法，其特征在于，所述(4.1)硬化工序：在进行热处理前，将锅身进行清洗，再放入热处理炉内，在400～650摄氏度的环境内热处理0.5～24小时，使得锅身表面形成硬度为HV400～1100、厚度为3～35微米的硬化层。
  14. 根据权利要求12所述的具有凹凸结构的物理不粘锅的制备方法，其特征在于，所述(4.2)氧化工序：将形成硬化层的锅身放入装有液体或气体的处理炉内，并在400～500摄氏度的环境内氧化0.5～2小时。
  15. 根据权利要求11所述的具有凹凸结构的物理不粘锅的制备方法，其特征在于，还包括：(5)打磨工序：对锅身内表面的预设区域进行机械抛光，将凹凸结构中的凸棱处的粗糙面去除，保留凹凸结构中的凹陷区上的粗糙面，进而得到不粘锅的锅身。
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CN211704307U (zh) * 2019-12-11 2020-10-20 江门市依山金属制品有限公司 一种具有凹凸花纹的不粘锅
CN111493648A (zh) * 2020-04-07 2020-08-07 浙江巴赫厨具有限公司 一种物理不粘锅及其制备方法

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CN114190774A (zh) * 2021-12-17 2022-03-18 武汉苏泊尔炊具有限公司 炊具及其制造方法
CN114190774B (zh) * 2021-12-17 2023-08-04 武汉苏泊尔炊具有限公司 炊具及其制造方法
CN115778164A (zh) * 2022-11-30 2023-03-14 浙江尚厨家居科技股份有限公司 一种无涂层不粘锅具及其制作方法
WO2024113983A1 (zh) * 2022-11-30 2024-06-06 西藏尚厨炊具科技有限公司 一种无涂层不粘锅具及其制作方法
CN116288138A (zh) * 2023-03-03 2023-06-23 浙江尚厨家居科技股份有限公司 一种无涂层不粘锅制造方法
WO2024207737A1 (zh) * 2023-04-07 2024-10-10 九阳股份有限公司 一种易清洗电热锅

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