CN114456625B - Hydrophobic weather-resistant antibacterial mildew-proof silicon-based coating and preparation method and application thereof - Google Patents

Hydrophobic weather-resistant antibacterial mildew-proof silicon-based coating and preparation method and application thereof Download PDF

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CN114456625B
CN114456625B CN202111683304.9A CN202111683304A CN114456625B CN 114456625 B CN114456625 B CN 114456625B CN 202111683304 A CN202111683304 A CN 202111683304A CN 114456625 B CN114456625 B CN 114456625B
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CN114456625A (en
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余龙飞
贾康乐
郑小珊
吴海福
李欢玲
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Institute of Chemical Engineering of Guangdong Academy of Sciences
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Abstract

The invention belongs to the technical field of functional coatings, and particularly discloses a hydrophobic weather-resistant antibacterial mildew-proof silicon-based coating as well as a preparation method and application thereof. The silicon-based coating is prepared by mixing a component A and a component B; the preparation raw materials of the component A comprise: alkali metal silicate, fluorocarbon resin dispersion liquid, organic silicon resin, amino resin, long-chain quaternary ammonium salt silane coupling agent, zinc butyrate and organic silicon wetting and leveling agent; the preparation raw materials of the component B comprise: an acidic silica sol; the preparation method of the silicon-based coating is used for preparing the silicon-based coating; the silicon-based hard coating is formed by curing a silicon-based coating. The invention overcomes the defects of poor weather resistance, easy pulverization, poor flexibility, easy cracking and the like of the conventional ceramic paint and breaks through the core technology of the high-strength high-weather-resistance hydrophobic silicon-based hard transparent paint; meanwhile, the surface energy of the coating can be reduced, the smoothness and the hydrophobicity of the coating can be improved, and the self-cleaning effect of the coating can be realized.

Description

Hydrophobic weather-resistant antibacterial mildew-proof silicon-based coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional coatings, and particularly relates to a hydrophobic weather-resistant antibacterial mildew-proof silicon-based coating as well as a preparation method and application thereof.
Background
The hot-melt fluorocarbon coating taking PVDF (polyvinylidene fluoride) as a main film forming substance has more than 50 years of development history in the field of building decoration, is widely applied to the fields of high-rise building outer walls, gymnasiums, airports, exhibition halls, sea-crossing bridges, power plants, chemical product storage tanks and the like by virtue of various colors, ultra-long weather resistance (more than 15 years outdoors) and the like, and occupies an absolute leading position. However, the conventional fluorocarbon coating has a rough surface and high surface energy (more than or equal to 38mN/m), and due to the increase of pollutants such as urban dust, oil smoke, acid rain, chemical dust and the like, the surface of the fluorocarbon coating is easy to generate the phenomena of color change, contamination and the like, and the fluorocarbon coating does not have the functions of contamination resistance, self-cleaning, antibiosis, mildew resistance, doodling prevention and the like, and can not meet the requirements of modern high-end urban buildings. In order to improve the stain-resistant self-cleaning capability of a wall surface coating, a hydrophobic hard coating which is not easy to attach pollutants or can be stripped and removed by the aid of natural effects of rainwater, wind power and the like is developed, the pollution problem of the wall surface is simply and conveniently solved, the coating has great market potential in the field of building decoration, and the coating becomes an important development direction of urban building decorative coatings.
Meanwhile, fluorocarbon coatings have poor fire resistance, generate fluorine-containing toxic gas when burning at high temperature, and are not beneficial to fire safety when used as building decoration materials. The fluorocarbon coating is difficult to degrade in the environment, the complete degradation in the environment needs more than 100 years, the micro plastic pollution of soil, water and the like is easily caused, and great environmental and cost burden is caused to the treatment after the use.
With the improvement of living standard of people, the comfort, safety and sanitary conditions of working and living environment are concerned more and more. Formaldehyde is a common harmful release substance in interior decoration materials, and bacteria and viruses are also important factors endangering health. The coating with the bacteriostatic function can greatly kill bacteria and viruses on the surface of an object, and the indoor antibacterial coating has great application requirements and development prospects.
The silicon-based inorganic coating takes alkali metal silicate as a main film forming material, and the coating has a series of advantages of friction resistance, flame retardance, easy cleaning and pollution prevention, food-grade contact safety and the like, and is a new class of green and environment-friendly hard coatings with wide application. The proper substances with the functions of hydrophobicity, easy cleaning, bacteriostasis and formaldehyde reduction are introduced into the silicon-based hard water paint, so that the technical effects of longer acting and higher safety can be achieved. However, since inorganic coatings, especially nano ceramic coatings, have many technical defects which are not negligible, their application is still limited to a few fields such as interior walls, floors, non-stick pans, etc.: (1) it is inconvenient to use. The traditional nano ceramic coating needs hydrolysis and curing time not less than 4 hours before use, and the addition amount of a siloxane raw material hydrolysis catalyst in the formula and the hydrolysis and curing process have direct influence on the final appearance effect of the coating, even cause coating failure; (2) the coating has high hardness but poor flexibility, and the coating is easy to crack and even fall off from a base material in the curing and using processes; (3) the common organic silicon ceramic coating has no adhesive force on most organic coatings, and can only be directly coated on the surfaces of some metal substrates with excellent self corrosion resistance and better thermal expansion coefficient matching as a single coating, and the application of the common organic silicon ceramic coating is greatly limited by the technical defect; (4) the traditional nano ceramic coating takes epoxy emulsion and acrylic emulsion as film forming toughening resin, has poor weather resistance and is not suitable for outdoor use.
Therefore, how to develop a silicon-based hard transparent coating which integrates hydrophobic self-cleaning, high weather resistance, antibacterial property and mildew resistance through technical innovation and is applied to outdoor buildings is a problem to be solved at present.
Disclosure of Invention
The invention provides a hydrophobic weather-resistant antibacterial mildew-proof silicon-based coating, a preparation method and application thereof, which are used for solving one or more technical problems in the prior art and at least providing a beneficial choice or creating conditions.
In order to overcome the technical problems, the first aspect of the invention provides a silicon-based coating.
Specifically, a silicon-based coating, the preparation raw material of which comprises a component A and a component B;
the preparation raw materials of the component A comprise: alkali metal silicate, fluorocarbon resin dispersion liquid, organic silicon resin, amino resin, long-chain quaternary ammonium salt silane coupling agent, zinc butyrate and organic silicon wetting and leveling agent;
the preparation raw materials of the component B comprise: an acidic silica sol.
Preferably, the alkali metal silicate is at least one selected from potassium silicate, sodium silicate and lithium silicate.
Further preferably, the alkali metal silicate is selected from potassium silicate and/or lithium silicate, the alkali metal silicate having a solids content of 40%.
Preferably, the fluorocarbon resin dispersion is selected from PVF (polyvinyl fluoride) resin dispersions.
More preferably, the content of the effective substance in the fluorocarbon resin dispersion liquid is 25-55%.
Preferably, the silicone resin is selected from silanol-containing MQ (M is a monofunctional Si-O unit; Q is a tetrafunctional Si-O unit) silicone resin and/or polyhedral oligomeric silsesquioxane (POSS).
Preferably, the molar ratio of M/Q of the silanol-containing MQ silicone resin is 0.6-3.0; further preferably, the molar ratio of M/Q of the silanol containing MQ silicone resin is 1.5 to 2.0.
Preferably, the silanol-containing MQ silicone resin has a weight average molecular weight of 1000-8000; further preferably, the silanol-containing MQ silicone resin has a weight average molecular weight of 3000-5000.
Preferably, the polyhedral oligomeric silsesquioxane is selected from Q of Aldrich 8 M 8 H 。
Preferably, the amino resin is at least one selected from potassium silicate, sodium silicate and lithium silicate.
Preferably, the structural formula of the long-chain quaternary ammonium salt silane coupling agent is as follows:
Figure BDA0003448364260000031
preferably, the chemical formula for preparing the long-chain quaternary ammonium salt silane coupling agent is as follows:
Figure BDA0003448364260000032
in the formula: r 1 Is C 16 -C 18 Alkyl radical, R 2 Is CH 3 Or CH 2 CH 3 。
Preferably, the organic silicon wetting and leveling agent is a long-chain alkyl-polyether co-modified organic silicon leveling agent, and the structural formula of the organic silicon wetting and leveling agent is as follows:
Figure BDA0003448364260000033
in the formula: x is 0-5 and n is 3-7.
Preferably, the particle size of the acidic silica sol is 2-20 nm; more preferably, the particle size of the acidic silica sol is 5 to 10 nm.
Preferably, the preparation raw material of the component A also comprises at least one of defoaming agent, isopropanol and deionized water.
Preferably, the raw materials for preparing the silicon-based coating comprise the following components in parts by weight:
the component A comprises:
Figure BDA0003448364260000041
and B component:
30-80 parts of acidic silica sol.
More preferably, the raw materials for preparing the silicon-based coating comprise the following components in parts by weight:
the component A comprises:
Figure BDA0003448364260000042
Figure BDA0003448364260000051
and B component:
40-70 parts of acidic silica sol.
Further preferably, the raw materials for preparing the silicon-based coating comprise the following components in parts by weight:
the component A comprises:
Figure BDA0003448364260000052
and B component:
45-55 parts of acidic silica sol.
In a second aspect of the invention, a method for preparing a silicon-based coating is provided.
In particular to a preparation method of a silicon-based coating, which is used for preparing the silicon-based coating.
Preferably, the preparation process of the component A comprises the following steps: mixing alkali metal silicate, fluorocarbon resin dispersion liquid, organic silicon resin, long-chain quaternary ammonium salt silane coupling agent, zinc butyrate, organic silicon wetting and leveling agent, isopropanol and defoaming agent, and adding deionized water at a constant speed under the stirring action to obtain the component A.
Preferably, the rotating speed of the stirring is 300-; further preferably, the rotation speed of the stirring is 500-1500 r/min.
Preferably, the temperature during stirring is 5-60 ℃; more preferably, the temperature during stirring is 10-40 ℃; further preferably, the temperature during the stirring is room temperature.
Preferably, the time for adding the deionized water at the constant speed is 15-60 minutes, and further preferably, the time for adding the deionized water at the constant speed is 30-40 minutes.
In a third aspect of the present invention, a silicon-based hard coating is provided.
Specifically, the silicon-based hard coating is formed by curing the silicon-based coating.
In a fourth aspect of the invention, a method for preparing a silicon-based hard coating is provided.
In particular to a preparation method of a silicon-based hard coating, which is used for the silicon-based hard coating.
Preferably, the preparation method of the silicon-based hard coating comprises the following steps: and mixing the component A and the component B, and curing to obtain the silicon-based hard coating.
Preferably, the construction window period at room temperature after the component A and the component B are mixed is more than 8 hours.
Preferably, the mixing mass ratio of the component A to the component B is (1-3): 1; further preferably, the mass ratio of the component A to the component B is (1.5-2.5): 1.
preferably, the curing temperature is 180-250 ℃; more preferably, the curing temperature is 200-245 ℃; further preferably, the temperature of the curing is 225-.
Preferably, the curing time is 5 to 30 minutes; further preferably, the curing time is 10 to 20 minutes.
In a fourth aspect of the invention, a silicon-based coating coatable application is provided.
Specifically, the silicon-based coating or the silicon-based hard coating is applied to photovoltaic power generation panels, glass, outdoor building aluminum veneers, vehicles or rail transit.
Preferably, the application method of the silicon-based coating comprises the following steps: spraying or rolling the silicon-based coating on a substrate, and baking and curing at the temperature of 225-235 ℃ for 10-20min, wherein the thickness of the coating is 20-50 mu m.
Preferably, the silicon-based hard coating has high transmittance, and does not affect the light transmittance of the photovoltaic power generation panel and the glass; meanwhile, in some fields with low or no requirement on light transmittance or fields with certain requirements on the color of a coating, the pigment can be added into the silicon-based coating according to actual requirements. Pigments common in the art do not adversely affect the hydrophobicity, hardness, and weatherability of the coating.
Compared with the prior art, the technical scheme of the invention at least has the following technical effects or advantages:
(1) the invention takes alkali metal silicate from natural sources as a main film forming component, thermoplastic fluorocarbon resin as toughening particles, organic silicon resin and acid silica sol as hardening components, and related active components (organic silicon resin, acid silica sol, long-chain quaternary ammonium salt silane coupling agent, zinc butyrate and organic silicon wetting and leveling agent) and amino resin are cured at high temperature to form a film, thereby overcoming the defects of poor weather resistance, easy pulverization, poor flexibility, easy cracking and the like of the conventional ceramic paint, and breaking through the core technology of the high-strength high-weather-resistance hydrophobic silicon-based hard transparent paint.
(2) According to the invention, the self-made long-chain quaternary ammonium salt silane coupling agent is used as a main sterilization and mildew prevention component, the long-chain quaternary ammonium salt silane coupling agent is catalyzed and hydrolyzed under an acidic condition and is subjected to a cross-linking reaction with silica sol, so that the long-chain structure and the PVF fluorocarbon resin have a synergistic effect, the surface tension of the coating is reduced, and the high hydrophobic property is provided. Meanwhile, the long-chain quaternary ammonium salt silane coupling agent is hydrolyzed and condensed, and zinc butyrate is coupled through Si-O-Zn bonds at high temperature, so that the quaternary ammonium salt and zinc oxide are synergistic, and the sterilization and mildew prevention effects are enhanced.
(3) The organic silicon leveling agent co-modified by the long-chain alkyl-polyether has small molecular weight, high dynamic surface activity and extremely low static surface tension (less than or equal to 22mN/m), can quickly wet most of the surfaces of base materials, provides a high-flatness paint film surface, and simultaneously improves the paint film adhesive force. Meanwhile, the extremely high surface activity of the long-chain alkyl-polyether co-modified organic silicon leveling agent can replace the use of an emulsifier and a dispersant in the component A, so that the good dispersion stability among the raw materials of the component A is ensured; in addition, in the high-temperature curing process, polyether chain segments at two ends of the long-chain alkyl-polyether co-modified organic silicon leveling agent molecule are broken and decomposed at high temperature, and the remaining long-chain alkyl polysiloxane chain segments migrate to the surface of a paint film and are cured with amino resin to generate fluorine-silicon synergistic interaction with PVF fluorocarbon resin, so that the surface energy of the coating is further reduced, the smoothness and the hydrophobicity of the coating are improved, and the self-cleaning effect of the coating is realized.
Drawings
FIG. 1 is a graph showing the contact angle of a silicon-based hard coating prepared in example 1 of the present invention with water;
FIG. 2 is a contact angle of a silicon-based hard coating prepared in example 2 of the present invention with water;
FIG. 3 is a scanning electron microscope image of a silicon-based hard coating prepared in example 4 of the present invention;
FIG. 4 shows the anti-Escherichia coli effect of the silicon-based hard coating prepared in example 3 of the present invention;
FIG. 5 shows the anti-Escherichia coli effect of the silicon-based hard coating prepared in comparative example 2 according to the present invention;
FIG. 6 is a blank set of anti-E.coli tests.
Detailed Description
The present invention is described in detail by the following examples to facilitate the understanding of the present invention by those skilled in the art, and it is necessary to point out that the examples are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and that the non-essential modifications and adjustments of the present invention by those skilled in the art should still fall within the scope of the present invention, and that the raw materials mentioned below are not specified in detail and are all commercially available products, and that the process steps or preparation methods not mentioned in detail are all known to those skilled in the art.
The following are the main raw materials used in the examples and comparative examples and their manufacturers: the fluorocarbon resin PVF dispersion is purchased from Zhonghua blue sky fluorine materials Co; the organic silicon wetting leveling agent is purchased from Guangdong golden cypress chemical Co., Ltd; the defoamer was purchased from kupffer chemical ltd, guangdong; the acidic silica sol was purchased from Suzhou Naddi microelectronics, Inc.
Example 1
A silicon-based coating is prepared from a component A and a component B in a mass ratio of 2: 1, wherein: the component A comprises the following raw materials:
sodium silicate (solids content) 500 g;
200 g of PVF fluorocarbon resin dispersion liquid (effective substance content is 40%);
silicone resin (M/Q ═ 1.5, molecular weight 4000)50 grams;
cyanut CYMEL 325 curing agent 50 g;
10 g of long-chain quaternary ammonium salt silane coupling agent (with a structural formula shown in a formula II);
Figure BDA0003448364260000081
(in the formula II: R 1 ＝C 16 Alkyl radical, R 2 ＝CH 2 CH 3 )
20 g of zinc butyrate;
10 g of organic silicon wetting and leveling agent (with a structural formula shown in a formula I);
Figure BDA0003448364260000082
(in the formula I, x is 0, n is 3)
1 g of CD-65 organic silicon defoamer;
150 g of isopropanol;
5 g of deionized water;
the component B is aqueous acidic silica sol of Minodian microelectronics Co., Ltd, the solid content is 30%, and the particle size is 10 nm.
A preparation method of a silicon-based coating comprises the following steps:
(1) adding deionized water into the component A except the deionized water at a constant speed of 800r/min for 35 minutes to obtain a component A;
(2) mixing the component A prepared in the step (1) with the component B in a mass ratio of 2: 1, obtaining the silicon-based coating of the embodiment.
Example 2
A silicon-based coating is prepared from a component A and a component B in a mass ratio of 1.5: 1, wherein: the component A comprises the following raw materials:
450 g of potassium silicate (solid content);
180 g of PVF fluorocarbon resin dispersion liquid (effective substance content is 40%);
silicone resin (M/Q ═ 1.5, molecular weight 3000)50 grams;
80 g of CyTe CYMEL 328 curing agent;
30 g of long-chain quaternary ammonium salt silane coupling agent (with a structural formula shown in a formula IV);
Figure BDA0003448364260000091
(in the formula IV: R) 1 ＝C 18 Alkyl radical, R 2 ＝CH 2 CH 3 )
10 g of zinc butyrate;
20 g of organic silicon wetting and leveling agent (with a structural formula shown in a formula III);
Figure BDA0003448364260000092
(in the formula III, x is 0 and n is 5)
3 g of CD-36 organic silicon defoamer;
100 g of isopropanol;
30 g of deionized water;
the component B is methanol system acidic silica sol of State Nandi microelectronics Inc., the solid content is 30%, and the particle size is 10 nm.
A preparation method of a silicon-based coating comprises the following steps:
(1) adding deionized water into the component A except deionized water at a constant speed of 500r/min for 30 minutes to obtain a component A;
(2) mixing the component A prepared in the step (1) with the component B in a mass ratio of 1.5: 1, obtaining the silicon-based coating of the embodiment.
Example 3
A silicon-based coating is prepared from a component A and a component B in a mass ratio of 2.5: 1, wherein: the component A comprises the following raw materials:
lithium silicate (solid content) 400 g;
150 g of PVF fluorocarbon resin dispersion (effective content 40%);
silicone resin (M/Q ═ 1.8, molecular weight 5000)80 g;
70 g of CyMEL 385 curing agent;
10 g of long-chain quaternary ammonium salt silane coupling agent (with the structural formula shown in the formula VI);
Figure BDA0003448364260000101
(formula (II)VI: r is 1 ＝C 18 Alkyl radical, R 2 ＝CH 3 )
30 g of zinc butyrate;
10 g of organic silicon wetting and leveling agent (with a structural formula shown in a formula V);
Figure BDA0003448364260000102
(in the formula V, x is 3, n is 7)
3 g of CD-36 organic silicon defoamer;
120 g of isopropanol;
30 g of deionized water;
the component B is ethanol system acidic silica sol of State Nandi microelectronics Inc., with solid content of 30% and particle size of 8 nm.
A preparation method of a silicon-based coating comprises the following steps:
(1) adding deionized water into the component A except the deionized water at a constant speed of 1000r/min for 35 minutes to obtain a component A;
(2) mixing the component A prepared in the step (1) with the component B in a mass ratio of 2.5: 1, obtaining the silicon-based coating of the embodiment.
Example 4
A silicon-based coating is prepared from a component A and a component B in a mass ratio of 2: 1, wherein: the component A comprises the following raw materials:
lithium silicate (solids content) 250 g;
180 g of PVF fluorocarbon resin dispersion liquid (effective substance content is 40%);
silicone resin (M/Q2.0, molecular weight 3000)80 grams;
100 g of CyTe CYMEL 303 curing agent;
30 g of long-chain quaternary ammonium salt silane coupling agent (with a structural formula shown in a formula VIII);
Figure BDA0003448364260000111
(in the formula VIII: R 1 ＝C 16 Alkyl radical, R 2 ＝CH 3 )
30 g of zinc butyrate;
30 g of organic silicon wetting and leveling agent (with a structural formula shown in a formula VII);
Figure BDA0003448364260000112
(in the formula VII, x is 5, n is 5)
2 g of CD-65 organic silicon defoamer;
100 g of isopropanol;
50 g of deionized water;
the component B is aqueous system acidic silica sol of State Nandi microelectronics Inc., the solid content is 30 percent, and the particle size is 10 nm.
A preparation method of a silicon-based coating comprises the following steps:
(1) adding deionized water into the component A except the deionized water at a constant speed of 1500r/min for 40 minutes to obtain a component A;
(2) mixing the component A prepared in the step (1) with the component B in a mass ratio of 2: 1, obtaining the silicon-based coating of the embodiment.
Comparative example 1
The difference between the comparative example 1 and the example 2 is that the raw materials for preparing the silicon-based coating of the comparative example 1 are not added with the cyanote CYMEL 328 curing agent, and the composition and the adding amount of other raw materials and the preparation method of the silicon-based coating are the same as those of the example 2.
Comparative example 2
The difference between comparative example 2 and example 2 is that zinc butyrate is not added to the raw materials for preparing the silicon-based coating of comparative example 2, and the composition and the addition amount of other raw materials and the preparation method of the silicon-based coating are the same as those of example 2.
Comparative example 3
The difference between the comparative example 3 and the example 2 is that the long-chain quaternary ammonium salt silane coupling agent with the structural formula IV shown in the formula IV is replaced by the long-chain quaternary ammonium salt silane coupling agent with the structural formula IX shown in the formula IX in the raw materials for preparing the silicon-based coating of the comparative example 3, and the composition and the addition amount of other raw materials and the preparation method of the silicon-based coating are the same as those in the example 2.
Figure BDA0003448364260000121
(formula IX wherein R 3 ＝CH 2 CH 3 )
Comparative example 4
The difference between the comparative example 4 and the example 2 is that the organosilicon wetting leveling agent with the structural formula shown in the formula III in the preparation raw material of the silicon-based coating of the comparative example 4 is replaced by the BYK-331 organosilicon leveling agent with the same mass, and the composition and the addition amount of other raw materials and the preparation method of the silicon-based coating are the same as those of the example 2.
Performance testing
The silicon-based paint samples prepared in examples 1-4 and comparative examples 1-4 were sprayed on common super white glass within 2 hours, baked and cured at 235 ℃ for 15 minutes to obtain a silicon-based hard coating with a thickness of 20-50 μm, and performance tests were performed on the coating film after cooling to room temperature, with the test results shown in table 1.
Wherein: and (3) antibacterial property test, referring to methods in GB 4789.3-2016 and GB 4789.10-2016, selecting gram-negative escherichia coli and gram-positive staphylococcus aureus as indicator strains to perform antibacterial property test on each coating sample, and calculating antibacterial efficiency according to the number of viable bacteria colonies and the following formula (1) so as to obtain the antibacterial effect.
E anti ＝(N-Ns)/N×100％
In the formula: e anti The antibacterial efficiency is achieved; n is the number of bacterial colonies in the uncoated coating sample; ns is the number of bacterial colonies in the coated sample.
Table 1: comparative table of performance test results of coating samples of each example and comparative example
Figure BDA0003448364260000131
Figure BDA0003448364260000141
As can be seen from Table 1, the coating films prepared in the embodiments 1-4 of the invention have the properties of high strength (high hardness and impact resistance), high light transmittance, high adhesion, high weather resistance, stain resistance, self-cleaning, antibiosis, mildew resistance, chemical solvent resistance and the like, the surface energy of the coating film is less than 25mN/m, the coating film belongs to a low-energy surface, the coating film has a higher water contact angle and better antifouling property, and all the properties are greatly superior to those of the comparative examples 1-4. Wherein: the paint films obtained in examples 1-2 had contact angles to water of 113.0 ° and 114.6 °, respectively, as shown in FIGS. 1-2, indicating that the surface of the coating was hydrophobic. Fig. 3 is a scanning electron microscope of the coating sample prepared in example 4 of the present invention, and it can be seen from fig. 3 that in example 4 in which the organic silicon wetting and leveling agent having the structural formula shown in formula vii is added, the coating surface is highly dense and smooth and has high flatness, thereby ensuring high light transmittance and stain resistance of the coating.
Compared with examples 1-4 of the invention, comparative example 1 has poor coating compactness, surface energy obviously higher than examples 1-4 and water contact angle lower than 100 degrees because no amino resin curing agent is adopted to participate in the high-temperature curing reaction, and the coating has low crosslinking density and greatly reduced mechanical property, weather resistance and mildew resistance because of lacking of the amino resin to participate in the curing reaction.
Comparative example 2 does not use zinc butyrate as a key antibacterial component, and only uses a quaternary ammonium silane coupling agent, so that the antibacterial mildew resistance and weather resistance of the antibacterial material are obviously lower than those of the examples 1-4 of the invention. Fig. 4 and 5 are graphs showing the escherichia coli resistant effect of the coating samples prepared in example 3 and comparative example 2 of the present invention, respectively, and it can be seen from comparison with the escherichia coli resistant test blank group of fig. 6 that the coating of example 3 has a good antibacterial effect, and the antibacterial performance is significantly better than that of comparative example 2.
Comparative example 3 adopts quaternary ammonium salt with a short carbon chain structure to replace a quaternary ammonium salt silane coupling agent with a long carbon chain structure, and because long carbon chain alkyl chains are lacked as hydrophobic and coating toughening particles, the surface energy of the quaternary ammonium salt silane coupling agent is more than 25mN/m, the obtained coating does not belong to a low surface energy surface, and the contact angle to water is lower than 100 degrees; meanwhile, the compatibility of the quaternary ammonium salt silane coupling agent with the carbon chain structure with bacteria is not as good as that of the quaternary ammonium salt silane coupling agent with the long carbon chain structure, so that the antibacterial mildew resistance and the self-cleaning stain resistance of the comparative example 3 are greatly reduced compared with those of the examples.
The preparation method comprises the following steps of comparing example 4, adopting BYK-331 as an organic silicon leveling agent, adopting acrylic emulsion as toughening emulsion, and adopting BYK-331 as a conventional macromolecular comb structure, wherein due to the lack of a BYK-331 conventional macromolecular comb structure, the organic silicon leveling agent modified by long-chain alkyl-polyether co-modification has the advantages of small specific molecular weight, high dynamic surface activity and extremely low static surface tension (less than or equal to 22mN/m), can quickly wet most of substrate surfaces, can be broken and decomposed in a high-temperature curing process, and then enables long-chain alkyl polysiloxane chain segments to migrate to the surface of a paint film and be cured with amino resin to generate fluorine-silicon synergistic effect with PVF fluorocarbon resin, so that the surface energy of the obtained coating is greatly higher than that of the example, and the contact angle to water is greatly lower than that of the comparison example. Meanwhile, comparative example 4 uses a conventional acrylic emulsion as toughening particles, resulting in poor weather resistance and chemical resistance.
In summary, in the embodiments 1 to 4 of the present invention, alkali metal silicate from natural sources is used as a main film forming component, thermoplastic fluorocarbon resin is used as toughening particles, organic silicon resin and acidic silica sol are used as hardening components, a long-carbon-chain quaternary ammonium salt silane coupling agent and zinc butyrate are used as composite antibacterial components, and related active components (organic silicon resin, acidic silica sol, long-chain quaternary ammonium salt silane coupling agent, zinc butyrate and organic silicon wetting leveling agent) and amino resin are cured at a high temperature to form a film, so that the defects that the conventional ceramic paint has poor weather resistance and is easy to pulverize, the conventional inorganic paint has poor flexibility and cracks, and the core technology of the high-strength high-weather resistance hydrophobic silicon-based hard transparent paint is broken through; the long-chain alkyl-polyether co-modified organic silicon flatting agent is broken and decomposed at high temperature and is solidified with the amino resin, and fluorine and silicon are generated with PVF fluorocarbon resin to realize synergistic interaction, so that the surface energy of the coating is further reduced, the smoothness and the hydrophobicity of the coating are improved, and the self-cleaning effect of the coating is realized.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.

Claims (10)

1. The silicon-based coating is characterized in that the preparation raw material of the silicon-based coating comprises a component A and a component B;
the preparation raw materials of the component A comprise: alkali metal silicate, fluorocarbon resin dispersion liquid, organic silicon resin, amino resin, long-chain quaternary ammonium salt silane coupling agent, zinc butyrate and organic silicon wetting and leveling agent;
the preparation raw materials of the component B comprise: an acidic silica sol;
the preparation raw materials of the silicon-based coating comprise the following components in parts by weight:
the component A comprises:
Figure FDA0003745556140000011
and B component:
30-80 parts of acidic silica sol;
the structural formula of the long-chain quaternary ammonium salt silane coupling agent is as follows:
Figure FDA0003745556140000012
in the formula: r 1 Is C 16 -C 18 Alkyl radical, R 2 Is CH 3 Or CH 2 CH 3 ；
The organic silicon wetting and leveling agent is a long-chain alkyl-polyether co-modified organic silicon leveling agent, and the structural formula is as follows:
Figure FDA0003745556140000021
in the formula: x is 0-5 and n is 3-7.
2. The silicon-based coating of claim 1, wherein the alkali metal silicate is selected from at least one of potassium silicate, sodium silicate, and lithium silicate;
the fluorocarbon resin dispersion is selected from PVF resin dispersions;
the organic silicon resin is selected from silanol-containing MQ silicon resin and/or polyhedral oligomeric silsesquioxane.
3. The silicon-based coating of claim 1, wherein the acidic silica sol has a particle size of 2-20 nm.
4. The silicon-based coating of claim 1, wherein the raw materials for preparing the component A further comprise, in parts by weight:
0.05-1 part of defoaming agent;
10-25 parts of isopropanol;
0-15 parts of deionized water.
5. A method for preparing a silicon-based coating, characterized in that the method is used for preparing the silicon-based coating according to any one of claims 1 to 4.
6. The method for preparing the silicon-based coating according to claim 5, wherein the preparation process of the A component comprises the following steps: mixing alkali metal silicate, fluorocarbon resin dispersion liquid, organic silicon resin, amino resin, long-chain quaternary ammonium salt silane coupling agent, zinc butyrate, organic silicon wetting and leveling agent, isopropanol and defoaming agent, and adding deionized water at a constant speed under the stirring action to obtain the component A.
7. A silicon-based hard coating, which is obtained by curing the silicon-based coating according to any one of claims 1 to 4.
8. A method for preparing a silicon-based hard coating, wherein the method is used for preparing the silicon-based hard coating according to claim 7.
9. The method for preparing a silicon-based hard coating according to claim 8, comprising the steps of: mixing the component A and the component B, and curing to obtain the silicon-based hard coating; the curing temperature is 180 ℃ and 250 ℃, and the curing time is 5-30 minutes.
10. Use of the silicon-based coating of any one of claims 1 to 4 or the silicon-based hard coating of claim 7 in photovoltaic power generation panels, glass, outdoor architectural aluminum veneers, vehicles or rail transit.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016080867A1 (en) * 2014-11-19 2016-05-26 Plekhanov Viadimir Leonidovich Coating system for preparing a hydrophobic coating
CN108659600A (en) * 2018-05-29 2018-10-16 曹颐戬 A kind of super-amphiphobic, automatically cleaning fluorine silicon coating material and preparation method thereof
CN108753011A (en) * 2018-06-26 2018-11-06 常州穗时新材料有限公司 A kind of hydrophilic Silicone hard coats and preparation method
CN111269596A (en) * 2020-04-09 2020-06-12 中山市美力德化工有限公司 Preparation method of inorganic polymer resin and water-based paint

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016080867A1 (en) * 2014-11-19 2016-05-26 Plekhanov Viadimir Leonidovich Coating system for preparing a hydrophobic coating
CN108659600A (en) * 2018-05-29 2018-10-16 曹颐戬 A kind of super-amphiphobic, automatically cleaning fluorine silicon coating material and preparation method thereof
CN108753011A (en) * 2018-06-26 2018-11-06 常州穗时新材料有限公司 A kind of hydrophilic Silicone hard coats and preparation method
CN111269596A (en) * 2020-04-09 2020-06-12 中山市美力德化工有限公司 Preparation method of inorganic polymer resin and water-based paint

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