[go: up one dir, main page]

CN114989722A - Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method - Google Patents

Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method Download PDF

Info

Publication number
CN114989722A
CN114989722A CN202210520760.XA CN202210520760A CN114989722A CN 114989722 A CN114989722 A CN 114989722A CN 202210520760 A CN202210520760 A CN 202210520760A CN 114989722 A CN114989722 A CN 114989722A
Authority
CN
China
Prior art keywords
coating
component
oleophobic
hydrophobic
resistant easy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210520760.XA
Other languages
Chinese (zh)
Inventor
朱博敏
杨自海
李远超
张兔子
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tunable Materials Co ltd
Original Assignee
Tunable Materials Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tunable Materials Co ltd filed Critical Tunable Materials Co ltd
Priority to CN202210520760.XA priority Critical patent/CN114989722A/en
Publication of CN114989722A publication Critical patent/CN114989722A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and a preparation method of the coating, and belongs to the technical field of coatings. A material comprising a hybrid of a first component and a second component, namely a (fluoro) siloxane and an inorganic material, and a method for preparing the same. The coating has cross-linking polymerization reaction through (fluoro) siloxane and a non-single inorganic (non) metal nano material, and is connected through chemical grafting copolymerization reaction, so that the organic and inorganic materials have better compatibility, and chemical bonding is mutually stacked to form a multiple nano composite structure, thereby ensuring the wear resistance and the long-acting property of the coating. The product obtained by hydrolytic polymerization reaction of inorganic filler and silane is rich in-CH on surface 3 Group to provideAnd the viscosity makes the non-stick property have good durability. The coating prepared by the preparation method has the advantages of good hydrophobic and oleophobic properties, oil stain resistance, easy cleaning, high temperature resistance, corrosion resistance and the like.

Description

Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method
Technical Field
The invention relates to a hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and a preparation method of the coating, and belongs to the technical field of coatings.
Background
Silicone resins have excellent thermal oxidative stability, electrical insulating properties and non-tackiness, however, pure silicone resins also have some disadvantages, such as poor temperature resistance, chemical resistance, corrosion resistance and low hardness. Although the modified silicone resin can improve some defects of the silicone resin, new problems occur, such as the hardness of the modified silicone resin is not greatly improved, the heat resistance is poor under the condition of low content of the silicone resin, the cost of the modified resin with high performance is still high, and the like.
The surface of the base material is sprayed with a layer of non-stick coating which takes polytetrafluoroethylene as a main raw material, the non-stick coating is tightly combined with the base material through high-temperature sintering at 420 ℃, and the non-stick coating plays a role in non-sticking by utilizing the strong chemical inertia of the non-stick coating. However, PFOA used as a raw material in the production of polytetrafluoroethylene may be harmful to the human body and the environment.
Ceramic coatings are well known in the coatings art. It belongs to the field of functional coating, and is a novel water-based inorganic coating. It is prepared by using nano inorganic compound as main component and water as dispersing agent and adding pigment and filler, etc. and after coating, it is usually heated to solidify to form coating film with similar performance to that of ceramic. The paint has the advantages of abundant raw material, convenient exploitation, low price and lower cost compared with the traditional paint. The coating is formed by reacting silica sol and silane to form a film, organic silicone oil is added to achieve the non-stick effect, and the formed coating does not have enough mechanical strength and wear resistance, so that the coating can be quickly worn and even peeled off to lose the protective effect on a base material after being impacted and mechanically acted for a long time. The non-stick property will gradually decrease with the loss of silicone oil with the prolonged service life, so there is a problem of insufficient non-stick durability.
Disclosure of Invention
The invention aims to provide a hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and a preparation method thereof, the preparation process is simple, the construction is convenient, and the prepared coating has the properties of hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean and the like.
In order to achieve the purpose, the invention provides the following technical scheme: a hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating comprises a first component and a second component, wherein the first component accounts for 50-65% of the mass percent, and the second component accounts for 35-50% of the mass percent;
the first component is an inorganic component, and the raw materials of the first component are as follows: 50-85% of inorganic filler, 0-10% of inorganic pigment and 5-50% of solvent;
the second component comprises the following raw materials in percentage: 85-90% of siloxane and/or fluorosilane, 1-2% of acid and 8-14% of solvent.
Further, the inorganic filler is water-dispersible nano-sol and/or nano-inorganic powder.
Further, the water-dispersible nano-scale sol is silica, alumina, zirconia or titania sol, the solid content is 10-50%, and the particle size is 10-150 nm.
Further, the nanoscale inorganic powder is nanoscale silicon oxide, aluminum oxide, zirconium oxide and titanium oxide powder, and the particle size of the nanoscale inorganic powder is 30-500 nm.
Further, the siloxane includes tetramethoxysilane, tetrapropoxysilane, methyltrimethoxysilane (MTMOS), Methyltriethoxysilane (MTEOS), methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane (PrTMOS), propyltriethoxysilane (PrTEOS), propyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropyldimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, tetramethylpropoxysilane, ethyltriethoxysilane, propyltriethoxysilane, and the mixture thereof, One or a mixture of more of tripropyl methoxy silane, tripropyl ethoxy silane and tripropyl propoxy silane;
the fluorosilane comprises one or a mixture of more of methyltrifluorosilane, trimethylfluorosilane, trifluoropropylmethyldichlorosilane, trifluoromethyltrimethoxysilane, 1,2, 2-trifluorovinyltriphenylsilane, t-butyldimethylsilyl trifluoromethanesulfonate, r-trifluoropropylmethylpolysiloxane, trifluoropropylmethylcyclotrisiloxane, bis (3,3, 3-trifluoropropyl) dimethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane and dodecafluoroheptylpropyltrimethoxysilane.
Further, the acid is one or more of formic acid, glacial acetic acid and citric acid.
Further, the solvent is one or a mixture of ethanol, ethylene glycol, isopropanol, n-propanol, n-butanol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether and butyl acetate.
The invention further provides a preparation method of the hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating.
Further, the curing is baking at 200-300 ℃ for 10-30 min.
Further, mixing the first component and the second component at 15-25 ℃, grinding and curing for 6-24 h.
The invention has the beneficial effects that: the invention provides a hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating, which comprises a first component and a second component, wherein the second component comprises siloxane and/or fluorosilane (hereinafter referred to as (fluoro) siloxane) and other components, and a material hybridized by the (fluoro) siloxane and an inorganic material and a preparation method thereof. The coating is connected by the cross-linking polymerization reaction of (fluoro) siloxane and non-single inorganic (non) metal nano material through chemical graft copolymerization reactionThe obtained organic and inorganic materials have better compatibility, and chemical bonding is stacked into a multiple nano composite structure, so that the wear resistance and the long-acting property of the coating are ensured. The product obtained by hydrolytic polymerization reaction of inorganic filler and silane is rich in-CH on surface 3 The groups provide non-tackiness, so that the non-tackiness has good durability.
According to the preparation method of the hydrophobic, oleophobic, non-sticky and oil stain resistant easy-to-clean coating, the coating prepared by the preparation method has excellent super-amphiphobic characteristics, the water contact angle can reach 155-160 degrees, the rolling angle can reach about 1-5 degrees, and for an alcohol water solution with the concentration of 20%, the contact angle can reach more than 100 degrees, so that the coating has good oleophobic property, and the advantages of inorganic filler and low surface energy (fluorine) siloxane are effectively combined, so that the hydrophobic property and the oleophobic property of the coating are remarkably improved. The water dispersible nanometer sol is added into the coating, so that the coating has good high temperature resistance and corrosion resistance. Meanwhile, after the nano-scale inorganic powder is added by taking the dispersion liquid as a carrier, better dispersion can be formed in the coating, the nano-scale inorganic powder is still maintained after film formation, and the temperature impact resistance of the coating is greatly improved. The second component in the coating can be siloxane without adding fluorosilane, so that the prepared coating does not contain fluorine elements, the adverse effect of the fluorine elements on the environment or individuals is reduced, if fluorine-containing groups are introduced, the coating has excellent performances of solvent resistance, chemical stability, lower surface energy and the like, and pollutants such as water, oil and the like are difficult to adhere to the surface of the coating, so that the coating has good stain resistance.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to make the technical solutions of the present invention practical in accordance with the contents of the specification, the following detailed description is given of preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is a diagram of a process for preparing a coating in an embodiment of the present application;
fig. 2 is a process diagram of the curing method in example 1 of the present application.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Furthermore, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating, which comprises a first component and a second component, wherein the first component accounts for 50-65% of the mass percentage, and the second component accounts for 35-50% of the mass percentage;
wherein the first component is an inorganic component, and the first component comprises the following raw materials in percentage by weight: 50-85% of inorganic filler, 0-10% of inorganic pigment and 5-50% of solvent;
the second component comprises the following raw materials in percentage: 85-90% of siloxane and/or fluorosilane, 1-2% of acid and 8-14% of solvent.
In detail, the inorganic filler is water dispersible nanometer sol and/or nanometer inorganic powder. Wherein the water dispersible nano sol is silica, alumina, zirconia or titania sol, the solid content is 10-50%, and the particle size is 10-150 nm; the nanoscale inorganic powder is nanoscale silicon oxide, aluminum oxide, zirconium oxide and titanium oxide powder, and the particle size of the nanoscale inorganic powder is 30-500 nm. The inorganic filler used may be other inorganic fillers having equivalent functions. The product obtained after the hydrolytic polymerization reaction of the inorganic filler and the silane is rich in-CH on the surface 3 And therefore has better non-stick properties. And the silane and the inorganic filler have a cross-linking polymerization reaction and are connected through a chemical graft copolymerization reaction, so that the organic and inorganic materials have better compatibility, the chemical bonding is stacked to form a multiple nano composite structure, and the wear resistance and the long-acting property of the coating are ensured.
The inorganic pigment can be adjusted according to actual needs, if the transparent coating is needed, the inorganic pigment is not needed to be added, if the transparent coating is needed, the titanium dioxide or zirconium white powder is added, if the transparent coating is needed, the cobalt black can be added, and the like, wherein the pigment to be added is not limited.
The solvent in the first component is one or more of ethanol, ethylene glycol, isopropanol, n-propanol, n-butanol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, and butyl acetate. It is to be noted that the solvent includes, but is not limited to, such a kind, and any solvent that satisfies experimental requirements and does not affect the reaction between the components may be used.
The second component includes a siloxane and/or fluorosilane, an acid, and a solvent.
Wherein the siloxane comprises tetramethoxysilane, tetrapropoxysilane, methyltrimethoxysilane (MTMOS), Methyltriethoxysilane (MTEOS), methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane (PrTMOS), propyltriethoxysilane (PrTEOS), propyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, methyltrimethoxysilane, dipropyldimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, and/or mixtures thereof, One or a mixture of more of tripropyl methoxy silane, tripropyl ethoxy silane and tripropyl propoxy silane;
the fluorosilane includes one or more of methyltrifluorosilane, trimethylsilane, trifluoropropylmethyldichlorosilane, trifluoromethyltrimethoxysilane, 1,2, 2-trifluorovinyltriphenylsilane, t-butyldimethylsilyl trifluoromethanesulfonate, r-trifluoropropylmethylpolysiloxane, trifluoropropylmethylcyclotrisiloxane, bis (3,3, 3-trifluoropropyl) dimethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, dodecafluoroheptylpropyltrimethoxysilane. The siloxane and fluorosilane are not limited herein, and other siloxanes and fluorosilanes can be used according to the application.
It should be noted that the second component may be formulated with pure siloxane to provide a coating that is free of fluorine, thereby avoiding environmental and health hazards associated with fluorine. If a small amount of fluorine element is added, the prepared coating has excellent performances of solvent resistance, chemical stability, lower surface energy and the like, and pollutants such as water, oil and the like are difficult to adhere to the surface of the coating, namely, the coating has good pollution resistance.
The acid is one or more of formic acid, glacial acetic acid and citric acid; the solvent in the second component is one or more of ethanol, ethylene glycol, isopropanol, n-propanol, n-butanol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, and butyl acetate. It is to be noted that the acid and the solvent include, but are not limited to, such species, and any solvent that satisfies the experimental requirements and does not affect the reaction between the components may be used.
The application also provides a preparation method of the hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating, which is to mix the components of the hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating to obtain the coating, and spray-coat the coating on the surface of the substrate and then cure the coating. Wherein, the curing is baking at 200-300 ℃ for 10-30 min; mixing the first component and the second component at 15-25 deg.C, grinding and aging for 6-24 h.
The present invention will be described in further detail with reference to specific examples.
Example 1
A hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-cleaning coating comprises the following raw material components in percentage: the first component is 50% and the second component is 50%.
The first component comprises the following raw materials in percentage by mass:
water dispersible nanoscale silica sol: 20 percent of
Nano-grade alumina powder: 25 percent of
Cobalt black: 5 percent of
Water + ethylene glycol ethyl ether: 50 percent of
Wherein, the water: ethylene glycol + ethylene glycol ethyl ether ═ 1: 1; the water dispersible nanometer silica sol is water dispersible nanometer silica with particle size of 10-100nm and silica content of 20-50%;
the second component comprises the following raw materials in percentage by mass:
siloxane: 85 percent of
Glacial acetic acid: 1 percent of
Ethylene glycol + ethylene glycol ethyl ether: 14 percent of
Wherein the siloxane is a mixture of methyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane and tripropylmethoxysilane. That is, in this example, pure siloxane was used without adding fluorosilane.
And (3) putting the first component into a tank mill for grinding and dispersing, wherein the ambient temperature is kept at 15-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is more than 4 hours until all precipitates are dispersed, thus obtaining the first component. And (4) stirring the second component at a low speed, and uniformly stirring to obtain the second component. After the first component and the second component are mixed, the pot mill is continuously used for mixing and curing, the ambient temperature is kept at 20-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is 18-20 hours. It should be noted that the grinding time has a correlation with the ambient temperature and the rotation speed. After the grinding and curing are finished, the coating is discharged and filtered by a filter cloth with 300 meshes and 400 meshes to obtain the coating which is hydrophobic, oleophobic, non-sticky, oil-stain-resistant and easy to clean.
Referring to fig. 1, the preparation process of the coating includes the steps of pre-treating the workpiece, spraying the coating on the surface of the pre-treated workpiece, and finally curing. The pretreatment comprises sand blasting, degreasing and oil removing and preheating which are sequentially carried out. Wherein, 60 meshes of 80 meshes of corundum sand or stainless steel sand is used for sand blasting, and the air pressure is 0.5-1.0 MPa; degreasing and oil yielding are used for removing surface sand grains and dust, and the surface of the workpiece is ensured to be clean without oil stains or other foreign matters; preheating makes the temperature of the workpiece reach 50-60 ℃. Then spraying, using compressed air to spray, wherein the caliber of a spray gun is 1.0-1.5mm, the atomization working pressure is 2.5-3.0kg/cm2, and the recommended film thickness is 20-30 μm. If the film layer is too thin, the coating that may be formed is prone to cracking and does not have the corresponding functional characteristics. The pretreatment process needs to be properly adjusted according to the base material (material, wall thickness, etc.) and construction conditions (such as ambient temperature, etc.) of the workpiece. And finally, curing, wherein the curing step is shown in figure 2 and comprises the steps of keeping at 90 ℃ for 10min and keeping at 250 ℃ for 15min in sequence.
Example 2
A hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-cleaning coating comprises the following raw material components in percentage: the first component is 60% and the second component is 40%.
The first component comprises the following raw materials in percentage by mass:
water dispersible nano silica sol: 40 percent of
Nano-grade alumina powder: 25 percent of
Zirconium white: 8 percent of
Water + ethylene glycol ethyl ether: 27 percent of
Wherein, the ratio of water: ethylene glycol + ethylene glycol ethyl ether ═ 1: 1; the water dispersible nanometer silica sol is water dispersible nanometer silica with the granularity of 10-100nm and the silica content of 20-50%;
the second component comprises the following raw materials in percentage by mass:
siloxane + fluorosilane: 86 percent of the total weight
Glacial acetic acid: 1 percent of
Ethylene glycol + ethylene glycol ethyl ether: 13 percent
Wherein, the siloxane is a mixture of methyltrimethoxysilane and trimethylchlorosilane, and the fluorosilane is a mixture of trifluoropropylmethyldichlorosilane and heptadecafluorodecyltrimethoxysilane.
And (3) putting the first component into a tank mill for grinding and dispersing, wherein the ambient temperature is kept at 15-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is more than 4 hours until all precipitates are dispersed, thus obtaining the first component. And (3) stirring the second component at a low speed, and uniformly stirring to obtain the second component. After the first component and the second component are mixed, the pot mill is continuously used for mixing and curing, the ambient temperature is kept at 20-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is 18-20 hours. It should be noted that the grinding time has a correlation with the ambient temperature and the rotation speed. After the grinding and curing are finished, the coating is discharged and filtered by a filter cloth with 300 meshes and 400 meshes to obtain the coating which is hydrophobic, oleophobic, non-sticky, oil-stain-resistant and easy to clean.
Referring to fig. 1, the preparation process of the coating includes the steps of pre-treating the workpiece, spraying the coating on the surface of the pre-treated workpiece, and finally curing. The pretreatment comprises sand blasting, degreasing and oil removing and preheating which are sequentially carried out. Wherein, 60 meshes of 80 meshes of corundum sand or stainless steel sand is used for sand blasting, and the air pressure is 0.5-1.0 MPa; degreasing the oil to remove surface sand grains and dust, and ensuring that the surface of the workpiece is clean without oil stains or other foreign matters; preheating to make the temperature of the workpiece reach 50-60 ℃. Then spraying with compressed air under the conditions of spray gun caliber of 1.0-1.5mm and atomizing pressure of 2.5-3.0kg/cm 2 The film thickness is recommended to be 20 to 30 μm. If the film layer is too thin, the coating that may be formed is prone to cracking and does not have the corresponding functional characteristics. The pretreatment process needs to be properly adjusted according to the base material (material, wall thickness, etc.) and construction conditions (such as ambient temperature, etc.) of the workpiece. And finally, curing, wherein the curing step is shown in figure 2 and comprises the steps of keeping at 90 ℃ for 10min and keeping at 250 ℃ for 15min in sequence.
Example 3
A hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-cleaning coating comprises the following raw material components in percentage: the first component is 72 percent, and the second component is 28 percent.
The first component comprises the following raw materials in percentage by mass:
water-dispersible nanoscale titanium sols: 50 percent of
Nano-level titanium oxide powder: 15 percent of
Titanium dioxide: 10 percent of
Water + isopropanol + ethanol: 25 percent of
Wherein, the water: isopropanol + ethanol ═ 1: 1; the water dispersible nanometer titanium sol is water dispersible nanometer titanium oxide with particle size of 10-100nm and titanium oxide content of 20-50%;
the second component comprises the following raw materials in percentage by mass:
siloxane + fluorosilane: 88 percent
Citric acid: 2 percent
Isopropanol + ethanol: 10 percent of
Wherein, the siloxane is a mixture of tripropyl fluoro silane and ethyl triethoxy silane, and the fluoro silane is a mixture of methyl trifluoro silane and diethyl difluoro silane.
And (3) putting the first component into a tank mill for grinding and dispersing, wherein the ambient temperature is kept at 20-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is more than 4 hours until all precipitates are dispersed, thus obtaining the first component. And (4) stirring the second component at a low speed, and uniformly stirring to obtain the second component. After the first component and the second component are mixed, the pot mill is continuously used for mixing and curing, the ambient temperature is kept at 20-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is 6-8 hours. It should be noted that the grinding time has a correlation with the ambient temperature and the rotation speed. After the grinding and curing are finished, the coating is discharged and filtered by filter cloth with 300-400 meshes to obtain the coating which is hydrophobic and oleophobic, non-sticky, resistant to oil dirt and easy to clean.
Referring to fig. 1, the preparation process of the coating includes the steps of pre-treating the workpiece, spraying the coating on the surface of the pre-treated workpiece, and finally curing. The pretreatment comprises sand blasting, degreasing and oil removing and preheating which are sequentially carried out. Wherein, 60 meshes of 80 meshes of corundum sand or stainless steel sand is used for sand blasting, and the air pressure is 0.5-1.0 MPa; degreasing the oil to remove surface sand grains and dust, and ensuring that the surface of the workpiece is clean without oil stains or other foreign matters; preheating to make the temperature of the workpiece reach 50-60 ℃. Then spraying with compressed air under the conditions of spray gun caliber of 1.0-1.5mm and atomizing pressure of 2.5-3.0kg/cm 2 The film thickness is recommended to be 20 to 30 μm. If the film layer is too thin, the coating that may be formed is prone to cracking and does not have the corresponding functional characteristics. The pretreatment process needs to be properly adjusted according to the base material (material, wall thickness and the like) and the construction conditions (such as environment temperature and the like) of the workpiece. And finally, curing, wherein the curing step comprises the steps of keeping at 90 ℃ for 10min and keeping at 300 ℃ for 10min in sequence.
Example 4
A hydrophobic and oleophobic, non-stick and oil-stain resistant easy-to-clean coating comprises the following raw material components in percentage by weight: the first component is 65% and the second component is 35%.
The first component comprises the following raw materials in percentage by mass:
water dispersible nano silica sol: 50 percent
Nano-grade zirconium oxide powder: 35 percent of
Antimony tin ash: 10 percent of
Water + ethylene glycol monobutyl ether + n-butanol: 5 percent
Wherein, the ratio of water: ethylene glycol monobutyl ether + n-butanol ═ 1: 1; the water dispersible nanometer silica sol is water dispersible nanometer titanium oxide with particle size of 10-100nm and titanium oxide content of 20-50%;
the second component comprises the following raw materials in percentage by mass:
siloxane + fluorosilane: 90 percent of
Formic acid: 2 percent of
Ethylene glycol monobutyl ether + n-butanol: 8 percent
Wherein, the siloxane is a mixture of methyltriethoxysilane and propyl trimethoxy silane, and the fluorosilane is a mixture of tridecafluorooctyl trimethoxy silane and dodecafluoroheptyl propyl trimethoxy silane.
And (3) putting the first component into a tank mill for grinding and dispersing, wherein the ambient temperature is kept at 20-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is more than 4 hours until all precipitates are dispersed, thus obtaining the first component. And (4) stirring the second component at a low speed, and uniformly stirring to obtain the second component. After the first component and the second component are mixed, the pot mill is continuously used for mixing and curing, the ambient temperature is kept at 20-25 ℃, the grinding speed is 100-140 r/min, and the grinding time is 24 hours. After the grinding and curing are finished, the coating is discharged and filtered by filter cloth with 300-400 meshes to obtain the coating which is hydrophobic and oleophobic, non-sticky, resistant to oil dirt and easy to clean.
Referring to fig. 1, the preparation process of the coating includes the steps of pre-treating the workpiece, spraying the coating on the surface of the pre-treated workpiece, and finally curing. The pretreatment comprises sand blasting, degreasing and oil removing and preheating which are sequentially carried out. Wherein, the sand blasting uses 60 meshes, 80 meshes and 1:1 corundum sand or stainless steelSand, air pressure 0.5-1.0 MPa; degreasing and oil yielding are used for removing surface sand grains and dust, and the surface of the workpiece is ensured to be clean without oil stains or other foreign matters; preheating to make the temperature of the workpiece reach 50-60 ℃. Then spraying with compressed air under the conditions of spray gun caliber of 1.0-1.5mm and atomizing pressure of 2.5-3.0kg/cm 2 The film thickness is 20-30 μm. If the film layer is too thin, the coating that may be formed is prone to cracking and does not have the corresponding functional characteristics. The pretreatment process needs to be properly adjusted according to the base material (material, wall thickness, etc.) and construction conditions (such as ambient temperature, etc.) of the workpiece. And finally, curing, wherein the curing step comprises the steps of keeping at 90 ℃ for 10min and keeping at 200 ℃ for 20min in sequence.
Tests prove that the hydrophobic, oleophobic, non-sticky, oil-stain-resistant and easy-to-clean coating prepared in the examples 1-4 has excellent super-amphiphobic characteristics, the water contact angle can reach 155-160 degrees, the rolling angle can be about 1-5 degrees, and for an alcohol aqueous solution with the concentration of 20%, the contact angle can reach more than 100 degrees, so that the hydrophobic, oleophobic, non-sticky and easy-to-clean coating has good oleophobic property.
In summary, the invention provides a hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating, which comprises a first component and a second component, namely a material hybridized by (fluoro) siloxane and an inorganic material, and a preparation method thereof. The coating is connected through a chemical grafting copolymerization reaction through a crosslinking polymerization reaction of (fluoro) siloxane and a non-single inorganic (non) metal nano material, so that the organic and inorganic materials have better compatibility, and the chemical bonding is stacked to form a multiple nano composite structure, thereby ensuring the wear resistance and the long-acting property of the coating. The product obtained by hydrolytic polymerization reaction of inorganic filler and silane is rich in-CH on surface 3 The groups provide non-tackiness, so that the non-tackiness has good durability.
According to the preparation method of the hydrophobic, oleophobic, non-sticky and oil stain resistant easy-to-clean coating, the coating prepared by the preparation method has excellent super-amphiphobic characteristics, the water contact angle can reach 155-160 degrees, the rolling angle can reach about 1-5 degrees, and for an alcohol water solution with the concentration of 20%, the contact angle can reach more than 100 degrees, so that the coating has good oleophobic property, and the advantages of inorganic filler and low surface energy (fluorine) siloxane are effectively combined, so that the hydrophobic property and the oleophobic property of the coating are remarkably improved. The water dispersible nanometer sol is added into the coating, so that the coating has good high temperature resistance and corrosion resistance. Meanwhile, after the nano-scale inorganic powder is added by taking the dispersion liquid as a carrier, better dispersion can be formed in the coating, the nano-scale inorganic powder still keeps after film forming, and the temperature impact resistance of the coating is greatly improved.
The second component in the coating can be siloxane without adding fluorosilane, so that the prepared coating does not contain fluorine elements, the adverse effect of the fluorine elements on the environment or individuals is reduced, if fluorine-containing groups are introduced, the coating has excellent performances of solvent resistance, chemical stability, lower surface energy and the like, and pollutants such as water, oil and the like are difficult to adhere to the surface of the coating, so that the coating has good stain resistance.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The hydrophobic and oleophobic, non-sticky and oil stain resistant easy-to-clean coating is characterized by comprising a first component and a second component, wherein the first component accounts for 50-65% of the mass percentage, and the second component accounts for 35-50% of the mass percentage;
the first component is an inorganic component, and the percentage of the raw materials of the first component is as follows: 50-85% of inorganic filler, 0-10% of inorganic pigment and 5-50% of solvent;
the second component comprises the following raw materials in percentage: 85-90% of siloxane and/or fluorosilane, 1-2% of acid and 8-14% of solvent.
2. The hydrophobic-oleophobic, non-stick, and stain-resistant easy-to-clean coating of claim 1, wherein the inorganic filler is a water-dispersible nanoscale sol and/or nanoscale inorganic powder.
3. The hydrophobic-oleophobic, non-stick, and greasy-resistant easy-to-clean coating of claim 2, wherein the water-dispersible nanoscale sol is a silica, alumina, zirconia, or titania sol having a solids content of 10-50% and a particle size of 10-150 nm.
4. The hydrophobic-oleophobic, non-sticky and oil stain resistant easy-to-clean coating of claim 2, wherein the nanoscale inorganic powder is nanoscale silica, alumina, zirconia and titania powder, and the particle size of the nanoscale inorganic powder is 30-500 nm.
5. The hydrophobic, oleophobic, non-stick, and stain resistant easy clean coating of claim 1 wherein the siloxane comprises tetramethoxysilane, tetrapropoxysilane, methyltrimethoxysilane (MTMOS), Methyltriethoxysilane (MTEOS), methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, propyltrimethoxysilane (PrTMOS), propyltriethoxysilane (PrTEOS), propyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropyldimethoxysilane, dipropyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, propyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and mixtures thereof, One or more of trimethylpropyloxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, tripropylmethoxysilane, tripropylethoxysilane and tripropylpropoxysilane;
the fluorosilane comprises one or a mixture of more of methyltrifluorosilane, trimethylfluorosilane, trifluoropropylmethyldichlorosilane, trifluoromethyltrimethoxysilane, 1,2, 2-trifluorovinyltriphenylsilane, tert-butyldimethylsilyl trifluoromethanesulfonate, r-trifluoropropylmethylpolysiloxane, trifluoropropylmethylcyclotrisiloxane, bis (3,3, 3-trifluoropropyl) dimethoxysilane, heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltrimethoxysilane and dodecafluoroheptylpropyltrimethoxysilane.
6. The hydrophobic oleophobic, non-stick, and greasy soil resistant easy to clean coating of claim 1, wherein the acid is a mixture of one or more of formic acid, glacial acetic acid, and citric acid.
7. The hydrophobic oleophobic, non-stick, and greasy dirt resistant easy clean coating of claim 1, wherein the solvent is one or more mixtures of ethanol, ethylene glycol, isopropanol, n-propanol, n-butanol, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, butyl acetate.
8. A preparation method of a hydrophobic and oleophobic, non-stick and oil stain resistant easy-to-clean coating is characterized in that a first component and a second component of the hydrophobic and oleophobic, non-stick and oil stain resistant easy-to-clean coating disclosed by any one of claims 1-7 are mixed to obtain the coating, and the coating is sprayed on the surface of a substrate and then cured to form the coating.
9. The method for preparing hydrophobic and oleophobic, non-stick and greasy dirt resistant easy-to-clean coating according to claim 8, wherein the curing is baking at 200-300 ℃ for 10-30 min.
10. The method of making a hydrophobic and oleophobic, non-stick and stain resistant easy-to-clean coating according to claim 8 wherein the first and second components are mixed, ground and aged for 6-24 hours at 15-25 ℃.
CN202210520760.XA 2022-05-13 2022-05-13 Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method Pending CN114989722A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210520760.XA CN114989722A (en) 2022-05-13 2022-05-13 Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210520760.XA CN114989722A (en) 2022-05-13 2022-05-13 Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method

Publications (1)

Publication Number Publication Date
CN114989722A true CN114989722A (en) 2022-09-02

Family

ID=83027291

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210520760.XA Pending CN114989722A (en) 2022-05-13 2022-05-13 Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method

Country Status (1)

Country Link
CN (1) CN114989722A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116694115A (en) * 2023-05-15 2023-09-05 镇江贝斯特新材料股份有限公司 A transparent hydrophobic and oleophobic coating and its preparation method and the formed transparent hydrophobic and oleophobic coating
CN119264810A (en) * 2024-10-01 2025-01-07 中山市泰源玻璃工艺制品有限公司 High temperature resistant, scratch resistant and easy-to-clean glass product and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205201A (en) * 2013-01-22 2013-07-17 浙江鹏孚隆科技有限公司 Non-stick ceramic paint and coating method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103205201A (en) * 2013-01-22 2013-07-17 浙江鹏孚隆科技有限公司 Non-stick ceramic paint and coating method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116694115A (en) * 2023-05-15 2023-09-05 镇江贝斯特新材料股份有限公司 A transparent hydrophobic and oleophobic coating and its preparation method and the formed transparent hydrophobic and oleophobic coating
CN119264810A (en) * 2024-10-01 2025-01-07 中山市泰源玻璃工艺制品有限公司 High temperature resistant, scratch resistant and easy-to-clean glass product and preparation method thereof

Similar Documents

Publication Publication Date Title
US7879449B2 (en) Non-stick ceramic coating composition and process
EP1835002B1 (en) Non-stick ceramic coating composition and process
CN103820021B (en) A kind of non-stick ceramic coating and preparation method thereof
US20140186639A1 (en) Non-stick ceramic coating composition and process
CN103849092B (en) Composite material micropowder, method for forming same, ceramic coating, and protective coating
CN105838169B (en) A kind of universal high-performance water-based glass ceramics glaze and preparation method thereof
CN112358617B (en) Composite organic silicon resin and high-temperature-resistant coating
CN114989722A (en) Hydrophobic and oleophobic, non-sticky and oil-stain-resistant easy-to-clean coating and coating preparation method
CN106479354B (en) A kind of antifouling anticorrosive nano polysiloxane coating materials of primer-topcoat in one and preparation method thereof
CN102911584B (en) A kind of anti-doodling and anti-affixing nano paint and preparation method thereof
CN107418405A (en) A kind of aqueous fluorine-containing polyurethane coating and preparation method thereof
CN101481554A (en) High-hardness high temperature resistant non-fluoride aqueous nonstick coating
WO2021139215A1 (en) Self-healing or reusable product, preparation method therefor, and application thereof
US20100075057A1 (en) Hydrophobic and scratch-resistant paints for metal surfaces and brake dust-repelling wheel coatings
JP2017218372A (en) Water-repellent article and method of manufacturing the same
CN1244655C (en) Paint of silicon-ceramic capable of resisting 900-1200 deg.C. organic high temp
CN109401488B (en) High-hardness wear-resistant anti-fouling inorganic nano ceramic modified wood coating and preparation method thereof
CN109401564B (en) High-weather-resistance hydrophobic self-cleaning metal curtain wall plate and preparation method thereof
CN110564187A (en) Anti-reflection fluorine-free super-hydrophobic self-cleaning nano film and preparation method thereof
JP6939142B2 (en) Paint for metal plate and manufacturing method of painted metal plate using it
CN117384546B (en) Ceramic coating for etching pot and preparation method and application thereof
CN104212341A (en) Far infrared emission high-temperature-resistant kitchen and bath paint and preparation method thereof
AU2012227320B2 (en) Non-stick ceramic coating composition and process
CN116218366B (en) Polymer ceramic super-hydrophilic anti-corrosion coating material, and preparation method and application thereof
CN117735854A (en) Self-cleaning heat-insulating coated glass and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20220902