WO2020235844A1

WO2020235844A1 - Method for manufacturing cooking utensil comprising thermochromatic composite coating layer and cooking utensil manufactured thereby

Info

Publication number: WO2020235844A1
Application number: PCT/KR2020/006085
Authority: WO
Inventors: 손재봉
Original assignee: 주식회사 셰프라인
Priority date: 2019-05-22
Filing date: 2020-05-08
Publication date: 2020-11-26
Also published as: KR102085595B1; JP6874106B2; CN113873924A; JP2020189076A

Abstract

The present invention relates to a method for manufacturing a cooking utensil comprising a thermochromatic composite coating layer and a cooking utensil manufactured thereby. In a specific embodiment, the method for manufacturing a cooking utensil comprising a thermochromatic composite coating layer comprises the steps of: forming a primer layer comprising a fluorine-based resin on the surface of a metal base; forming a toning layer by applying a toning coating agent comprising matrix resin and a toning pigment onto at least a portion of the surface of the primer layer; forming a thermochromatic layer by applying a thermochromatic coating agent comprising a thermochromatic compound and a chromatic pigment onto at least a portion of the surface of the primer layer; and forming a top coating layer by applying a top coating agent onto the surface of the primer layer with the thermochromatic layer formed thereon and heat-treating same, wherein the top coating agent comprises: 100 parts by weight of a fluorine-based base resin; 10-50 parts by weight of an alkoxy silane compound; 5-50 parts by weight of a first pigment; 0.5-15 parts by weight of molybdenum disulfide; and 1-15 parts by weight of a phosphate ester-based compound.

Description

Cooking utensil manufacturing method including thermochromic composite coating layer and cooking utensil manufactured thereby

The present invention relates to a cooking utensil manufacturing method including a thermochromic composite coating layer and a cooking utensil manufactured thereby.

The heating cookware, such as a frying pan, a grilling plate, and a pot, is made of a metal material, and the heating cookware has a coating layer having heat resistance and corrosion resistance on a surface where the food material to be cooked directly contacts.

On the other hand, when cooking using such a cooking utensil for heating, there is a problem in that it is difficult for a user to accurately determine how much the cooking utensil is heated to the fire. In order to solve this problem, cooking utensils capable of grasping the heating state by thermal discoloration of the coating layer have been produced by applying and curing a coating agent including a Zion pigment on the surface of the cooking utensil to form a thermochromic coating layer.

As a background technology related to the present invention, Republic of Korea Patent Publication No. 10-1686414 (announced on December 14, 2016, title of the invention: a ceramic coating layer capable of displaying a heating state and a method of manufacturing a ceramic paint, a coating method thereof, and a heating device using the coating method. ).

One object of the present invention is to provide a cooking utensil manufacturing method including a thermochromic composite coating layer capable of easily identifying the heating state of the cooking utensil.

Another object of the present invention is to provide a cooking utensil manufacturing method including a thermochromic composite coating layer having excellent wear resistance, durability, and interlayer adhesion of the composite coating layer.

Another object of the present invention is to provide a cooking utensil manufacturing method including a thermochromic composite coating layer having excellent thermal conductivity and antifouling properties and excellent non-stick properties in which food materials do not stick to the surface of the composite coating layer during cooking. Is to do.

Another object of the present invention is to provide a cookware manufactured by the cookware manufacturing method.

One aspect of the present invention relates to a method for manufacturing a cookware including a thermochromic composite coating layer. In one embodiment, the cooking appliance manufacturing method including the thermochromic composite coating layer comprises: forming a primer layer containing a fluorine-based resin on a surface of a metal substrate; Forming a toning layer by applying a toning coating comprising a matrix resin and a toning pigment to at least a portion of the surface of the primer layer; Forming a thermochromic layer by applying a thermochromic coating agent including a thermochromic compound and a color change pigment on at least a portion of the surface of the primer layer; And applying a top coating agent to the surface of the primer layer on which the thermochromic layer is formed and heat treatment to form a top coating layer, wherein the top coating agent includes 100 parts by weight of a fluorine-based base resin; 10 to 50 parts by weight of an alkoxy silane compound; 5 to 50 parts by weight of the first pigment; 0.5 to 15 parts by weight of molybdenum disulfide; And 1 to 15 parts by weight of a phosphate ester compound, wherein the toning pigment contains titanium oxide, and the color change pigment contains iron oxide red.

In one embodiment, the heat treatment may be performed at 380 to 450°C.

In one embodiment, the top coating agent further includes 0.5 to 5 parts by weight of germanium oxide based on 100 parts by weight of the fluorine-based base resin, and the germanium oxide and phosphoric acid ester compound may be included in a weight ratio of 1:1 to 1:5.

In one embodiment, the toning layer and the thermochromic layer may be formed using pad printing, respectively.

In one embodiment, the primer layer includes 100 parts by weight of a fluorine-based base resin; 1 to 40 parts by weight of a second pigment; 1 to 15 parts by weight of a phosphoric acid ester compound; And germanium oxide 0.5 to 5 parts by weight; It may be formed from a primer comprising a.

In one embodiment, the fluorine-based resin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ) May include one or more of.

In one embodiment, the toning coating agent comprises 100 parts by weight of a matrix resin and 0.5 to 50 parts by weight of a toning pigment, and the thermochromic coating agent includes 100 parts by weight of a thermochromic compound and 0.5 to 30 parts by weight of a color change pigment, and the thermochromic The compound may include one or more of a mercury iodide complex salt and a vanadium oxide.

In one embodiment, the first pigment may include at least one of carbon black, perylene red, manganese ferrite black, copper chromite black, bismuth vanadate, iron hydroxide yellow, chromium oxide green, and cobalt aluminate blue.

Another aspect of the present invention relates to cookware manufactured by the cookware manufacturing method. In one embodiment, the cookware is a metal substrate; A primer layer comprising a fluorine-based resin formed on at least one surface of the metal substrate; A toning layer formed on at least a portion of the surface of the primer layer; A thermochromic layer formed on at least a portion of the surface of the primer layer; And a top coating layer formed on the surface of the primer layer and the thermochromic layer, wherein the top coating layer comprises: 100 parts by weight of a fluorine-based base resin; 10 to 50 parts by weight of an alkoxy silane compound; 5 to 50 parts by weight of the first pigment; 0.5 to 15 parts by weight of molybdenum disulfide; And 1 to 15 parts by weight of a phosphate ester compound; and the toning layer is formed from a toning coating comprising a matrix resin and a toning pigment, and the thermochromic layer is a thermochromic compound and a color change pigment It is formed from a thermochromic coating comprising a, the toning pigment includes titanium oxide, the color change pigment includes iron oxide red.

When the cookware including the thermochromic composite coating layer according to the present invention is applied, the thermochromic layer does not appear on the surface at room temperature, and when heated above a predetermined temperature, the thermochromic layer appears on the surface of the cookware, making it possible to identify. It is possible to easily identify the heating state of cooking utensils, and the abrasion resistance, durability of the thermochromic composite coating layer and the adhesion between the layers of the composite coating layer are excellent, thermal conductivity is excellent, and antifouling properties are excellent, making it easy to clean and manage. , When cooking, food ingredients do not stick to the surface of the composite coating layer, and non-stick properties may be excellent.

1 is a flow chart showing a cooking utensil manufacturing method according to an embodiment of the present invention.

Figure 2 schematically shows a cooking utensil manufacturing method of the present invention.

3 is a photograph of a cookware manufactured according to Example 1.

4 is a photograph of the cookware manufactured according to Example 1 after heating.

In describing the present invention, if it is determined that a detailed description of a related known technology or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In addition, terms to be described later are terms defined in consideration of functions in the present invention and may vary according to the intentions or customs of users and operators, and thus their definitions should be made based on the contents throughout the present specification describing the present invention.

열변색성 복합코팅층을 포함하는 조리기구 제조방법Cookware manufacturing method including a thermochromic composite coating layer

One aspect of the present invention relates to a method for manufacturing a cookware including a thermochromic composite coating layer. 1 is a flow chart showing a cooking utensil manufacturing method according to an embodiment of the present invention, Figure 2 schematically shows the cooking utensil manufacturing method of the present invention. 1 and 2, the cooking utensil manufacturing method includes (S10) forming a primer layer; (S20) forming a toning layer; (S30) forming a thermochromic layer; And (S40) forming a top coating layer and heat treatment step. More specifically, the cooking appliance manufacturing method including the thermochromic composite coating layer includes the steps of (S10) forming a primer layer containing a fluorine-based resin on the surface of a metal substrate; (S20) forming a toning layer by applying a toning coating comprising a matrix resin and a toning pigment to at least a portion of the surface of the primer layer; (S30) forming a thermochromic layer by applying a thermochromic coating agent including a thermochromic compound and a discoloration pigment to at least a portion of the surface of the primer layer; And (S40) forming a top coating layer by applying a top coating agent to the surface of the primer layer on which the thermochromic layer is formed and heat treatment.

In the present specification, the term "thermochromic composite coating layer" is to be defined as including a primer layer, a toning layer, a thermochromic layer, and a top coating layer.

Hereinafter, a method for manufacturing a cookware including a thermochromic composite coating layer according to the present invention will be described in detail step by step.

(S10) 프라이머층 형성단계(S10) Primer layer formation step

The step is a step of forming a primer layer by applying and drying a primer agent containing a fluorine-based resin on at least a portion of the metal substrate.

Referring to FIG. 2(a), the primer layer 20 may be formed on a surface where the metal substrate 10 and the food are in contact. In one embodiment, the metal substrate 10 may include one or more of aluminum, aluminum alloy, copper, magnesium, aluminum plated steel, iron, and stainless steel.

In one embodiment, before applying the primer agent, the surface of the metal substrate to which the primer agent is to be applied may be subjected to sand blasting. During the sand blasting, the surface area of the metal substrate is increased, so that adhesion of the primer layer may be excellent.

In one embodiment, the primer layer includes 100 parts by weight of a fluorine-based base resin; 5 to 50 parts by weight of a second pigment; 1 to 15 parts by weight of a phosphoric acid ester compound; And germanium oxide 0.5 to 5 parts by weight; may be formed from a primer comprising a.

In one embodiment, the fluorine-based resin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ) May include one or more of. When the fluorine-based resin is applied, the primer layer may have excellent chemical resistance, abrasion resistance, durability and heat resistance. For example, it may include one or more of polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

In one embodiment, the second pigment may include at least one of carbon black, perylene red, manganese ferrite black, copper chromite black, bismuth vanadate, iron hydroxide yellow, chromium oxide green, and cobalt aluminate blue. For example, manganese ferrite black and perylene red may be included. In one embodiment, the second pigment may be included in 1 to 40 parts by weight based on 100 parts by weight of the fluorine-based resin. When included in the above range, it is possible to prevent degradation of durability and mechanical properties of the primer layer without deteriorating the mixability and dispersibility of the primer agent. For example, 5 to 20 parts by weight may be included.

In one embodiment, the average particle diameter of the second pigment may be 5 ~ 30㎛. In the above range, dispersibility and mixing properties may be excellent.

The phosphoric acid ester compound may be included for the purpose of improving durability of the primer layer of the present invention and adhesion to the substrate. The phosphoric acid ester compound may be a phosphoric acid ester compound including at least one of a hydroxy group and a carboxyl group.

In one embodiment, the phosphoric acid ester-based compound is included in 1 to 15 parts by weight based on 100 parts by weight of the fluorine-based resin. When included in the above range, the durability and adhesion of the primer layer are excellent, and the viscosity of the primer agent can be prevented from being excessively increased. For example, 1 to 8 parts by weight may be included.

The germanium oxide may be included for the purpose of improving interlayer adhesion between the metal substrate, the primer layer and the top coating layer of the present invention. In one embodiment, the germanium oxide is included in 0.5 to 5 parts by weight based on 100 parts by weight of the fluorine-based resin. Under the above conditions, the mixing and dispersibility of the primer agent of the present invention may be excellent, and interlayer adhesion of the primer layer may be excellent. For example, 1 to 3 parts by weight may be included.

In one embodiment, the germanium oxide and phosphoric acid ester compound may be included in a weight ratio of 1:1 to 1:5. When included in the above weight ratio range, the blendability and workability of the primer agent are excellent, and interlayer adhesion and durability of the primer layer can be achieved. For example, germanium oxide and phosphoric acid ester compounds may be included in a weight ratio of 1:2 to 1:4.

In one embodiment, the primer agent may further include a solvent. The solvent is water, alcohol having 1 to 10 carbon atoms, toluene, xylene, diisobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, ethanol, Butyl cellosolve, cyclohexane, n-butyl acetate, N-methylpyrrolidone, dimethylformamide, ethyl acetate, acetone, methyl acetate, isobutyl acetate, isopropyl acetate, and dimethyl carbonate. In one embodiment, the alcohol having 1 to 10 carbon atoms may include one or more of methanol, ethanol, propanol, isopropanol, n-butanol, and isobutanol.

The solvent may be included in an amount of 10 to 500 parts by weight based on 100 parts by weight of the fluorine-based base resin. When included in the above range, it is easy to adjust the viscosity of the components of the primer agent, and dispersibility and workability may be excellent.

In one embodiment, the primer agent may further include additives such as a surfactant, a leveling agent, and an antifoaming agent. The additive may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the fluorine-based base resin.

The primer agent can be prepared by a conventional method.

In one embodiment, the primer may be applied and dried at 80 to 160°C to form a primer layer. When drying under the above conditions, the smoothness and durability of the primer layer may be excellent. The primer may be applied by a conventional method. For example, it can be applied using an air spray gun.

In one embodiment, the primer agent may be applied one or more times by changing the color of the second pigment, respectively. For example, 100 parts by weight of a fluorine-based base resin on one side of the metal substrate; 5 to 50 parts by weight of a second pigment including perylene red; 1 to 15 parts by weight of a phosphoric acid ester compound; And 0.5 to 5 parts by weight of germanium oxide; after forming a first primer layer by applying a first primer comprising: 100 parts by weight of a fluorine-based base resin on at least a portion of the surface of the first primer layer; 5 to 50 parts by weight of a second pigment including manganese ferrite black or carbon black; 1 to 15 parts by weight of a phosphoric acid ester compound; And 0.5 to 5 parts by weight of germanium oxide, and drying at 80 to 160° C. to form a second primer layer. When drying under the above conditions, the smoothness and durability of the primer layer may be excellent. The primer may be applied by a conventional method. For example, it can be applied using an air spray gun.

In one embodiment, the thickness of the primer layer may be 5 ~ 30㎛. The durability of the primer layer may be excellent under the above thickness condition.

(S20) 조색층 형성단계(S20) Toning layer formation step

The step is a step of forming a toning layer including a matrix resin and a toning pigment on at least a part of the surface of the primer layer. In the above step, a toning layer 30 may be formed by pad printing a toning coating agent on at least a part of the surface of the primer layer 20 as shown in FIG. 2(b).

In one embodiment, the toning coating agent may include a matrix resin and a toning pigment. When included in the above range, workability and durability of the toning layer may be excellent.

For example, the matrix resin may include one or more of polyether ether ketone, polyurethane, polyethylene sulfide, polyphenylene sulfide, ethyl cellulose, polyvinyl alcohol, and polyvinylpyrrolidone, but is not limited thereto.

In one embodiment, the toning pigment includes titanium oxide. The titanium oxide (TiO ₂ ) is used to represent a white color, and the color (pattern) of the thermochromic layer that appears when heating the cooking utensils to be described later can be more clearly identified.

In one embodiment, the average particle diameter of the toning pigment may be 5 ~ 30㎛. In the above range, the dispersibility and heat discoloration effect may be excellent.

In one embodiment, the toning coating agent may include 100 parts by weight of the matrix resin and 0.5 to 50 parts by weight of the toning pigment. When included in the above range, the dispersibility and mixing properties of the toning coating agent components are excellent, and the adhesion of the coating layer may be excellent.

In one embodiment, the toning coating agent may further include a solvent. The solvent is water, alcohol having 1 to 10 carbon atoms, toluene, xylene, diisobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, ethanol, Butyl cellosolve, cyclohexane, N-methylpyrrolidone, dimethylformamide, n-butyl acetate, ethyl acetate, acetone, methyl acetate, isobutyl acetate, isopropyl acetate, and dimethyl carbonate. In one embodiment, the alcohol having 1 to 10 carbon atoms may include one or more of methanol, ethanol, propanol, isopropanol, n-butanol, and isobutanol.

In one embodiment, the solvent may be included in an amount of 10 to 300 parts by weight based on 100 parts by weight of the matrix resin. When included in the above range, it is easy to adjust the viscosity of the components of the toning coating agent, and it may be excellent in mixability, dispersibility and workability.

In one embodiment, the toning coating may be dried after pad printing or application. The drying may be carried out under the conditions of 80 ~ 150 ℃. Durability of the toning layer may be excellent under the above conditions.

In one embodiment, the thickness of the toning layer may be 1 ~ 30㎛. Durability of the toning layer may be excellent under the above thickness condition.

(S30) 열변색층 형성단계(S30) Thermochromic layer forming step

The step of forming a thermochromic layer 40 by pad printing a thermochromic coating agent containing a thermochromic compound and a color change pigment on at least a part of the surface of the primer layer 20 as shown in FIG. 2(c). to be.

In one embodiment, the thermochromic coating agent may include 100 parts by weight of a thermochromic compound and 0.5 to 30 parts by weight of a color change pigment. When included in the above range, workability and heat discoloration efficiency and reliability may be excellent.

In the case of a conventional heating device, a phenomenon in which heat discoloration occurs when heated above a predetermined temperature is used, but there is a problem in that it is difficult to identify the heating state because it is not easy to check the heat discoloration during heating. On the other hand, in the present invention, discoloration of the thermochromic layer does not occur at room temperature, so that the thermochromic layer (pattern) is not visible, but when heated above a predetermined temperature, discoloration (pattern) of the thermochromic layer appears. It was found that it can be easily identified. In particular, in one embodiment, a red pigment such as perylene red is applied to the first or second pigment of the primer layer or the top coating layer, so that the thermochromic layer and the color are combined to be formed so that it is not visible to the naked eye at room temperature. May be.

In one embodiment, the color change pigment includes iron oxide red. When a thermochromic layer is formed using the discoloration pigment under the above conditions, it is possible to have excellent discernability and excellent aesthetics to the user. Particularly, at room temperature, the color (or pattern) of the thermochromic layer does not appear on the surface of the cookware, and when heated to a predetermined temperature, the color (or pattern) is discolored and thus the color (or pattern) appears, thereby providing excellent identification.

In one embodiment, the average particle diameter of the color change pigment may be 5 ~ 30㎛. In the above range, the dispersibility and heat discoloration effect may be excellent.

In one embodiment, the color change pigment may be included in 0.5 to 30 parts by weight based on 100 parts by weight of the thermochromic compound. When included in the above range, the dispersibility and workability of the components of the thermochromic coating agent may be excellent. When included in the above range, workability and heat discoloration efficiency and reliability may be excellent.

The thermochromic compound may include at least one of a mercury iodide complex salt and a vanadium oxide.

In one embodiment, the mercury iodide complex salt may include at least one of disilver tetraiodomercurate (Ag ₂ HgI ₄ ) and dicoper tetraiodomercurate (Cu ₂ HgI ₄ ). .

In one embodiment, the thermochromic coating agent may further include a solvent. The solvent is water, alcohol having 1 to 10 carbon atoms, toluene, xylene, diisobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, ethanol, Butyl cellosolve, cyclohexane, n-butyl acetate, N-methylpyrrolidone, dimethylformamide, ethyl acetate, acetone, methyl acetate, isobutyl acetate, isopropyl acetate, and dimethyl carbonate. In one embodiment, the alcohol having 1 to 10 carbon atoms may include one or more of methanol, ethanol, propanol, isopropanol, n-butanol, and isobutanol.

In one embodiment, the solvent may be included in an amount of 10 to 300 parts by weight based on 100 parts by weight of the thermochromic compound. When included in the above range, the dispersibility and workability of the components of the thermochromic coating agent may be excellent.

In one embodiment, the thermochromic layer may be formed using pad printing.

In one embodiment, the thermochromic coating may be dried after pad printing or application. In one embodiment, the drying may be performed under conditions of 80 to 150°C. Durability of the thermochromic layer may be excellent under the above conditions.

In one embodiment, the thickness of the thermochromic layer may be 1 to 30 μm. Durability of the thermochromic layer may be excellent under the above thickness condition.

(S40) 탑코팅층 형성 및 열처리 단계(S40) Top coating layer formation and heat treatment step

The step is a step of forming a top coating layer 50 by applying a top coating agent containing a fluorine-based resin on the surface of the primer layer on which the thermochromic layer 40 is formed as shown in FIG. 2(d) and heat treatment. In one embodiment, the top coating layer may be formed on the surface of the toning layer 30, the surface of the thermochromic layer 40, and the surface of the primer layer 20 as shown in FIG. 2(d). If the heat treatment is not applied, defects may occur, such as a decrease in adhesion of the coating layer and a decrease in surface smoothness of the coating layer.

The top coating layer may prevent damage to the toning layer and the thermochromic layer, have excellent non-stick properties of cooked food materials, and have excellent wear resistance, thermal conductivity, chemical resistance, smoothness and durability.

In addition, when the top coating layer of the present invention is formed, the thermochromic layer does not appear on the surface at room temperature, and when heated to a predetermined temperature or higher, the thermochromic layer appears and thus can be identified.

In one embodiment, the top coating agent is 100 parts by weight of a fluorine-based base resin; 10 to 50 parts by weight of an alkoxy silane compound; 5 to 50 parts by weight of the first pigment; 0.5 to 15 parts by weight of molybdenum disulfide; And 1 to 15 parts by weight of a phosphoric acid ester compound.

In one embodiment, the fluorine-based resin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoro alkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride (PVDF). ) May include one or more of. When the fluorine-based resin is applied, smoothness, chemical resistance, durability and heat resistance of the top coating layer may be excellent.

The alkoxy silane compound may be included to improve adhesion and durability between the top coating layer, the toning layer, the thermochromic layer, and the primer layer.

In one embodiment, the alkoxy silane is glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, methacryloylpropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, methacrylo It may include one or more of ylpropyltriethoxysilane and glycidoxypropyltriethoxysilane.

The alkoxy silane compound may be included in 10 to 50 parts by weight based on 100 parts by weight of the fluorine-based base resin. When the alkoxysilane compound is included in an amount of less than 10 parts by weight, durability and adhesion of the top coating layer are reduced, and when it contains more than 50 parts by weight, the blendability and workability of the top coating agent, and the smoothness and appearance of the top coating layer may be poor. I can. For example, 15 to 35 parts by weight may be included.

In one embodiment, the first pigment may include at least one of carbon black, perylene red, manganese ferrite black, copper chromite black, bismuth vanadate, iron hydroxide yellow, chromium oxide green, and cobalt aluminate blue. I can. For example, manganese ferrite black and perylene red may be included.

In one embodiment, the first pigment is included in 5 to 50 parts by weight based on 100 parts by weight of the fluorine-based resin. When included in the above range, dispersibility is excellent, and durability and mechanical properties of the top coating layer can be prevented from deteriorating. When the first pigment is included in an amount of less than 5 parts by weight, the effect of addition is insignificant, and when it is included in an amount exceeding 50 parts by weight, sufficient dispersion in the top coating agent is difficult, and the appearance and durability of the top coating layer may be deteriorated. For example, 10 to 40 parts by weight may be included.

In one embodiment, the average particle diameter of the first pigment may be 5 ~ 30㎛. In the above range, dispersibility and mixing properties may be excellent.

The molybdenum disulfide (MoS ₂ ) may be included for the purpose of improving the lubricity of the top coating layer. In one embodiment, the molybdenum disulfide may be included in 0.5 to 15 parts by weight based on 100 parts by weight of the fluorine-based base resin. When included in the above range, the dispersibility is excellent, and the lubricity of the top coating layer and the non-stick properties in which food ingredients do not stick to the surface of the top coating layer may be excellent. For example, 3 to 15 parts by weight may be included.

The phosphoric acid ester compound may be included for the purpose of improving durability of the top coating layer of the present invention and adhesion to the substrate. The phosphoric acid ester compound may be a phosphoric acid ester compound including at least one of a hydroxy group and a carboxyl group.

In one embodiment, the phosphoric acid ester-based compound is included in 1 to 15 parts by weight based on 100 parts by weight of the fluorine-based resin. When included in the above range, durability and adhesion of the top coating layer are excellent, and the viscosity of the top coating agent can be prevented from being excessively increased. When the phosphoric acid ester-based compound is included in an amount of less than 1 part by weight, the adhesion of the top coating layer is deteriorated. For example, 1 to 8 parts by weight may be included.

In one embodiment, the top coating agent may further include 0.5 to 5 parts by weight of germanium oxide based on 100 parts by weight of the fluorine-based base resin. The germanium oxide may be included for the purpose of improving the interlayer adhesion of the top coating layer of the present invention. When the germanium oxide is included in an amount of less than 0.5 parts by weight, the adhesion of the top coating layer of the present invention is lowered, and when it is included in an amount exceeding 5 parts by weight, the mixability of the top coating agent decreases, and smoothness and appearance may be poor. For example, 1 to 3 parts by weight may be included.

In one embodiment, the average particle diameter of the germanium oxide may be 0.1 ~ 20㎛. In the above range, dispersibility and blendability are excellent, and interlayer adhesion of the top coating layer may be excellent.

In one embodiment, the germanium oxide and phosphoric acid ester compound may be included in a weight ratio of 1:1 to 1:5. When included in the above weight ratio range, the blendability and workability of the top coating agent are excellent, the interlayer adhesion and durability of the top coating layer are excellent, and the smoothness and appearance of the top coating layer may be excellent at the same time. For example, germanium oxide and phosphoric acid ester compounds may be included in a weight ratio of 1:2 to 1:4.

In one embodiment, the average particle diameter of the molybdenum disulfide may be 1 ~ 80㎛. In the above range, dispersibility and mixing properties may be excellent.

In one embodiment, the top coating agent may further include a solvent. The solvent is water, alcohol having 1 to 10 carbon atoms, toluene, xylene, diisobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, 1-methoxy-2-propanol, ethanol, Butyl cellosolve, cyclohexane, n-butyl acetate, N-methylpyrrolidone, dimethylformamide, ethyl acetate, acetone, methyl acetate, isobutyl acetate, isopropyl acetate, and dimethyl carbonate. In one embodiment, the alcohol having 1 to 10 carbon atoms may include one or more of methanol, ethanol, propanol, isopropanol, n-butanol, and isobutanol.

The solvent may be included in an amount of 10 to 500 parts by weight based on 100 parts by weight of the fluorine-based base resin. When included in the above range, the dispersibility and workability of the components of the top coating agent may be excellent.

In one embodiment, the top coating agent may further include additives such as a surfactant, a leveling agent, and an antifoaming agent. The additive may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the fluorine-based base resin.

In one embodiment, the heat treatment may be performed at 380 to 450°C. Under the above conditions, the primer layer, the toning layer, the thermochromic layer, and the top coating layer are cured, so that interlayer adhesion and durability may be excellent.

In one embodiment, the thickness of the top coating layer may be 5 ~ 30㎛. In one embodiment, the thickness of the top coating layer may be measured from the surface of the thermochromic layer. Durability of the top coating layer may be excellent under the above thickness condition.

열변색성 복합코팅층을 포함하는Including a thermochromic composite coating layer 조리기구 제조방법에 의해 제조된 조리기구Cooking utensils manufactured by the cooking utensil manufacturing method

Another aspect of the present invention relates to cookware manufactured by the cookware manufacturing method. In one embodiment, the cookware is a metal substrate; A primer layer comprising a fluorine-based resin formed on at least one surface of the metal substrate; A toning layer formed on at least a part of the surface of the primer layer; A thermochromic layer formed on at least a part of the surface of the primer layer; And a top coating layer formed on the surface of the thermochromic layer, wherein the top coating layer comprises: 100 parts by weight of a fluorine-based base resin; 10 to 50 parts by weight of an alkoxy silane compound; 5 to 50 parts by weight of the first pigment; 0.5 to 15 parts by weight of molybdenum disulfide; 1 to 15 parts by weight of a phosphoric acid ester compound; And 0.5 to 5 parts by weight of germanium oxide; and 100 parts by weight of a fluorine-based base resin in the top coating layer; 10 to 50 parts by weight of an alkoxy silane compound; 5 to 50 parts by weight of the first pigment; 0.5 to 15 parts by weight of molybdenum disulfide; And 1 to 15 parts by weight of a phosphoric acid ester compound; It is formed from a top coating agent comprising, the toning layer is formed from a toning coating agent comprising a matrix resin and a toning pigment, and the thermochromic layer is formed from a thermochromic coating agent comprising a thermochromic compound and a color change pigment, The toning pigment includes titanium oxide, and the color change pigment includes iron oxide red.

The top coating agent further includes 0.5 to 5 parts by weight of germanium oxide based on 100 parts by weight of the fluorine-based base resin, and the germanium oxide and phosphate ester compound may be included in a weight ratio of 1:1 to 1:5.

Since the primer agent and the top coating agent constituting the primer layer, the toning coating agent and the thermochromic layer coating agent constituting the toning layer, the same components and contents as described above may be applied, a description thereof will be omitted.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, the following examples are for aiding understanding of the present invention, and the scope of the present invention is not limited to the following examples.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this has been presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense. Contents not described herein can be sufficiently technically inferred by those skilled in the art, and thus description thereof will be omitted.

실시예 및 비교예Examples and Comparative Examples

Components used in Examples and Comparative Examples are as follows.

First primer agent and second primer agent

(A) Fluorine base resin: Polytetrafluoroethylene (PTFE) and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) were used.

(B) Second pigment: Perylene red (first primer) and manganese ferrite black (second primer).

(C) A carboxyl group-containing phosphate ester compound was used.

(D) Germanium oxide having an average particle diameter of 10 μm was used.

(E) Additive: A surfactant and an antifoaming agent were used.

(F) Distilled water was used as a solvent.

Top coating agent

(B) Alkoxy silane compound: Glycidoxypropyltriethoxysilane was used.

(C) First pigment: manganese ferrite black was used.

(D) Molybdenum disulfide was used.

(E) A carboxyl group-containing phosphate ester compound was used.

(F) Germanium oxide having an average particle diameter of 10 μm was used.

(G) Additive: A surfactant and an antifoaming agent were used.

(H) Distilled water was used as the solvent.

실시예 1~2 및 비교예 1~6Examples 1 to 2 and Comparative Examples 1 to 6

(1) Primer layer formation: After degreasing one surface of the metal substrate (stainless steel), pretreatment was performed by sandblasting using 60 mesh aluminum oxide. Then, the components and contents shown in Table 1 were applied, but only the type of the second pigment was changed to prepare a first primer agent and a second primer agent. A first primer layer was formed by spraying a first primer on the pretreated surface of the metal substrate, and then a second primer was applied to the edge of the surface of the first primer layer using a spray. It dried at ~100 ℃ to form a second primer layer. The sum of the thicknesses of the first and second primer layers was 12 to 15 μm.

(2) Toning layer and thermochromic layer formation: A toning coating comprising 100 parts by weight of a matrix resin (polyphenylene sulfide) and 30 parts by weight of a toning pigment (titanium dioxide) is applied to a part of the surface on which the second primer layer is formed. A toning layer (specific pattern type) having a thickness of 5 to 10 μm was formed. Then, a thermochromic coating agent including 100 parts by weight of a thermochromic compound (Ag ₂ HgI ₄ ) and 15 parts by weight of a discoloration pigment (iron oxide red) was applied to the central part of the surface of the second primer layer, and 5 to 10 μm A thick thermochromic layer was formed.

(3) Top coating layer formation and heat treatment: A top coating agent containing the components and contents of Table 2 below was prepared and coated on the surfaces of the toning layer, the thermochromic layer, and the second primer layer using a conventional method, and then 430 Heat treatment at ~440 ℃ to form a top coating layer 12 ~ 15㎛ thickness to prepare a cooking utensils (frying pan).

[Table 1]

[Table 2]

Property evaluation method

For Examples 1 to 2 and Comparative Examples 1 to 6, the physical properties of the composite coating layer were evaluated according to the following items, and the results are shown in Table 3 below.

(1) Appearance: Examples and Comparative Examples The appearance of cracks in the composite coating layer was visually observed and evaluated according to the following three criteria (◎: no cracking, △: partial cracking X: severe cracking).

(2) Evaluation of corrosion resistance: The cookware of Examples and Comparative Examples was immersed in a 5% NaCl solution at 35° C. for 100 hours in accordance with JIS K 5400 9.1 standards, and then taken out, and thermochromic properties of the Examples and Comparative Examples The coating film corrosion state of the composite coating layer was observed and evaluated according to the following three criteria (◎: no coating film corrosion, △: partial corrosion occurrence, X: severe corrosion occurrence).

(3) Pencil hardness: Measured according to JIS K5600-5-4.

(4) Evaluation of Adhesion: For the composite coating layers of Examples and Comparative Examples, adhesion was evaluated by a cross-cut tape peeling test according to JIS K 5400. With respect to the total number of crosscuts (100), the number of crosscuts that were not peeled off was shown.

(5) Evaluation of antifouling properties: 20 ml of soy sauce was added dropwise to the surface of the cooking utensils on which the composite coating layer was formed, and heated at 200° C. to crush the soy sauce. Then, when the surface of the composite coating layer was removed using a cloth soaked in water, the antifouling property was evaluated for ease of operation (◎: easy to remove contaminants, △: contaminants are removed, but it takes a long time, X: for a long time Removal does not remove almost any contaminants).

(6) Abrasion resistance evaluation: Whether the coating film is damaged after rotating 15000 times at a load of 3 kg and a speed of 60 rpm using a taber wear tester on the surface of the cooking utensils of Examples and Comparative Examples on which the composite coating layer is formed. Was confirmed and evaluated ((◎: no damage, △: part of the coating film was damaged, X: most of the coating film was damaged).

[Table 3]

3 is a photograph of the cookware manufactured according to Example 1, and FIG. 4 is a photograph of the cookware manufactured according to Example 1 after heating. 3 and 4, in the case of the embodiment of the present invention, discoloration does not occur at room temperature, so that the thermochromic layer is not visible, but when heated above a predetermined temperature, discoloration (pattern) of the thermochromic layer appears. It can be seen that the heating state of the appliance can be easily identified.

In addition, referring to the results of Table 3, Examples 1 to 3 in which the composite coating layer according to the present invention is applied are excellent in abrasion resistance of the thermochromic composite coating layer and adhesion between the coating layers, and are easy to clean and manage due to excellent antifouling properties. In addition, it was found that the non-stick characteristic of the composite coating layer was excellent in preventing the food ingredients from sticking to the surface during cooking. On the other hand, in the case of Comparative Examples 1 to 6 deviating from the present invention, it was found that the appearance, abrasion resistance, adhesion, or antifouling properties were lower than those of Examples 1 to 3.

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims

Forming a primer layer containing a fluorine-based resin on the surface of the metal substrate;

Forming a toning layer by applying a toning coating comprising a matrix resin and a toning pigment to at least a portion of the surface of the primer layer;

Forming a thermochromic layer by applying a thermochromic coating agent including a thermochromic compound and a color change pigment on at least a portion of the surface of the primer layer; And

And forming a top coating layer by applying a top coating agent to the surface of the primer layer on which the thermochromic layer is formed and heat treatment,

The top coating agent 100 parts by weight of a fluorine-based base resin; 10 to 50 parts by weight of an alkoxy silane compound; 5 to 50 parts by weight of the first pigment; 0.5 to 15 parts by weight of molybdenum disulfide; And 1 to 15 parts by weight of a phosphoric ester-based compound; and

The toning pigment comprises titanium oxide, and the color change pigment comprises iron oxide red.
The method of claim 1, wherein the heat treatment is performed at 380 to 450°C.
The method of claim 1,

The top coating agent further comprises 0.5 to 5 parts by weight of germanium oxide based on 100 parts by weight of the fluorine-based base resin,

The germanium oxide and the phosphoric acid ester-based compound is a cooking utensil manufacturing method comprising a thermochromic composite coating layer, characterized in that contained in a weight ratio of 1:1 to 1:5.
The method of claim 1, wherein the toning layer and the thermochromic layer are formed using pad printing, respectively.
The method of claim 1, wherein the primer layer comprises 100 parts by weight of a fluorine-based base resin;

1 to 40 parts by weight of a second pigment;

1 to 15 parts by weight of a phosphoric acid ester compound; And

Germanium oxide 0.5 to 5 parts by weight; Cooking utensils manufacturing method comprising a thermochromic composite coating layer, characterized in that formed from a primer comprising a.
The method of claim 1, wherein the fluorine-based resin is polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and polyvinylidene fluoride. Cooking utensil manufacturing method comprising a thermochromic composite coating layer comprising at least one of (PVDF).
The method of claim 1,

The toning coating agent comprises 100 parts by weight of a matrix resin and 0.5 to 50 parts by weight of a toning pigment,

The thermochromic coating agent includes 100 parts by weight of a thermochromic compound and 0.5 to 30 parts by weight of a color change pigment,

The thermochromic compound is a cooking appliance manufacturing method comprising a thermochromic composite coating layer, characterized in that it comprises at least one of a mercuric iodide complex salt and vanadium oxide.
The method of claim 1, wherein the first pigment comprises at least one of carbon black, perylene red, manganese ferrite black, copper chromite black, bismuth vanadate, iron hydroxide yellow, chromium oxide green, and cobalt aluminate blue. Cooking utensils manufacturing method comprising a thermochromic composite coating layer.
Metal substrate;

A primer layer comprising a fluorine-based resin formed on at least one surface of the metal substrate;

A toning layer formed on at least a portion of the surface of the primer layer;

A thermochromic layer formed on at least a portion of the surface of the primer layer; And

Including; a top coating layer formed on the surface of the primer layer and the thermochromic layer,

The top coating layer includes 100 parts by weight of a fluorine-based base resin; 10 to 50 parts by weight of an alkoxy silane compound; 5 to 50 parts by weight of the first pigment; 0.5 to 15 parts by weight of molybdenum disulfide; And 1 to 15 parts by weight of a phosphoric acid ester-based compound; it is formed from a top coating agent comprising,

The toning layer is formed from a toning coating comprising a matrix resin and a toning pigment,

The thermochromic layer is formed from a thermochromic coating comprising a thermochromic compound and a color change pigment,

The cooking utensil, characterized in that the toning pigment contains titanium oxide, and the color change pigment contains iron oxide red.