A long-lasting anti-fouling artistic coating and preparation method thereof

Abstract

The present application relates to a long-lasting anti-fouling art coating, including polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile at a content of 15-25%, a water-based resin at a content of 30-70%, a low-viscosity hydroxy silicone oil at a content of 5-25%, a solvent at a content of 1-50%, an inorganic powder at a content of 0-25%, and other additives at a content of 0-15%, and the total content of each component meets 100%. The polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile, combined with water-based resin and low-viscosity hydroxy silicone oil, can effectively improve the lubricity of the coating surface, present the initial gloss for a long time, and have a long-lasting anti-fouling effect. At the same time, even if the dust phenomenon appears in the corners of the artistic pattern, a simple air purge or water mist spray can reproduce the original appearance of the artistic pattern.

Description

Technical Field

[0001] The present application belongs to the field of coatings, and specifically relates to a long-lasting anti-fouling artistic coating and a preparation method thereof. Background Art

[0002] Paint is used to form a thin film on the surface of an object to protect, decorate or other purposes. Paint is generally composed of film-forming substances (resins, emulsions), pigments (including body pigments), solvents and additives (auxiliaries).

[0003] Artistic paint is a special new type of wall decoration art material, which has entered the domestic market for less than 20 years. Artistic paint can be applied with various textures to achieve a wallpaper-like decorative effect. Some special artistic paints can also be applied with a three-dimensional effect, and the effect of artistic decoration is more prominent. Although artistic paint can be applied on the wall to form beautiful patterns, which are three-dimensional and rich; however, the three-dimensional patterns formed by the application of artistic paint are difficult to present their original patterns on the wall for a long time.

[0004] Artistic paint is used for decoration of the interior and exterior walls of buildings, and needs to have functions such as waterproof, hydrophobic, dustproof, and flame retardant. However, since artistic paint is generally applied on the wall through a special brushing process to form a three-dimensional, multi-layered pattern, the surface flatness of the artistic paint pattern is very low, and it is difficult to obtain good hydrophobic performance (in comparison, ordinary wall paint is brushed flat and easy to obtain a good hydrophobic effect. Therefore, after ordinary wall paint is brushed, the paint layer on the wall can often maintain its original state for a long time, and it is difficult to maintain a long-lasting pattern. In addition, the uneven surface of the artistic paint pattern is prone to dust and usually needs to be scrubbed. Scrubbing will further destroy the waterproof and dustproof effects of the artistic paint pattern, and further accelerate the life decay of the artistic paint pattern.

[0005] Ensuring that artistic paint patterns can present artistic patterns that are timeless has always been a difficult problem that the industry wants to solve. To this end, the present invention aims to provide a long-lasting anti-fouling artistic paint and a preparation method thereof, so that the artistic patterns formed by the long-lasting anti-fouling artistic paint after brushing can be timeless. Summary of the invention

[0006] The main features of the long-lasting antifouling artistic coating of the present invention are that it comprises polydopamine microspheres loaded with a short-chain curing agent modified with brominated pyrrole nitrile and low-viscosity hydroxy silicone oil.

[0007] A long-lasting antifouling artistic coating, comprising polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile, water-based resin, low-viscosity hydroxy silicone oil, solvent, inorganic powder, and other additives. Among them, the content of polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile is 15-25%, the content of water-based resin is 30-70%, the content of low-viscosity hydroxy silicone oil is 5-25%, the content of solvent is 1-50%, the content of inorganic powder is 0-25%, the content of other additives is 0-15%, and the total content of each component meets 100%.

[0008] Furthermore, the water-based resin is selected from one or more of water-based fluorocarbon resin, water-based silicone resin, water-based alkyd resin, water-based epoxy resin, water-based polyurethane resin, and water-based acrylate resin.

[0009] Furthermore, the low-viscosity hydroxy silicone oil is a hydroxy silicone oil with a viscosity of less than 1000 mPa·S, preferably a hydroxy silicone oil with a viscosity of less than 500 mPa·S.

[0010] Furthermore, the solvent is selected from one or more of water, methanol, ethanol, isopropanol, propylene glycol, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate, benzene, toluene, xylene, ethylene glycol methyl ether, acetone, pentanone, ethyl acetate, and butyl acetate, preferably water or ethyl acetate.

[0011] Furthermore, the inorganic powder is selected from one or more of titanium dioxide, silicon dioxide, zirconium oxide, aluminum oxide, zinc oxide, aluminum silicate, calcium carbonate, barium sulfate, bentonite, and perlite.

[0012] Furthermore, the other auxiliary agents are selected from one or more of surfactants, dispersants, wetting agents, thickeners, leveling agents, defoaming agents, and anti-aging agents.

[0013] Further preferably, a long-lasting anti-fouling artistic coating includes 15-25% of polydopamine microspheres loaded with a short-chain curing agent modified with brominated pyrrole carbonitrile, 30-70% of an aqueous resin, 5-25% of a low-viscosity hydroxyl silicone oil, 5-10% of water, 5-10% of ethyl acetate, 0-25% of an inorganic powder, 1-3% of hydroxyethyl cellulose, and 1-3% of a polyether siloxane leveling agent, and the total content of each component meets 100%.

[0014] Furthermore, the polydopamine microspheres loaded with the brominated pyrrole nitrile-modified short-chain curing agent of the present application are obtained by directly placing the preparation process of the brominated pyrrole nitrile-modified short-chain curing agent in the dispersion environment where the polydopamine microspheres exist. The specific preparation steps are as follows:

[0015] First, isocyanate propyl triethoxysilane is dispersed in a solvent, and then the mesoporous polydopamine microspheres are dispersed in the solvent. Finally, bromopyrrole nitrile is added to the mixed solution. After reacting at 40-55° C. for 3-6 hours, the solvent is removed to obtain polydopamine microspheres loaded with a short-chain curing agent modified with bromopyrrole nitrile.

[0016] The solvent is preferably ethyl acetate. Furthermore, the mass ratio of the isocyanate propyl triethoxysilane, the mesoporous polydopamine microspheres, the bromopyrrole carbonitrile and the ethyl acetate is (4-6): (6-8): (6-8): (25-30).

[0017] The mesoporous polydopamine microspheres can be prepared by referring to the preparation method disclosed in CN114276681A.

[0018] Furthermore, in the process of preparing the polydopamine microspheres loaded with the short-chain curing agent modified by bromopyrrolecarbonitrile, the mixture of the products after the reaction at 40-55° C. for 3-6 hours can be directly used to prepare the long-lasting anti-fouling artistic coating.

[0019] A method for preparing a long-lasting anti-fouling artistic coating comprises mixing polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile, a water-based resin, a low-viscosity hydroxy silicone oil, a solvent, an inorganic powder, and other additives in proportion and stirring the mixture evenly.

[0020] In this application, it is proposed to prepare a short-chain curing agent modified by brominated pyrrole nitrile directly in a polydopamine microsphere dispersion medium environment, and load the short-chain curing agent modified by brominated pyrrole nitrile on polydopamine microspheres, which is beneficial to improve the anti-aging performance and hydrophobicity of the paint coating, and can also effectively maintain the paint coating in a long-lasting and new state. In long-lasting anti-fouling artistic coatings, further combining water-based resins and low-viscosity hydroxy silicone oils can effectively improve the lubricity of the paint coating surface, persist in showing the initial gloss, and have a long-lasting anti-fouling effect. At the same time, even if dust appears in the corners of the artistic pattern, a simple air purge or water mist spray can reproduce the original appearance of the artistic pattern. DETAILED DESCRIPTION

[0021] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and carefully in combination with embodiments below, but the protection scope of the present invention is not limited to the following specific embodiments.

[0022] Unless otherwise defined, all technical terms used hereinafter have the same meaning as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Unless otherwise specifically stated, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or can be prepared by existing methods.

[0023] Preparation Example 1

[0024] The preparation method of mesoporous polydopamine microspheres comprises the following specific steps:

[0025] 1) Formation of composite mesogen template

[0026] Add 25 ml of deionized water to a conical flask, add 4 g of 25% polyacrylic acid (average molecular weight of about 240,000 g / mol) and 0.54 g of cetylpyridinium chloride monohydrate into the deionized water and stir to dissolve until the solution becomes colorless and transparent, then add an ammonia solution (25 wt %), adjust the pH value to 9-10, the transparent solution will instantly turn into a milky white suspension with a small amount of white agglomerates, and stir magnetically at room temperature for 30 minutes until the white agglomerates generated in the solution disappear, to obtain a template emulsion.

[0027] 2) Formation of polydopamine / silica nanocomposites

[0028] 0.25 g of dopamine hydrochloride was dissolved in 5 g of deionized water to prepare 5.25 g of dopamine hydrochloride solution, 1.8 g of ethyl orthosilicate and 5.25 g of dopamine hydrochloride aqueous solution were added to the template emulsion, stirred for 30 minutes until well mixed, and then stirred continuously at 500 rpm at 26°C for 24 hours.

[0029] 3) Organic template removal

[0030] The reactant obtained in step 2) is centrifuged to separate the obtained product from the template emulsion, and the product is subjected to Soxhlet extraction using a mixture of hydrochloric acid (35wt%) and ethanol (99.8wt%) in a volume ratio of 95:5 as an extractant to remove the organic template, thereby obtaining hierarchical mesoporous polydopamine / silica nanocomposite microspheres;

[0031] 4) Silica removal

[0032] The polydopamine / silica nanocomposite microspheres obtained after Soxhlet extraction in step 3) are soaked in hydrofluoric acid solution to remove silica in the composite, and the treated product is washed with molecular water to neutrality, and freeze-dried at minus 30 degrees Celsius to obtain mesoporous polydopamine microspheres.

[0033] Preparation Example 2

[0034] The preparation method of polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile comprises the following specific steps:

[0035] First, 2.47 g of isocyanatepropyltriethoxysilane was dispersed in 13.60 g of ethyl acetate, and then 3.50 g of mesoporous polydopamine microspheres were added. Finally, 3.49 g of bromopyrrolecarbonitrile was added to the mixed solution. After reacting at 45 °C for 4 h, the solvent was removed to obtain polydopamine microspheres loaded with a short-chain curing agent modified with bromopyrrolecarbonitrile.

[0036] Preparation Example 3

[0037] The preparation method of tridecafluorooctyltrimethoxysilane-loaded polydopamine microspheres, the specific preparation steps are as follows:

[0038] 1 g of tridecafluorooctyl trimethoxysilane was dispersed in 100 mL of ethanol solvent and the mesoporous poly (1) was added.

[0039] The polydopamine microspheres were stirred at room temperature for 5 h, and finally separated by high-speed centrifugation, washed with deionized water, and dried to prepare tridecafluorooctyltrimethoxysilane-loaded polydopamine microspheres.

[0040] Example 1

[0041] A long-lasting anti-fouling artistic coating comprises 20% of polydopamine microspheres loaded with a short-chain curing agent modified by brominated pyrrole nitrile prepared in Preparation Example 2, 40% of an aqueous silicone resin, 10% of a hydroxy silicone oil with a viscosity of 420 mPa·S, 8% of water, 8% of ethyl acetate, 12% of bentonite, 1% of hydroxyethyl cellulose and 1% of a polyether siloxane leveling agent.

[0042] Example 2

[0043] A long-lasting anti-fouling artistic coating comprises 15% of polydopamine microspheres loaded with a short-chain curing agent modified by brominated pyrrole nitrile prepared in Preparation Example 2, 35% of a water-based organic silicone resin, 20% of a hydroxy silicone oil with a viscosity of 420 mPa·S, 5% of water, 10% of ethyl acetate, 14% of bentonite, and 1% of a polyether siloxane leveling agent.

[0044] Example 3

[0045] A long-lasting anti-fouling artistic coating comprises 25% of polydopamine microspheres loaded with a short-chain curing agent modified by brominated pyrrole nitrile prepared in Preparation Example 2, 35% of an aqueous silicone resin, 10% of a hydroxy silicone oil with a viscosity of 350 mPa·S, 8% of water, 8% of ethyl acetate, 12% of bentonite, 1% of hydroxyethyl cellulose and 1% of a polyether siloxane leveling agent.

[0046] Example 4

[0047] A long-lasting anti-fouling artistic coating comprises: 15% of polydopamine microspheres loaded with a short-chain curing agent modified by brominated pyrrole nitrile prepared in Preparation Example 2, 40% of an aqueous organic silicone resin, 15% of a hydroxy silicone oil with a viscosity of 650 mPa·S, 8% of water, 8% of ethyl acetate, 12% of bentonite, 1% of hydroxyethyl cellulose, and 1% of a polyether siloxane leveling agent.

[0048] Example 5

[0049] An artistic coating comprises 20% of polydopamine microspheres loaded with a short-chain curing agent modified by brominated pyrrole nitrile prepared in Preparation Example 2, 40% of a water-based organic silicone resin, 10% of a hydroxy silicone oil with a viscosity of 3000 mPa·S, 8% of water, 8% of ethyl acetate, 12% of bentonite, 1% of hydroxyethyl cellulose and 1% of a polyether siloxane leveling agent.

[0050] Example 6

[0051] An artistic coating comprises 15% of tridecafluorooctyltrimethoxysilane-loaded polydopamine microspheres prepared in Preparation Example 3, 40% of an aqueous silicone resin, 15% of a hydroxy silicone oil with a viscosity of 650 mPa·S, 8% of water, 8% of ethyl acetate, 12% of bentonite, 1% of hydroxyethyl cellulose, and 1% of a polyether siloxane leveling agent.

[0052] Example 7

[0053] An artistic coating comprises 20% dopamine micron powder, 45% water-based silicone resin, 10% hydroxy silicone oil with a viscosity of 420 mPa·S, 8% water, 8% ethyl acetate, 7% bentonite, 1% hydroxyethyl cellulose and 1% polyether siloxane leveling agent.

[0054] Example 8

[0055] An artistic coating comprises 20% of polydopamine microspheres loaded with a short-chain curing agent modified by brominated pyrrole nitrile prepared in Preparation Example 2, 40% of a water-based silicone resin, 8% of water, 8% of ethyl acetate, 20% of bentonite, 2% of hydroxyethyl cellulose, and 2% of a polyether siloxane leveling agent.

[0056] Example 9

[0057] A long-lasting anti-fouling artistic coating comprises 20% of polydopamine microspheres loaded with a short-chain curing agent modified by brominated pyrrole nitrile prepared in Preparation Example 2, 45% of a water-based organic silicone resin, 10% of a hydroxy silicone oil with a viscosity of 420 mPa·S, 10% of water, 12% of bentonite, 1% of hydroxyethyl cellulose, and 2% of a polyether siloxane leveling agent.

[0058] Test example

[0059] The performance of the artistic coatings of Examples 1 to 9 was tested and the evaluation method was as follows:

[0060] Hardness: Pencil hardness, GB / T6739-2006.

[0061] Observe the surface gloss after 60 days: visual inspection (10 points is the full score)

[0062] Observe and compare the dust situation after 60 days: visual inspection (the results are divided into three levels: more, less, and very little).

[0063] Recovery status after air purging: visual inspection (the results are divided into three levels: unable to recover, basically recovered, and completely recovered).

[0064] The results of various performance tests are shown in Table 1.

[0065] Table 1

[0066]

[0067]

[0068] From the test results in Table 1, it can be found that the long-lasting anti-fouling artistic paint of the present application has a high hardness, can still maintain the original glossiness after a long time, and the artistic pattern is timeless. There is very little dust after a long time, and it can be restored to its original state by simple air blowing, and has excellent long-term anti-fouling properties.

Claims

1. A long-lasting anti-fouling artistic coating, characterized in that: The invention comprises: polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile with a content of 15-25%, a water-based resin with a content of 30-70%, a low-viscosity hydroxy silicone oil with a content of 5-25%, a solvent with a content of 1-50%, an inorganic powder with a content of 0-25%, and other additives with a content of 0-15%, and the total content of each component meets 100%; The preparation steps of the polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile are as follows; First, isocyanate propyl triethoxysilane is dispersed in a solvent, then mesoporous polydopamine microspheres are dispersed in a solvent, and finally bromopyrrole nitrile is added to the mixed solution, and after reacting at 40-55° C. for 3-6 hours, the solvent is removed to obtain polydopamine microspheres loaded with a short-chain curing agent modified by bromopyrrole nitrile; The low-viscosity hydroxy silicone oil is a hydroxy silicone oil with a viscosity of less than 1000 mPa·S.

2. A long-lasting anti-fouling artistic paint as claimed in claim 1, characterized in that: The water-based resin is selected from one or more of water-based fluorocarbon resin, water-based silicone resin, water-based alkyd resin, water-based epoxy resin, water-based polyurethane resin, and water-based acrylate resin.

3. The long-lasting anti-fouling artistic paint according to claim 1, characterized in that: The low-viscosity hydroxy silicone oil is a hydroxy silicone oil with a viscosity of less than 500 mPa·S.

4. The long-lasting anti-fouling artistic paint according to claim 1, characterized in that: The solvent is selected from one or more of water, methanol, ethanol, isopropanol, propylene glycol, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate, ethylene glycol methyl ether, acetone, pentanone, ethyl acetate, and butyl acetate.

5. The long-lasting anti-fouling artistic paint according to claim 1, characterized in that: The inorganic powder is selected from one or more of titanium dioxide, silicon dioxide, zirconium oxide, aluminum oxide, zinc oxide, aluminum silicate, calcium carbonate, barium sulfate, bentonite, and perlite.

6. The long-lasting anti-fouling artistic paint according to claim 1, characterized in that: The other auxiliary agents are selected from one or more of surfactants, dispersants, thickeners, leveling agents, defoamers, and anti-aging agents.

7. The long-lasting anti-fouling artistic paint according to claim 1, characterized in that: The invention comprises polydopamine microspheres loaded with a short-chain curing agent modified with brominated pyrrole nitrile at a content of 15-25%, an aqueous resin at a content of 30-70%, a low-viscosity hydroxy silicone oil at a content of 5-25%, water at a content of 5-10%, ethyl acetate at a content of 5-10%, an inorganic powder at a content of 0-25%, hydroxyethyl cellulose at a content of 1-3%, and a polyether siloxane leveling agent at a content of 1-3%, and the total content of each component meets 100%.

8. A long-lasting anti-fouling artistic paint according to any one of claims 1 to 7, characterized in that: In the step of preparing polydopamine microspheres loaded with a short-chain curing agent modified with bromopyrrole nitrile, the solvent is ethyl acetate, and the mass ratio of isocyanate propyltriethoxysilane, mesoporous polydopamine microspheres, bromopyrrole nitrile, and ethyl acetate is (4-6):(6-8):(6-8):(25-30).

9. A method for preparing a long-lasting anti-fouling artistic coating according to any one of claims 1 to 8, characterized in that: The polydopamine microspheres loaded with the short-chain curing agent modified by bromopyrrole nitrile, water-based resin, low-viscosity hydroxy silicone oil, solvent, inorganic powder and other additives are mixed in proportion and stirred evenly.

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