CN113122133A - Dynamic hydrophobic and oleophobic coating, preparation method, use method and dynamic hydrophobic and oleophobic coating - Google Patents
Dynamic hydrophobic and oleophobic coating, preparation method, use method and dynamic hydrophobic and oleophobic coating Download PDFInfo
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- CN113122133A CN113122133A CN202110422602.6A CN202110422602A CN113122133A CN 113122133 A CN113122133 A CN 113122133A CN 202110422602 A CN202110422602 A CN 202110422602A CN 113122133 A CN113122133 A CN 113122133A
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- 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
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- 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
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention relates to the technical field of surface protection coating materials, in particular to a dynamic hydrophobic and oleophobic coating, a preparation method, a use method and a dynamic hydrophobic and oleophobic coating, wherein the dynamic hydrophobic and oleophobic coating is prepared from the following raw materials: the paint comprises, by weight, 2-15 parts of multi-mercapto resin, 10-30 parts of siloxane polymer containing carbon-carbon double bonds and 49-86.9 parts of solvent, wherein sufficient crosslinking sites are provided by the multi-mercapto resin, a large number of crosslinking sites are provided by the carbon-carbon double bonds in a branched chain of the siloxane polymer containing the carbon-carbon double bonds, and a chain segment of the siloxane polymer has good flexibility and is easy to migrate to the surface of a paint to form a polymer brush with low surface energy, so that the hydrophobic and oleophobic properties of a coating are improved. The mercapto-containing resin and the siloxane polymer containing carbon-carbon double bonds are subjected to multifunctional reaction and high crosslinking to form a compact network structure, so that the coating has the characteristic of high hardness, and the conditions that the coating is damaged by physical friction and chemical corrosion to cause the exposure of a base material and the loss of the protective effect are avoided.
Description
Technical Field
The invention relates to the technical field of surface protective coating materials, in particular to a dynamic hydrophobic and oleophobic coating, a preparation method, a use method and a dynamic hydrophobic and oleophobic coating.
Background
The dynamic hydrophobic-oleophobic coating refers to the dynamic hydrophobic-lyophobic capability that when water and organic medium with low surface energy are contacted with the coating, when the coating is inclined to a certain angle, liquid drops can easily slide off the surface of the coating without leaving marks. The dynamic hydrophobic and oleophobic coating has wide application value in human production and life, and can be applied to the fields of fingerprint-proof touch screens, self-cleaning clothes, non-stick pans, range hoods, crude oil transportation pipelines and the like. However, with the increase of the number of times of use of the existing dynamic amphiphobic coating, the coating is damaged due to physical friction and chemical corrosion, so that the optical performance of the coating is reduced, the hydrophobic and oleophobic capabilities are greatly reduced or even completely lost, and the substrate is exposed and loses the protective effect, so that the invention of the dynamic amphiphobic coating with good optical transparency and mechanical stability is necessary.
Disclosure of Invention
The embodiments of the present invention are directed to solving at least one of the technical problems occurring in the prior art or the related art.
To this end, it is an object of embodiments of the present invention to provide a dynamic amphiphobic coating.
Another object of an embodiment of the present invention is to provide a method for using a dynamic amphiphobic coating.
It is a further object of embodiments of the present invention to provide a dynamic amphiphobic coating.
In order to achieve the above object, the technical solution of the first aspect of the present invention provides a dynamic amphiphobic coating, which is prepared from the following raw materials in parts by weight:
2-15 parts of multi-mercapto resin, 10-30 parts of siloxane polymer containing carbon-carbon double bonds and 49-86.9 parts of solvent.
In addition, the dynamic amphiphobic coating in the technical scheme provided by the embodiment of the invention can also have the following additional technical characteristics:
in one embodiment of the present invention, the dynamic amphiphobic coating further comprises:
1-5 parts of fluorine modified mercapto resin; 0.1-1 part of photoinitiator.
In one embodiment of the present invention, the solvent comprises: at least one of ethyl acetate, tetrahydrofuran, butyl acetate, N-dimethylformamide, or acetone.
The technical scheme of the second aspect of the invention provides a preparation method of any one of the dynamic amphiphobic coating, and the preparation method comprises the following steps:
mixing multi-sulfhydryl resin and siloxane polymer containing carbon-carbon double bonds in a solvent to obtain a resin solution;
adding a photoinitiator into the resin solution for mixing to obtain the dynamic amphiphobic coating.
In one embodiment of the present invention, the preparation method of the dynamic amphiphobic coating further comprises:
preparing fluorine modified sulfhydryl resin;
the step of obtaining the resin solution comprises:
mixing the multi-sulfhydryl resin, the siloxane polymer containing carbon-carbon double bonds and the fluorine modified sulfhydryl resin in a solvent to obtain a resin solution.
In one embodiment of the present invention, the preparation of the fluorine-modified mercapto resin comprises:
mixing 20-40 parts of fluorine-containing acrylate and 10-30 parts of multi-mercapto resin in 29-69.7 parts of acetone solution to obtain a mixed solution;
removing the acetone in the mixed solution.
In one embodiment of the present invention, the preparation of the fluorine-modified mercapto resin further comprises:
adding the mixed solution into a catalyst, and stirring for 8-24 h;
the catalyst is any one of diethylamine, dipropylamine, dibutylamine or tributylamine.
The technical scheme of the third aspect of the invention provides a use method of the dynamic amphiphobic coating, which is characterized in that the use method of the dynamic amphiphobic coating comprises the following steps:
coating the dynamic amphiphobic coating on the surface of a substrate;
drying the base material coated with the dynamic hydrophobic and oleophobic coating;
and drying the base material, and carrying out ultraviolet curing to obtain the dynamic hydrophobic and oleophobic coating.
In one technical scheme of the invention, the drying of the base material coated with the dynamic amphiphobic coating comprises the following steps:
drying for 10min to 2h at the drying temperature of 40 ℃ to 100 ℃.
In the technical scheme of the fourth aspect of the invention, a dynamic amphiphobic coating is provided, and is prepared by any one of the using methods of the dynamic amphiphobic coating.
Compared with the prior art, the invention at least comprises the following beneficial effects:
the invention utilizes the multi-sulfhydryl resin as the matrix resin of the dynamic double-hydrophobic coating, the multi-sulfhydryl resin provides sufficient crosslinking sites, the siloxane polymer containing carbon-carbon double bonds has a flexible main chain and a branched chain, wherein the carbon-carbon double bonds in the branched chain provide a large number of crosslinking sites, and the chain segment of the siloxane polymer has better flexibility and is easy to migrate to the surface of the coating to form a polymer brush with low surface energy, thereby improving the hydrophobic and oleophobic properties of the coating. When the dynamic hydrophobic and oleophobic coating is cured into the dynamic hydrophobic and oleophobic coating, the mercapto-containing resin and the siloxane polymer containing carbon-carbon double bonds are highly crosslinked through a multifunctional reaction to form a compact network structure, so that the coating has the characteristic of high hardness, and the conditions that the coating is damaged due to physical friction and chemical corrosion, so that the base material is exposed and the protective effect is lost are avoided.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a schematic flow diagram of a process for preparing a dynamic amphiphobic coating according to the invention;
FIG. 2 shows a schematic flow diagram of a method of using a dynamic amphiphobic coating according to the invention;
FIG. 3 shows a high resolution scanning electron microscope image of a dynamic amphiphobic coating made according to one embodiment of the present invention.
Detailed Description
The present invention is further described in detail below with reference to the drawings and examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined 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. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The embodiment of the invention provides a dynamic amphiphobic coating which is prepared from the following raw materials in parts by weight: 2-15 parts of multi-mercapto resin, 10-30 parts of siloxane polymer containing carbon-carbon double bonds and 49-86.9 parts of solvent. The multi-mercapto resin is used as matrix resin of the dynamic double-hydrophobic coating, sufficient crosslinking sites are provided by the multi-mercapto resin, the siloxane polymer containing carbon-carbon double bonds has a flexible main chain and a flexible branched chain, wherein the carbon-carbon double bonds in the branched chain also provide a large number of crosslinking sites, and the chain segments of the siloxane polymer have good flexibility and are easy to migrate to the surface of the coating to form a polymer brush with low surface energy, so that the hydrophobic and oleophobic properties of the coating are improved. When the dynamic hydrophobic and oleophobic coating is cured into the dynamic hydrophobic and oleophobic coating, the mercapto-containing resin and the siloxane polymer containing carbon-carbon double bonds are highly crosslinked through a multifunctional reaction to form a compact network structure, so that the coating has the characteristic of high hardness, and the conditions that the coating is damaged due to physical friction and chemical corrosion, so that the base material is exposed and the protective effect is lost are avoided. And the mercapto-alkene reaction has the advantages of rapid and uniform crosslinking and low shrinkage rate, so that the microstructure of the surface of the coating is uniform and flat, a large-area phase separation area causing light scattering is not included, and the optical transparency of the coating is improved.
Further, the dynamic amphiphobic coating also comprises: 1-5 parts of fluorine modified mercapto resin; 0.1-1 part of photoinitiator. The fluorocarbon chain is provided by adding the fluorine modified sulfydryl resin and the crosslinking sites on the carbon-carbon double bonds of the siloxane polymer containing the carbon-carbon double bonds for combination, and after the coating is cured into the coating, the fluorocarbon chain further reduces the surface energy of the coating, improves the hydrophobic and oleophobic capabilities of the coating, and prevents water and oil from converging on the surface of the coating. It is understood that 0 part of fluorine modified sulfydryl resin can be selected as the dynamic amphiphobic coating, when the 0 part of fluorine modified sulfydryl resin is used, the hydrophobic and oleophobic properties of the coating are endowed by a polysiloxane chain segment by a low surface energy chemical component, the contact angle of the coating to water and oil is low, but the sliding angle to water and oil is less than 10 degrees, and the excellent dynamic amphiphobic property is realized.
Further, the above solvent includes: at least one of ethyl acetate, tetrahydrofuran, butyl acetate, N-dimethylformamide, or acetone. The solvent has the characteristics of strong solubility and environmental protection, and the multi-sulfhydryl resin and the siloxane polymer containing carbon-carbon double bonds are put into the solvent, so that the dissolving speed can be accelerated, and the efficiency of preparing the coating is improved.
Referring to fig. 1, an embodiment of the present invention provides a preparation method of a dynamic amphiphobic coating, specifically including:
step S10: mixing the multi-mercapto resin and the siloxane polymer containing carbon-carbon double bonds in a solvent to obtain a resin solution.
The multi-sulfhydryl resin and the siloxane polymer containing the carbon-carbon double bond are put into a solvent containing at least one of ethyl acetate, tetrahydrofuran, butyl acetate, N-dimethylformamide or acetone, so that the multi-sulfhydryl resin and the siloxane polymer containing the carbon-carbon double bond are dissolved in the solvent, the siloxane polymer containing the carbon-carbon double bond and the multi-sulfhydryl resin provide sufficient crosslinking sites, and the chain segment of the siloxane polymer containing the carbon-carbon double bond has better flexibility and is easy to migrate to the surface of the coating to form a polymer brush with low surface energy, thereby improving the hydrophobic and oleophobic properties of the coating. When the dynamic hydrophobic and oleophobic coating is cured into the dynamic hydrophobic and oleophobic coating, the mercapto-containing resin and the siloxane polymer containing carbon-carbon double bonds are highly crosslinked through a multifunctional reaction to form a compact network structure, so that the coating has the characteristic of high hardness, and the conditions that the coating is damaged due to physical friction and chemical corrosion, so that the base material is exposed and the protective effect is lost are avoided. The polythiol resin is any one of trimethylolpropane tris (3-mercaptopropionate), 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tris-2, 1-ethanediol ester, and pentaerythritol tetrakis (3-mercaptopropionate). The siloxane having a carbon-carbon double bond is polymerized into any one of (acryloyloxy) methylsiloxane homopolymer, copolymer of (acetoxypropyl) methylsiloxane and dimethylsiloxane, and methyl-vinyl (siloxane and polysiloxane).
Further, step S10 specifically includes:
2-15 parts of multi-sulfhydryl resin and 10-30 parts of siloxane polymer containing carbon-carbon double bonds are selected by weight and dissolved in 49-86.9 parts of solvent at room temperature.
Step S20: adding a photoinitiator into the resin solution for mixing to obtain the dynamic amphiphobic coating.
Adding a photoinitiator into the resin solution for mixing, wherein the photoinitiator can be any one of benzoin ethyl ether, benzoin dimethyl ether, 2-hydroxy-2-methyl propiophenone or 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone, is a free radical photoinitiator and can have certain light absorption capacity in an ultraviolet light region or a visible light region, and when light energy is absorbed, initiator molecules transition from a ground state to an excited singlet state and transition from systems to excited triplets; after the excited singlet state or triplet state is subjected to unimolecular or bimolecular chemical action, free radical active fragments capable of initiating monomer polymerization are generated, and after the dynamic amphiphobic coating absorbs light energy, under the action of a photoinitiator, the multi-mercapto resin and the siloxane polymer containing carbon-carbon double bonds are subjected to polyfunctional group reaction, and are rapidly crosslinked and cured to form a compact network structure, so that the coating has the characteristic of high hardness.
Further, step S20 specifically includes:
selecting 0.1-1 parts of photoinitiator by weight, adding the photoinitiator into the resin solution under the condition of keeping out of the sun, and stirring for 30min to 6h to obtain the transparent dynamic amphiphobic coating.
Step S10 further includes: preparing fluorine modified sulfhydryl resin; and mixing the multi-mercapto resin, the siloxane polymer containing the carbon-carbon double bond and the fluorine modified mercapto resin in a solvent to obtain the resin solution. The preparation method comprises the steps of preparing fluorine modified sulfydryl resin, adding the prepared fluorine modified sulfydryl resin, the siloxane polymer containing carbon-carbon double bonds and the multi-sulfydryl resin into a solvent, mixing to form a resin solution, combining crosslinking sites on the carbon-carbon double bonds of the fluorine modified sulfydryl resin and the siloxane polymer containing carbon-carbon double bonds to provide fluorocarbon chains, and after the coating is cured into the coating, further reducing the surface energy of the coating, improving the hydrophobic and oleophobic capabilities of the coating, and preventing water and oil from being gathered on the surface of the coating. In the fluorine modified sulfydryl resin, sulfydryl-alkene reaction has the advantages of rapid and uniform crosslinking and low shrinkage rate, so that the microstructure of the surface of the coating is uniform and flat, a large-area phase separation area causing light scattering is not included, and the optical transparency of the coating is improved.
Further, the step of mixing the multi-mercapto resin, the siloxane polymer containing a carbon-carbon double bond, and the fluorine-modified mercapto resin in a solvent to obtain the resin solution specifically includes:
2-15 parts of multi-sulfhydryl resin, 10-30 parts of siloxane polymer containing carbon-carbon double bonds and 0-5 parts of fluorine modified sulfhydryl resin are selected by weight and dissolved in 49-86.5 parts of solvent at room temperature.
The above-mentioned steps for preparing the fluorine-modified mercapto resin include: mixing fluorine-containing acrylate and multi-mercapto resin in an acetone solution to obtain a mixed solution; removing acetone in the mixed solution; wherein, 20-40 parts of fluorine-containing acrylate, 10-30 parts of multi-mercapto resin and 29-69.7 parts of acetone. The fluorine-containing acrylate and the multi-mercapto resin form fluorine-modified mercapto resin, and the fluorine-modified mercapto resin has a plurality of crosslinking sites and can be combined with the crosslinking sites on the carbon-carbon double bonds of the siloxane polymer containing the carbon-carbon double bonds, so that the hydrophobic and oleophobic capabilities of the coating are improved, and water and oil are prevented from converging on the surface of the coating. And the mercapto-alkene reaction has the advantages of rapid and uniform crosslinking and low shrinkage rate, so that the microstructure of the surface of the coating is uniform and flat, a large-area phase separation area causing light scattering is not included, and the optical transparency of the coating is improved. Wherein the fluorine-containing acrylate is any one of trifluoroethyl acrylate, heptafluorobutyl acrylate, 1H,2H, 2H-perfluorohexyl acrylate, 1H-perfluoroheptyl acrylate, 1H,2H, 2H-perfluorooctyl acrylate, 1H-perfluorodecyl acrylate or 1H,1H,2H, 2H-perfluorodecyl acrylate.
Further, the step of preparing the fluorine-modified mercapto resin specifically includes:
selecting 20-40 parts by weight of fluorine-containing acrylate and 10-30 parts by weight of multi-mercapto resin, adding 29-69.7 parts by weight of acetone solution at room temperature, adding 0.3-1 part by weight of catalyst for catalysis, wherein the catalyst is any one of diethylamine, dipropylamine, dibutylamine or tributylamine, stirring for 8-24 h, and removing acetone by a rotary evaporation method to obtain the fluorine-modified mercapto resin.
Referring to fig. 2, an embodiment of the present invention provides a method for using a dynamic amphiphobic coating, specifically including:
step S30: and (3) coating the dynamic amphiphobic coating on the surface of the substrate. The dynamic amphiphobic coating is coated on the surface of the base material by any one of a spin coating method, a flow coating method, a dip coating method and a spray coating method. The base material can be various materials of metal and nonmetal, when the base material is metal, aluminum material, iron material and the like can be selected, when the base material is nonmetal, inorganic nonmetal materials such as glass and ceramic can be selected, and organic polymer materials such as polyethylene terephthalate, polymethyl methacrylate and polycarbonate can also be selected.
Step S40: and drying the base material coated with the dynamic amphiphobic coating. The hydrophobic and oleophobic coating is dried in a light-resistant environment, so that the coating is prevented from flowing from the base material, and the base material is prevented from being covered unevenly.
Step S50: and drying the base material, and carrying out ultraviolet curing to obtain the dynamic hydrophobic and oleophobic coating. Drying the substrate coated with the dynamic amphiphobic coating in a dark environment, then placing the substrate in an ultraviolet curing machine, and curing the substrate by irradiating ultraviolet light for 5-20 min, wherein due to the fact that the dynamic amphiphobic coating contains a photoinitiator, when the dynamic amphiphobic coating absorbs the ultraviolet light energy, initiator molecules are transited from a ground state to an excited singlet state, and are transited from an intersystem to an excited triplet state; after the excited singlet state or triplet state is subjected to unimolecular or bimolecular chemical action, free radical active fragments capable of initiating monomer polymerization are generated, and after the dynamic amphiphobic coating absorbs light energy, under the action of a photoinitiator, the multi-mercapto resin and the siloxane polymer containing carbon-carbon double bonds are subjected to polyfunctional group reaction, and are rapidly crosslinked and cured to form a compact network structure, so that the coating has the characteristic of high hardness.
Step S40 further includes: drying for 10 to 2 hours at the drying temperature of 40 to 100 ℃.
And (3) putting the base material coated with the dynamic amphiphobic coating into an oven for drying, wherein the drying temperature is controlled to be between 40 ℃ and 100 ℃, and the drying time is controlled to be between 10h and 2 h.
The embodiment of the invention provides a dynamic amphiphobic coating, which is prepared by the using method of the dynamic amphiphobic coating, so that the dynamic amphiphobic coating has all the advantages of the dynamic amphiphobic coating. And the dynamic hydrophobic and oleophobic coating has the advantages of high transparency, good adhesive force, high curing efficiency, short time consumption and low processing cost.
In order to clearly understand the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following embodiments. The specific examples described herein relate to specific data only to illustrate the present invention and are not intended to limit the invention.
Example 1:
dissolving 7 parts of trimethylolpropane tris (3-mercaptopropionate) and 20 parts of a copolymer of (acetoxypropyl) methyl siloxane and dimethyl siloxane in 72.7 parts of ethyl acetate, adding 1 part of benzoin dimethyl ether under the condition of keeping out of the sun, and magnetically stirring for 2 hours to obtain the dynamic amphiphobic coating. And finally, immersing the substrate in the dynamic amphiphobic coating for 5min, taking out, drying at 80 ℃ for 0.5h, putting into an ultraviolet curing machine, and performing ultraviolet curing for 10min to obtain the dynamic amphiphobic coating.
Example 2:
and (2) putting 20 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.5 part of dibutylamine and 54.5 parts of acetone into a flask, starting magnetic stirring, uniformly mixing, dropwise adding 25 parts of 1H,1H,2H, 2H-perfluorodecyl acrylate into the solution, magnetically stirring for 10 hours, and performing rotary evaporation to remove the acetone to obtain the fluorine modified mercapto resin.
Dissolving 2 parts of pentaerythritol tetrakis (3-mercaptopropionate), 10 parts of (acryloyloxy) methyl siloxane homopolymer and 1 part of prepared fluorine modified mercapto resin in 86.9 parts of ethyl acetate, adding 0.1 part of benzoin ethyl ether under the condition of keeping out of the sun, and magnetically stirring for 30min to obtain the dynamic amphiphobic coating. And finally, coating the dynamic amphiphobic coating on a base material by using a curtain coating method, drying for 2h at 40 ℃, putting into an ultraviolet curing machine, and carrying out ultraviolet curing for 5min to obtain the dynamic amphiphobic coating.
Example 3:
and (2) putting 10 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.3 part of diethylamine and 69.7 parts of acetone into a flask, starting magnetic stirring, uniformly mixing, dropwise adding 20 parts of 1H,1H,2H, 2H-perfluorooctyl acrylate into the solution, magnetically stirring for 8 hours, and performing rotary evaporation to remove the acetone to obtain the fluorine modified mercapto resin.
Dissolving 1 part of the prepared fluorine modified mercapto resin, 10 parts of pentaerythritol tetrakis (3-mercaptopropionate) and 20 parts of (acryloyloxy) methyl siloxane homopolymer in 68.4 parts of tetrahydrofuran, adding 0.6 part of 2-hydroxy-2-methyl propiophenone under the condition of keeping out of the sun, and stirring for 2 hours by magnetic force to obtain the dynamic amphiphobic coating. And finally, spraying the dynamic amphiphobic coating on a base material, baking for 0.5h at 80 ℃, putting the base material into an ultraviolet curing machine, and performing ultraviolet curing for 20min to obtain the dynamic amphiphobic coating.
Example 4:
and (2) putting 30 parts of pentaerythritol tetrakis (3-mercaptopropionate), 1 part of diethylamine and 29 parts of acetone into a flask, starting magnetic stirring, uniformly mixing, dropwise adding 40 parts of 1H,1H,2H, 2H-perfluorooctyl acrylate into the solution, magnetically stirring for 24 hours, and performing rotary evaporation to remove the acetone to obtain the fluorine modified mercapto resin.
Dissolving 5 parts of the self-made fluorine modified mercapto resin, 15 parts of 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tri-2, 1-glycol ester and 30 parts of methyl-vinyl (siloxane and polysiloxane) in 49 parts of ethyl acetate, adding 1 part of benzoin ethyl ether under the condition of keeping out of the sun, and stirring for 6 hours by magnetic force to obtain the dynamic amphiphobic coating. And finally, spin-coating the dynamic amphiphobic coating on a substrate at the rotation speed of 1000r/min for 2min, drying at 100 ℃ for 10min, putting the substrate into an ultraviolet curing machine, and performing ultraviolet curing for 10min to obtain the dynamic amphiphobic coating.
Comparative example 1:
dissolving 7 parts of tripropylene glycol diacrylate and 20 parts of (acryloyloxy) methyl siloxane homopolymer in 72.7 parts of ethyl acetate, adding 0.3 part of benzoin ethyl ether under the condition of keeping out of the sun, and magnetically stirring for 2 hours to obtain the dynamic amphiphobic coating. And finally, immersing the substrate in the dynamic amphiphobic coating for 5min, taking out, drying at 80 ℃ for 0.5h, putting into an ultraviolet curing machine, and performing ultraviolet curing for 10min to obtain the dynamic amphiphobic coating.
Comparative example 2:
25 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.1 part of dibutylamine and 48.9 parts of acetone are put into a flask, magnetic stirring is started, after uniform mixing, 26 parts of 1H,1H,2H, 2H-perfluorodecyl acrylate is dropwise added into the solution, magnetic stirring is carried out for 10 hours, and the acetone is removed through rotary evaporation to obtain the fluorine modified mercapto resin.
Dissolving 3 parts of the self-made fluorine modified mercapto resin, 7 parts of trimethylolpropane tris (3-mercaptopropionate) and 30 parts of a copolymer of triallyl isocyanurate and dimethyl siloxane in 59 parts of ethyl acetate, adding 1 part of benzoin dimethyl ether under the condition of keeping out of the sun, and stirring for 2 hours by magnetic force to obtain the dynamic amphiphobic coating. And finally, immersing the substrate in the dynamic amphiphobic coating for 5min, taking out, drying at 80 ℃ for 0.5h, putting into an ultraviolet curing machine, and performing ultraviolet curing for 10min to obtain the dynamic amphiphobic coating.
(comparative example 2 is that 10 parts of pentaerythritol tetrakis (3-mercaptopropionate), 0.3 part of dibutylamine and 69.7 parts of acetone are put into a flask, magnetic stirring is started, after uniform mixing, 20 parts of 1H,1H,2H, 2H-perfluorodecyl acrylate is dropwise added into the solution, the solution is magnetically stirred for 10 hours, and the acetone is removed by rotary evaporation to prepare the fluorine modified mercapto resin.
Dissolving 2 parts of trimethylolpropane tris (3-mercaptopropionate), 10 parts of triallyl isocyanurate and 1 part of the prepared fluorine-modified mercapto resin in 86.9 parts of ethyl acetate, adding 0.1 part of benzoin ethyl ether under the condition of keeping out of the sun, and magnetically stirring for 30min to obtain the dynamic amphiphobic coating. And finally, coating the dynamic hydrophobic and oleophobic coating on a base material by using a curtain coating method, drying for 1h at the temperature of 80 ℃, putting into an ultraviolet curing machine, and performing ultraviolet curing for 5min to obtain the transparent coating. )
The above examples 1 to 4 and comparative examples 1 and 2 were subjected to a hardness test, a contact angle to water, a sliding angle test, a contact angle to hexadecane and a sliding angle test, respectively. See Table 1
| Test items | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Hardness of pencil | 9H | 8H | 9H | 8H | 3H | 5H |
| WCA(°) | 103.0 | 116.5 | 113.2 | 110.4 | 100.2 | 118.0 |
| WSA(°) | 23.2 | 38.0 | 32.3 | 28.4 | 35.4 | 87.2 |
| OCA(°) | 35.2 | 76.1 | 63.2 | 50.9 | 28.5 | 81.2 |
| OSA(°) | 2.1 | 10.0 | 8.5 | 6.0 | 13.5 | 45.4 |
TABLE 1
Where WCA in table 1 is the contact angle of the coating to water, WSA is the sliding angle of the coating to water, OCA is the contact angle of the coating to hexadecane, and OSA is the sliding angle of the coating to hexadecane.
From the test data in table 1, it can be known that the dynamic amphiphobic coating prepared by the method of the present application has a lower sliding angle for low surface tension liquid drops such as water and hexadecane, and the substrate coated with the dynamic amphiphobic coating is not easily corroded by acid, alkali, salt and other solutions besides good dynamic hydrophobic oleophobic property, and the dynamic amphiphobic coating has good hardness and good adhesion to glass and plastic substrates.
In the description of the present invention, the terms "plurality" or "a plurality" refer to two or more, and unless otherwise specifically limited, the terms "upper", "lower", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are merely for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention; the terms "connected," "mounted," "secured," and the like are to be construed broadly and include, for example, fixed connections, removable connections, or integral connections; may be directly connected or indirectly connected through an intermediate. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description of the present invention, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In the present invention, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The dynamic amphiphobic coating is characterized by being prepared from the following raw materials in parts by weight:
2-15 parts of multi-mercapto resin, 10-30 parts of siloxane polymer containing carbon-carbon double bonds and 49-86.9 parts of solvent.
2. The dynamic amphiphobic coating of claim 1, further comprising:
1-5 parts of fluorine modified mercapto resin;
0.1-1 part of photoinitiator.
3. The dynamic amphiphobic coating of claim 1, characterized in that:
the solvent comprises: at least one of ethyl acetate, tetrahydrofuran, butyl acetate, N-dimethylformamide, or acetone.
4. A method for preparing a dynamic amphiphobic coating according to any one of claims 1 to 3, wherein the method for preparing the dynamic amphiphobic coating comprises the following steps:
mixing the multi-mercapto resin and the siloxane polymer containing carbon-carbon double bonds in a solvent to obtain a resin solution;
adding a photoinitiator into the resin solution for mixing to obtain the dynamic amphiphobic coating.
5. The method for preparing the dynamic amphiphobic coating according to claim 4, characterized in that: the preparation method further comprises the following steps:
preparing fluorine modified sulfhydryl resin;
the step of obtaining a resin solution comprises:
and mixing the multi-mercapto resin, the siloxane polymer containing the carbon-carbon double bond and the fluorine modified mercapto resin in a solvent to obtain the resin solution.
6. The method for preparing the dynamic amphiphobic coating according to claim 5, characterized in that: the preparation of the fluorine-modified mercapto resin comprises:
mixing 20-40 parts of fluorine-containing acrylate and 10-30 parts of multi-mercapto resin in 29-69.7 parts of acetone solution to obtain a mixed solution;
and removing the acetone in the mixed solution.
7. The method for preparing the dynamic amphiphobic coating according to claim 6, characterized in that: the preparation of the fluorine-modified mercapto resin further comprises:
adding 0.3-1 part of catalyst into the mixed solution, and stirring for 8-24 h;
the catalyst is any one of diethylamine, dipropylamine, dibutylamine or tributylamine.
8. A method of using the dynamic amphiphobic coating of any one of claims 1 to 7, wherein the method of using the dynamic amphiphobic coating comprises:
applying the dynamic amphiphobic coating of any of claims 1 to 7 to a surface of a substrate;
drying the base material coated with the dynamic hydrophobic and oleophobic coating;
and drying the base material and then carrying out ultraviolet curing to obtain the dynamic hydrophobic and oleophobic coating.
9. The method of using the dynamic amphiphobic coating of claim 8, characterized in that: the drying of the substrate coated with the dynamic amphiphobic coating comprises the following steps:
drying for 10min to 2h at the drying temperature of 40 ℃ to 100 ℃.
10. A dynamic amphiphobic coating, characterized in that it is prepared by the use of the method according to claim 8 or 9.
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| CN114907741A (en) * | 2022-04-27 | 2022-08-16 | 首航科环(泉州)纳米涂料有限公司 | Environment-friendly hydrophobic nano coating and preparation method and use method thereof |
| CN116891683A (en) * | 2023-09-04 | 2023-10-17 | 北京特思迪半导体设备有限公司 | Polydimethylsiloxane amphiphobic coating, preparation method and application |
| CN117343565A (en) * | 2023-12-05 | 2024-01-05 | 北京特思迪半导体设备有限公司 | Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof |
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| CN106366294A (en) * | 2016-09-29 | 2017-02-01 | 西安交通大学 | Fluorine-containing hydrophobic epoxy curing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114907741A (en) * | 2022-04-27 | 2022-08-16 | 首航科环(泉州)纳米涂料有限公司 | Environment-friendly hydrophobic nano coating and preparation method and use method thereof |
| CN116891683A (en) * | 2023-09-04 | 2023-10-17 | 北京特思迪半导体设备有限公司 | Polydimethylsiloxane amphiphobic coating, preparation method and application |
| CN116891683B (en) * | 2023-09-04 | 2023-11-28 | 北京特思迪半导体设备有限公司 | Polydimethylsiloxane amphiphobic coating, preparation method and application |
| CN117343565A (en) * | 2023-12-05 | 2024-01-05 | 北京特思迪半导体设备有限公司 | Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof |
| CN117343565B (en) * | 2023-12-05 | 2024-02-13 | 北京特思迪半导体设备有限公司 | Preparation method of amphiphobic coating, prepared amphiphobic coating and application thereof |
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