CN112266637B - Nano antibacterial antiseptic hydrosol coating composition - Google Patents
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- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
- C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
The invention discloses a nano antibacterial anticorrosion hydrosol coating composition; the composition comprises the following components in percentage by mass based on the total mass of the composition: nano silica sol: the element silicon in the sol accounts for 0.1-5% of the total composition, and the particle metal or the mixture of the particle metals: 5-40%, zinc nitroisophthalate: 0.01-2%, other binders: 3-30%, water-soluble organic solvent: 5-40%, deionized water: 5 to 40 percent. According to the system, the nano antibacterial and anticorrosive hydrosol coating composition is lower in curing film-forming temperature and higher in crosslinking density after being cured and formed at low temperature through the catalysis and corrosion inhibition of the zinc nitroisophthalate, and has excellent anticorrosive capability after being cured at low temperature.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a nano antibacterial anticorrosive hydrosol coating composition; in particular to a nano antibacterial anticorrosion hydrosol coating composition which is baked at 100 ℃, cured and formed into a film, the thickness of a dry film of the coating is 7-10 mu m, and the neutral salt spray test is more than 1000 h.
Background
At present, the baking curing temperature of the environment-friendly nano water-based anticorrosive composition sold on the market is recommended to be above 300 ℃, and the cured coating can meet the minimum anticorrosive requirement of a client (the film thickness of a dry film of the coating is 7-10 mu m, and the neutral salt spray test is more than 1000 h). After the environment-friendly nano water-based anticorrosive composition sold in the market is baked at 100 ℃, the neutral salt spray test of a dry film thickness coating of 7-10 mu m is below 72h and far reaches 1000h which is not required by customers. However, tempering temperature of many metal parts is required to be lower than 250 ℃, even lower than 150 ℃, so that the currently marketed environment-friendly nano water-based anticorrosive composition cannot meet the anticorrosive requirement of customers.
In addition, the environment-friendly nano aqueous antiseptic composition sold in the market at present is easy to generate bacteria during storage, so that an antibacterial agent needs to be added. Whereas common antimicrobial agents have a negative effect on the corrosion protection capability of the coating, especially for thin-coated coatings.
From a search of the prior patent literature, patent CN101365763A discloses a process for preparing epoxy silane oligomers under acidic conditions, which comprises reacting a glycidoxysilane and/or a cycloaliphatic epoxy silane having 2 or 3 alkoxy groups and optionally a copolymerizable silane different from the glycidoxysilane and the cycloaliphatic epoxy silane with less than 1.5 equivalents of water in the presence of a catalyst, wherein the water is continuously fed during the reaction. Compounding with granular metal to form anticorrosive composition, and when the curing temperature is lower than 450 deg.F (232 deg.C), the neutral salt fog time is less than or equal to 72 hr; the corrosion protection requirements of customers cannot be met.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a nano antibacterial anticorrosive hydrosol coating composition.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention relates to a nano antibacterial antiseptic hydrosol coating composition, which comprises the following components in percentage by mass based on the total mass of the composition:
nano silica sol: the element silicon in the sol accounts for 0.1 to 5 percent of the total weight of the composition,
particulate metal or mixture of particulate metals: 5 to 40 percent of the total weight of the mixture,
zinc nitroisophthalate: 0.01 to 2 percent of the total weight of the mixture,
other binders: 3 to 30 percent of the total weight of the mixture,
water-soluble organic solvent: 5 to 40 percent of
Deionized water: 5 to 40 percent.
In one embodiment of the present invention, the nano-silica sol has an average particle diameter of silica sol particles of 5 to 800 nm. In nano silica sol, if the size of the silica sol ion is too large, the film forming property of the composition will be affected.
As an embodiment of the present invention, the nano silica sol contains one or more of amino, vinyl or epoxy functional groups.
As an embodiment of the invention, the zinc nitroisophthalate has an average particle size D50 in the range of 1 to 10 μm. If the particle size of the zinc nitroisophthalate is too large, the final composition will not produce a dry film 7-10um coating.
As an embodiment of the invention, the particulate metal or mixture of particulate metals is selected from zinc, aluminum or a mixture of zinc and aluminum, or from an alloy of at least one of zinc, aluminum and at least one of manganese, magnesium, tin, nickel, stainless steel, rare earth alloy Galfan.
As an embodiment of the invention, the other adhesive can be one or a mixture of several of sodium silicate aqueous solution, potassium silicate aqueous solution, lithium silicate aqueous solution, nano titanium dioxide sol, nano zirconium dioxide sol, nano aluminum oxide sol, aqueous acrylic emulsion, aqueous phenolic resin emulsion and aqueous amino resin emulsion.
As an embodiment of the invention, the other binder is chosen from a nano titanium dioxide (zirconium) sol in which the elemental titanium (zirconium) constitutes 0-2% by mass of the total composition, preferably 0.5-1%.
As an embodiment of the invention, the other binder is selected from nano alumina sol in which the proportion of the element aluminum in the sol is 0-2% by mass, preferably 0.5-1% by mass, based on the total mass of the composition.
As an embodiment of the invention, the other binder is selected from a composition of nano alumina sol and nano titania (zirconium) sol, wherein the sum of the mass of the element aluminum and the element titanium (zirconium) in the sol accounts for 0-2%, preferably 0.5-1% of the total mass of the composition.
As an embodiment of the present invention, the water-soluble organic solvent is selected from: one or more of propylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol and ketone.
As an embodiment of the invention, the composition also comprises 0.01-5% of aqueous wetting dispersant, 0.01-5% of thickening agent, 0.01-5% of defoaming agent, 0.05-1% of base material wetting agent, 0.1-5% of corrosion inhibitor and 0.01-5% of pH regulator in percentage by mass of the total mass of the composition.
The invention also relates to a steel or iron base material anticorrosion and antibacterial coating which is prepared by spraying, dipping or brushing the composition on a steel, iron, galvanized steel or aluminum base material and baking. The baking is carried out by convection or infrared for 10-60 minutes or by induction for 10 seconds-5 minutes at a temperature of 100-350 ℃.
As an embodiment of the invention, the dry film thickness of the coating is 3 to 55 μm.
Compared with the prior art, the invention has the following beneficial effects:
1) the nano antibacterial anticorrosion hydrosol coating composition can be cured at low temperature and has excellent anticorrosion capability through the catalysis of the zinc nitroisophthalate; in addition, the nitroisophthalic acid zinc has a good corrosion inhibition effect;
2) the environment-friendly nano water-based anticorrosive composition sold in the market is easy to generate bacteria during storage, an antibacterial agent needs to be added, and the common antibacterial agent has a side effect on the anticorrosive capacity of a coating, especially a thin coating; according to the invention, the nano metal sol is added, so that the composition has a good antibacterial effect under the condition of not adding an antibacterial agent;
3) after the existing product is baked and cured at 100 ℃ to form a film, the thickness of a dry film of the coating is 7-10 mu m, and the neutral salt spray test is less than or equal to 72 h; if the existing product needs to be coated with a dry film with the thickness of 7-10 mu m and the neutral salt spray test is more than 1000h, the baking temperature is more than 300 ℃. But the baking temperature of a plurality of parts cannot be higher than 150 ℃, which is an unsolved contradiction; after the composition is baked and cured at 100 ℃ to form a film, the film thickness of a dry film of the coating is 7-10 mu m, and the neutral salt spray test is more than 1000 h.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The nano antibacterial antiseptic hydrosol coating composition is based on granular metal or a mixture of granular metals, nano silica sol, optional other binders, water soluble organic solvent and water.
1) The nanosilica sols are available directly from the market. Can also be prepared by the following method: a certain mass of water, hydrochloric acid and 1/3 mass of isopropanol were mixed well and slowly added dropwise to the silane. And reacting for 3 hours under the stirring condition to obtain colorless and transparent nano silicon dioxide hydrosol. Wherein the mass content of water is 0.1-90%, the mass content of hydrochloric acid is 0-1%, and the mass content of silane is 1-99%. The silane can be gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane (GYLMO), and also can be gamma- (2, 3-epoxypropoxy) propyl triethoxy silane (GYLEO) or gamma-aminopropyl triethoxy silane; characterized by containing at least one hydrolyzable siloxy functional group.
The content of the element silicon in the nano silicon dioxide sol accounts for 0.1-5% of the total mass of the nano antibacterial and antiseptic hydrosol coating composition, and is more favorably 0.5-1.5%.
2) The molecular formula of the zinc nitroisophthalate is as shown in the following formula, and the zinc nitroisophthalate is used as a catalyst and accounts for 0.01-2% of the total mass ratio of the nano antibacterial anticorrosive hydrosol coating composition, and more favorably 0.5-1%.
The zinc nitroisophthalate has two functions in the nano antibacterial and antiseptic hydrosol coating composition:
a. after the environment-friendly nano water-based anticorrosive composition sold in the market is cured to form a film at a lower curing temperature (such as 100 ℃), the crosslinking density of the coating formed by the film is lower than that of the coating formed by curing the film at a high curing temperature (such as 320 ℃). Thus, the corrosive molecules will quickly pass through the low temperature cured coating, causing corrosion to the substrate. Many experimental tests have shown that if the coating thickness is below 10 μm, corrosion molecules can penetrate through the coating (bake cure at 100 ℃) within 24 hours causing corrosion of the substrate. Whereas the time for which the metal particles in the composition, such as zinc powder or aluminium powder, act as corrosion protection is usually after 24 hours. Therefore, corrosion of the substrate may occur therebetween. The zinc nitroisophthalate has the function of inhibiting short-term corrosion, and the corrosion within 24h can be avoided if the zinc nitroisophthalate is added.
b. The zinc nitroisophthalate has a synergistic catalytic effect on the curing of the nano sol. This can greatly reduce the curing temperature of the nano sol and improve the crosslinking density of the nano sol under the low-temperature curing condition. Wherein the nanosol comprises: nano alumina sol, nano silica sol, nano titania sol and nano zirconia sol.
3) The particulate metal or mixture of particulate metals is selected from zinc and aluminium and alloys of zinc and aluminium, or mixtures of zinc and aluminium, or alloys of zinc and aluminium with manganese, magnesium, tin, nickel, stainless steel, rare earth alloys Galfan. The shape may be spherical or plate-like, preferably plate-like, and the particle size distribution D50 is 0.5-50 μm. It accounts for 5-45% of the total mass of the composition, more advantageously 20-40%.
4) The other adhesive can be one or a mixture of more of sodium silicate aqueous solution, potassium silicate aqueous solution, lithium silicate aqueous solution, nano titanium dioxide sol, nano zirconium dioxide sol, nano aluminum oxide sol, aqueous acrylic emulsion, aqueous phenolic resin emulsion and aqueous amino resin emulsion. The content of the nano antibacterial anticorrosion hydrosol coating composition is 3-30% by mass, and the content of the nano antibacterial anticorrosion hydrosol coating composition is more favorably 5-20% by mass. It is further advantageous if the further binder is a composition of a nano-alumina sol and a nano-titania (zirconium) sol, the sum of the masses of the elements aluminum and titanium (zirconium) in the sol making up 0 to 2%, preferably 0.5 to 1%, of the total mass of the composition.
Wherein the nano alumina sol is also called AlOOH hydrosol or boehmite sol, and is a colloidal solution of positively charged monohydrate alumina particles dispersed in water.
The nano alumina hydrosol can be directly purchased from the market. Or it may be prepared by hydrolysis of aluminum isopropoxide, aluminum nitrate or aluminum chloride as a precursor. The preparation process is mainly that deionized water is added into a container and heated to 80 ℃. The previously ground aluminum isopropoxide was added slowly with stirring and stirred under reflux for 1h to allow complete hydrolysis and formation of boehmite precipitate. Evaporating isopropanol in the precipitate to dryness, adding hydrochloric acid water solution, and stirring to dissolve the precipitate completely. Stirring and refluxing for 6h at the temperature of 80 ℃ to prepare the warm and definite nano alumina sol. The general reaction preparation steps and involved reaction formulas are as follows:
hydrolysis:
polymerization:
wherein, the nano titanium dioxide sol or the nano zirconium dioxide sol can be directly purchased from the market. Or prepared by the following method: dissolving titanium tetrachloride (molecular formula TiCl 4)/zirconium tetrachloride (molecular formula TiCl4) in a certain amount of deionized water, and stirring at 10 deg.C for 1.5h to obtain a transparent solution. Then, an aqueous sodium hydroxide solution was slowly added to the solution under the condition that the pH was 7, a large amount of white precipitate was generated, and the precipitate was sufficiently washed with deionized water. Adding 0.1mol/l hydrochloric acid aqueous solution, slowly dripping into the white precipitate, and adjusting pH to 1.4-2. Fully stirring at room temperature, and aging to obtain the transparent nano titanium dioxide/zirconium dioxide hydrosol.
5) The liquid medium of the nano antibacterial antiseptic hydrosol coating composition is mainly a composition of water and a water-soluble organic solvent. The water-soluble organic solvent is selected from: propylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, other alcohols, ketones, and mixtures thereof. The content of the nano antibacterial anticorrosion hydrosol coating composition is 5-40% by mass, and more favorably 10-30% by mass.
6) The nano antimicrobial antiseptic hydrosol coating composition further comprises 0.05-5% of an aqueous wetting dispersant, relative to the total mass of the composition. More advantageously, the proportion is 0.1 to 0.5%.
7) The nano antimicrobial antiseptic hydrosol coating composition further comprises 0.05-5% of a thickener relative to the total mass of the composition. The thickener may be selected from: xanthan gum, cellulose thickening agent, associative polyurethane thickening agent, polyurea modified thickening agent, silicate thickening agent and bentonite thickening agent. A more advantageous option is a cellulosic thickener.
8) The nano antimicrobial antiseptic hydrosol coating composition further comprises 0.05-5% of a defoaming agent, relative to the total mass of the composition. More advantageously, the proportion is 0.1 to 0.5%.
9) The nano antimicrobial antiseptic hydrosol coating composition may further comprise 0.05-1% of a substrate wetting agent, relative to the total mass of the composition.
10) The nano antimicrobial antiseptic hydrosol coating composition may further comprise 0.1-5% of a corrosion inhibitor selected from the group consisting of zinc phosphate, zinc aluminum phosphate, aluminum tripolyphosphate, zinc silicate, zinc aluminum silicate.
The following examples illustrate the manner in which the invention may be employed;
and, in each example, preparation of a nano antibacterial antiseptic hydrosol coating composition: the components of the nano antibacterial anticorrosive hydrosol coating composition are physically mixed and then uniformly mixed in a high-speed dispersion mode. I.e., for performance testing.
Preparation of test panels: unless otherwise indicated, the test panels were Q-panel cold rolled steel panels, available from Kelly trade, Inc. The test plate is polished by using abrasive paper P80, then degreased and cleaned by using a degreasing agent, and dried for later use. And (3) coating the nano antibacterial anticorrosive hydrosol coating composition on the pretreated test board in an air spraying manner. After curing by baking, the relevant properties were tested. The adhesion test is carried out according to the GB/T9286-1998 standard, and the corrosion resistance is evaluated by testing the neutral salt spray resistance according to the GB/T1771-2007 standard.
Example 1
The embodiment relates to a nano antibacterial anticorrosion hydrosol coating composition, which comprises the following components in percentage by weight:
TABLE 1
Remarking:1the nano silicon dioxide sol of affluent silicon materials company has 5 percent of element silicon and 500nm of grain diameter D50,
2nitro-m-xylene zinc, purchased from carbofuran, with a particle size D50 of 5um,
3the flaky metallic zinc powder of the Aika company has a particle size D50 of 13um,
4ica's flaky metallic aluminum powder having a particle size D50 of 15um,
5the zinc phosphate powder of Haibo chemical industry has a particle size D50 of 6 um.
The results of the performance tests are shown in table 2 below:
TABLE 2
| Item | Remarks for note | Composition 1 | Composition 2 | Composition 3 |
| Baking temperature | 100℃ | 40min | 40min | 40min |
| Film thickness of dry film | Dry film thickness gauge test | 7-10μm | 7-10μm | 7-10μm |
| Adhesive force of hundred grids | GB/T 9286-1998 | Level 0 | Level 0 | Level 0 |
| Antibacterial ability | How long the bacteria grow after storage | 3 months old | 3 months old | 3 months old |
| Neutral salt spray test | GB/T 1771-2007 | 638h | 620h | 696h |
Example 2
The embodiment relates to a nano antibacterial anticorrosion hydrosol coating composition, which comprises the following components in percentage by weight:
TABLE 3
The performance test results are shown in table 4:
TABLE 4
| Item | Remarks for note | Composition 4 | Composition 5 | Composition 6 |
| Baking temperature | 100℃ | 40min | 40min | 40min |
| Film thickness of dry film | Dry film thickness gauge test | 5-7μm | 5-7μm | 5-7μm |
| Adhesive force of hundred grids | GB/T 9286-1998 | Level 0 | Level 0 | Level 0 |
| Antibacterial ability | How long the bacteria grow after storage | >12 months old | >12 months old | >12 months old |
| Neutral salt spray test | GB/T 1771-2007 | 1416h | 1080h | 1104h |
Example 3
The embodiment relates to a nano antibacterial anticorrosion hydrosol coating composition, which comprises the following components in percentage by weight:
TABLE 5
The results of the sexual tests are shown in Table 6
TABLE 6
Example 4
This example examined the effect of temperature on corrosion resistance, and the results of the corrosion resistance test are given in table 7 below:
TABLE 7
The results of the sexual tests are shown in Table 8
TABLE 8
In summary, combination 11 is the most preferred combination of the above compositions, and after curing at 100 ℃, the 7-10um dry film has a neutral salt spray resistance test of over 1000 hours.
According to the system, the nano antibacterial and anticorrosive hydrosol coating composition is lower in curing film-forming temperature and higher in crosslinking density after being cured and formed at low temperature through the catalysis and corrosion inhibition of the zinc nitroisophthalate, and has excellent anticorrosive capability after being cured at low temperature.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (9)
1. The nano antibacterial anticorrosion hydrosol coating composition is characterized by comprising the following components in percentage by mass based on the total mass of the composition:
nano silica sol: the element silicon in the sol accounts for 0.1 to 5 percent of the total weight of the composition,
particulate metal or mixture of particulate metals: 5 to 40 percent of the total weight of the mixture,
zinc nitroisophthalate: 0.01 to 2 percent of the total weight of the mixture,
other binders: 3 to 30 percent of the total weight of the mixture,
water-soluble organic solvent: 5 to 40 percent of the total weight of the mixture,
deionized water: 5 to 40 percent;
the other adhesive is one or a mixture of several of nano titanium dioxide sol, nano zirconium dioxide sol and nano alumina sol.
2. The nano antibacterial anticorrosive hydrosol coating composition according to claim 1, wherein the nano silica sol has an average particle size of 5 to 800 nm.
3. The nano-antimicrobial antiseptic hydrosol coating composition of claim 2 wherein the nano-silica sol contains one or more of amino, vinyl or epoxy functional groups.
4. The nano-antimicrobial antiseptic hydrosol coating composition of claim 1 wherein the zinc nitroisophthalate has an average particle size D50 of 1-10 μ ι η.
5. A nano-antibacterial antiseptic hydrosol coating composition according to claim 1 wherein the particulate metal or mixture of particulate metals is selected from zinc, aluminum or a mixture of zinc and aluminum or an alloy of at least one of zinc, aluminum with at least one of manganese, magnesium, tin, nickel, stainless steel, rare earth alloy Galfan.
6. The nano-antimicrobial antiseptic hydrosol coating composition of claim 1 wherein the water soluble organic solvent is selected from the group consisting of: one or more of propylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol and ketone.
7. The nano-antibacterial antiseptic hydrosol coating composition according to claim 1, characterized in that the composition further comprises 0.01-5% of aqueous wetting dispersant, 0.01-5% of thickener, 0.01-5% of defoamer, 0.05-1% of base material wetting agent, 0.1-5% of corrosion inhibitor and 0.01-5% of pH regulator in mass percentage based on the total mass of the composition.
8. An anti-corrosive and antibacterial coating for steel or iron substrates, characterized in that the coating is prepared by spraying, dipping or brushing the composition of any one of claims 1 to 7 on a steel, iron or galvanized steel substrate and baking; the baking is carried out by convection or infrared for 10-60 minutes or by induction for 10 seconds-5 minutes at a temperature of 100-350 ℃.
9. The steel or iron substrate anti-corrosive and antibacterial coating according to claim 8, wherein said coating has a dry film thickness of 3-55 μm.
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| US20040072941A1 (en) * | 2001-02-13 | 2004-04-15 | Ralf Nickolaus | Aqueous coating substance that is substantially or completely free of volatile organic substances, method for producing the same and the use thereof |
| WO2004033565A1 (en) * | 2002-10-10 | 2004-04-22 | Basf Corporation | Coating compositions having improved 'direct to metal' adhesion and method of improving corrosion resistance |
| CN108165165A (en) * | 2017-12-13 | 2018-06-15 | 湖南航天磁电有限责任公司 | A kind of preparation method of Nd-Fe-B magnetic material surface recombination corrosion-inhibiting coating |
| CN108659581A (en) * | 2018-04-27 | 2018-10-16 | 成都今天化工有限公司 | A method of preparing super abrasive nano-titanium porcelain coating |
| CN110655811A (en) * | 2019-10-24 | 2020-01-07 | 广东工业大学 | Novel environment-friendly chromium-free zinc-aluminum coating and preparation method thereof |
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Effective date of registration: 20230613 Address after: 215300 Laoshan Road, Yushan Town, Kunshan City, Suzhou City, Jiangsu Province Patentee after: Yao Xiayin Address before: 225824 No.9, Dudong formation, Jiangzhuang village, Xiaji Town, Baoying County, Yangzhou City, Jiangsu Province Patentee before: Xu Ling |