CN110591475B - Antibacterial and anticorrosive water-based paint and preparation method thereof - Google Patents
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Abstract
The invention relates to an antibacterial and anticorrosive water-based paint and a preparation method thereof, wherein the paint has double functions of antibacterial and anticorrosive, can prevent chemical corrosion and effectively prevent biological corrosion, and comprises the following raw material components: the coating comprises rare earth functionalized water-based acrylic resin, antibacterial and anticorrosive nano microspheres, tripropylene glycol butyl ether, a flatting agent, a wetting agent, a defoaming agent, a dispersing agent, a multifunctional auxiliary agent AMP-95, a thickening agent and deionized water; according to the antibacterial and anticorrosive water-based paint prepared by the invention, the added antibacterial and anticorrosive nano microspheres can be stably dispersed in the water-based paint, the stability is good, after the coating is dried, organic matters on the shell of the antibacterial and anticorrosive nano microspheres can be connected with film-forming resin, and can be durably and stably present in the coating, and the antibacterial and anticorrosive water-based paint has the characteristics of high hardness, good corrosion resistance, stable and uniform dispersion, good storage stability and the like; the paint is widely used for marine paint, woodenware paint and metal anticorrosive paint, and has great application potential.
Description
Technical Field
The invention relates to a water-based paint, in particular to an antibacterial and anticorrosive water-based paint and a preparation method thereof, belonging to the technical field of water-based functional paints.
Background
With the development of economy and the continuous progress of science and technology, people have stronger and stronger environmental protection consciousness, and the country takes energy conservation and emission reduction as an important work to carry out comprehensive popularization, so that various industries develop towards the directions of green, environmental protection and science and technology. The water-based paint becomes an important development direction, and the existing water-based metal paint generally has the problems of short corrosion prevention period, high requirement on surface treatment, poor dispersion stability of pigments and fillers, easy occurrence of flash erosion after coating and the like. Can't satisfy the use demand of market to metallic paint, in addition, steel construction for the surface anticorrosive paint among the prior art can not effective antibiotic, under some to the higher condition of sanitary requirement, need often carry out artifical disinfection and sterilization and could use, and the metal corrosion includes: chemical corrosion, biological corrosion, and the like.
At present, most of the using and construction environments are moist and warm, microorganisms are easy to breed bacteria and propagate in the environment, a large amount of microorganisms such as fungi and mold can be bred in the coating for a long time, the coating can be damaged by the mass propagation of the microorganisms, the biological corrosion is caused, and the service life of the coating is greatly reduced.
Therefore, the development of a water-based paint which can prevent both chemical corrosion and biological corrosion meets the requirements of the current market and complex environment.
Disclosure of Invention
In order to solve the technical problems existing at present, the invention aims to provide an antibacterial and anticorrosive water-based paint.
The invention also provides a preparation method of the antibacterial and anticorrosive water-based paint.
An antibacterial anticorrosion water-based paint is characterized in that: the antibacterial and anticorrosive paint has the dual functions of antibiosis and anticorrosion, can prevent chemical corrosion and effectively prevent biological corrosion, and comprises the following raw material components: the coating comprises rare earth functionalized water-based acrylic resin, antibacterial and anticorrosive nano microspheres, tripropylene glycol butyl ether, a flatting agent, a wetting agent, a defoaming agent, a dispersing agent, a multifunctional auxiliary agent AMP-95, a thickening agent and deionized water. A preparation method of an antibacterial and anticorrosive water-based paint comprises the following preparation steps:
1) adding 3.0-6.0 parts by weight of antibacterial and anticorrosive nano-microspheres into 6.0-10.0 parts by weight of tripropylene glycol butyl ether and 5.0-10.0 parts by weight of deionized water, heating to 65-70 ℃, ultrasonically dispersing and dissolving to release effective antibacterial and anticorrosive particles, and then cooling to room temperature to obtain an active mixed solution;
2) adding 20.0-35.0 parts of rare earth functionalized water-based acrylic resin and 50.0-80.0 parts of fluorine modified acrylic water-based resin into a dispersion tank, uniformly stirring at normal temperature, then adding 0.2-0.5 part of dispersing agent, 0.2-0.8 part of wetting agent, 0.2-0.6 part of defoaming agent, 0.2-0.8 part of flatting agent and the active mixed liquid, and uniformly stirring at normal temperature;
3) and adding 0.2-0.6 part of multifunctional auxiliary agent AMP-95 to adjust the pH value to 7.5-8.0, then adding 0.1-0.6 part of thickening agent and a proper amount of deionized water, and adjusting to a specified viscosity to obtain the antibacterial anticorrosive water-based paint.
The rare earth functionalized water-based acrylic resin comprises the following components: the acrylic acid soft monomer, the acrylic acid hard monomer, the hydroxyethyl acrylate, the polyisocyanate, the hydroxyl Schiff base monomer, the rare earth solution, the sodium ethoxide ethanol solution, the absolute ethanol, the acrylic acid, the azobisisobutyronitrile, the emulsifier, the neutralizer and the deionized water.
The preparation method of the antibacterial and anticorrosive nano-microsphere comprises the following steps:
a. adding 0.2-0.8 part of azobisisobutyronitrile into 8.5-16.0 parts of silane coupling agent, 10.0-20.0 parts of hydroxyethyl methacrylate phosphate and 12.0-25.0 parts of castor oil by weight, stirring for dissolving, mixing with 10.0-16.0 parts of absolute ethanol solution of polyvinylpyrrolidone, heating to 85 ℃ under the protection of nitrogen, stirring for reacting for 14.0-18.0 h to obtain organic nano microspheres, washing the organic nano microspheres with ethanol, and drying in vacuum;
b. adding 3.0-7.0 parts of silver nitrate into 4.0-8.0 parts of 1mol/L sulfuric acid, ultrasonically dispersing for 0.5-1.0 h, then adding 10.0-20.0 parts of ethanol, slowly adding 20.0-40.0 parts of deionized water and 3.5-9.0 parts of sodium hydroxide, reacting for 3.0-5.0 h under stirring at 25-35 ℃, then adding 3.0-5.5 parts of hydrogen peroxide, and ultrasonically stirring for 5.0-8.0 h to obtain a solution X;
c. transferring the solution X to a high-pressure reaction kettle, filling nitrogen into the high-pressure reaction kettle, putting the reaction kettle into an oven with the temperature of 130-150 ℃, reacting for 24.0-28.0 h, taking out the reaction kettle, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a solid I;
d. adding the obtained solid I, organic nano microspheres and 3.5-8.0 parts of graphene oxide into 50.0-80.0 parts of dimethyl sulfoxide, performing ultrasonic dispersion, transferring the solution to a high-pressure reaction kettle, filling nitrogen into the reaction kettle, putting the reaction kettle into a drying oven at the temperature of 140-160 ℃, reacting for 12.0-16.0 hours, taking out the reaction kettle, naturally cooling to room temperature, and washing with deionized water and ethanol to obtain the antibacterial and anticorrosive nano microspheres.
The graphene oxide is prepared by a Hummers method, a Staudemaier method or a Brodie method; further, the graphene oxide is prepared by a Hummers method.
The silane coupling agent is one or a combination of more of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane.
The antibacterial anticorrosive water-based paint prepared by the invention has the following advantages:
1) the antibacterial and anticorrosive water-based paint prepared by the invention is added with antibacterial and anticorrosive nano microspheres, the antibacterial and anticorrosive nano microspheres can be stably dispersed in the water-based paint, the stability is good, and after the coating is dried, organic matters on the shell of the antibacterial and anticorrosive nano microspheres can be connected with film-forming resin and can be durably and stably existed in the coating.
2) The modified polyurethane has the characteristics of high hardness, good mechanical property, high crosslinking density, good wear resistance, good corrosion resistance, stable and uniform dispersion, good storage stability and the like; the paint is widely used for marine paint, woodenware paint and metal anticorrosive paint, and has great application potential.
Detailed Description
The following examples further describe the antibacterial and anticorrosive water-based paint of the present invention. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
An antibacterial and anticorrosive nano microsphere A is prepared by the following steps:
a. adding 0.5 part of azobisisobutyronitrile into 12.0 parts of vinyltriethoxysilane, 14.0 parts of hydroxyethyl methacrylate phosphate and 18.0 parts of castor oil by weight, stirring and dissolving, then mixing with 12.0 parts of absolute ethanol solution of polyvinylpyrrolidone, heating to 85 ℃ under the protection of nitrogen, stirring and reacting for 16 hours to obtain organic nano microspheres, then washing the organic nano microspheres with ethanol, and performing vacuum drying;
b. adding 5.0 parts of silver nitrate into 6.0 parts of 1mol/L sulfuric acid, performing ultrasonic dispersion for 1.0h, then adding 15.0 parts of ethanol, slowly adding 30.0 parts of deionized water and 6.2 parts of sodium hydroxide, reacting for 4.0h under stirring at 25-35 ℃, then adding 4.0 parts of hydrogen peroxide, and performing ultrasonic stirring for 7.0h to obtain a solution X;
c. transferring the solution X to a high-pressure reaction kettle, filling nitrogen into the high-pressure reaction kettle, putting the reaction kettle into a drying oven with the temperature of 140 ℃, reacting for 28 hours, taking out the reaction kettle, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a solid I;
d. adding the obtained solid I, organic nano microspheres and 6.0 parts of graphene oxide into 65.0 parts of dimethyl sulfoxide, performing ultrasonic dispersion, transferring the solution to a high-pressure reaction kettle, filling nitrogen into the high-pressure reaction kettle, putting the reaction kettle into a 160 ℃ oven, reacting for 14.0h, taking out, naturally cooling to room temperature, and washing with deionized water and ethanol to obtain the antibacterial and anticorrosive nano microspheres A.
Example 2
An antibacterial and anticorrosive nano microsphere B is prepared by the following steps:
a. adding 0.6 part of azobisisobutyronitrile into 16.0 parts of gamma-methacryloxypropyltrimethoxysilane, 11.0 parts of hydroxyethyl methacrylate phosphate and 20.0 parts of castor oil by weight, stirring and dissolving, then mixing with 14.0 parts of absolute ethanol solution of polyvinylpyrrolidone, heating to 85 ℃ under the protection of nitrogen, stirring and reacting for 16.0h to obtain organic nano microspheres, then washing the organic nano microspheres with ethanol, and performing vacuum drying;
b. adding 6.5 parts of silver nitrate into 7.0 parts of 1mol/L sulfuric acid, performing ultrasonic dispersion for 1.0h, then adding 18.0 parts of ethanol, slowly adding 35.0 parts of deionized water and 7.3 parts of sodium hydroxide, reacting for 5.0h under stirring at 25-35 ℃, then adding 5.0 parts of hydrogen peroxide, and performing ultrasonic stirring for 8.0h to obtain a solution X;
c. transferring the solution X to a high-pressure reaction kettle, filling nitrogen into the high-pressure reaction kettle, putting the reaction kettle into a drying oven at the temperature of 150 ℃, reacting for 26.0, taking out the reaction kettle, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a solid I;
d. adding the obtained solid I, organic nano microspheres and 7.0 parts of graphene oxide into 72.0 parts of dimethyl sulfoxide, performing ultrasonic dispersion, transferring the solution to a high-pressure reaction kettle, filling nitrogen into the high-pressure reaction kettle, putting the reaction kettle into a 160 ℃ oven, reacting for 14.0h, taking out, naturally cooling to room temperature, and washing with deionized water and ethanol to obtain the antibacterial and anticorrosive nano microspheres B.
Example 3
An antibacterial and anticorrosive nano microsphere C is prepared by the following steps:
a. adding 0.3 part of azobisisobutyronitrile into 9.0 parts of vinyltrimethoxysilane, 12.0 parts of hydroxyethyl methacrylate phosphate and 12.0 parts of castor oil by weight, stirring for dissolving, then mixing with 11.0 parts of absolute ethanol solution of polyvinylpyrrolidone, heating to 85 ℃ under the protection of nitrogen, stirring for reacting for 16.0 hours to obtain organic nano microspheres, then washing the organic nano microspheres with ethanol, and performing vacuum drying;
b. adding 3.5 parts of silver nitrate into 5.5 parts of 1mol/L sulfuric acid, performing ultrasonic dispersion for 0.5-1.0 h, then adding 13.0 parts of ethanol, slowly adding 26.0 parts of deionized water and 6.0 parts of sodium hydroxide, reacting for 5.0h under stirring at 25-35 ℃, then adding 3.5 parts of hydrogen peroxide, and performing ultrasonic stirring for 7.0h to obtain a solution X;
c. transferring the solution X to a high-pressure reaction kettle, filling nitrogen into the high-pressure reaction kettle, putting the reaction kettle into a drying oven at the temperature of 150 ℃, reacting for 26.0h, taking out the reaction kettle, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a solid I;
d. adding the obtained solid I, organic nano microspheres and 4.2 parts of graphene oxide into 60.0 parts of dimethyl sulfoxide, performing ultrasonic dispersion, transferring the solution to a high-pressure reaction kettle, filling nitrogen into the high-pressure reaction kettle, putting the reaction kettle into a 160 ℃ oven, reacting for 14.0h, taking out, naturally cooling to room temperature, and washing with deionized water and ethanol to obtain the antibacterial and anticorrosive nano microspheres C.
Example 4
A preparation method of an antibacterial and anticorrosive water-based paint comprises the following preparation steps:
1) adding 5.0 parts by weight of antibacterial and anticorrosive nano-microspheres A into 8.5 parts by weight of tripropylene glycol butyl ether and 8.0 parts by weight of deionized water, heating to 68 ℃, ultrasonically dispersing and dissolving to release effective antibacterial and anticorrosive particles, and then cooling to room temperature to obtain an active mixed solution;
2) adding 30.0 parts of rare earth functionalized water-based acrylic resin and 70.0 parts of fluorine modified acrylic water-based resin into a dispersion tank, uniformly stirring at normal temperature, then adding 0.4 part of dispersing agent, 0.6 part of wetting agent, 0.4 part of defoaming agent, 0.6 part of flatting agent and the active mixed solution, and uniformly stirring at normal temperature;
3) and adding 0.4 part of multifunctional auxiliary AMP-95 to adjust the pH value to 7.5-8.0, then adding 0.4 part of thickening agent and 20.0 parts of deionized water, and adjusting to a specified viscosity to obtain the antibacterial anticorrosive water-based paint. Viscosity; 25 ℃, 4 cup painted test: 45 minutes, 26 seconds.
Example 5
A preparation method of an antibacterial and anticorrosive water-based paint comprises the following preparation steps:
1) adding 4.0 parts by weight of antibacterial and anticorrosive nano microspheres B into 7.0 parts by weight of tripropylene glycol butyl ether and 7.0 parts by weight of deionized water, heating to 66 ℃, ultrasonically dispersing and dissolving to release effective antibacterial and anticorrosive particles, and then cooling to room temperature to obtain an active mixed solution;
2) adding 20.0 parts of rare earth functionalized water-based acrylic resin and 78.0 parts of fluorine modified acrylic water-based resin into a dispersion tank, uniformly stirring at normal temperature, then adding 0.3 part of dispersing agent, 0.5 part of wetting agent, 0.5 part of defoaming agent, 0.5 part of flatting agent and the active mixed solution, and uniformly stirring at normal temperature;
3) and adding 0.4 part of multifunctional auxiliary AMP-95 to adjust the pH value to 7.5-8.0, and then adding 0.4 part of thickening agent and 18.0 parts of deionized water to adjust the viscosity to the specified value. And obtaining the antibacterial anticorrosive water-based paint. Viscosity; 25 ℃, 4 cup painted test: 45 minutes 08 seconds.
Example 6
A preparation method of an antibacterial and anticorrosive water-based paint comprises the following preparation steps:
1) adding 6.0 parts by weight of antibacterial and anticorrosive nano microspheres C into 10.0 parts by weight of tripropylene glycol butyl ether and 9.0 parts by weight of deionized water, heating to 70 ℃, ultrasonically dispersing and dissolving to release effective antibacterial and anticorrosive particles, and then cooling to room temperature to obtain an active mixed solution;
2) adding 32.0 parts of rare earth functionalized water-based acrylic resin and 80.0 parts of fluorine modified acrylic water-based resin into a dispersion tank, uniformly stirring at normal temperature, then adding 0.5 part of dispersing agent, 0.7 part of wetting agent, 0.5 part of defoaming agent, 0.7 part of flatting agent and the active mixed solution, and uniformly stirring at normal temperature;
3) and adding 0.6 part of multifunctional auxiliary AMP-95 to adjust the pH value to 7.5-8.0, and then adding 0.5 part of thickening agent and 22.0 parts of deionized water to adjust the viscosity to the specified value. And obtaining the antibacterial anticorrosive water-based paint. Viscosity; 25 ℃, 4 cup painted test: 46 minutes and 18 seconds.
According to relevant standards, the examples of the invention are compared and tested with the conventional anticorrosive paint (comparative example 1) and the conventional antibacterial paint (comparative example 2), and the tested performance indexes are shown in table 1.
Wherein, the drying speed is as follows: detection is carried out according to the specification of GB 1728;
adhesion force: the test was carried out using the cross-cut method, as specified in GB/T1720-1988;
hardness: measuring the hardness of the paint film according to GB/T6739-2006 color paint and a pencil cleaning method;
water resistance: detecting according to the regulation of GB/T1733-93;
salt spray resistance: detecting according to the regulation of GB/T1771-1991;
filiform corrosivity: detecting according to the regulation of GB/T13452.4-92;
and (3) antibacterial property: the detection is carried out according to the regulation of HG/T3950-2007 antimicrobial paint.
Table 1: the performance of the examples is compared with that of comparative examples 1 and 2
It can be seen from table 1 that the water resistance, adhesion, hardness, salt spray resistance, escherichia coli resistance, aspergillus niger resistance, filiform corrosion resistance, and the like of the samples of examples 4, 5, 6 of the present invention are much better than those of the conventional anticorrosive paint (comparative example 1) and the conventional antibacterial paint (comparative example 2).
After the sample is aged for 3 years, the antibacterial performance of the coating is detected according to the standard of HG/T3950-2007 antibacterial paint, and the detected antibacterial performance indexes are shown in Table 2:
table 2: the examples are compared with comparative examples 1 and 2 for simulating the antibacterial performance after 3-year aging:
it can be seen from table 2 that the samples of examples 4, 5 and 6 of the present invention have little decrease in antibacterial performance, while the conventional antibacterial coating has a large decrease in antibacterial performance, because the antibacterial and anticorrosive nanospheres can be stably and durably stored in the coating, are not easily decomposed, fall off, and migrate, and have lasting and effective antibacterial performance.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. An antibacterial anticorrosion water-based paint is characterized in that: has the dual functions of antibiosis and anticorrosion, not only can prevent chemical corrosion, but also can effectively prevent biological corrosion, and the used raw material components comprise: the preparation method comprises the following steps of preparing rare earth functionalized water-based acrylic resin, fluorine modified acrylic water-based resin, antibacterial and anticorrosive nano microspheres, tripropylene glycol butyl ether, a flatting agent, a wetting agent, a defoaming agent, a dispersing agent, a multifunctional assistant AMP-95, a thickening agent and deionized water, wherein the preparation method of the antibacterial and anticorrosive nano microspheres comprises the following steps:
a. adding 0.2-0.8 part of azobisisobutyronitrile into 8.5-16.0 parts of silane coupling agent, 10.0-20.0 parts of hydroxyethyl methacrylate phosphate and 12.0-25.0 parts of castor oil by weight, stirring for dissolving, mixing with 10.0-16.0 parts of absolute ethanol solution of polyvinylpyrrolidone, heating to 85 ℃ under the protection of nitrogen, stirring for reacting for 14.0-18.0 h to obtain organic nano microspheres, washing the organic nano microspheres with ethanol, and drying in vacuum;
b. adding 3.0-7.0 parts of silver nitrate into 4.0-8.0 parts of 1mol/L sulfuric acid, ultrasonically dispersing for 0.5-1.0 h, then adding 10.0-20.0 parts of ethanol, slowly adding 20.0-40.0 parts of deionized water and 3.5-9.0 parts of sodium hydroxide, reacting for 3.0-5.0 h under stirring at 25-35 ℃, then adding 3.0-5.5 parts of hydrogen peroxide, and ultrasonically stirring for 5.0-8.0 h to obtain a solution X;
c. transferring the solution X into a high-pressure reaction kettle, filling nitrogen, putting the reaction kettle into an oven with the temperature of 130-150 ℃ for reaction for 24.0-28.0 h, taking out, naturally cooling to room temperature, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain a solid I;
d. adding the obtained solid I, organic nano microspheres and 3.5-8.0 parts of graphene oxide into 50.0-80.0 parts of dimethyl sulfoxide, performing ultrasonic dispersion, transferring the solution into a high-pressure reaction kettle, filling nitrogen, putting the reaction kettle into a drying oven at 140-160 ℃, reacting for 12.0-16.0 hours, taking out, naturally cooling to room temperature, and washing with deionized water and ethanol to obtain the antibacterial and anticorrosive nano microspheres;
the antibacterial anticorrosive water-based paint comprises the following preparation steps:
1) adding 3.0-6.0 parts by weight of antibacterial and anticorrosive nano-microspheres into 6.0-10.0 parts by weight of tripropylene glycol butyl ether and 5.0-10.0 parts by weight of deionized water, heating to 65-70 ℃, ultrasonically dispersing and dissolving to release effective antibacterial and anticorrosive particles, and then cooling to room temperature to obtain an active mixed solution;
2) adding 20.0-35.0 parts of rare earth functionalized water-based acrylic resin and 50.0-80.0 parts of fluorine modified acrylic water-based resin into a dispersion tank, uniformly stirring at normal temperature, then adding 0.2-0.5 part of dispersing agent, 0.2-0.8 part of wetting agent, 0.2-0.6 part of defoaming agent, 0.2-0.8 part of flatting agent and the active mixed liquid, and uniformly stirring at normal temperature;
3) and adding 0.2-0.6 part of multifunctional auxiliary agent AMP-95 to adjust the pH value to 7.5-8.0, then adding 0.1-0.6 part of thickening agent and a proper amount of deionized water, and adjusting to a specified viscosity to obtain the antibacterial anticorrosive water-based paint.
2. The antibacterial anticorrosive water-based paint according to claim 1, characterized in that: the rare earth functionalized water-based acrylic resin comprises the following components: the acrylic acid soft monomer, the acrylic acid hard monomer, the hydroxyethyl acrylate, the polyisocyanate, the hydroxyl Schiff base monomer, the rare earth solution, the sodium ethoxide ethanol solution, the absolute ethanol, the acrylic acid, the azobisisobutyronitrile, the emulsifier, the neutralizer and the deionized water.
3. The antibacterial anticorrosive water-based paint according to claim 1, characterized in that: the graphene oxide is prepared by a Hummers method, a Staudemaier method or a Brodie method.
4. The antibacterial anticorrosive water-based paint according to claim 1, characterized in that: the silane coupling agent is one or a combination of more of gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, vinyl triethoxysilane and vinyl trimethoxysilane.
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| CN107814895A (en) * | 2017-10-31 | 2018-03-20 | 湖南辰砾新材料有限公司 | A kind of rare earth metal coordination modified aqueous polyurethane luminous resin and preparation method thereof |
| CN108192483A (en) * | 2017-12-28 | 2018-06-22 | 安徽明珠颜料科技有限公司 | A kind of preparation method of graphene oxide Antimicrobial preservative coating |
| CN109535911A (en) * | 2018-10-31 | 2019-03-29 | 韶关市合众化工有限公司 | A kind of antibacterial aqueous finishing coat of high-efficient and lasting |
| CN109852174A (en) * | 2018-12-14 | 2019-06-07 | 河北晨阳工贸集团有限公司 | Aqueous anti-algae antibiotic paint and preparation method thereof |
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| CN107814895A (en) * | 2017-10-31 | 2018-03-20 | 湖南辰砾新材料有限公司 | A kind of rare earth metal coordination modified aqueous polyurethane luminous resin and preparation method thereof |
| CN108192483A (en) * | 2017-12-28 | 2018-06-22 | 安徽明珠颜料科技有限公司 | A kind of preparation method of graphene oxide Antimicrobial preservative coating |
| CN109535911A (en) * | 2018-10-31 | 2019-03-29 | 韶关市合众化工有限公司 | A kind of antibacterial aqueous finishing coat of high-efficient and lasting |
| CN109852174A (en) * | 2018-12-14 | 2019-06-07 | 河北晨阳工贸集团有限公司 | Aqueous anti-algae antibiotic paint and preparation method thereof |
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