CN113913091A - Antibacterial powder coating and preparation method thereof - Google Patents
Antibacterial powder coating and preparation method thereof Download PDFInfo
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- CN113913091A CN113913091A CN202111462922.0A CN202111462922A CN113913091A CN 113913091 A CN113913091 A CN 113913091A CN 202111462922 A CN202111462922 A CN 202111462922A CN 113913091 A CN113913091 A CN 113913091A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an antibacterial powder coating and a preparation method thereof, wherein the antibacterial powder coating is prepared from the following raw materials: e51 epoxy resin, NH3307 polyester resin, superfine barium sulfate, levelling agent, smooth degasifier and magnesium hydrate coat chitosan biguanide salt, chitosan biguanide salt has good antibacterial property, but decompose easily under the ultraviolet irradiation, the antibacterial aging is short, the invention coats a layer of magnesium hydrate on the surface of chitosan biguanide salt, can delay the decomposition of chitosan biguanide salt effectively, thus lengthen antibacterial aging; in addition, the magnesium hydroxide belongs to an inorganic antibacterial agent, and is synergistic with the chitosan biguanide salt to improve the antibacterial effect of the coating.
Description
Technical Field
The invention relates to the technical field of paint preparation, in particular to an antibacterial powder paint and a preparation method thereof.
Background
The powder coating is a novel solid powdery coating without solvent, has the characteristics of no solvent, no pollution, recoverability, environmental protection, energy and resource saving, labor intensity reduction, high mechanical strength of a coating film and the like, is more and more concerned by people with excellent environmental protection characteristic, greatly improves the living environment quality of people and reduces the threat of microorganisms and germs to the human health, is a thermosetting powder coating consisting of resin, a curing agent, an antibacterial agent, pigment, filler and an auxiliary agent, is generally manufactured by a melting extruder mixing method, is coated by an electrostatic powder coating method, realizes an antibacterial function by adding the antibacterial agent into the powder coating, and is a novel coating with antibacterial and bactericidal properties.
The antibacterial agent added in the coating mainly comprises a natural antibacterial agent, an organic antibacterial agent and an inorganic antibacterial agent, chitosan is an excellent natural antibacterial agent, and the structure of the antibacterial agent contains reaction functional groups such as amino, hydroxyl and the like, but the antibacterial property of chitosan is poor, a large amount of chitosan is required to have certain antibacterial property, and the performance of the coating is inevitably reduced when the large amount of chitosan is introduced into the coating.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an antibacterial powder coating and a preparation method thereof, and solves the technical problem that the traditional coating is short in antibacterial aging.
In order to achieve the purpose, the invention adopts the following technical scheme:
an antibacterial powder coating is composed of the following raw materials in parts by weight: 20-25 parts of E51 epoxy resin, 30-35 parts of NH3307 polyester resin, 15-25 parts of superfine barium sulfate, 1-2 parts of flatting agent, 1-2 parts of smoothing degasifier and 5-10 parts of magnesium hydroxide coated chitosan biguanide salt.
Preferably, the preparation method of the magnesium hydroxide coated chitosan biguanide salt comprises the following steps:
(1) adding chitosan into a hydrochloric acid solution, stirring and dissolving, then adding absolute ethyl alcohol for precipitation, stirring, filtering, and drying to obtain chitosan hydrochloride;
(2) adding chitosan hydrochloride into deionized water, stirring and mixing uniformly, adjusting the pH value of the solution to 2-3, then adding dicyandiamide for reaction, and after the reaction is finished, washing and drying a reaction product to obtain chitosan biguanide salt;
(3) adding chitosan biguanide salt into an isopropanol solvent, then adding glutaraldehyde, reacting, and after the reaction is finished, filtering, washing and vacuum drying a reaction product to obtain cross-linked chitosan biguanide salt;
(4) dispersing the crosslinked chitosan biguanide salt in a sodium hydroxide aqueous solution, dropwise adding a magnesium chloride solution under a stirring state for reaction, and after the reaction is finished, aging, filtering, washing and drying to obtain the magnesium hydroxide coated chitosan biguanide salt.
Preferably, in the step (1), the mass ratio of the chitosan to the hydrochloric acid solution is 5-10:60-80, and the mass fraction of the hydrochloric acid solution is 20-30%.
Preferably, in the step (2), the mass ratio of the chitosan hydrochloride to the dicyandiamide is 2-6: 1.5-8.
Preferably, in the step (2), the reaction temperature is 90-100 ℃, and the reaction time is 2-3 h.
Preferably, in the step (3), the mass ratio of the chitosan biguanide salt to the glutaraldehyde is 1: 1-2.
Preferably, in the step (3), the reaction temperature is 40-60 ℃ and the reaction time is 2-3 h.
Preferably, in the step (4), the mass ratio of the cross-linked chitosan biguanide salt to the aqueous solution of sodium hydroxide to the aqueous solution of magnesium chloride is 1:30-50:10-20, the mass fraction of the aqueous solution of sodium hydroxide is 10-30%, and the mass fraction of the aqueous solution of magnesium chloride is 10-20%.
Preferably, in the step (4), the stirring speed is 300-400r/min, the reaction temperature is 25-50 ℃, and the reaction time is 0.5-2 h.
The invention also provides a preparation method of the antibacterial powder coating, which comprises the following steps: e51 epoxy resin, NH3307 polyester resin, superfine barium sulfate, flatting agent, smoothing degasifier and magnesium hydroxide coated chitosan biguanide salt are put into a mixing tank according to the weight parts, premixed for 5-10min, then the premixed material is melted and extruded, the extruded sheet is put into a ball mill for grinding, the rotating speed of the ball mill is 1800 plus 2000rpm, and the ground coarse powder passes through a 200-mesh sieve through a rotary sieve, thus obtaining the antibacterial powder coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides an antibacterial powder coating and a preparation method thereof, wherein the antibacterial agent magnesium hydroxide coated chitosan biguanide salt is prepared by firstly taking chitosan as a raw material to prepare chitosan hydrochloride, then carrying out nucleophilic addition reaction on the chitosan hydrochloride and dicyandiamide to obtain the chitosan biguanide salt, in order to reduce the solubility of the chitosan biguanide salt, crosslinking the chitosan biguanide salt by using a crosslinking agent glutaraldehyde, and then coating a layer of magnesium hydroxide on the surface of the chitosan biguanide salt to obtain the magnesium hydroxide coated chitosan biguanide salt.
(2) The chitosan biguanide salt has good antibacterial performance, but is easy to decompose under the irradiation of ultraviolet light, and the antibacterial aging is short; in addition, magnesium hydroxide belongs to an inorganic antibacterial agent, magnesium ions can be released after the magnesium hydroxide is exposed in the air for a long time, and chitosan biguanide salt has a certain chelation effect on the magnesium ions, so that the release of the magnesium ions can be relieved, and the antibacterial aging is further prolonged.
Detailed Description
The present invention will be described in more detail with reference to specific preferred embodiments, but the present invention is not limited to the following embodiments.
It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention are commercially available.
E51 epoxy resin was purchased from Shandong Chuangying chemical Co., Ltd;
NH3307 polyester resin was purchased from zenith materials science and technology limited;
leveling agents are available from PV88 of dengli chemical, germany;
the smoothing degasifier is purchased from SA500 of New Material Co., Ltd;
the molecular weight of the chitosan used in the invention is 200000, and the deacetylation degree is 85%.
Example 1
A preparation method of antibacterial powder coating comprises the following steps:
(1) preparation of magnesium hydroxide coated chitosan biguanide salt
Adding 10g of chitosan into 100g of 20 wt% hydrochloric acid solution, stirring for dissolving, then adding absolute ethyl alcohol for precipitation, stirring, filtering, and drying to obtain chitosan hydrochloride;
adding 10g of chitosan hydrochloride into 100mL of deionized water, stirring and mixing uniformly, adjusting the pH value of the solution to 2, then adding 20g of dicyandiamide, reacting for 2 hours at 90 ℃, washing and drying a reaction product after the reaction is finished, thus obtaining the chitosan biguanide salt;
adding 10g of chitosan biguanide salt into 200mL of isopropanol solvent, then adding 15g of glutaraldehyde, reacting for 2h at 50 ℃, and after the reaction is finished, filtering, washing and vacuum drying the reaction product to obtain the cross-linked chitosan biguanide salt;
dispersing 10g of cross-linked chitosan biguanide salt in 100g of 15 wt% sodium hydroxide aqueous solution, dropwise adding 20g of 10 wt% magnesium chloride solution at the rotation speed of 400r/min, reacting at 30 ℃ for 1h, and after the reaction is finished, aging, filtering, washing and drying to obtain the magnesium hydroxide coated chitosan biguanide salt.
(2) Preparation of antibacterial powder coating
Putting 20g E51 epoxy resin, 30g NH3307 polyester resin, 15g superfine barium sulfate, 1g flatting agent PV88, 1g smoothing degasifier SA500 and 5g magnesium hydroxide coated chitosan biguanide salt into a mixing tank, premixing for 5min, then carrying out melt extrusion on the premix, putting the extruded sheet into a ball mill for grinding, wherein the rotating speed of the ball mill is 1800rpm, and screening the ground coarse powder through a 200-mesh sieve by using a rotary screening sieve to obtain the antibacterial powder coating.
Example 2
A preparation method of antibacterial powder coating comprises the following steps:
(1) preparation of magnesium hydroxide coated chitosan biguanide salt
Adding 10g of chitosan into 100g of 25 wt% hydrochloric acid solution, stirring for dissolving, then adding absolute ethyl alcohol for precipitation, stirring, filtering, and drying to obtain chitosan hydrochloride;
adding 10g of chitosan hydrochloride into 100mL of deionized water, stirring and mixing uniformly, adjusting the pH value of the solution to 2, then adding 15g of dicyandiamide, reacting for 2 hours at 95 ℃, after the reaction is finished, washing and drying the reaction product to obtain chitosan biguanide salt;
adding 10g of chitosan biguanide salt into 200mL of isopropanol solvent, then adding 18g of glutaraldehyde, reacting for 2h at 40 ℃, and after the reaction is finished, filtering, washing and vacuum drying the reaction product to obtain the cross-linked chitosan biguanide salt;
dispersing 10g of cross-linked chitosan biguanide salt in 100g of 10 wt% sodium hydroxide aqueous solution, dropwise adding 25g of 10 wt% magnesium chloride solution at the rotation speed of 400r/min, reacting at 30 ℃ for 1h, and after the reaction is finished, aging, filtering, washing and drying to obtain the magnesium hydroxide coated chitosan biguanide salt.
(2) Preparation of antibacterial powder coating
22g E51 epoxy resin, 34g NH3307 polyester resin, 18g superfine barium sulfate, 1.5g flatting agent PV88, 1.5g smoothing degasifier SA500 and 7g magnesium hydroxide coated chitosan biguanide salt are put into a mixing tank to be premixed for 5min, then the premixed material is melted and extruded, the extruded sheet-shaped material is put into a ball mill to be ground, the rotating speed of the ball mill is 1800rpm, and the ground coarse powder passes through a 200-mesh sieve through a rotary sieve, thus obtaining the antibacterial powder coating.
Example 3
A preparation method of antibacterial powder coating comprises the following steps:
(1) preparation of magnesium hydroxide coated chitosan biguanide salt
Adding 10g of chitosan into 100g of 25 wt% hydrochloric acid solution, stirring for dissolving, then adding absolute ethyl alcohol for precipitation, stirring, filtering, and drying to obtain chitosan hydrochloride;
adding 10g of chitosan hydrochloride into 100mL of deionized water, stirring and mixing uniformly, adjusting the pH value of the solution to 2, then adding 25g of dicyandiamide, reacting for 2 hours at 90 ℃, after the reaction is finished, washing and drying the reaction product to obtain chitosan biguanide salt;
adding 10g of chitosan biguanide salt into 200mL of isopropanol solvent, then adding 12g of glutaraldehyde, reacting for 2h at 40 ℃, and after the reaction is finished, filtering, washing and vacuum drying the reaction product to obtain the cross-linked chitosan biguanide salt;
dispersing 10g of cross-linked chitosan biguanide salt in 100g of 10 wt% sodium hydroxide aqueous solution, dropwise adding 30g of 10 wt% magnesium chloride solution at the rotation speed of 400r/min, reacting at 30 ℃ for 1h, and after the reaction is finished, aging, filtering, washing and drying to obtain the magnesium hydroxide coated chitosan biguanide salt.
(2) Preparation of antibacterial powder coating
Putting 25g E51 epoxy resin, 32g of NH3307 polyester resin, 20g of superfine barium sulfate, 2g of flatting agent PV88, 1.5g of smoothing degasifier SA500 and 8g of magnesium hydroxide coated chitosan biguanide salt into a mixing tank, premixing for 5min, then carrying out melt extrusion on the premix, putting the extruded sheet into a ball mill for grinding, wherein the rotating speed of the ball mill is 1800rpm, and sieving the ground coarse powder through a rotary sieve and a 200-mesh sieve to obtain the antibacterial powder coating.
Example 4
A preparation method of antibacterial powder coating comprises the following steps:
(1) preparation of magnesium hydroxide coated chitosan biguanide salt
Adding 10g of chitosan into 100g of 25 wt% hydrochloric acid solution, stirring for dissolving, then adding absolute ethyl alcohol for precipitation, stirring, filtering, and drying to obtain chitosan hydrochloride;
adding 10g of chitosan hydrochloride into 100mL of deionized water, stirring and mixing uniformly, adjusting the pH value of the solution to 2, then adding 30g of dicyandiamide, reacting for 2 hours at 90 ℃, after the reaction is finished, washing and drying the reaction product to obtain chitosan biguanide salt;
adding 10g of chitosan biguanide salt into 200mL of isopropanol solvent, then adding 20g of glutaraldehyde, reacting for 2h at 40 ℃, and after the reaction is finished, filtering, washing and vacuum drying the reaction product to obtain the cross-linked chitosan biguanide salt;
dispersing 10g of cross-linked chitosan biguanide salt in 100g of 10 wt% sodium hydroxide aqueous solution, dropwise adding 30g of 15 wt% magnesium chloride solution at the rotation speed of 400r/min, reacting at 30 ℃ for 1h, and after the reaction is finished, aging, filtering, washing and drying to obtain the magnesium hydroxide coated chitosan biguanide salt.
(2) Preparation of antibacterial powder coating
Putting 20g E51 epoxy resin, 35g NH3307 polyester resin, 22g superfine barium sulfate, 1g flatting agent PV88, 2g smoothing degasifier SA500 and 10g magnesium hydroxide coated chitosan biguanide salt into a mixing tank, premixing for 5min, then carrying out melt extrusion on the premix, putting the extruded sheet into a ball mill for grinding, wherein the rotating speed of the ball mill is 1800rpm, and screening the ground coarse powder through a 200-mesh sieve by using a rotary screening sieve to obtain the antibacterial powder coating.
Comparative example 1
A preparation method of antibacterial powder coating comprises the following steps:
(1) preparation of chitosan biguanide salt
Adding 10g of chitosan into 100g of 25 wt% hydrochloric acid solution, stirring for dissolving, then adding absolute ethyl alcohol for precipitation, stirring, filtering, and drying to obtain chitosan hydrochloride;
adding 10g of chitosan hydrochloride into 100mL of deionized water, stirring and mixing uniformly, adjusting the pH value of the solution to 2, then adding 25g of dicyandiamide, reacting for 2 hours at 90 ℃, after the reaction is finished, washing and drying the reaction product to obtain the chitosan biguanide salt.
(2) Preparation of antibacterial powder coating
Putting 25g E51 epoxy resin, 32g of NH3307 polyester resin, 20g of superfine barium sulfate, 2g of flatting agent PV88, 1.5g of smoothing degasifier SA500 and 8g of chitosan biguanide salt into a mixing tank, premixing for 5min, then carrying out melt extrusion on the premix, putting the extruded sheet into a ball mill for grinding, wherein the rotating speed of the ball mill is 1800rpm, and screening the ground coarse powder through a rotary screen by a 200-mesh screen to obtain the antibacterial powder coating.
The antibacterial powder coatings prepared in examples 1-4 and comparative example 1 are applied to a steel matrix, and then the antibacterial performance of the steel matrix is tested according to HG/T3950-2007 standard, and the test results are shown in the following table:
as can be seen from the table, the coating prepared by the invention has good lasting antibacterial performance, and still has good antibacterial effect after 12 months of use, and the chitosan biguanide salt in the comparative example 1 is not coated by magnesium hydroxide, and the antibacterial performance begins to be obviously reduced after 6 months of use.
Finally, it is to be noted that: the above examples do not limit the invention in any way. It will be apparent to those skilled in the art that various modifications and improvements can be made to the present invention. Accordingly, any modification or improvement made without departing from the spirit of the present invention is within the scope of the claimed invention.
Claims (10)
1. The antibacterial powder coating is characterized by comprising the following raw materials in parts by weight: 20-25 parts of E51 epoxy resin, 30-35 parts of NH3307 polyester resin, 15-25 parts of superfine barium sulfate, 1-2 parts of flatting agent, 1-2 parts of smoothing degasifier and 5-10 parts of magnesium hydroxide coated chitosan biguanide salt.
2. The antibacterial powder coating of claim 1, wherein the preparation method of the magnesium hydroxide-coated chitosan biguanide salt comprises the following steps:
(1) adding chitosan into a hydrochloric acid solution, stirring and dissolving, then adding absolute ethyl alcohol for precipitation, stirring, filtering, and drying to obtain chitosan hydrochloride;
(2) adding chitosan hydrochloride into deionized water, stirring and mixing uniformly, adjusting the pH value of the solution to 2-3, then adding dicyandiamide for reaction, and after the reaction is finished, washing and drying a reaction product to obtain chitosan biguanide salt;
(3) adding chitosan biguanide salt into an isopropanol solvent, then adding glutaraldehyde, reacting, and after the reaction is finished, filtering, washing and vacuum drying a reaction product to obtain cross-linked chitosan biguanide salt;
(4) dispersing the crosslinked chitosan biguanide salt in a sodium hydroxide aqueous solution, dropwise adding a magnesium chloride solution under a stirring state for reaction, and after the reaction is finished, aging, filtering, washing and drying to obtain the magnesium hydroxide coated chitosan biguanide salt.
3. The antibacterial powder coating of claim 2, wherein in step (1), the mass ratio of chitosan to hydrochloric acid solution is 5-10:60-80, and the mass fraction of hydrochloric acid solution is 20-30%.
4. The antibacterial powder coating according to claim 2, wherein in step (2), the mass ratio of chitosan hydrochloride to dicyandiamide is 2-6: 1.5-8.
5. The antibacterial powder coating of claim 2, wherein in step (2), the reaction temperature is 90-100 ℃ and the reaction time is 2-3 h.
6. The antibacterial powder coating of claim 2, wherein in step (3), the mass ratio of the chitosan biguanide salt to glutaraldehyde is 1: 1-2.
7. The antibacterial powder coating of claim 2, wherein in step (3), the reaction temperature is 40-60 ℃ and the reaction time is 2-3 h.
8. The antibacterial powder coating of claim 2, wherein in step (4), the mass ratio of the crosslinked chitosan biguanide salt to the aqueous sodium hydroxide solution to the magnesium chloride solution is 5:30-50:10-20, the mass fraction of the aqueous sodium hydroxide solution is 10-30%, and the mass fraction of the magnesium chloride solution is 10-20%.
9. The antibacterial powder coating as claimed in claim 2, wherein in the step (4), the stirring speed is 300-400r/min, the reaction temperature is 25-50 ℃, and the reaction time is 0.5-2 h.
10. A method of preparing an antimicrobial powder coating according to any one of claims 1 to 9, characterized in that the method comprises the steps of: e51 epoxy resin, NH3307 polyester resin, superfine barium sulfate, flatting agent, smoothing degasifier and magnesium hydroxide coated chitosan biguanide salt are put into a mixing tank according to the weight parts, premixed for 5-10min, then the premixed material is melted and extruded, the extruded sheet is put into a ball mill for grinding, the rotating speed of the ball mill is 1800 plus 2000rpm, and the ground coarse powder passes through a 200-mesh sieve through a rotary sieve, thus obtaining the antibacterial powder coating.
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| CN202111462922.0A CN113913091A (en) | 2021-12-02 | 2021-12-02 | Antibacterial powder coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033264A (en) * | 2007-04-24 | 2007-09-12 | 武汉大学 | Chitosan biguanide hydrochloride, preparation method and use thereof |
| CN110157294A (en) * | 2019-05-28 | 2019-08-23 | 六安科瑞达新型材料有限公司 | A kind of antibacterial powder paint |
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2021
- 2021-12-02 CN CN202111462922.0A patent/CN113913091A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033264A (en) * | 2007-04-24 | 2007-09-12 | 武汉大学 | Chitosan biguanide hydrochloride, preparation method and use thereof |
| CN110157294A (en) * | 2019-05-28 | 2019-08-23 | 六安科瑞达新型材料有限公司 | A kind of antibacterial powder paint |
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Application publication date: 20220111 |