CN112898876A - High-adhesion nano-silver composite cationic epoxy resin antibacterial coating and preparation method thereof - Google Patents
High-adhesion nano-silver composite cationic epoxy resin antibacterial coating and preparation method thereof Download PDFInfo
- Publication number
- CN112898876A CN112898876A CN202110341283.6A CN202110341283A CN112898876A CN 112898876 A CN112898876 A CN 112898876A CN 202110341283 A CN202110341283 A CN 202110341283A CN 112898876 A CN112898876 A CN 112898876A
- Authority
- CN
- China
- Prior art keywords
- nano
- silver
- epoxy resin
- antibacterial
- mother liquor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Plant Pathology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a high-adhesion nano-silver composite cationic epoxy resin antibacterial coating and a preparation method thereof, wherein the coating is prepared from the following substances in percentage by mass: 0.01-0.05% of nano-silver mother liquor, 20-60% of cationic epoxy resin, 0.01-1% of 2-mercaptoimidazole and 10-20% of epoxy curing agent; the nano silver mother liquor is prepared from 1 to 5 percent of nano silicon dioxide, 0.01 to 1 percent of silver nitrate, 0.01 to 1 percent of sodium citrate and 0.01 to 0.5 percent of ascorbic acid; according to the invention, the Ag is used for loading the silicon dioxide, so that the using amount of the silver is reduced, the specific surface area of the Ag is increased, the antibacterial effect is promoted, meanwhile, the cationic epoxy resin with an epoxy group and quaternary ammonium salt cations is utilized, the quaternary ammonium salt cations have a certain antibacterial effect, so that the antibacterial effect of the coating can be further promoted, the epoxy group participates in the polymerization of the curing agent, and the quaternary ammonium salt cations and the nano-silver can form a certain weak bond and effect, so that the adhesive force of the nano-silver is increased; can ensure the antibacterial durability of the antibacterial coating.
Description
Technical Field
The invention relates to the field of coatings, in particular to a high-adhesion nano-silver composite cationic epoxy resin antibacterial coating.
Background
Under the influence of new crown epidemic spread worldwide in 2020, people pay more and more attention to the safety awareness of living and health. Since epidemic situations, various products with 'antibiosis' and 'disinfection' are popular, the field of paint is no exception, and the antibacterial paint has an absolute ratio in the future paint market. The antibacterial coating is mainly applied to public places such as hospitals, schools, airports, stations, restaurants, libraries and the like, and can effectively reduce the cross infection and contact infection probability of the public places. But the antibacterial coating in the current market has the problems of poor antibacterial effect, short antibacterial lasting effect and the like.
CN106366782A discloses an aqueous antibacterial wood lacquer and a preparation method and application thereof, the patent application specifically discloses an aqueous antibacterial wood lacquer and a preparation method and application thereof, the aqueous antibacterial wood lacquer is prepared by taking 5-20% of modified nano boehmite slurry, 0.2-1% of modified nano silver solution, 40-65% of deionized water, 2-5% of sodium dodecyl benzene sulfonate, 5-10% of methyl methacrylate, 0.05-0.15% of ammonium persulfate, 3-8% of methacryloxypropyl trimethoxy silane, 2-5% of hydroxyethyl acrylate, 0.5-1% of acrylic acid, 9-20% of styrene, 5.5-10% of butyl acrylate, 0.25-0.5% of potassium persulfate, 0.1-0.2% of defoaming agent, 0.4-0.6% of thickening agent and 2-5% of film forming auxiliary agent as raw materials, the water-based antibacterial wood lacquer with excellent stability, paint film surface hardness and antibacterial performance is obtained. However, such coatings still do not solve the problem of short duration of antimicrobial activity.
Therefore, those skilled in the art have been devoted to develop an antibacterial coating material having improved antibacterial aging properties.
Disclosure of Invention
In view of the defects in the prior art, the invention provides the antibacterial coating which has good adhesive force, has excellent antibacterial property and can effectively kill ninety percent of escherichia coli, staphylococcus aureus and candida albicans, and meanwhile, the antibacterial coating has good adhesive force, can effectively prolong the effective antibacterial time of the antibacterial coating and ensure the antibacterial timeliness.
In order to achieve the aim, the invention provides a high-adhesion nano-silver composite cationic epoxy resin antibacterial coating which is prepared from the following substances in percentage by mass: 1 to 5 percent of nano silver mother liquor, 20 to 60 percent of cationic epoxy resin, 0.01 to 1 percent of 2-mercaptoimidazole and 10 to 20 percent of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 1-5% of nano-silicon dioxide, 0.01-1% of silver nitrate, 0.01-1% of sodium citrate and 0.01-0.5% of ascorbic acid.
More preferably, in order to further increase the adhesion, the 0.01% -1% of 2-mercaptoimidazole may be replaced by 0.01% -1% of octa- (6-mercapto-6-deoxy) -gamma-cyclodextrin.
More preferably, in order to improve the adhesion of the nano silver on the silica particles, the 0.01% -1% of 2-mercaptoimidazole can be replaced by 0.01% -0.5% of 16-mercaptohexadecanoic acid and 0.01% -1% of silane coupling agent KH 560.
A preparation method of a high-adhesion nano-silver composite cationic epoxy resin antibacterial coating specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percent, and then sequentially adding 1-5% of nano silicon dioxide, 0.01-1% of silver nitrate, 0.01-1% of sodium citrate and 0.01-0.5% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.01-0.05% of the nano-silver mother liquor prepared in the step 1, 20-60% of cationic epoxy resin, 0.01-1% of 2-mercaptoimidazole and 10-20% of epoxy curing agent, and uniformly stirring at the speed of 90-110 r/min.
The sulfydryl in the 2-sulfydryl imidazole in the formula can form a coordination effect with silver, and meanwhile, the sulfydryl can be used as a curing agent to promote the cross-linking curing of epoxy resin, so that the adhesive force of Ag loaded on silicon dioxide nanoparticles can be improved, and the antibacterial capability of the coating is further ensured.
More preferably, in order to further increase the adhesion, the step 2 is replaced by the following steps: according to the mass percentage, deionized water is added into a second reaction kettle, then 0.01-0.05% of the nano-silver mother liquor prepared in the step 1, 20-60% of cationic epoxy resin, 0.01-1% of octa- (6-mercapto-6-deoxidation) -gamma-cyclodextrin and 10-20% of epoxy curing agent are sequentially added, and the mixture is uniformly stirred at the speed of 90-110 r/min.
The sulfydryl of the octa- (6-sulfydryl-6-deoxidation) -gamma-cyclodextrin in the step can react with silver to increase the adhesive force of Ag, meanwhile, the hydroxyl of the cyclodextrin can be crosslinked with the hydroxyl of silicon dioxide, and the hydroxyl of the cyclodextrin can also form hydrogen bond action with ammonium ions on the cationic epoxy resin to jointly act to improve the adhesive force.
More preferably, in order to improve the adhesion of the nano silver to the silica particles, the step 2 is replaced by the following steps: according to the mass percentage, deionized water is added into a second reaction kettle, then 0.01-0.05% of the nano-silver mother liquor prepared in the step 1, 20-60% of cationic epoxy resin, 0.01-0.5% of 16-mercapto hexadecanoic acid, 0.01-1% of silane coupling agent KH560 and 10-20% of epoxy curing agent are sequentially added, and the mixture is uniformly stirred at the speed of 90-110 r/min.
In the step, 0.01 to 0.5 percent of 16-mercapto hexadecanoic acid and 0.01 to 1 percent of silane coupling agent KH560 are used for replacing 0.01 to 1 percent of 2-mercaptoimidazole. Mainly considering that the mercapto group of the 16-mercapto hexadecanoic acid can form a coordination effect with silver, and the carboxyl group of the 16-mercapto hexadecanoic acid can form a bond with the amino group of the cationic epoxy resin, so that the adhesive force of the silver-loaded silicon dioxide nanoparticles can be improved; meanwhile, after the silane coupling agent KH560 is hydrolyzed, the silica end can be bonded with the hydroxyl group on the surface of the silicon dioxide, and the epoxy group at the other end reacts with the curing agent, so that the adhesive force of the nano-silver is improved. Under the combined action of the two substances, the adhesive force of the nano silver can be improved, and the antibacterial effect is further ensured.
According to the invention, the Ag is used for loading the silicon dioxide, so that the using amount of the silver is reduced, the specific surface area of the Ag is increased, the antibacterial effect is promoted, meanwhile, the cationic epoxy resin with an epoxy group and quaternary ammonium salt cations is utilized, the quaternary ammonium salt cations have a certain antibacterial effect, so that the antibacterial effect of the coating can be further promoted, the epoxy group participates in the polymerization of the curing agent, and the quaternary ammonium salt cations and the nano-silver can form a certain weak bond and effect, so that the adhesive force of the nano-silver is increased; in addition, the adhesive force of the nano-silver is improved by the aid of auxiliaries such as 2-mercaptoimidazole, octa- (6-mercapto-6-deoxy) -gamma-cyclodextrin, 16-mercaptohexadecanoic acid and a silane coupling agent KH560, and the antibacterial durability of the antibacterial coating can be guaranteed.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The types and brands of the raw materials used in the examples were selected as follows:
nano-silica-purchased from Nanjing Xiancheng nanomaterial science and technology Limited, nano-silica KH570, particle size of 20 nm, purity of 99%;
silver nitrate-purchased from industrial grade, pure product, of chemical corporation, spain;
sodium citrate-purchased from Ningxiang Xinyang chemical Co., Ltd., purity 99%;
ascorbic acid-purchased from Shanghai Michelin Biotechnology Limited, Industrial grade, pure;
cationic epoxy resin-purchased from Wanqing chemical technology, Inc., industrial grade, pure product;
2-mercaptoimidazole-purchased from Nanjing sbeiyuan pharmaceutical technology, Inc., purity: 97 percent;
epoxy hardener-procured in Shanghai Gu bang New Material science and technology Limited, Industrial grade, purity: 100 percent;
octa- (6-mercapto-6-deoxy) - γ -cyclodextrin-purchased from Shanghai Michelin Biotechnology Ltd, purity: 100 percent;
16-mercaptohexadecanoic acid-purchased from sahn chemical technology (shanghai) ltd, purity: 99 percent;
silane coupling agent KH 560-purchased from Hengqiao industries, Ltd., purity: 99 percent.
Example 1
A high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is prepared from the following substances in percentage by mass: 0.05% of nano-silver mother liquor, 45% of cationic epoxy resin, 1% of 2-mercaptoimidazole and 20% of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 5% of nano-silicon dioxide, 1% of silver nitrate, 1% of sodium citrate and 0.5% of ascorbic acid.
The preparation method of the antibacterial coating specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percent, and then sequentially adding 4% of nano silicon dioxide, 1% of silver nitrate, 1% of sodium citrate and 0.5% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.05% of the nano-silver mother liquor prepared in the step 1, 45% of cationic epoxy resin, 1% of 2-mercaptoimidazole and 20% of epoxy curing agent, and uniformly stirring at the speed of 110 r/min.
Example 2
A high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is prepared from the following substances in percentage by mass: 0.01% of nano silver mother liquor, 60% of cationic epoxy resin, 0.5% of 2-mercaptoimidazole and 10% of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 1% of nano-silicon dioxide, 0.01% of silver nitrate, 0.01% of sodium citrate and 0.01% of ascorbic acid.
The preparation method of the antibacterial coating specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percent, and then sequentially adding 5% of nano silicon dioxide, 0.01% of silver nitrate, 0.01% of sodium citrate and 0.01% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.01 percent of the nano-silver mother liquor prepared in the step 1, 60 percent of cationic epoxy resin, 0.5 percent of 2-mercaptoimidazole and 10 percent of epoxy curing agent, and uniformly stirring at the speed of 90-110 r/min.
The raw material percentage statistics for example 1 and example 2 are shown in the table below.
The nano-silver mother liquor prepared in examples 1 and 2 was subjected to bactericidal test detection according to quantitative bactericidal test of suspension 5.2.1 of WS/T650-2019 evaluation method of antibacterial and bacteriostatic effects. The test is suitable for measuring the antibacterial effect of liquid antibacterial products (such as liquid antibacterial liquid, antibacterial spray and the like) on microorganisms, the selected strains in the test are respectively staphylococcus aureus (ATCC6538), escherichia coli (8099) and candida albicans (ATCC10321), and the detection results are as follows:
the test data in the table show that the nano silver mother liquor has extremely strong bactericidal effect and can kill more than 99.9 percent of the three strains. This provides a guarantee that the antibacterial coating of the invention has excellent antibacterial property.
The specific surface area of the silver is slightly reduced due to the reduction of the silver content and the content of the nano silicon dioxide, but the sterilization rate is still kept at 99.7%, and the nano silver mother liquor obtained according to the formula and the preparation method has extremely high sterilization rate, thereby providing guarantee for the sterilization effect of the antibacterial coating.
The antibacterial coatings of examples 1 and 2 were then subjected to a cross-hatch test, referred to the industry norm (GB/T9286-1998) cross-hatch test for paint and varnish films, with the test results given in the following table:
description of the drawings: the grid test grades are divided into six grades, namely 0 grade, 1 grade, 2 grade, 3 grade, 4 grade and 5 grade.
Wherein, 0 level-represents that the cutting edge is completely smooth and no lattice falls off;
level 1-indicates that there is little coating peeling at the cut intersection, but the cross cut area is not affected significantly more than 5%;
level 2-which means that there is coating shedding at the intersection of the cuts and/or along the edges of the cuts, the cross cut area affected is significantly greater than 5%, but not significantly greater than 15%;
grade 3-meaning that the coating is partly or completely detached in large fragments along the cut edge and/or partly or completely detached at different sites of the grid, the cross-cut area affected is significantly greater than 15%, but not significantly greater than 35%;
grade 4-which means that the coating peels off along large pieces of the cutting edge and/or some squares partially or completely, the cross-cut area affected is significantly greater than 35%, but not significantly greater than 65%;
grade 5-indicating that the process of exfoliation exceeded grade 4.
For general purposes, the first three grades can meet the requirements, and the examples 1 and 2 belong to the 1 st grade, so that the antibacterial coating prepared by the invention has better adhesive force. The antibacterial coating prepared by the method has excellent adhesive force and also provides guarantee for the antibacterial persistence.
Finally, the continuous antibacterial test was performed on examples 1 and 2 according to the continuous antibacterial test of "WS/T650-2019 antibacterial and bacteriostatic effect evaluation method" 5.2.7. The experiment is used for identifying the antibacterial effect of the long-acting antibacterial product. The test strains were still Staphylococcus aureus (ATCC6538), Escherichia coli (8099), Candida albicans (ATCC 10321).
The test steps are as follows:
1. preparation of Long-acting antimicrobial sample
The carrier used by the long-acting antibacterial agent, such as a wood board, a metal board, a plastic board and the like, is cut into 50mm multiplied by 50mm to prepare an antibacterial sample wafer, namely the metal board selected by the invention. Coating the antibacterial agent on the surface of the sample wafer according to the coating requirement of the antibacterial coating, and drying at room temperature for later use as an experimental group; sample wafers which were not subjected to any treatment after pressure steam sterilization treatment alone were used as a control group; both sets of coupons were stored in the laboratory at room temperature.
2. Long-acting antibacterial experimental steps
The method generally comprises laboratory tests and field tests, wherein the laboratory tests and the test processes are selected, two groups of sample wafers are stored at room temperature until the antibacterial duration action time is 7d, 15d, 30d, 60d, 90d and 120d respectively, and then the experimental group and the control group are taken out for testing. Dyeing a 24-hour fresh culture bacterial suspension on a carrier, putting the carrier of the experimental group-infected bacteria into a neutralizer 10min after the carrier acts for the specified time in the specification, uniformly mixing, diluting and inoculating; and simultaneously, carrying out parallel test by using a control group sample plate to infect bacteria, putting a control group infectious bacteria carrier into the diluent at the same time, uniformly mixing, diluting and inoculating. The final results are observed by culturing the bacterial propagules for 48 hours at 36 +/-1 ℃ and culturing the aspergillus niger for 72 hours at 30 +/-1 ℃, and the recovery bacterial amount after the control vector is infected is 1.0 multiplied by 104 CFU/tablet to 9.0 multiplied by 104 CFU/tablet. Taking the test same batch of diluent, neutralizer and culture medium as negative control. The test was repeated 3 times and the sterilization rate was calculated. The sterilization rate is calculated in the following way
Wherein X represents the bactericidal rate, A represents the recovered bacterial load of the control sample in the unit of CFU/sample, and B represents the recovered bacterial load of the test sample in the unit of CFU/sample. The specific test results are shown in the table below.
According to the judgment result of the continuous antibacterial test of WS/T650-2019 antibacterial and bacteriostatic effect evaluation method 5.2.7, the sterilization rate is more than or equal to 90 percent, and the continuous antibacterial effect in the time period can be judged. Through the experiments, the invention has long-acting and continuous antibacterial property within 90 days. The sterilizing rate is reduced due to the shedding of the paint and the like in the period of 90 days to 120 days, but is basically maintained at 85 percent.
The antibacterial coating has excellent bactericidal property and adhesive force, provides basic guarantee for the continuous antibacterial property of the antibacterial coating, and finally realizes the continuous antibacterial property for about 90 days.
Example 3
A high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is prepared from the following substances in percentage by mass: 0.05% of nano-silver mother liquor, 45% of cationic epoxy resin, 1% of octa- (6-mercapto-6-deoxidation) -gamma-cyclodextrin and 20% of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 4% of nano-silicon dioxide, 0.5% of silver nitrate, 0.5% of sodium citrate and 0.25% of ascorbic acid.
The preparation method of the antibacterial coating specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percent, and then sequentially adding 4% of nano silicon dioxide, 0.5% of silver nitrate, 0.5% of sodium citrate and 0.25% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.05% of the nano-silver mother liquor prepared in the step 1, 45% of cationic epoxy resin, 1% of octa- (6-mercapto-6-deoxy) -gamma-cyclodextrin and 20% of epoxy curing agent, and uniformly stirring at the speed of 110 r/min.
Example 4
A high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is prepared from the following substances in percentage by mass: 0.01 percent of nano silver mother liquor, 60 percent of cationic epoxy resin, 0.5 percent of octa- (6-sulfydryl-6-deoxidation) -gamma-cyclodextrin and 10 percent of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 2% of nano-silicon dioxide, 0.1% of silver nitrate, 0.1% of sodium citrate and 0.3% of ascorbic acid.
The preparation method of the antibacterial coating specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percent, and then sequentially adding 2% of nano silicon dioxide, 0.1% of silver nitrate, 0.1% of sodium citrate and 0.3% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.01 percent of the nano-silver mother liquor prepared in the step 1, 60 percent of cationic epoxy resin, 0.5 percent of octa- (6-mercapto-6-deoxidation) -gamma-cyclodextrin and 10 percent of epoxy curing agent, and uniformly stirring at the speed of 90-110 r/min.
The raw material percentage statistics for example 3 and example 4 are shown in the table below.
The nano-silver mother liquor prepared in examples 3 and 2 was subjected to a sterilization test according to WS/T650-2019 evaluation method for antibacterial and bacteriostatic effects 5.2.1 quantitative suspension sterilization test, which is suitable for the determination of the antibacterial effect of liquid antibacterial products (such as liquid antibacterial liquid, antibacterial spray, etc.) on microorganisms, and the test results are as follows:
the experimental data in the table above can conclude that the nano-silver mother liquor obtained according to the formula and the preparation method has extremely high bactericidal rate, provides guarantee for the bactericidal effect of the antibacterial coating, and has stable bactericidal effect within the range of the formula.
The antibacterial coatings of examples 3 and 4 were then subjected to a cross-hatch test, according to the industry norm (GB/T9286-1998) cross-hatch test for paint and varnish films, with the test results given in the following table:
description of the drawings: the grid test grades are divided into six grades, namely 0 grade, 1 grade, 2 grade, 3 grade, 4 grade and 5 grade.
Wherein, 0 level-represents that the cutting edge is completely smooth and no lattice falls off;
level 1-indicates that there is little coating peeling at the cut intersection, but the cross cut area is not affected significantly more than 5%;
level 2-which means that there is coating shedding at the intersection of the cuts and/or along the edges of the cuts, the cross cut area affected is significantly greater than 5%, but not significantly greater than 15%;
grade 3-meaning that the coating is partly or completely detached in large fragments along the cut edge and/or partly or completely detached at different sites of the grid, the cross-cut area affected is significantly greater than 15%, but not significantly greater than 35%;
grade 4-which means that the coating peels off along large pieces of the cutting edge and/or some squares partially or completely, the cross-cut area affected is significantly greater than 35%, but not significantly greater than 65%;
grade 5-indicating that the process of exfoliation exceeded grade 4.
For general purposes, the first three grades can meet the requirements, and the grades of 0 and 1 are respectively adopted in the embodiment 1 and the embodiment 2 of the invention, which shows that the adhesion can be improved by selecting octa- (6-mercapto-6-deoxy) -gamma-cyclodextrin. The adhesive force of the antibacterial coating is further enhanced, and the antibacterial continuity of the antibacterial coating is guaranteed.
Finally, the continuous antibacterial test was performed on examples 3 and 4 according to the continuous antibacterial test of "WS/T650-2019 antibacterial and bacteriostatic effect evaluation method" 5.2.7. The experiment is used for identifying the antibacterial effect of the long-acting antibacterial product. The test strains were still Staphylococcus aureus (ATCC6538), Escherichia coli (8099), Aspergillus niger (ATCC 16404).
The test steps are as follows:
1. preparation of Long-acting antimicrobial sample
The carrier used by the long-acting antibacterial agent, such as a wood board, a metal board, a plastic board and the like, is cut into 50mm multiplied by 50mm to prepare an antibacterial sample wafer, namely the metal board selected by the invention. Coating the antibacterial agent on the surface of the sample wafer according to the coating requirement of the antibacterial coating, and drying at room temperature for later use as an experimental group; sample wafers which were not subjected to any treatment after pressure steam sterilization treatment alone were used as a control group; both sets of coupons were stored in the laboratory at room temperature.
2. Long-acting antibacterial experimental steps
In generalThe method comprises a laboratory test and a field test, wherein the laboratory test and the test process are selected, two groups of sample wafers are stored at room temperature until the antibacterial duration action time is 7d, 15d, 30d, 60d, 90d and 120d respectively, and then the experimental group and the control group are taken out for testing. Dyeing a 24-hour fresh culture bacterial suspension on a carrier, putting the carrier of the experimental group-infected bacteria into a neutralizer 10min after the carrier acts for the specified time in the specification, uniformly mixing, diluting and inoculating; and simultaneously, carrying out parallel test by using a control group sample plate to infect bacteria, putting a control group infectious bacteria carrier into the diluent at the same time, uniformly mixing, diluting and inoculating. The final results are observed by culturing the bacterial propagules for 48 hours at 36 +/-1 ℃ and culturing the aspergillus niger for 72 hours at 30 +/-1 ℃, and the recovery bacterial amount after the control vector is infected is 1.0 multiplied by 104 CFU/tablet to 9.0 multiplied by 104 CFU/tablet. Taking the test same batch of diluent, neutralizer and culture medium as negative control. The test was repeated 3 times and the sterilization rate was calculated. The sterilization rate is calculated in the following way
Wherein X represents the bactericidal rate, A represents the recovered bacterial load of the control sample in the unit of CFU/sample, and B represents the recovered bacterial load of the test sample in the unit of CFU/sample. The specific test results are shown in the table below.
According to the judgment result of the continuous antibacterial test of WS/T650-2019 antibacterial and bacteriostatic effect evaluation method 5.2.7, the sterilization rate is more than or equal to 90 percent, and the continuous antibacterial effect in the time period can be judged. The experiments can confirm that the octa- (6-mercapto-6-deoxy) -gamma-cyclodextrin is selected, so that the adhesive force of silver is improved, the continuous bactericidal performance of the antibacterial coating is prolonged, and the bactericidal rate can be kept at about 90% even in 120 days.
Example 5
A high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is prepared from the following substances in percentage by mass: 0.05% of nano-silver mother liquor, 45% of cationic epoxy resin, 0.5% of 16-mercaptohexadecanoic acid, 1% of silane coupling agent KH560 and 20% of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 5% of nano-silicon dioxide, 1% of silver nitrate, 1% of sodium citrate and 0.5% of ascorbic acid.
The preparation method of the antibacterial coating specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percentage, and then sequentially adding 5% of nano silicon dioxide, 1% of silver nitrate, 1% of sodium citrate and 0.5% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.05% of the nano-silver mother liquor prepared in the step 1, 45% of cationic epoxy resin, 0.5% of 16-mercaptohexadecanoic acid, 1% of silane coupling agent KH560 and 20% of epoxy curing agent, and uniformly stirring at the speed of 110 r/min.
Example 6
A high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is prepared from the following substances in percentage by mass: 0.01 percent of nano-silver mother liquor, 60 percent of cationic epoxy resin, 0.01 percent of 16-mercapto hexadecanoic acid, 0.01 percent of silane coupling agent KH560 and 10 percent of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 1% of nano-silicon dioxide, 0.01% of silver nitrate, 0.01% of sodium citrate and 0.01% of ascorbic acid.
The preparation method of the antibacterial coating specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percent, and then sequentially adding 1% of nano silicon dioxide, 0.01% of silver nitrate, 0.01% of sodium citrate and 0.01% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.01 percent of the nano-silver mother liquor prepared in the step 1, 60 percent of cationic epoxy resin, 0.01 percent of 16-mercaptohexadecanoic acid, 0.01 percent of silane coupling agent KH560 and 10 percent of epoxy curing agent, and uniformly stirring at the speed of 90-110 r/min.
The raw material percentage statistics for example 5 and example 6 are shown in the table below.
The nano-silver mother liquor prepared in examples 5 and 2 was subjected to a sterilization test according to WS/T650-2019 evaluation method for antibacterial and bacteriostatic effects 5.2.1 quantitative suspension sterilization test, which is suitable for the determination of the antibacterial effect of liquid antibacterial products (such as liquid antibacterial liquid, antibacterial spray, etc.) on microorganisms, and the test results are as follows:
the experimental data in the table above can conclude that the nano-silver mother liquor obtained according to the formula and the preparation method has extremely high bactericidal rate, and provides guarantee for the bactericidal effect of the antibacterial coating. The proportion of the nano-silver mother liquor in the group of embodiments is completely the same as that of the nano-silver in the embodiments 1 and 2, and a control group can be formed with the embodiments 1 and 2, so that the continuous antibacterial property of the antibacterial coating can be improved or not under the condition that the sterilizing effect of the nano-silver mother liquor is consistent.
Next, the adhesion of examples 5 and 6 was tested. The test was carried out according to the industry Standard (GB/T9286-1998) test for marking paint and varnish films, the test results being given in the following table:
description of the drawings: the grid test grades are divided into six grades, namely 0 grade, 1 grade, 2 grade, 3 grade, 4 grade and 5 grade.
Wherein, 0 level-represents that the cutting edge is completely smooth and no lattice falls off;
level 1-indicates that there is little coating peeling at the cut intersection, but the cross cut area is not affected significantly more than 5%;
level 2-which means that there is coating shedding at the intersection of the cuts and/or along the edges of the cuts, the cross cut area affected is significantly greater than 5%, but not significantly greater than 15%;
grade 3-meaning that the coating is partly or completely detached in large fragments along the cut edge and/or partly or completely detached at different sites of the grid, the cross-cut area affected is significantly greater than 15%, but not significantly greater than 35%;
grade 4-which means that the coating peels off along large pieces of the cutting edge and/or some squares partially or completely, the cross-cut area affected is significantly greater than 35%, but not significantly greater than 65%;
grade 5-indicating that the process of exfoliation exceeded grade 4.
For general purposes, the first three grades can meet the requirements, and the examples 1 and 2 belong to the 0 th grade, so that the antibacterial coating prepared by the invention has the best adhesive force.
Through the grazing test, it can be seen that the adhesive force can be effectively improved by firstly using 16-mercaptohexadecanoic acid and the silane coupling agent KH560 in the embodiment, the adhesive force of the coating is better than that of all the embodiments, and the continuous bactericidal property of the antibacterial coating can be improved.
Finally, examples 5 and 6 were subjected to a continuous antibacterial test in accordance with "WS/T650-2019 antibacterial and bacteriostatic effect evaluation method" 5.2.7 continuous antibacterial test. The experiment is used for identifying the antibacterial effect of the long-acting antibacterial product. The test strains were still Staphylococcus aureus (ATCC6538), Escherichia coli (8099), Aspergillus niger (ATCC 16404).
The test steps are as follows:
1. preparation of Long-acting antimicrobial sample
The carrier used by the long-acting antibacterial agent, such as a wood board, a metal board, a plastic board and the like, is cut into 50mm multiplied by 50mm to prepare an antibacterial sample wafer, namely the metal board selected by the invention. Coating the antibacterial agent on the surface of the sample wafer according to the coating requirement of the antibacterial coating, and drying at room temperature for later use as an experimental group; sample wafers which were not subjected to any treatment after pressure steam sterilization treatment alone were used as a control group; both sets of coupons were stored in the laboratory at room temperature.
2. Long-acting antibacterial experimental steps
The method generally comprises laboratory tests and field tests, wherein the laboratory tests and the test processes are selected, two groups of sample wafers are stored at room temperature until the antibacterial duration action time is 7d, 15d, 30d, 60d, 90d and 120d respectively, and then the experimental group and the control group are taken out for testing. Dyeing a 24-hour fresh culture bacterial suspension on a carrier, putting the carrier of the experimental group-infected bacteria into a neutralizer 10min after the carrier acts for the specified time in the specification, uniformly mixing, diluting and inoculating; and simultaneously, carrying out parallel test by using a control group sample plate to infect bacteria, putting a control group infectious bacteria carrier into the diluent at the same time, uniformly mixing, diluting and inoculating. The final results are observed by culturing the bacterial propagules for 48 hours at 36 +/-1 ℃ and culturing the aspergillus niger for 72 hours at 30 +/-1 ℃, and the recovery bacterial amount after the control vector is infected is 1.0 multiplied by 104 CFU/tablet to 9.0 multiplied by 104 CFU/tablet. Taking the test same batch of diluent, neutralizer and culture medium as negative control. The test was repeated 3 times and the sterilization rate was calculated. The sterilization rate is calculated in the following way
Wherein X represents the bactericidal rate, A represents the recovery bacterial load of the control sample in CFU/sample, and B represents the test
The sample recovery bacterial load is in CFU/sample. The specific test results are shown in the table below.
According to the judgment result of a continuous antibacterial test of 'WS/T650-2019 antibacterial and bacteriostatic effect evaluation method' 5.2.7, the sterilization rate of 120 days is still more than or equal to 90%, the invention selects 16-mercaptohexadecanoic acid and a silane coupling agent KH560, can effectively improve the adhesive force of the antibacterial coating, and further improves the continuous antibacterial property of the antibacterial coating.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (6)
1. A high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is characterized in that: the composite material is prepared from the following substances in percentage by mass: 0.01-0.05% of nano-silver mother liquor, 20-60% of cationic epoxy resin, 0.01-1% of 2-mercaptoimidazole and 10-20% of epoxy curing agent;
wherein the nano-silver mother liquor is prepared from 1-5% of nano-silicon dioxide, 0.01-1% of silver nitrate, 0.01-1% of sodium citrate and 0.01-0.5% of ascorbic acid.
2. The high-adhesion nano-silver composite cationic epoxy resin antibacterial coating as claimed in claim 1, which is characterized in that: the 0.01 to 1 percent of 2-mercaptoimidazole can be replaced by 0.01 to 1 percent of octa- (6-mercapto-6-deoxidation) -gamma-cyclodextrin.
3. The high-adhesion nano-silver composite cationic epoxy resin antibacterial coating as claimed in claim 1, which is characterized in that: the 0.01-1% of 2-mercaptoimidazole can be replaced by 0.01-0.5% of 16-mercaptohexadecanoic acid and 0.01-1% of silane coupling agent KH 560.
4. A preparation method of a high-adhesion nano-silver composite cationic epoxy resin antibacterial coating is characterized by comprising the following steps: the method specifically comprises the following steps:
step 1, adding deionized water into a first reaction kettle according to mass percent, and then sequentially adding 1-5% of nano silicon dioxide, 0.01-1% of silver nitrate, 0.01-1% of sodium citrate and 0.01-0.5% of ascorbic acid; stirring uniformly at normal temperature to obtain nano silver mother liquor which takes silicon dioxide as a carrier and is loaded with silver for later use;
and 2, adding deionized water into a second reaction kettle according to the mass percentage, then sequentially adding 0.01-0.05% of the nano-silver mother liquor prepared in the step 1, 20-60% of cationic epoxy resin, 0.01-1% of 2-mercaptoimidazole and 10-20% of epoxy curing agent, and uniformly stirring at the speed of 90-110 r/min.
5. The preparation method of the high-adhesion nano-silver composite cationic epoxy resin antibacterial coating as claimed in claim 4, which is characterized in that: the step 2 is replaced by the following steps: according to the mass percentage, deionized water is added into a second reaction kettle, then 0.01-0.05% of the nano-silver mother liquor prepared in the step 1, 20-60% of cationic epoxy resin, 0.01-1% of octa- (6-mercapto-6-deoxidation) -gamma-cyclodextrin and 10-20% of epoxy curing agent are sequentially added, and the mixture is uniformly stirred at the speed of 90-110 r/min.
6. The preparation method of the high-adhesion nano-silver composite cationic epoxy resin antibacterial coating as claimed in claim 4, which is characterized in that: the step 2 is replaced by the following steps: according to the mass percentage, deionized water is added into a second reaction kettle, then 0.01-0.05% of the nano-silver mother liquor prepared in the step 1, 20-60% of cationic epoxy resin, 0.01-0.5% of 16-mercapto hexadecanoic acid, 0.01-1% of silane coupling agent KH560 and 10-20% of epoxy curing agent are sequentially added, and the mixture is uniformly stirred at the speed of 90-110 r/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110341283.6A CN112898876A (en) | 2021-03-30 | 2021-03-30 | High-adhesion nano-silver composite cationic epoxy resin antibacterial coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110341283.6A CN112898876A (en) | 2021-03-30 | 2021-03-30 | High-adhesion nano-silver composite cationic epoxy resin antibacterial coating and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112898876A true CN112898876A (en) | 2021-06-04 |
Family
ID=76109766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110341283.6A Pending CN112898876A (en) | 2021-03-30 | 2021-03-30 | High-adhesion nano-silver composite cationic epoxy resin antibacterial coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112898876A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115636885A (en) * | 2022-10-26 | 2023-01-24 | 湖北中医药大学 | Quaternary ammonium cyclodextrin, preparation method and application thereof, silver nanoparticle cyclodextrin compound, and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623897A (en) * | 2004-11-19 | 2005-06-08 | 中国乐凯胶片集团公司 | Process for preparing silicon dioxide of carrying nano silver |
| CA2742237A1 (en) * | 2008-10-31 | 2010-05-06 | Dsm Ip Assets B.V. | Antifouling coating composition comprising functionalized nanoparticules |
| CN104559648A (en) * | 2013-10-21 | 2015-04-29 | 大连市沙河口区中小微企业服务中心 | Bactericidal coating |
| CN106085187A (en) * | 2016-08-23 | 2016-11-09 | 上海海事大学 | A kind of high adhesion force low-surface-energy carries silver antifouling paint and preparation method thereof |
| CN107189585A (en) * | 2017-06-28 | 2017-09-22 | 福州大学 | A kind of SiO 2 supported nanometer silver water anti-bacteria coating and preparation method thereof |
| CN111423806A (en) * | 2020-05-28 | 2020-07-17 | 天津博苑高新材料有限公司 | Nano-alumina antibacterial coating and preparation method thereof |
| CN112160007A (en) * | 2020-09-25 | 2021-01-01 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral electrophoresis stainless steel and preparation method thereof |
-
2021
- 2021-03-30 CN CN202110341283.6A patent/CN112898876A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1623897A (en) * | 2004-11-19 | 2005-06-08 | 中国乐凯胶片集团公司 | Process for preparing silicon dioxide of carrying nano silver |
| CA2742237A1 (en) * | 2008-10-31 | 2010-05-06 | Dsm Ip Assets B.V. | Antifouling coating composition comprising functionalized nanoparticules |
| CN104559648A (en) * | 2013-10-21 | 2015-04-29 | 大连市沙河口区中小微企业服务中心 | Bactericidal coating |
| CN106085187A (en) * | 2016-08-23 | 2016-11-09 | 上海海事大学 | A kind of high adhesion force low-surface-energy carries silver antifouling paint and preparation method thereof |
| CN107189585A (en) * | 2017-06-28 | 2017-09-22 | 福州大学 | A kind of SiO 2 supported nanometer silver water anti-bacteria coating and preparation method thereof |
| CN111423806A (en) * | 2020-05-28 | 2020-07-17 | 天津博苑高新材料有限公司 | Nano-alumina antibacterial coating and preparation method thereof |
| CN112160007A (en) * | 2020-09-25 | 2021-01-01 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral electrophoresis stainless steel and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王际平: "《中国纺织品整理及进展 第2卷》", 31 May 2015, 中国轻工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115636885A (en) * | 2022-10-26 | 2023-01-24 | 湖北中医药大学 | Quaternary ammonium cyclodextrin, preparation method and application thereof, silver nanoparticle cyclodextrin compound, and preparation method and application thereof |
| CN115636885B (en) * | 2022-10-26 | 2023-08-11 | 湖北中医药大学 | Quaternary ammonium cyclodextrin and preparation method and application thereof, silver nanoparticle cyclodextrin compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105174500B (en) | A kind of waste water treating agent, preparation method and method of wastewater treatment | |
| US20090136742A1 (en) | Ag-containing solution, antibacterial resin composition comprising the solution and antibacterial resin coated steel plate | |
| Cui et al. | Development of a novel silver ions-nanosilver complementary composite as antimicrobial additive for powder coating | |
| CN109880470B (en) | Preparation method of water-based acrylate time-delay antibacterial coating | |
| CN111849282B (en) | Monoatomic antibacterial and disinfectant interior wall coating and preparation method thereof | |
| González et al. | Sol–gel coatings doped with encapsulated silver nanoparticles: inhibition of biocorrosion on 2024-T3 aluminum alloy promoted by Pseudomonas aeruginosa | |
| CN112029413A (en) | Salt-fog-resistant antibacterial graphene coating for aluminum alloy surface and preparation method thereof | |
| CN110621747A (en) | Composite resin containing silver nanoparticles | |
| CN113150647A (en) | Antibacterial coating for touch screen | |
| CN112898876A (en) | High-adhesion nano-silver composite cationic epoxy resin antibacterial coating and preparation method thereof | |
| Jegel et al. | Transparent polycarbonate coated with CeO 2 nanozymes repel Pseudomonas aeruginosa PA14 biofilms | |
| CN105062314A (en) | High-low-temperature resistant UV plastic coating and preparation method thereof | |
| Liu et al. | Recent progress in fabrications, mechanisms and developments of photo-responsive marine antifouling coatings | |
| CN111808481B (en) | Monoatomic algae-killing and sterilizing water tank coating and preparation method thereof | |
| CN106587291B (en) | Preparation and application of yttrium oxide-ferroferric oxide composite nano antibacterial material | |
| CN110527341B (en) | Antibacterial synergistic anti-bacterial adhesion material and preparation method and application thereof | |
| CN113100253B (en) | Preparation method of carbon oxide nanohorn/sodium alginate-silver composite antibacterial agent, antibacterial coating and antibacterial film | |
| CN104592835B (en) | A kind of environment protection ship finish paint | |
| Khodashenas et al. | Evaluation of the effective factors on size and anti-bacterial properties of biosynthesized silver nanoparticles | |
| CN114540804B (en) | Amino modified polysiloxane-based chromium-free passivation solution and preparation method thereof | |
| CN113402964A (en) | Antibacterial coating material, preparation method thereof, antibacterial coating and product | |
| CN114231104A (en) | Electromagnetic shielding colored sandstone coating and preparation method and application thereof | |
| JPH09157550A (en) | Antibacterial resin composition | |
| CN114797829B (en) | Visible light catalytic nano antibacterial material and manufacturing method thereof | |
| Guo et al. | Bimetallic peroxide nanocatalytic gel for water disinfection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210604 |
|
| RJ01 | Rejection of invention patent application after publication |