A hydrophobic and oleophobic coating material, and a preparation method and application thereof

Abstract

The application discloses a kind of hydrophobic and oleophobic coating and its preparation method and application, the hydrophobic and oleophobic coating includes the following preparation raw materials: siloxane, organic base, isocyanate, resin auxiliary agent;The mass ratio of siloxane and organic base is (1000~100):5;The mass ratio of siloxane and isocyanate is (0.1~10):1;The mass ratio of siloxane and resin auxiliary agent is (0.1~10):1.The hydrophobic and oleophobic coating in the application is synergized by siloxane, organic base, isocyanate, resin auxiliary agent four kinds of components, so as to obtain the coating with high transparency, stronger adhesion, excellent waterproof, antifouling, anticorrosion, wear resistance, durability, UV resistance and other functions, which can be applied to the protection of plastic, glass, metal, non-metal substrate, and can be compounded with various resin materials, with good expandability, can be applied to different products and different application fields.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of materials, in particular to a hydrophobic and oleophobic coating and a preparation method and application thereof. BACKGROUND

[0002] A double-soluble coating refers to a coating with hydrophobic and oleophobic properties. When water droplets or oil droplets fall on the surface, the adhesion is weak and they can quickly slide off. It is generally considered that the sliding angle of water droplets or oil droplets on the surface of a double-soluble material is less than 10°. In the prior art, the preparation of a double-soluble coating is usually approached from two aspects: one is to obtain a double-soluble coating by injecting a low-surface-energy liquid with lubricity into a porous micro-nano structure. This kind of smooth porous coating with lubricity and double-soluble properties (SLIPS) is also a common strategy in the current research on double-soluble coatings. However, the lubricating liquid of this kind of coating is still prone to loss and other problems, which need to be solved. The other is a double-soluble coating obtained by grafting a low-surface-energy polymer on the surface of a substrate. Through the surface liquid-repellent effect of the low-surface-energy substance, the coating achieves the functions of hydrophobicity, oleophobicity and protection. However, this kind of coating often has the following shortcomings: the preparation process and conditions are harsh, the substrate dependency is strong, and the thickness of the coating is relatively thin, resulting in limited mechanical strength and durability, which limits its wide application. A common problem in existing double-soluble technology is that the process for preparing a double-soluble coating is complex, and the surface anti-fouling performance is limited, often requiring fluorinated substances to reinforce, and the coating is also often difficult to have high hardness and other properties. These deficiencies greatly limit the application of double-soluble coatings. SUMMARY

[0003] In order to overcome at least one of the problems existing in the prior art, one of the purposes of the present application is to provide a hydrophobic and oleophobic coating.

[0004] The second purpose of the present application is to provide a preparation method of a hydrophobic and oleophobic coating.

[0005] The third purpose of the present application is to provide a product.

[0006] The fourth purpose of the present application is to provide an application of a hydrophobic and oleophobic coating in the fields of engineering, transportation and manufacturing.

[0007] In order to achieve the above-mentioned purposes, the technical solution adopted by the present application is as follows:

[0008] The first aspect of the present application provides a hydrophobic and oleophobic coating, which comprises the following preparation raw materials: siloxane, organic base, isocyanate and resin additive. The mass ratio of the siloxane and the organic base is (1000-100):5. The mass ratio of the siloxane and the isocyanate is (0.1-10):1. The mass ratio of the siloxane and the resin additive is (0.1-10):1.

[0009] In the present application, the siloxane and isocyanate in the coating will undergo crosslinking reaction, thereby forming a paint film with high hardness on the surface of the substrate. The present application utilizes low surface energy siloxane, isocyanate and resin adjuvant, the three undergo chemical crosslinking reaction, obtaining a coating with high transparency, high hardness, high wear resistance, strong hydrophobic and oleophobic properties, which can form a surface smooth coating through conventional coating steps, and the coating has strong mechanical strength, adhesion, good transparency and low cost.

[0010] Preferably, the siloxane is selected from at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, polymethylalkylsiloxane, polydimethylsiloxane, hydroxyl silicone oil, amino silicone oil, hydrogen-containing silicone oil, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, bis(triethoxysilyl)methane, 1,2-bis(triethoxysilyl)ethane, dodecyltrimethoxysilane, dodecyltriethoxysilane, methyltris(butanoneoxime)silane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, γ-aminopropyl-triethoxysilane, γ-glycidoxypropyl-propyltrimethoxysilane, vinyltris(butanoneoxime)silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, g-aminopropyltrimethoxysilane, vinyltrimethoxysilane.

[0011] Preferably, the siloxane comprises siloxane A and siloxane B, and the mass ratio of siloxane A to siloxane B is (0.1-100):1; the siloxane A is linear silicone oil and / or small molecule silane containing two hydrolyzable functional groups; the siloxane B is small molecule silane containing not less than three hydrolyzable functional groups.

[0012] Preferably, the mass ratio of siloxane A to siloxane B is (1-10):1; further preferably, the mass ratio of siloxane A to siloxane B is (5-10):1.

[0013] Preferably, the hydrolyzable functional group comprises at least one of -OR, -NH x R y , -SR, -COOR; the R is selected from at least one of C1-C8 linear or branched alkyl, cycloalkyl, aralkenyl; x is 0, 1 or 2; x+y=2 or 3.

[0014] Preferably, the siloxane A is selected from at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, polymethylalkylsiloxane, polydimethylsiloxane, hydroxyl silicone oil, amino silicone oil, hydrogen-containing silicone oil.

[0015] Preferably, the siloxane B is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, di(triethoxysilyl)methane, 1,2-di(triethoxysilyl)ethane, dodecyltrimethoxysilane, dodecyltriethoxysilane, methyltribenzothionoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, γ-aminopropyl-triethoxysilane, γ-epoxypropoxypropyl-propyltrimethoxysilane, vinyltribenzothionoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, g-aminopropyltrimethoxysilane, vinyltrimethoxysilane.

[0016] The present application takes full advantage of the high hydrophobic and oleophobic properties and excellent antifouling properties of siloxane A, the coupling properties and strong adhesion of siloxane B, and the occurrence of reversible hydrolysis / condensation reaction between siloxane A and siloxane B under the catalysis of organic base, as well as the addition polymerization between the siloxane component, the resin auxiliary agent and the isocyanate component, so as to effectively improve the crosslinking degree and hardness of the system, thereby preparing a coating containing polysiloxane component, having high hardness, high wear resistance, excellent adhesion, high antifouling property, high corrosion resistance, high weather resistance and double-solvent properties, having significant application prospects and excellent economic and social benefits.

[0017] Preferably, the organic base is selected from at least one of diethylamine, triethylamine, triethylenediamine, n-propylamine, isopropylamine, 1,2-propanediamine, tetramethylethylenediamine, hexamethylenetetramine, diethylenetriamine, triethanolamine, urea, tetramethylammonium hydroxide, N,N-dimethylaniline, aniline, quinoline, pyridine, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, sodium ethoxide, n-butyllithium.

[0018] Preferably, the mass ratio of the siloxane to the isocyanate is (0.5-2):1.

[0019] Preferably, the isocyanate is selected from at least one of isophorone diisocyanate, toluene diisocyanate, diphenyl methane diisocyanate, m-xylylene diisocyanate, dicyclohexyl methane diisocyanate, hexamethylene diisocyanate. The isocyanate can react with the silicon hydroxyl in the siloxane component to form crosslinking points to enhance the hardness and wear resistance of the coating system.

[0020] Preferably, the mass ratio of the siloxane to the resin aid is (1-3) : 1.

[0021] Preferably, the resin aid contains at least one functional group selected from hydroxyl, epoxy, amino, and carboxyl. The resin aid in the present application can react with the isocyanate and be incorporated into the composition units of the matrix of the coating system.

[0022] Preferably, the resin aid is selected from at least one of phenol formaldehyde resin, urea formaldehyde resin, melamine formaldehyde resin, epoxy resin, hydroxyl acrylate resin, and epoxy acrylate resin.

[0023] Preferably, the coating further contains a solvent, and the mass ratio of the solvent to the siloxane is (0.01-100) : 1. Further preferably, the mass ratio of the solvent to the siloxane is (0.1-10) : 1; more preferably, the mass ratio of the solvent to the siloxane is (0.2-5) : 1.

[0024] Preferably, the solvent is selected from at least one of methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, diisopropyl ether, tetrahydrofuran, ethyl acetate, methyl acetate, propylene oxide, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, benzene, toluene, xylene, styrene, butyl toluene, vinyl toluene, trichloroethylene, dichloromethane, chlorobenzene, dichlorobenzene, carbon disulfide, carbon tetrachloride, n-pentane, n-hexane, cyclohexane, octane, hexadecane, and liquid paraffin.

[0025] The present application provides a hydrophobic and oleophobic coating with relatively low cost, good hydrophobic and oleophobic properties, strong adhesion, corrosion resistance, UV resistance, and high wear resistance. The hydrophobic and oleophobic coating is prepared by reacting linear siloxane (i.e., siloxane A) and crosslinking type siloxane molecules (i.e., siloxane B) with isocyanate, successfully applying hydrophobic organic silicon and isocyanate to the preparation of the double-solvent protective coating, and through the surface treatment method of coating and curing the substrate, a double-solvent protective coating is prepared. The coating has high transparency, good mechanical properties, strong adhesion, wear resistance, double-solvent effect, UV resistance, and corrosion resistance, and is suitable for the protection of various metal, plastic, non-metallic substrate, and electronic components and other products.

[0026] The second aspect of the present application provides a preparation method of the hydrophobic and oleophobic coating provided in the first aspect of the present application, comprising the following steps:

[0027] The hydrophobic and oleophobic coating is prepared by mixing the siloxane and the organic base, and then mixing and reacting with the isocyanate and the resin additive.

[0028] Preferably, the preparation method is mixing the siloxane, the organic base and the solvent, and then mixing and reacting with the isocyanate and the resin additive; further preferably, the preparation method is mixing the siloxane, the organic base and the solvent at 0-90℃ for 0.01-5h, and then mixing and reacting with the isocyanate and the resin additive for 0.01-5h.

[0029] The third aspect of the present application provides a product comprising a hydrophobic and oleophobic coating, which is prepared by coating and curing the hydrophobic and oleophobic coating according to the first aspect of the present application.

[0030] Preferably, the coating step is performed by spin coating, drop coating, dip coating, brush coating, blade coating or spray coating.

[0031] Preferably, the curing temperature is 0-180℃.

[0032] Preferably, the curing time is 0.1-48h.

[0033] Preferably, the product comprises a plastic material, a metal material or a non-metal material.

[0034] Preferably, the material comprises a building material, a textile or an electronic material.

[0035] The fourth aspect of the present application provides the use of the hydrophobic and oleophobic coating according to the first aspect of the present application in the fields of engineering, transportation and manufacturing.

[0036] Preferably, the engineering comprises building engineering, marine engineering and aerospace engineering.

[0037] The hydrophobic and oleophobic coating of the present application has the advantages of simple preparation method, easy operation, mild reaction conditions, environmental protection, low pollution, wide raw material sources, low cost, and suitability for batch production.

[0038] The hydrophobic and oleophobic coating of the present application has the advantages of simple preparation method, easy operation, mild reaction conditions, environmental protection, low pollution, wide raw material sources, low cost, and suitability for batch production. BRIEF DESCRIPTION OF DRAWINGS

[0039] Figure 1Figure for water droplet adhesion prevention test on the surface of the coating in Example 1.

[0040] Figure 2 Figure for ethylene glycol droplet adhesion prevention test on the surface of the coating in Example 4.

[0041] Figure 3 Figure for water column scouring anti-adhesion prevention test on the surface of the coating in Example 2 after the sash test.

[0042] Figure 4 Figure for acid corrosion resistance test of the blank iron sheet and the iron sheet containing the coating in Example 3.

[0043] Figure 5 Figure for change of hydrophobicity of the coating in Example 4 during ultraviolet irradiation.

[0044] Figure 6 Figure for transparency test of the coating in Example 7. DETAILED DESCRIPTION

[0045] The specific implementation of the present application is further described in detail below in combination with the drawings and examples, but the implementation and protection of the present application are not limited thereto. It should be noted that if the following processes are not specifically described in detail, they can be implemented or understood by those skilled in the art with reference to the prior art. If the reagents or instruments used are not marked with the manufacturer, they are conventional products that can be purchased on the market.

[0046] Example 1:

[0047] The present example provides a transparent wear-resistant omniphobic coating, which is prepared from the following raw materials: siloxane, diethylamine, hydroxy acrylate resin, diphenyl methane diisocyanate, and solvent. The siloxane is a mixture of dimethyl dimethoxy silane and dodecyl triethoxy silane with a mass ratio of 5:1. The mass ratio of siloxane to diethylamine is 100:2. The mass ratio of siloxane to hydroxy acrylate resin is 1:0.6. The mass ratio of siloxane to diphenyl methane diisocyanate is 1:0.9. The solvent is a mixture of ethanol and ethyl acetate with a mass ratio of 1:5. The mass ratio of siloxane to solvent is 1:1.

[0048] The transparent wear-resistant omniphobic coating in the present example is prepared by the following method, and the specific steps are as follows:

[0049] Firstly, dimethyldimethoxysilane and dodecyltriethoxysilane are mixed in a mass ratio of 5:1 and dissolved in a mixed solvent of ethanol and ethyl acetate (mass ratio of 1:5), 2% (based on the total mass of siloxane) of diethylamine is added, and the siloxane reaction solution is obtained by stirring at 65°C for 60 minutes. According to the mass ratio of siloxane to hydroxy acrylate resin of 1:0.6, the hydroxy acrylate resin is added to the siloxane reaction solution and stirred for 10 minutes. According to the mass ratio of siloxane to isocyanate of 1:0.9, diphenylmethane diisocyanate is added to the above reaction solution and stirred for 10 minutes to prepare the transparent wear-resistant omniphobic coating of this example.

[0050] The transparent wear-resistant omniphobic coating of this example is sprayed on the surface of the substrate, and the coated substrate is cured at 70°C for 1h to obtain the transparent wear-resistant omniphobic coating.

[0051] Example 2:

[0052] This example provides a transparent wear-resistant omniphobic coating, which is made of siloxane, tetramethylammonium hydroxide, epoxy acrylate resin and toluene diisocyanate, and solvent, wherein the siloxane is a mixture of diethyldimethoxysilane and n-octyltrimethoxysilane in a mass ratio of 10:1, the mass ratio of siloxane to tetramethylammonium hydroxide is 100:0.3, the mass ratio of siloxane to epoxy acrylate resin is 3:1, the mass ratio of siloxane to toluene diisocyanate is 1:0.9, the solvent is a mixture of ethanol and toluene in a mass ratio of 1:8, and the mass ratio of siloxane to solvent is 2:1.

[0053] The transparent wear-resistant omniphobic coating of this example is prepared by the following method, and the specific steps are as follows:

[0054] Firstly, diethyldimethoxysilane and n-octyltrimethoxysilane are mixed in a mass ratio of 10:1 and dissolved in a solvent of ethanol and toluene (mass ratio of 1:8), 0.3% (based on the total amount of siloxane) of tetramethylammonium hydroxide is added, and the siloxane reaction solution is obtained by stirring at 80°C for 60 minutes. According to the mass ratio of siloxane to resin additive of 3:1, the epoxy acrylate resin is added to the siloxane reaction solution and stirred for 5 minutes. According to the mass ratio of siloxane to isocyanate of 1:0.9, toluene diisocyanate is added to the above reaction solution and stirred for 10 minutes to prepare the transparent wear-resistant omniphobic coating of this example.

[0055] The transparent wear-resistant omniphobic coating of this example is sprayed on the surface of the substrate, and the coated substrate is cured at 80°C for 1h to obtain the transparent wear-resistant omniphobic coating.

[0056] Example 3:

[0057] The example provides a kind of transparent wear-resistant dual-repellent coating, which is made of siloxane, n-propylamine, epoxy resin and toluene diisocyanate, solvent preparation raw materials, wherein, siloxane is the mixture of dimethyl dimethoxysilane and tetramethoxysilane with mass ratio of 3:1, the mass ratio of siloxane and n-propylamine is 100:1.5, the mass ratio of siloxane and epoxy resin is 1:0.5, the mass ratio of siloxane and toluene diisocyanate is 1:1, the solvent is tetrahydrofuran, and the mass ratio of siloxane and solvent is 1:2.

[0058] The transparent wear-resistant dual-repellent coating in the example is prepared by the following preparation method, and the specific steps are as follows:

[0059] First, dimethyl dimethoxysilane and tetramethoxysilane are mixed in tetrahydrofuran solvent according to a mass ratio of 3:1, and n-propylamine with a mass fraction of 1.5% (based on the total amount of siloxane) is added, and stirred at 50°C for 2h to obtain a siloxane reaction solution. According to the mass ratio of siloxane:epoxy resin is 1:0.5, epoxy resin is added to the siloxane reaction solution, and stirred for 5min. According to the mass ratio of siloxane:isocyanate is 1:1, toluene diisocyanate is added to the above reaction solution, and stirred for 10min to obtain the transparent wear-resistant dual-repellent coating in the example.

[0060] The transparent wear-resistant dual-repellent coating in the example is sprayed on the surface of the substrate, and the coated substrate is cured at 50°C for 3h to obtain a transparent wear-resistant dual-repellent coating.

[0061] Example 4:

[0062] The example provides a kind of transparent wear-resistant dual-repellent coating, which is made of siloxane, n-propylamine, epoxy resin and toluene diisocyanate, solvent preparation raw materials, wherein, siloxane is the mixture of dimethyl dimethoxysilane and tetramethoxysilane with mass ratio of 3:1, the mass ratio of siloxane and n-propylamine is 100:1.5, the mass ratio of siloxane and epoxy resin is 1:0.5, the mass ratio of siloxane and toluene diisocyanate is 1:1, the solvent is tetrahydrofuran, and the mass ratio of siloxane and solvent is 1:2.

[0063] The transparent wear-resistant dual-repellent coating in the example is prepared by the following preparation method, and the specific steps are as follows:

[0064] The hydroxyl silicone oil and dodecyl triethoxysilane are mixed in a mass ratio of 10:1 and dissolved in ethanol and xylene (mass ratio 1:8) solvent, 0.5% (based on the total amount of siloxane) of tetramethylammonium hydroxide is added, and the mixture is stirred and reacted at 80°C for 60 min to obtain a siloxane reaction solution. The epoxy acrylate resin is added to the siloxane reaction solution in a mass ratio of 3:1, and stirred for 10 min. Hexamethylene diisocyanate is added to the above reaction solution in a mass ratio of 1:1.3, and stirred for 10 min to obtain the transparent wear-resistant omniphobic coating of this example.

[0065] The transparent wear-resistant omniphobic coating of this example is sprayed on the surface of the substrate, and the coated substrate is cured at 80°C for 1 h to obtain the transparent wear-resistant omniphobic coating.

[0066] Example 5:

[0067] This example provides a transparent wear-resistant omniphobic coating, which is made of siloxane, triethylamine, phenolic resin, toluene diisocyanate, and solvent as raw materials, wherein the siloxane is a mixture of amino silicone oil and hexadecyl trimethoxysilane in a mass ratio of 5:1, the mass ratio of siloxane to triethylamine is 100:1.5, the mass ratio of siloxane to phenolic resin is 5:1, the mass ratio of siloxane to toluene diisocyanate is 1:2, the solvent is a mixture of acetone and carbon tetrachloride in a mass ratio of 1:4, and the mass ratio of siloxane to solvent is 1:3.

[0068] The transparent wear-resistant omniphobic coating of this example is prepared by the following method, and the specific steps are as follows:

[0069] The amino silicone oil and hexadecyl trimethoxysilane are mixed in a mass ratio of 5:1 and dissolved in acetone and carbon tetrachloride (mass ratio 1:4) solvent, 1.5% (based on the total amount of siloxane) of triethylamine is added, and the mixture is stirred and reacted at 60°C for 2 h to obtain a siloxane reaction solution. The phenolic resin is added to the siloxane reaction solution in a mass ratio of 5:1, and stirred for 10 min. Toluene diisocyanate is added to the above reaction solution in a mass ratio of 1:2, and stirred for 10 min to obtain the transparent wear-resistant omniphobic coating of this example.

[0070] The transparent wear-resistant omniphobic coating of this example is sprayed on the surface of the substrate, and the coated substrate is cured at 50°C for 12 h to obtain the transparent wear-resistant omniphobic coating.

[0071] Example 6:

[0072] The example provides a kind of transparent wear-resistant dual-repellent coating, which is made of preparation raw materials of siloxane, tetramethylammonium hydroxide, urea formaldehyde resin and toluene diisocyanate, solvent, wherein, the mass ratio of polydimethylsiloxane and n-octyltrimethoxysilane in siloxane is 10:1, the mass ratio of siloxane and tetramethylammonium hydroxide is 100:0.5, the mass ratio of siloxane and urea formaldehyde resin is 5:1, the mass ratio of siloxane and toluene diisocyanate is 1:1, the mass ratio of isopropyl alcohol and dimethylbenzene in solvent is 1:5, and the mass ratio of siloxane and solvent is 1:3.

[0073] The transparent wear-resistant dual-repellent coating in the example is prepared by the following preparation method, and the specific steps are as follows:

[0074] First, polydimethylsiloxane and n-octyltrimethoxysilane are mixed in isopropyl alcohol and dimethylbenzene (mass ratio 1:5) solvent according to a mass ratio of 10:1, and 0.5% (based on the total amount of siloxane) tetramethylammonium hydroxide is added, and stirred at 80°C for 60 minutes to obtain a siloxane reaction solution. According to the mass ratio of siloxane to urea formaldehyde resin, urea formaldehyde resin is added to the siloxane reaction solution, and stirred for 10 minutes. According to the mass ratio of siloxane to isocyanate, toluene diisocyanate is added to the above reaction solution, and stirred for 10 minutes to obtain the transparent wear-resistant dual-repellent coating in the example.

[0075] The transparent wear-resistant dual-repellent coating in the example is sprayed on the surface of the substrate, and the coated substrate is cured at 50°C for 12 hours to obtain a transparent wear-resistant dual-repellent coating.

[0076] Example 7:

[0077] The example provides a kind of transparent wear-resistant dual-repellent coating, which is made of preparation raw materials of siloxane, tetramethylammonium hydroxide, urea formaldehyde resin and toluene diisocyanate, solvent, wherein, the mass ratio of polydimethylsiloxane and n-octyltrimethoxysilane in siloxane is 10:1, the mass ratio of siloxane and tetramethylammonium hydroxide is 100:0.5, the mass ratio of siloxane and urea formaldehyde resin is 5:1, the mass ratio of siloxane and toluene diisocyanate is 1:1.3, the mass ratio of ethanol and dimethylbenzene in solvent is 1:8, and the mass ratio of siloxane and solvent is 1:1.

[0078] The transparent wear-resistant dual-repellent coating in the example is prepared by the following preparation method, and the specific steps are as follows:

[0079] The hydroxyl silicone oil and n-octyl trimethoxysilane are mixed in a mass ratio of 20:1 and dissolved in an ethanol and xylene (mass ratio 1:8) solvent, 0.5% (based on the total amount of siloxane) of tetramethylammonium hydroxide is added, and the mixture is stirred and reacted at 80°C for 60 min to obtain a siloxane reaction solution. The epoxy resin is added to the siloxane reaction solution in a siloxane:epoxy resin mass ratio of 5:1, and stirred for 10 min. The toluene diisocyanate is added to the above reaction solution in a siloxane:isocyanate mass ratio of 1:1.3, and stirred for 10 min to obtain the transparent wear-resistant omniphobic coating of this example.

[0080] The transparent wear-resistant omniphobic coating of this example is sprayed on the surface of the substrate, and the coated substrate is cured at 80°C for 1 h to obtain the transparent wear-resistant omniphobic coating.

[0081] Comparative Example 1:

[0082] This example provides an omniphobic coating made from siloxane, diethylamine, hydroxy acrylic resin, and solvent, wherein the siloxane is a mixture of dimethyl dimethoxysilane and dodecyl triethoxysilane in a mass ratio of 5:1, the mass ratio of siloxane to diethylamine is 100:2, the mass ratio of siloxane to hydroxy acrylic resin is 1:0.6, the solvent is a mixture of ethanol and ethyl acetate in a mass ratio of 1:5, and the mass ratio of siloxane to solvent is 1:1.

[0083] The omniphobic coating of this example is prepared by the following method, and the specific steps are as follows:

[0084] The dimethyl dimethoxysilane and dodecyl triethoxysilane are mixed in a mass ratio of 5:1 and dissolved in a mixed solvent of ethanol and ethyl acetate (mass ratio 1:5), 2% (based on the total amount of siloxane) of diethylamine is added, and the mixture is stirred and reacted at 65°C for 60 min to obtain a siloxane reaction solution. The hydroxy acrylic resin is added to the siloxane reaction solution in a siloxane:hydroxy acrylic resin mass ratio of 1:0.6, and stirred for 10 min to obtain the omniphobic coating of this example.

[0085] The omniphobic coating of this example is sprayed on the surface of the substrate, and the coated substrate is cured at 70°C for 1 h to obtain the omniphobic coating.

[0086] Comparative Example 2:

[0087] The example provides a kind of amphiphobic coating, which is made of siloxane, tetramethylammonium hydroxide, epoxy acrylate resin, toluene diisocyanate, solvent preparation raw material, wherein, siloxane is n-octyl trimethoxysilane, the mass ratio of siloxane and tetramethylammonium hydroxide is 100:0.3, the mass ratio of siloxane and epoxy acrylate resin is 3:1, the mass ratio of siloxane and toluene diisocyanate is 1:0.9, solvent is the mixture of ethanol and toluene with mass ratio of 1:8, and the mass ratio of siloxane and solvent is 2:1.

[0088] The amphiphobic coating in the example is prepared by the following preparation method, and the specific steps are as follows:

[0089] First, n-octyl trimethoxysilane is dissolved in ethanol and toluene (mass ratio 1:8) solvent, and 0.3% (based on the total amount of siloxane) tetramethylammonium hydroxide is added, and stirred at 80°C for 60 min to obtain a siloxane reaction solution. According to the mass ratio of siloxane to epoxy acrylate resin, epoxy acrylate resin is added to the siloxane reaction solution, and stirred for 5 min. According to the mass ratio of siloxane to isocyanate, toluene diisocyanate is added to the above reaction solution, and stirred for 10 min to obtain the amphiphobic coating in the example.

[0090] The amphiphobic coating in the example is sprayed on the surface of the substrate, and the coated substrate is cured at 80°C for 1 h to obtain the amphiphobic coating.

[0091] Comparative Example 3:

[0092] The example provides a kind of amphiphobic coating, which is made of siloxane, tetramethylammonium hydroxide, epoxy acrylate resin, toluene diisocyanate, solvent preparation raw material, wherein, siloxane is n-octyl trimethoxysilane, the mass ratio of siloxane and tetramethylammonium hydroxide is 100:0.3, the mass ratio of siloxane and epoxy acrylate resin is 3:1, the mass ratio of siloxane and toluene diisocyanate is 1:0.9, solvent is the mixture of ethanol and toluene with mass ratio of 1:8, and the mass ratio of siloxane and solvent is 2:1.

[0093] The amphiphobic coating in the example is prepared by the following preparation method, and the specific steps are as follows:

[0094] First, n-octyl trimethoxysilane is dissolved in ethanol and toluene (mass ratio 1:8) solvent, and 0.3% (based on the total amount of siloxane) tetramethylammonium hydroxide is added, and stirred at 80°C for 60 min to obtain a siloxane reaction solution. According to the mass ratio of siloxane to epoxy acrylate resin, epoxy acrylate resin is added to the siloxane reaction solution, and stirred for 5 min. According to the mass ratio of siloxane to isocyanate, toluene diisocyanate is added to the above reaction solution, and stirred for 10 min to obtain the amphiphobic coating in the example.

[0095] The amphiphobic coating of the present example is obtained by spraying the amphiphobic coating on the surface of the substrate and curing the coated substrate at 50°C for 3h.

[0096] Comparative Example 4:

[0097] The present example provides an amphiphobic coating prepared from the following raw materials: silicone, tetramethylammonium hydroxide, epoxy acrylate resin, hexamethylene diisocyanate, and solvent, wherein the silicone is hydroxyl silicone oil, the mass ratio of the silicone to the tetramethylammonium hydroxide is 100:0.5, the mass ratio of the silicone to the epoxy acrylate resin is 3:1, the mass ratio of the silicone to the hexamethylene diisocyanate is 1:1.3, the solvent is a mixture of ethanol and dimethylbenzene with a mass ratio of 1:8, and the mass ratio of the silicone to the solvent is 1:1.

[0098] The amphiphobic coating of the present example is prepared by the following method, and the specific steps are as follows:

[0099] The hydroxyl silicone oil is first dissolved in the solvent of ethanol and dimethylbenzene (mass ratio of 1:8), and 0.5% (based on the total amount of silicone) of tetramethylammonium hydroxide is added, and stirred at 80°C for 60min to obtain a silicone reaction solution. The epoxy acrylate resin is added to the silicone reaction solution according to a mass ratio of 3:1, and stirred for 10min. The hexamethylene diisocyanate is added to the above reaction solution according to a mass ratio of 1:1.3, and stirred for 10min to obtain the amphiphobic coating of the present example.

[0100] The amphiphobic coating of the present example is obtained by spraying the amphiphobic coating on the surface of the substrate and curing the coated substrate at 80°C for 1h.

[0101] Performance test

[0102] The properties of the coating formed by the amphiphobic coating in Examples 1-4 and Comparative Examples 1-8 coated on the substrate are tested according to the following test methods, and the specific test methods are as follows:

[0103] (1) Pencil hardness test

[0104] Different hardness pencils are used to test the hardness of the coating, starting from the hardest 9H, decreasing by 3H, 2H, H, then HB which is moderately hard, and then B, 2B to the softest 6B. The front surface of the sample to be tested is fixed upwards, the pencil is clamped on the clamp and forms a 45° angle with the surface of the coating, and the tip of the pencil is pressed on the coating under the weight and pushed across the surface of the coating. Different pencils are tested on the surface of the coating from hard to soft until the pencil hardness at which the coating is not scratched is determined, and this hardness represents the hardness of the tested coating.

[0105] (2) Adhesion test, the adhesion of the coating is tested according to the crosshatch test method in the existing test standard, wherein the smaller the adhesion test value is, the higher the adhesion is.

[0106] (3) Advancing contact angle and receding contact angle

[0107] The advancing contact angle and receding contact angle of the coating surface at room temperature are measured by a contact angle measuring instrument. The test method is that about 5 μL of liquid droplet (water droplet and oil droplet are tested) is continuously added to the surface of the coating, the periphery of the liquid droplet will wriggle forward, and the angle at which the wriggle just occurs is taken as the advancing contact angle of the liquid droplet. If a small amount of liquid is taken out from the liquid droplet on the surface of the coating, the periphery of the liquid droplet will shrink, and the angle at which the shrinkage just occurs is taken as the receding contact angle of the liquid droplet, wherein the oil droplet is n-hexadecane liquid. The smaller the difference between the advancing and receding contact angles of the liquid droplet on the surface is, the higher the omniphobic performance of the surface is.

[0108] (4) Alcohol rubbing test

[0109] A 500g weight is pressed on 2 layers of gauze, the gauze is fully soaked with alcohol, and the gauze is rubbed back and forth on the coating at a speed of 2 seconds per round at a distance of 20 cm until obvious coating peeling occurs on the tested surface.

[0110] The properties of the omniphobic coating prepared from the coating in Examples 1-7 and Comparative Examples 1-4 according to the above test method are shown in Table 1.

[0111] Table 1 Test results of properties of the coating

[0112]

[0113] As shown in Table 1, the coating layers prepared in Examples 1-7 have high hardness, strong adhesion, good transparency, and low water droplet hysteresis angle on the surface, showing good anti-adhesion effect and good alcohol wiping resistance. Compared with Examples 1-7, no isocyanate component is added in Comparative Example 1, and the hardness of the surface is low, only about 2B, which affects the durability of the coating layer. In Comparative Example 2, no low-surface-energy bifunctional siloxane is added, and the hydrophobicity of the surface is low, which does not have good anti-adhesion, hydrophobic and oleophobic properties. In Comparative Example 3, no organic base is added, and the adhesion is about 2, which does not have good adhesion, and the coating layer in the grid area falls off, and the surface contact angle hysteresis effect is large, which does not have good double-solvent resistance. In Comparative Example 4, no multifunctional siloxane is added, and the adhesion is significantly reduced, and the coating layer in the grid area falls off, which is not as good as the coating layer in Examples 1-7. By comparing Examples 1-7 and Comparative Example 1, it can be seen that the isocyanate component is a key factor for improving the wear resistance of the coating layer. Examples 1-7 with added isocyanate component can withstand multiple alcohol rubbing, while the alcohol resistance and wear resistance of the sample in Comparative Example 1 without added isocyanate component are low.

[0114] (5) Anti-droplet adhesion test

[0115] Two glass substrates with a length of about 76 mm were taken, and the omniphobic coating in Example 1 and Example 4 was coated on the two glass substrates respectively, thereby forming an omniphobic coating on the two glass substrates, and then the two glass substrates were placed at an angle of 45° respectively, 15 μL of water droplets was dropped on the top surface of the glass substrate coated with the coating in Example 1, and the diagrams at the time of dropping the water droplets, the water droplets sliding to the middle position of the glass substrate, and the water droplets sliding to the bottom of the glass substrate were recorded respectively, as shown in Figure 1 , wherein, Figure 1 (a), Figure 1 (b), and Figure 1 (c) are the test diagrams at the time of dropping the water droplets, the water droplets sliding to the middle position of the glass substrate, and the water droplets sliding to the bottom of the glass substrate respectively, the time required for the water droplets to slide from the top of the glass substrate to the middle position is 0.4 s, and the time required for the water droplets to slide from the top of the glass substrate to the bottom is 0.6 s, which shows that the omniphobic coating in Example 1 has excellent hydrophobicity. 15 μL of ethylene glycol droplets was dropped on the top surface of the glass substrate coated with the coating in Example 4, and the diagrams at the time of dropping the ethylene glycol droplets, the ethylene glycol droplets sliding to the middle position of the glass substrate, and the ethylene glycol droplets sliding to the bottom of the glass substrate were recorded respectively, as shown in Figure 2 , wherein, Figure 2 (a), Figure 2 (b), and Figure 2(c) the test figures of the ethylene glycol liquid drop when being dropped, when sliding to the middle position of the glass substrate, and when sliding to the bottom of the glass substrate, respectively, the time required for the ethylene glycol liquid drop to slide from the top of the glass substrate to the middle position is 1.1s, and the time required for the ethylene glycol liquid drop to slide from the top of the glass substrate to the bottom is 2.9s, it can be known that the omniphobic coating in Example 4 has excellent oleophobicity.

[0116] The surface of the coating in Example 2 subjected to the cross-hatch test method is washed by a water column to test the waterproof drop adsorption effect, and the specific test results are shown in Figure 3 Figure 3 It can be known that the coating in Example 2 does not peel off after being cut by the cross-hatch blade, and the surface still maintains good waterproof performance, which further indicates that the coating formed by the coating material in the application has excellent bonding and waterproof effects.

[0117] (6) Acid corrosion resistance effect

[0118] The blank iron sheet and the iron sheet coated with the coating in Example 3 are both placed in a 0.1mol / L hydrochloric acid solution for 3 days, and then taken out to observe the surface corrosion effect, and the specific test results are shown in Figure 4 Figure 4 It can be known that the surface of the blank iron sheet is completely corroded, while the surface of the iron sheet coated with the coating in Example 3 does not show corrosion phenomenon, indicating that the coating formed by the coating material in the application has excellent acid corrosion resistance.

[0119] (7) Anti-ultraviolet irradiation test

[0120] The coating material in Example 4 is coated on a glass substrate to form an omniphobic coating on the glass substrate, then the coating is subjected to ultraviolet light irradiation for 40 minutes under the condition of ultraviolet light power of 85W and wavelength of 365nm, then the advancing angle value, the receding angle value and the advancing / receding angle difference value of the coating are tested, and the test results are plotted, and the specific as shown in Figure 5 Figure 5 It can be known that the hydrophobic performance of the coating surface does not change obviously under 40 minutes of ultraviolet light irradiation, showing anti-ultraviolet stability; the hydrophobicity of the coating gradually starts to decrease after 40 minutes of irradiation, indicating that the coating has good anti-ultraviolet function.

[0121] (8) Transparency test results

[0122] The coating material in Example 7 is coated on a transparent glass substrate, and then the transparency of the transparent glass substrate is observed, and the specific as shown in Figure 6 It is found that coating the coating material in Example 7 on the glass substrate does not affect the transparency of the glass substrate, indicating that the coating material in the application has excellent transparency. ​​​

[0123] In summary, the coating in the present application can be coated on flexible or rigid, flat or rough plastic, glass, metal, non-metal and other substrates to achieve the functions of anti-fouling, self-cleaning, water-proof, anti-freezing, anti-fog, anti-corrosion, UV resistance and the like, and is widely used in the fields of metal protection, building waterproofing, fabric treatment, packaging and the like. In addition, the coating prepared by using the coating in the present application has the advantages of good adhesion, strong hydrophobicity and oleophobicity, low cost, high wear resistance, high transparency, corrosion resistance, strong UV resistance, wide applicability and the like, and the preparation method of the coating is simple and easy to operate, the materials used are stable in chemical properties, the raw materials are matched, and the preparation process is simple and efficient.

[0124] The above has made a detailed description of the embodiments of the present application, but the present application is not limited to the above embodiments, and various changes can be made within the knowledge range possessed by those skilled in the art without departing from the purpose of the present application. In addition, the embodiments of the present application and the features in the embodiments can be combined with each other without conflict.

Claims

1. A hydrophobic and oleophobic coating, characterized in that: The preparation materials include the following: siloxane, organic base, isocyanate, and resin additives; the mass ratio of siloxane to organic base is (1000~100):5; the mass ratio of siloxane to isocyanate is (0.1~10):1; and the mass ratio of siloxane to resin additives is (0.1~10):

1. The siloxane includes siloxane A and siloxane B, with a mass ratio of siloxane A to siloxane B of (0.1-100):1; siloxane A is a small molecule silane containing two hydrolyzable functional groups; siloxane B is a small molecule silane containing not less than three hydrolyzable functional groups. The siloxane A is selected from at least one of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, and dipropyldiethoxysilane. And / or, the siloxane B is selected from methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, bis(triethoxysilyl)methane, 1,2-bis(triethoxysilyl)ethane, dodecyltrimethoxysilane, dodecyltriethoxysilane, etc. At least one of the following: silane, methyltributanone oxime silane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropylpropyltrimethoxysilane, vinyltributanone oxime silane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and vinyltrimethoxysilane; The isocyanate is selected from at least one of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, isophenyl dimethyl isocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate; The resin additive is selected from at least one of phenolic resin, urea-formaldehyde resin, melamine-formaldehyde resin, epoxy resin, hydroxyl acrylic resin, and epoxy acrylate resin. A siloxane and an organic base are mixed to obtain a siloxane reaction solution, which is then mixed and reacted with isocyanate and resin additives to prepare the hydrophobic and oleophobic coating.

2. The hydrophobic and oleophobic coating according to claim 1, characterized in that: The organic base is selected from at least one of diethylamine, triethylamine, triethylenediamine, n-propylamine, isopropylamine, 1,2-propanediamine, tetramethylethylenediamine, hexamethylenetetramine, diethylenetriamine, triethanolamine, urea, tetramethylammonium hydroxide, N,N-dimethylmethylamine, aniline, quinoline, pyridine, lithium diisopropylamino, potassium bis(trimethylsilyl)amino, sodium ethoxide, and n-butyllithium.

3. The hydrophobic and oleophobic coating according to claim 1, characterized in that: The coating also contains a solvent, and the mass ratio of the solvent to the siloxane is (0.01-100):

1.

4. The hydrophobic and oleophobic coating according to claim 3, characterized in that: The solvent is selected from at least one of methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, diethyl ether, diisopropyl ether, tetrahydrofuran, ethyl acetate, methyl acetate, propylene oxide, acetone, methyl butyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, benzene, toluene, xylene, styrene, butyltoluene, vinyltoluene, trichloroethylene, dichloromethane, chlorobenzene, dichlorobenzene, carbon disulfide, carbon tetrachloride, n-pentane, n-hexane, cyclohexane, octane, hexadecane, and liquid paraffin.

5. The method for preparing the hydrophobic and oleophobic coating according to any one of claims 1 to 4, characterized in that: Includes the following steps: A siloxane and an organic base are mixed to obtain a siloxane reaction solution, which is then mixed and reacted with isocyanate and resin additives to prepare the hydrophobic and oleophobic coating.

6. A product, characterized in that: The coating includes a hydrophobic and oleophobic coating, wherein the hydrophobic and oleophobic coating is formed by applying and curing the hydrophobic and oleophobic coating according to any one of claims 1 to 4.

7. The application of the hydrophobic and oleophobic coating according to any one of claims 1 to 4 in the fields of engineering, transportation, and manufacturing.

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