HK1136841B - A waterborne and nonstick polyether sulfone coating composition without perfluoro-octanoic acid and preparation method thereof - Google Patents
A waterborne and nonstick polyether sulfone coating composition without perfluoro-octanoic acid and preparation method thereof Download PDFInfo
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- HK1136841B HK1136841B HK10102130.5A HK10102130A HK1136841B HK 1136841 B HK1136841 B HK 1136841B HK 10102130 A HK10102130 A HK 10102130A HK 1136841 B HK1136841 B HK 1136841B
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Description
Technical Field
The invention relates to a coating composition and a preparation method thereof, in particular to an environment-friendly water-based polyether sulfone non-stick coating composition without perfluorooctanoic acid (PFOA) and a preparation method thereof. The coating composition is mainly used for the non-stick coating of electric rice cookers and can also be used for the non-stick coating of other cookers.
Background
The polyether sulfone has the characteristics of good heat resistance, steam resistance, corrosion resistance, light color, colorability, nontoxicity and the like, and is an excellent engineering plastic, so the polyether sulfone can be used for non-stick coatings and used as an adhesive of the coatings.
However, the non-stick coating mainly based on polyether sulfone used in domestic electric cooker market is a solvent system, and an organic solvent is completely adopted as a diluting solvent, so that the development of a water-based polyether sulfone non-stick coating system is urgently needed to solve the problem of environmental protection.
On the other hand, the non-stick coating contained in the cookware also comprises polytetrafluoroethylene emulsion. In general, polytetrafluoroethylene emulsion is prepared from perfluorooctanoic acid compound (such as perfluorooctanoic acid amine), so that it is difficult to avoid that the polytetrafluoroethylene emulsion contains perfluorooctanoic acid impurity.
In recent two years, domestic non-stick coatings made of polytetrafluoroethylene emulsion are concerned about the fact that the coating contains perfluorooctanoic acid, and although the fact that the non-stick coating film on the last non-stick pan does not contain any perfluorooctanoic acid is proved finally, the polytetrafluoroethylene emulsion is determined to reduce the original content of 95% perfluorooctanoic acid in 2010 and completely does not contain perfluorooctanoic acid in 2015.
In CN1069336C patent, polyether sulfone anti-sticking paint sintered at high and low temperature for cooking utensils and household appliances is proposed, the low temperature mentioned in the patent refers to 280 deg.C, the high temperature refers to 380 deg.C, the disadvantage of the patent is that the solvent and diluent used in the paint are organic solvents such as N-methyl pyrrolidone, butanone or acetone, toluene, xylene, dimethyl acetamide, etc.
CN1104465C mentions that polyether sulfone, polyamide imide or polyimide, fluorine resin and aluminum foil are used as primer of tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA) powder coating, and the primer has good adhesion to substrate and PFA finish, and has better corrosion resistance. The solvent used in the primer is N-methyl pyrrolidone, diacetone alcohol or the like. The disadvantages are that: the solvents and diluents used are also organic solvents.
In the patent CN1051790C, there is a mention of using a polyamideimide resin or a polyethersulfone resin as a binder in a primer in combination with a melt viscosity of at least 1010Pobber polytetrafluoroethylene and melt viscosity of 103～105Copolymers of perfluoropropyl vinyl ether of poise and tetrafluoroethylene (PFA) or melt viscosities of 103-108Tetrafluoroethylene/hexafluoropropylene copolymer (FEP) in the poise range as the second component fluorocarbon resin, this primer in the form of a water dispersion, can be coated on substrates having a surface roughness of less than 2 microns with good adhesion. The disadvantage is that the polytetrafluoroethylene used in this patent is in emulsion form. And the resin used by the finish paint is mainly polytetrafluoroethylene in emulsion form and contains perfluorooctanoic acid,
in view of the above, there is a lack in the art of a perfluorooctanoic acid-free waterborne polyethersulfone non-stick coating.
Therefore, the polyethersulfone non-stick coating which uses distilled water as a diluent during spraying, reduces the dosage of an organic solvent, meets the requirement of environmental protection, does not contain perfluorooctanoic acid (PFOA), and meets the requirement of harmlessness to human bodies is urgently needed in the field.
Disclosure of Invention
The invention aims to obtain a water-based polyether sulfone non-stick coating composition, which adopts distilled water as a diluent during spraying, reduces the dosage of an organic solvent, meets the requirement of environmental protection, does not contain perfluorooctanoic acid (PFOA), and achieves the requirement of harmlessness to a human body.
The second purpose of the invention is to obtain a preparation method of the water-based polyether sulfone non-stick coating.
A third object of the present invention is to obtain a non-stick coating for coating cookware.
A fourth object of the invention is to obtain a cooker with a surface coated with a non-stick coating.
In a first aspect of the invention, there is provided an aqueous polyethersulfone non-stick coating composition comprising:
(1)8-25 wt% of a polyether sulfone,
(2)2-15 wt% fluorocarbon polymer without perfluorooctanoic acid,
(3)40 to 90 wt% of an aqueous dispersion, and
(4)0 to 20 wt% of a coloring toner.
In one embodiment of the present invention, the fluorocarbon polymer of component (2) that is free of perfluorooctanoic acid is selected from the group consisting of: a powdered fluorocarbon;
preferably, the average particle size of the powdery fluorocarbon compound is 2-20 μm,
more preferably, the average particle size is in the range of 3 to 10 μm.
In one embodiment of the invention, the fluorocarbon polymer free of perfluorooctanoic acid of component (2) is selected from: polytetrafluoroethylene or tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene/perfluoromethyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, or combinations thereof.
In one embodiment of the present invention, the aqueous dispersion comprises 25 to 66 wt% of distilled water, 33 to 44 wt% of a solvent capable of dissolving polyethersulfone, and 0 to 33 wt% of an amphoteric solvent incapable of dissolving polyethersulfone, based on the total weight of the aqueous dispersion.
In one embodiment of the present invention, the coloring toner is selected from carbon black, copper manganese oxide black, copper manganese cobalt oxide black, manganese black, black iron oxide, ultramarine, phthalocyanine blue green, chromium oxide , cobalt blue, cobalt green, titanium yellow, titanium self-powder, pearl powder, aluminum paste, or a combination thereof.
In one embodiment of the invention, the cooking utensil further comprises 0.1-3 wt% of additives suitable for cooking utensils,
preferably, the cookware-suitable additive is selected from a toner dispersant, a surfactant, an anti-blooming agent, a rheological agent, or a combination thereof.
Preferably, the additive suitable for cookware is 0.5 to 2 wt% of the total weight of the composition.
The invention provides a preparation method of a water-based polyether sulfone non-stick coating, which comprises the following steps:
grinding the composition as claimed in any one of claims 1 to 5 to obtain the water-based polyether sulfone non-stick coating.
Preferably, the grinding time is 30 to 40 hours.
In one embodiment of the invention, the grinding comprises two or more stages,
in the first stage, 8-25 wt% of polyether sulfone and 40-90 wt% of aqueous dispersion liquid are ground for 24-30 hours to obtain ground polyether sulfone grinding liquid,
in the second stage, the polyether sulfone grinding fluid obtained in the first stage is mixed with the following components:
2 to 15 wt% of a fluorocarbon polymer free of perfluorooctanoic acid, 0 to 20 wt% of a toner for coloration, optionally 0.1 to 3 wt% of an additive suitable for a toner for coloration,
and grinding the obtained mixture for 6-10 hours to obtain the coating.
In a third aspect, the present invention provides a non-stick coating for coating cookware, said coating being obtained by applying the coating composition of the present invention to the surface of the cookware.
In a fourth aspect of the present invention, there is provided a cookware with a non-stick coating on the surface thereof, wherein the cookware is coated with the coating composition of the present invention to form the non-stick coating.
Detailed Description
The inventor of the invention has conducted extensive and intensive research, and by improving the preparation process, the polyether sulfone non-stick coating is obtained, wherein perfluorooctanoic acid (PFOA) is completely not contained, and the aqueous dispersion is adopted, so that the risk of the perfluorooctanoic acid is overcome, and the environment is better protected. The present invention has been completed based on this finding.
Various aspects of the invention are described in detail below.
As used herein, the term "aqueous dispersion" has the same meaning as "diluent".
Water-based polyether sulfone non-stick coating composition
The water-based polyethersulfone non-stick coating composition of the present invention comprises:
(1)8-25 wt% of a polyether sulfone,
(2)2-15 wt% fluorocarbon polymer without perfluorooctanoic acid,
(3)40 to 90 wt% of an aqueous dispersion, and
(4)0 to 20 wt% of a coloring toner.
Preferably, the polyethersulfone comprises 10-20 wt% of the total weight of the composition.
Preferably, the fluorocarbon polymer without perfluorooctanoic acid is present in an amount of 4 to 10 wt% based on the total weight of the composition.
Preferably, the toner for coloration accounts for 0 to 15 wt% of the total weight of the composition.
Preferably, the aqueous dispersion comprises 30 to 60 wt% of the total weight of the composition.
The composition of the present invention may further contain other conventional components suitable for use in cookers, as long as the object of the present invention is not limited. In one embodiment, 0.1 to 3 wt.% of an additive suitable for a toner powder for coloring, such as, in particular, a dispersant, a surfactant, an anti-blooming agent, a rheological agent, or a combination thereof, is also added to the toner powder for coloring. The above formulation can also be adjusted by those skilled in the art according to the needs of the cooker as long as the adjustment does not limit the object of the present invention. For example, dispersants such as Disperbyk-190 from BYK, germany, anti-blooming agents including but not limited to DC Q2-5211 from Dow Corning, rheological agents including but not limited to Bentone EW, organic bentonite such as from Elementis Specialties, may be added as other components suitable for use in cookware.
The individual components of the invention are described in detail below:
(1) polyether sulfone
The polyethersulfones of the present invention are conventional in the art. Specifically, for example, the structural formula is as follows:
the polymerization degree n of the polyethersulfone is not particularly limited as long as it does not limit the specific object of the present invention. Preferably, n is selected from 50 to 75, and more preferably 60 to 70.
The weight percentage of the polyether sulfone in the coating composition is 8-25 wt%, and the optimal range is 10-20 wt%.
(2) Fluorocarbon polymers free of perfluorooctanoic acid
The component (2) fluorocarbon polymer free of perfluorooctanoic acid is selected from: powdered fluorocarbon.
Preferably, the average particle size of the powdery fluorocarbon compound is in a range of 2-20 μm, and more preferably, the average particle size is in a range of 3-10 μm.
"fluorocarbon polymers" which are polymers having a fluorine-substituted main chain have been known for a long time and have been widely used because of various desired properties such as heat resistance, chemical resistance, weather resistance, ultraviolet stability and the like. Examples of various fluorocarbon polymers are described in "modern fluoropolymers" published by John Scheirs, Inc., Wiley scientific Press 1997. The fluorocarbon polymer may be a partially fluorinated backbone, with half at least 40 wt% fluorinated, or a perfluorinated backbone. Specific examples of the fluoropolymer include Polytetrafluoroethylene (PTFE), tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA copolymer), tetrafluoroethylene/perfluoromethyl vinyl ether copolymer (MFA copolymer), copolymer of Tetrafluoroethylene (TFE) and Hexafluoropropylene (HFP) (FEP polymer), ethylene-tetrafluoroethylene copolymer (ETFE), terpolymer of tetrafluoroethylene/hexafluoropropylene/vinyl fluoride (THV), and polyvinyl fluoride Polymer (PVDF).
Preferably, the fluorocarbon polymer free of perfluorooctanoic acid of component (2) is selected from: polytetrafluoroethylene or tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer (FEP), or combinations thereof. As used herein, "alkyl" includes C1-C4 alkyl groups, including but not limited to methyl, ethyl, propyl, or combinations thereof.
More preferably, in the tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, the "alkyl" is selected from propyl, methyl, or combinations thereof, i.e., the copolymer is selected from tetrafluoroethylene/perfluoropropyl vinyl ether copolymer (PFA), tetrafluoroethylene/perfluoromethyl vinyl ether copolymer (MFA), or combinations thereof. The "/" meaning is equivalent to "and" unless indicated to the contrary.
The polymerization degree and molecular weight distribution of the polytetrafluoroethylene are not particularly limited as long as the object of the present invention is not limited. The melting point of polytetrafluoroethylene is preferably selected to be 317-.
The polymerization degree and molecular weight distribution of the tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer are not particularly limited as long as the object of the present invention is not limited. The copolymerization mode and the copolymer segment distribution of the copolymer are not particularly limited as long as the object of the present invention is not limited. The tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer is preferably selected to have a melting point of 280-310 ℃.
The polymerization degree and molecular weight distribution of the tetrafluoroethylene/hexafluoropropylene copolymer are not particularly limited as long as the object of the present invention is not limited. The copolymerization mode and the copolymer segment distribution of the copolymer are not particularly limited as long as the object of the present invention is not limited. The tetrafluoroethylene/hexafluoropropylene copolymer is preferably selected to have a melting point of 240-275 ℃.
Specific examples of the above polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene/hexafluoropropylene copolymer are also described in "modern fluoropolymers" published by John Scheirs, Wiley scientific Press 1997.
The most suitable fluorocarbon polymer without perfluorooctanoic acid (PFOA) in the present invention is polytetrafluoroethylene, the most important reason being its non-tackiness and economical nature. The polytetrafluoroethylene used in the invention, which does not contain perfluorooctanoic acid (PFOA), is more preferably micropowder polytetrafluoroethylene, most preferably polytetrafluoroethylene micropowder obtained by degrading polytetrafluoroethylene produced by a suspension polymerization mode through electron beam irradiation and grinding, wherein the particle size range of the polytetrafluoroethylene micropowder is 2-20 μm, and the optimal particle size range is 3-10 μm.
The weight percentage range of the fluorocarbon polymer in the coating composition of the invention is 2-15 wt%, and the optimal weight percentage range is 4-10 w%.
(3) Aqueous dispersion
The aqueous dispersion liquid comprises 25-66% of distilled water, 33-44% of solvent capable of dissolving polyether sulfone and 0-33% of amphoteric solvent incapable of dissolving polyether sulfone, wherein the weight of the aqueous dispersion liquid is calculated.
Preferably, the aqueous dispersion may further contain a solvent capable of dissolving polyethersulfone in an amount of 33 to 44 wt% based on the weight of the aqueous dispersion.
The "suitable solvents that can dissolve polyethersulfone" include a variety of solvents that allow polyethersulfone to dissolve therein. Specifically for example selected from N-methylpyrrolidone, dimethylacetamide, gamma-butyrolactone or combinations thereof.
The 'amphoteric solvent' is a solvent which can be mixed with water and a solvent capable of dissolving polyether sulfone. Typically a glycol monoalkyl ether, preferably a 2 to 4 carbon glycol monoalkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or combinations thereof.
More preferably, the amphoteric solvent is selected from: ethylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, or combinations thereof.
For example, in one embodiment of the invention, the aqueous dispersion comprises a suitable solvent which dissolves polyethersulfone, such as N-methylpyrrolidone, dimethylacetamide, gamma-butyrolactone, an amphoteric solvent such as ethylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol methyl ether.
(4) Toner for coloring
The present invention can select a proper nontoxic coloring toner according to a desired color, and the specific kind thereof is not limited. The coloring toner is used for decoration, and the coloring toner in the invention generally refers to a toner which is nontoxic and can resist high temperature (for example, no color change at 380 ℃ for 15 minutes),
In one embodiment of the present invention, the coloring toner is selected from carbon black, copper manganese oxide black, copper manganese cobalt oxide black, manganese black, black iron oxide, ultramarine, phthalocyanine blue green, chromium oxide , cobalt blue, cobalt green, titanium yellow, titanium dioxide, pearl powder, aluminum paste, or a combination thereof.
The toner for coloring the composition of the invention is mainly used for decoration, the toner for coloring in the invention is nontoxic and can resist high temperature (no color change at 380 ℃ for 15 minutes), and can be carbon black or copper manganese oxide black, or copper manganese cobalt oxide black, or manganese black, or iron oxide black, or ultramarine blue, or phthalocyanine blue-green, or chromium oxide , or cobalt blue, or cobalt green, or titanium yellow, or titanium dioxide, or pearl powder or aluminum paste, the selection of the toner for coloring is completely selected according to the required color, and can be used singly or by mixing two or more than two.
The coloring toner is 0-20 wt% of the coating of the present invention, and the most preferable range is 0-15 wt%.
(5) Other additive compositions suitable for cookware
The composition of the present invention may further contain other additive components suitable for use in cookers, as long as the object of the present invention is not limited. Specifically, for example, a toner dispersant, an anti-blooming agent, a rheological agent, a surfactant, or a combination thereof.
The "dispersant" of the toner of the present invention is not particularly limited as long as it does not limit the object of the present invention. For example, a dispersant for cookware coatings, which is conventional in the art, may be used.
The "flowering inhibitor" of the present invention is not particularly limited as long as it does not limit the object of the present invention. For example, a conventional art-recognized anti-blooming agent for a cookware coating may be used.
The "rheological agent" of the present invention is not particularly limited as long as it does not limit the object of the present invention. For example, using conventional art rheology agents for cookware coatings
The "surfactant" of the present invention is not particularly limited as long as it does not limit the object of the present invention. Conventional cookware coating surfactants in the art may be used.
The other additive component (5) suitable for cookers is contained in the coating composition of the present invention in an amount of 0 to 3% by weight, preferably 0.1 to 3% by weight, and the most preferable range composition is 0.5 to 2% by weight.
Preparation method
The invention relates to a preparation method of a water-based polyether sulfone non-stick coating, which comprises the following steps:
grinding the composition for 30-40 hours to obtain the water-based polyether sulfone non-stick coating.
In one embodiment of the invention, the grinding comprises two or more stages,
in the first stage, 8-25 wt% of polyether sulfone and 40-90 wt% of aqueous dispersion liquid are ground for 24-30 hours to obtain ground polyether sulfone grinding liquid,
in the second stage, the polyether sulfone grinding fluid obtained in the first stage is mixed with the following components:
2 to 15 wt% of a fluorocarbon polymer free of perfluorooctanoic acid, 0 to 20 wt% of a toner for coloration, optionally 0.1 to 3 wt% of an additive suitable for a toner for coloration,
and grinding the obtained mixture for 6-10 hours to obtain the coating.
The invention relates to an environment-friendly water-based polyether sulfone non-stick coating without perfluorooctanoic acid (PFOA), which is prepared by uniformly dispersing polyether sulfone, fluoropolymer, coloring toner and other additives in water and an amphoteric solvent according to the main principle of the preparation method, and the preparation method of the environment-friendly water-based polyether sulfone non-stick coating without perfluorooctanoic acid (PFOA) comprises the following steps: the polyether sulfone and a proper solvent capable of dissolving the polyether sulfone, such as N-methyl pyrrolidone, dimethylacetamide and gamma-butyrolactone, an amphoteric solvent, such as ethylene glycol butyl ether, diethylene glycol butyl ether and propylene glycol methyl ether, a surfactant and water are ground for 24-30 hours by a proper grinding device, such as a ball mill pot, then a dispersing agent, a fluoropolymer, a coloring toner (except aluminum paste and pearl powder), an anti-blooming agent and water are added into the ball mill pot, and then the mixture is ground for 6-10 hours, and then the aluminum paste or pearl powder is added according to requirements, so that the environment-friendly water-based polyether sulfone non-stick coating without perfluorooctanoic acid (PFOA) can be obtained.
The above preparation methods are only routine synthetic routes for the compositions of the present invention, and one skilled in the art can prepare the coating compositions of the present invention by adjusting different methods according to the above examples. The coating composition thus prepared may be further ground and dispersed.
Non-stick coating for coating cookware
The non-stick coating for coating cookware according to the present invention is obtained by applying the coating composition of the present invention to the cookware surface.
The coating method of the coating layer is not particularly limited as long as it does not limit the object of the present invention. For example, the surface of the base material of the cooker is first degreased to ensure that the surface is free from grease, dust and contaminants, and is appropriately roughened to increase the adhesion; the coating composition of the present invention is uniformly applied to the roughened surface to obtain the cooker of the present invention.
The coating thickness of the coating layer is not particularly limited as long as it does not limit the object of the present invention.
The coating time of the coating layer is not particularly limited as long as it does not limit the object of the present invention. Generally, after the coating is coated, baking the coating for 10 to 15 minutes at 380 to 400 ℃ according to the specific proportioning requirement of the coating, and drying the coating to form a film.
The coating area of the coating layer is not particularly limited as long as it covers the surface of the cooker.
Cooking utensils
The invention provides a cooker with a non-stick coating coated on the surface, wherein the non-stick coating is obtained by coating the surface of the cooker with the coating composition.
The coating method of the cooker is not particularly limited as long as it does not limit the object of the present invention. For example, the surface of the base material of the cooker is first degreased to ensure that the surface is free from grease, dust and contaminants, and is appropriately roughened to increase the adhesion; the coating composition of the present invention is uniformly applied to the roughened surface to obtain the cooker of the present invention.
The surface of the cooker refers to a surface of the cooker which is in contact with food or a surface which may touch food during use.
The cooker of the present invention is not particularly limited as long as it does not limit the object of the present invention. Such as electric cookers, woks, electric autoclaves, broil ovens, cake molds, and the like. Preferably, the cookware is selected from rice cookers.
The material of the cooker is not particularly limited, and generally, the material of the electric cooker is generally pure aluminum, aluminum alloy or aluminum-plated iron plate.
Main advantages
The main advantages of the invention are as follows:
(1) the fluoropolymer powder completely free of the perfluorooctanoic acid is adopted instead of the polytetrafluoroethylene emulsion containing the perfluorooctanoic acid, so that the fear of the perfluorooctanoic acid is eliminated, and the consumer can eat the perfluorooctanoic acid healthier.
(2) The invention provides a composition of an environment-friendly water-based polyether sulfone non-stick coating without perfluorooctanoic acid (PFOA) and a preparation method thereof, wherein water is used as a diluent of the coating, so that the environmental protection problem (1) in the background of the invention is solved, and a fluorocarbon polymer without perfluorooctanoic acid can be used as a non-stick source. The environment-friendly water-based polyether sulfone non-stick coating has a coating film which has good adhesion to a base material of aluminum metal or aluminum alloy or aluminum-plated iron or chromium-plated iron or stainless steel jun, and also has good steam resistance, corrosion resistance and long-term non-stick property. The physical properties of a coating film formed by the environment-friendly water-based polyether sulfone non-stick coating without perfluorooctanoic acid (PFOA) are equivalent to those of an oily polyether sulfone non-stick coating.
The compound provided by the invention can be synthesized by using commercially available raw materials and a traditional chemical conversion mode.
Other aspects of the invention will be apparent to those skilled in the art in view of the disclosure herein.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not specified, in the following examples are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Unless defined or stated otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention.
Example 1
The invention uses 80-mesh corundum to perform roughening treatment on the electric rice cooker in a light sand blasting mode.
Then adding proper water as a diluent of the coating, adjusting to proper spraying viscosity, spraying the coating on a base material of an electric cooker, preheating the coating in an oven at 150-180 ℃ for 3-5 minutes, then placing the coating in the oven at 380-400 ℃, baking the coating for 10-15 minutes, cooling and then carrying out various physical property tests.
The coating composition formulation is as follows in table 1:
table 1: base coating formulation 1
| Raw materials | Weight percent (%) |
| Polyether sulfone | 14 |
| Polytetrafluoroethylene micropowder 2 | 8 |
| N-methyl pyrrolidone | 26 |
| Ethylene glycol monobutyl ether | 13 |
| Rheological agent 3 | 0.3 |
| Titanium white powder | 8.3 |
| Carbon ink | 0.4 |
| Dispersant iv | 0.1 |
| Surfactant (c) | 1.0 |
| Anti-blooming agent: |) | 0.1 |
| Distilled water | 28.8 |
| In total | 100 |
Physical Properties test data see the Performance examples.
The polymerization degree of the polyether sulfone is 69, and the mark is Solvay Advanced Polymer PES RADEL A704P
(ii) Polytetrafluoroethylene Fine powder, Polymist XPP-519 available from Solvay Solexis, Solvay, Belgium, having an average particle diameter of 3.0. mu.m.
③ Bentone EW of organic bentonite produced by Elementis Specialties of America as rheological agent
Dispersant Disperbyk-190 from Debyk (BYK)
Surfactant is nonionic surfactant Triton X-100 produced by Dow Chemical
Sixthly, the anti-blooming agent is DC Q2-5211 produced by Dow coming (Dow Corning).
Example 2
The preparation and application methods of this example are the same as example 1, except that the formulation is as in table 2 below:
table 2: base coating formulation 2
| Raw materials | Weight percent (%) |
| Polyether sulfone | 17 |
| Polytetrafluoroethylene micropowder 2 | 6 |
| Tetrafluoroethylene/hexafluoropropylene copolymer (FEP) (-) | 3 |
| N-methyl pyrrolidone | 27 |
| Ethylene glycol monobutyl ether | 13 |
| Rheological agent IV | 0.4 |
| Carbon ink | 1.6 |
| Pearl powder | 0.7 |
| Water-based aluminum paste | 1.5 |
| Dispersant (c) | 0.5 |
| Interfacial agent | 1.1 |
| Anti-blooming agent | 0.1 |
| Distilled water | 28.1 |
| In total | 100 |
Physical Properties test data see the Performance examples.
The degree of polymerization of polyethersulfone was 50, obtained as Gafone 3600RP from Gharda Chemicals, India
② Polytetrafluoroethylene micropowder, available from UltraflonMP-30 produced by Laurel Products LLC of USA, having an average particle diameter of 12 μm
③ tetrafluoroethylene/hexafluoropropylene copolymer (FEP) Ultraflon FP-10 produced by Laurel Products LLC, USA, the average particle diameter is 4.1 μm
(iv) the rheological agent is Bentone EW of organobentonite produced by Elementis Specialties, USA
Fifthly, the dispersant is Disperbyk-190 produced by German Bike (BYK)
Sixthly, the surfactant is nonionic surfactant Triton X-100 produced by Dow Chemical
The anti-blooming agent is DC Q2-5211 produced by Dow Corning (Dow Corning).
Example 3:
the preparation and application methods of this example are the same as example 1, except that the formulation is as in table 3 below:
TABLE 3 basic paint formulation 3
| Raw materials | Weight percent (%) |
| Polyether sulfone | 14 |
| Polytetrafluoroethylene micropowder 2 | 6 |
| Tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA) (-) | 2 |
| N-methyl pyrrolidone | 26 |
| Ethylene glycol monobutyl ether | 13 |
| Rheological agent IV | 0.3 |
| Titanium white powder | 8.3 |
| Carbon ink | 0.4 |
| Dispersant (c) | 0.1 |
| Interfacial agent | 1.0 |
| Anti-blooming agent | 0.1 |
| Distilled water | 28.8 |
| In total | 100 |
Physical Properties test data see the Performance examples.
The polymerization degree of the polyether sulfone is 69, and the mark is Solvay advanced Polymer PES RADEL A704P
(ii) Polytetrafluoroethylene Fine powder, Polymist XPP-519 available from Solvay Solexis, Solvay, Belgium, having an average particle diameter of 3.0 μm
(iii) tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA), Hyflon PFA 7010 available from Solvay Solexis, Belgium, having an average particle size of 30 μm
(iv) the rheological agent is Bentone EW of organobentonite produced by Elementis Specialties, USA
Fifthly, the dispersant is Disperbyk-190 produced by German Bike (BYK)
Sixthly, the surfactant is nonionic surfactant Triton X-100 produced by Dow Chemical
The anti-blooming agent is DC Q2-5211 produced by Dow Corning (Dow Corning).
Example 4:
the preparation and application methods of this example are the same as example 1, except that the formulation is as in table 4 below:
table 4: base coating formulation 4
| Raw materials | Weight percent (%) |
| Polyether sulfone | 25 |
| Tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA) ② | 7 |
| Tetrafluoroethylene/hexafluoropropylene copolymer (FEP) (-) | 8 |
| Gamma-butyrolactone | 17 |
| Diethylene glycol butyl ether | 13 |
| Rheological agent IV | 0.5 |
| Iron oxide black | 3.0 |
| Pearl powder | 0.7 |
| Water-based aluminum paste | 1.3 |
| Titanium white powder | 8.0 |
| Dispersing agent (c) | 0.5 |
| Surface active agent | 1.5 |
| Anti-blooming agent | 0.5 |
| Distilled water | 17 |
| In total | 100 |
The polymerization degree of the polyether sulfone is 69, and the mark is Solvay Advanced Polymer PES RADEL A704P
② tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA) Hyflon PFA 7010 available from Solvay Solexis, Solvay, Belgium having an average particle size of 30 μm
③ tetrafluoroethylene/hexafluoropropylene copolymer (FEP) Ultraflon FP-10 produced by Laurel Products LLC, USA, the average particle diameter is 4.1 μm
Example 5:
the preparation and application methods of this example are the same as example 1, except that the formulation is as in table 5 below:
table 5: base coating Ketone side 5
| Raw materials | Weight percent (%) |
| Polyether sulfone | 8 |
| Tetrafluoroethylene/hexafluoropropylene copolymer (FEP) (-) | 2 |
| Dimethylacetamide | 27 |
| Propylene glycol methyl ether | 13 |
| Rheological agent IV | 0.5 |
| Pearl powder | 1.3 |
| Titanium white powder | 8.3 |
| Carbon ink | 0.4 |
| Dispersant (c) | 0.1 |
| Interfacial agent | 1.0 |
| Anti-blooming agent | 0.1 |
| Distilled water | 38.3 |
| In total | 100 |
The polymerization degree of the polyether sulfone is 69, and the mark is Solvay Advanced Polymer PES RADEL A704P
(ii) tetrafluoroethylene/hexafluoropropylene copolymer (FEP) available as Ultraflon FP-10 from Laurel Products LLC, USA, with an average particle size of 4.1 μm
(iv) the rheological agent is Bentone EW of organobentonite produced by Elementis Specialties, USA
Fifthly, the dispersant is Disperbyk-190 produced by German Bike (BYK)
Sixthly, the surfactant is nonionic surfactant Triton X-100 produced by Dow Chemical
Seventhly, the anti-blooming agent is DC Q2-5211 produced by Dow Corning
Example 6:
the preparation and application methods of this example are the same as example 1, except that the formulation is as follows in table 6:
table 6: base coating formulation 6
| Raw materials | Weight percent (%) |
| Polyether sulfone | 8 |
| Polytetrafluoroethylene micropowder 2 | 2 |
| Dimethylacetamide | 30 |
| Anti-blooming agent | 0.1 |
| Distilled water | 60 |
| In total | 100 |
The polymerization degree of the polyether sulfone is 69, and the mark is Solvay Advanced Polymer PES RADEL A704P
(ii) Polytetrafluoroethylene Fine powder, Polymist XPP-519 available from Solvay Solexis, Solvay, Belgium, having an average particle diameter of 3.0 μm
③ the anti-blooming agent is DC Q2-5211 produced by Dow Corning
Comparative example 1
The preparation and application methods of this example are the same as example 1, except that the formulation is as in table 2 below:
table 4: comparative example coating formulation 1
| Raw materials | Weight percent (%) |
| Polyether sulfone | 20 |
| Polytetrafluoroethylene micropowder 2 | 1.5 |
| N-methyl pyrrolidone | 30 |
| Ethylene glycol monobutyl ether | 8 |
| Rheological agent 3 | 0.3 |
| Titanium white powder | 9.0 |
| Carbon ink | 0.5 |
| Dispersant iv | 0.2 |
| Surfactant (c) | 1.0 |
| Anti-blooming agent: |) | 0.1 |
| Distilled water | 29.4 |
| In total | 100 |
Physical Properties test data see the Performance examples.
The polymerization degree of the polyether sulfone is 69, and the mark is Solvay Advanced Polymer PES RADEL A704P
(ii) Polytetrafluoroethylene Fine powder, Polymist XPP-519 available from Solvay Solexis, Solvay, Belgium, having an average particle diameter of 3.0 μm
③ Bentone EW of organic bentonite produced by Elementis Specialties of America as rheological agent
Dispersant Disperbyk-190 from Debyk (BYK)
Surfactant is nonionic surfactant Triton X-100 produced by Dow Chemical
Sixthly, the anti-blooming agent is DC Q2-5211 produced by Dow Corning
Comparative example 2
The preparation and application methods of this example are the same as example 1, except that the formulation is as in table 2 below:
TABLE 6 comparative example coating formulation 2
| Raw materials | Weight percent (%) |
| Polyether sulfone | 14 |
| Polytetrafluoroethylene micropowder 2 | 8 |
| N-methyl pyrrolidone | 34 |
| Ring (C)Hexanones | 5 |
| Butanone | 24.9 |
| Toluene | 4.5 |
| Rheological agent 3 | 0.6 |
| Titanium white powder | 8.3 |
| Carbon ink | 0.4 |
| Dispersant iv | 0.2 |
| Anti-blooming agent | 0.1 |
| In total | 100 |
Physical Properties test data see the Performance examples.
The polymerization degree of the polyether sulfone is 69, and the mark is Solvay Advanced Polymer PES RADEL A704P
(ii) Polytetrafluoroethylene Fine powder, Polymist XPP-519 available from Solvay Solexis, Solvay, Belgium, having an average particle diameter of 3.0 μm
(iii) the rheological agent is Degussa Areosil R972
The dispersant is BYK-164 produced by German Bike (BYK)
Sixthly, the anti-blooming agent is DC 230 produced by Dow coming (Dow Corning)
The base material of the electric cooker is usually pure aluminum, aluminum alloy or aluminum-plated iron plate, and the base material is first degreased to ensure that the surface is free from grease, dust and pollutants, and is appropriately roughened to increase the adhesion with the base material. The invention uses 80-mesh corundum to perform roughening treatment by light sand blasting. Then adding proper water as a diluent of the coating, adjusting to proper spraying viscosity, spraying the coating on a base material of an electric cooker, preheating the coating in an oven at 150-180 ℃ for 3-5 minutes, then placing the coating in an oven at 380-400 ℃, baking the coating for 10-15 minutes, cooling the coating, then carrying out various physical property tests such as coating thickness, coating gloss, coating thickness, coating hardness and grid-crossing adhesion, adopting a national standard test method as shown in the following table 1,
TABLE 1
| Test items | Test method |
| Film thickness of coating film | GB/T 13452.2-92 |
| Gloss of coating film | GB 9754-88 |
| Hardness of coating film | GB/T 6739-1996 |
| Close adhesion of the cut | GB/T 9286-1998 |
The non-stick test, the hydrochloric acid resistance test and the rice cooking test are carried out according to the following test methods:
a non-sticking test method mainly comprises the steps of carrying out an egg frying test, placing a pot on a gas stove for heating, measuring the surface temperature of the pot by using a far infrared thermometer, beating eggs when the surface temperature reaches 170-180 ℃, heating for 3-4 minutes, using a wooden shovel to shovel the eggs, judging whether residues exist, continuously carrying out the test for 5 times, and passing the test if no residues exist.
Acid resistance test: mixing 37% hydrochloric acid and pure water at a weight ratio of 1: 2, pouring into an electric cooker, boiling in a gas oven for 15min, pouring out hydrochloric acid, cooling with water, standing for 1 day to see whether the skin has paint or blister, and if not, indicating that the test is passed.
And (3) rice cooking test: mixing 1 part of rice and 2 parts of water, pouring the mixture into an electric cooker, cooking rice by using an electric rice cooker, taking out the electric cooker after the rice is cooked (about 40 minutes), cooling for about 5 minutes, pouring out the cooked rice, judging whether the rice remained in the electric cooker is easy to remove or whether paint is removed from a coating film, stopping testing if the rice is not sticky or the paint is not removed, and otherwise, continuing testing.
From the above test results, as shown in table two, it is shown that the environmentally friendly water-based polyethersulfone non-stick coating without perfluorooctanoic acid (PFOA) of the present invention has good long-term non-stick property and steam resistance, and the physical properties are equivalent to those of general oily polyethersulfone non-stick coatings.
TABLE 2
| Physical Properties | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Thickness of coating film | 20-25μm | 20-25μm | 20-25μm | 20-25μm | 20-25μm | 20-25μm | 20-25μm | 20-25μm |
| Gloss of the coating film at an angle of 60 ° | 23-27 | 26-30 | 24-28 | 20-25 | 15-18 | 35-40 | 28-33 | 24-28 |
| Hardness of coating film | 2H | 2H | 2H | 2H | 2H | H | 3H | 2H |
| Close adhesion of the cut | Level 0 | Level 0 | Level 0 | Level 0 | Level 0 | Level 0 | Level 0 | Level 0 |
| Non-stick test | By passing | By passing | By passing | By passing | By passing | By passing | Do not pass through | By passing |
| Hydrochloric acid resistance test | By passing | By passing | By passing | By passing | By passing | By passing | By passing | By passing |
| Rice cooking test | More than 500 times | More than 500 times | More than 500 times | More than 500 times | 400 times (one time) | 480 times (twice) | 180 times (times) | More than 500 times |
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (11)
1. An aqueous polyethersulfone non-stick coating composition comprising:
(1)8-25 wt% of polyether sulfone, wherein the polymerization degree n of the polyether sulfone is selected from 50-75;
(2)2 to 15 weight percent of a fluorocarbon polymer free of perfluorooctanoic acid, said component (2) fluorocarbon polymer free of perfluorooctanoic acid being selected from the group consisting of: a powdered fluorocarbon; the average particle size range of the powdery fluorocarbon is 2-20 mu m, and the fluorocarbon is selected from the following group: polytetrafluoroethylene or tetrafluoroethylene/perfluoro C1-C4 alkyl vinyl ether copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, or combinations thereof;
(3)40-90 wt% of an aqueous dispersion, wherein the aqueous dispersion comprises 25-66 wt% of distilled water, 33-44 wt% of a solvent capable of dissolving polyethersulfone and 0-33 wt% of an amphoteric solvent incapable of dissolving polyethersulfone, and the weight of the aqueous dispersion is calculated by the total weight of the aqueous dispersion; and
(4)0 to 20 wt% of a coloring toner.
2. The composition as claimed in claim 1, wherein the fluorocarbon is selected from tetrafluoroethylene/perfluoromethyl vinyl ether copolymers.
3. The composition according to claim 1, wherein the powdered fluorocarbon compound has an average particle size ranging from 3 to 10 μm.
4. The composition as claimed in claim 1, wherein the powdered fluorocarbon is polytetrafluoroethylene micropowder obtained by degrading polytetrafluoroethylene produced by suspension polymerization by electron beam irradiation and grinding.
5. The composition of claim 1,
the coloring toner is selected from carbon black, copper manganese oxide black, copper manganese cobalt oxide black, manganese black, iron oxide black, ultramarine, phthalocyanine blue-green, chromium oxide green, cobalt blue, cobalt green, titanium yellow, titanium dioxide, pearl powder, aluminum paste or a combination thereof.
6. The composition of claim 1,
the solvent capable of dissolving the polyether sulfone is selected from N-methyl pyrrolidone, dimethyl acetamide, gamma-butyrolactone or the combination thereof;
the amphoteric solvent incapable of dissolving polyethersulfone is selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or combinations thereof.
7. The composition of claim 1,
further comprising 0.1 to 3 wt% of an additive suitable for cookware, based on the total weight of the composition; the additives suitable for cookware are selected from toner dispersants, surfactants, anti-blooming agents, rheological agents, or combinations thereof.
8. The preparation method of the water-based polyether sulfone non-stick coating is characterized by comprising the following steps of:
grinding the composition as claimed in any one of claims 1 to 7 to obtain the water-based polyether sulfone non-stick coating.
9. The method of claim 8,
the grinding comprises two or more stages,
in the first stage, 8-25 wt% of polyether sulfone and 40-90 wt% of aqueous dispersion liquid are ground for 24-30 hours to obtain ground polyether sulfone grinding liquid,
in the second stage, the polyether sulfone grinding fluid obtained in the first stage is mixed with the following components:
2 to 15 wt% of a fluorocarbon polymer free of perfluorooctanoic acid, 0 to 20 wt% of a toner for coloration, optionally 0.1 to 3 wt% of an additive suitable for a toner for coloration,
and grinding the obtained mixture for 6-10 hours to obtain the coating.
10. A non-stick coating for coating cookware, characterized in that said coating is obtained by applying a coating composition according to any one of claims 1 to 7 on the cookware surface.
11. A cookware coated with a non-stick coating, wherein the surface of the cookware is coated with the coating composition of any one of claims 1 to 7 to form the non-stick coating.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810034222XA CN101525518B (en) | 2008-03-05 | 2008-03-05 | Composition of water-based polyether sulfone non-stick coating without perfluorooctanoic acid and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1136841A1 HK1136841A1 (en) | 2010-07-09 |
| HK1136841B true HK1136841B (en) | 2013-02-08 |
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