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CN102511503A - Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method - Google Patents

Efficient and environmentally-friendly antibacterial and mildewproof inorganic composite nano-powder slurry and its preparation method Download PDF

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CN102511503A
CN102511503A CN2011104012273A CN201110401227A CN102511503A CN 102511503 A CN102511503 A CN 102511503A CN 2011104012273 A CN2011104012273 A CN 2011104012273A CN 201110401227 A CN201110401227 A CN 201110401227A CN 102511503 A CN102511503 A CN 102511503A
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powder slurry
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inorganic composite
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CN102511503B (en
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吴进怡
柴柯
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Institute of Corrosion Science and Technology
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Hainan University
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Abstract

本发明涉及抗菌材料领域,具体为一种利用纳米氧化镁与其他纳米无机物复合得到高效环保抗菌防霉无机复合纳米粉浆及其制备方法。以纳米氧化镁为主体,其与纳米氧化锌、纳米氧化钛、纳米氧化铜、纳米氧化亚铜、纳米氧化银、纳米硫化锌、纳米氧化锆、纳米氧化钇、纳米氧化铝、纳米氧化钙中的一种或一种以上无机物复合组成纳米粉浆;按重量百分比计,纳米粉浆中纳米氧化镁0.1~40%,其它无机物0.01~40%,高分子分散剂0.5~12%,余量为溶剂。将纳米无机物按预定比例高速分散进入高分子分散剂和溶剂组成的溶液中,再经球磨,制成纳米复合粉浆。该纳米复合粉浆应用在抗菌涂料、除臭剂、纺织品、纸制品、塑料、橡胶、水处理剂、船舶保护剂、化妆品等方面。The invention relates to the field of antibacterial materials, in particular to a high-efficiency, environment-friendly, antibacterial, anti-mildew, and anti-mildew inorganic composite nano-powder slurry obtained by compounding nano-magnesia and other nano-inorganic substances and a preparation method thereof. With nano-magnesia as the main body, it is mixed with nano-zinc oxide, nano-titanium oxide, nano-copper oxide, nano-cuprous oxide, nano-silver oxide, nano-zinc sulfide, nano-zirconia, nano-yttrium oxide, nano-alumina, and nano-calcium oxide. One or more than one inorganic substance compounded to form a nano-powder slurry; by weight percentage, in the nano-powder slurry, 0.1-40% of nano-magnesia, 0.01-40% of other inorganic substances, 0.5-12% of polymer dispersant, and the remaining The amount is solvent. The nano-inorganic matter is dispersed into a solution composed of a polymer dispersant and a solvent at a high speed according to a predetermined ratio, and then ball-milled to make a nano-composite slurry. The nanocomposite powder slurry is used in antibacterial coatings, deodorants, textiles, paper products, plastics, rubber, water treatment agents, ship protection agents, cosmetics and the like.

Description

A kind of high-efficiency environment friendly antibacterial and mouldproof inorganic composite nano powder slurry and preparation method thereof
Technical field
The present invention relates to the anti-biotic material field, be specially a kind of nano magnesia and compound high-efficiency environment friendly antibacterial and mouldproof inorganic composite nano powder slurry and preparation method thereof that obtains of other nano-inorganic substances of utilizing.
Background technology
Bacterium and mould growing in people's living environment and some article, not only harm humans health, and contaminated environment, damage product.Therefore, the research of high-efficiency environment friendly antibacterial mildew inhibitor and the utilization to the protection human health, bettering people's living environment has crucial meaning.Mostly traditional antibacterial agent is organic antibacterial agent; Its sterilization speed is fast; Exploitation is ripe with operation technique, but exist in various degree toxicity, to skin stimulation is arranged, bad smell is arranged, volatile, drug effect short, can not broad-spectrum sterilization, complicated operation, once invest shortcomings such as bigger.
Summary of the invention
What the object of the present invention is to provide a kind of efficient, long acting antibiotic mildew-resistant, environmental protection utilizes the compound inorganic composite nano powder slurry that obtains of inorganic matter such as nano magnesia, and its preparation method is simple to operate, easy control of process conditions, cost are low.
Technical scheme of the present invention is:
A kind of high-efficiency environment friendly antibacterial and mouldproof inorganic composite nano powder slurry by the suspension of nano-inorganic substance, macromolecule dispersing agent and solvent composition, forms dispersion highly uniformly through disperseing and grinding the back; With the nano magnesia is main body, compound composition nano powder slurry such as one or more inorganic matters in itself and nano zine oxide, nano-titanium oxide, nano cupric oxide, nano cuprous oxide, nano phase ag_2 o, nano-zinc sulfide, nano zircite, nano yttrium oxide, nano aluminium oxide, the nano calcium oxide etc.By weight percentage; In the nano powder slurry, the content of nano magnesia is 0.1~40% (preferred 1~30%), and other inorganic content is 0.01~40% (preferred 0.03~30%); Macromolecule dispersing agent content is 0.5~12% (preferred 1~8%), and surplus is a solvent.
The preparation method of said high-efficiency environment friendly antibacterial and mouldproof inorganic composite nano powder slurry; The high degree of dispersion system of utilizing nano magnesia and described one or more nano-inorganic substances in the solution of macromolecule dispersing agent and solvent composition, to form, the inorganic composite nano powder for preparing a series of compositions is starched.Is raw material less than the magnesia powder of 100nm and average particle size particle size less than described one or more nano-inorganic substances of 100nm with average particle size particle size; Its high speed dispersion is got in the solution of macromolecule dispersing agent and solvent composition by predetermined ratio; Rate of dispersion is that 400~3000rpm (is preferably 500~2500rpm); Jitter time is 2~120min (being preferably 5~60); Mixture (is preferably 40min~15h), forms the inorganic composite nano powder slurry of high degree of dispersion through ball milling 20min~20h.The ball milling method of said mixture is planetary, drum-type or oscillatory type ball grinding method.
Macromolecule dispersing agent wherein is TPO, polycarboxylic acid, polycarboxylic acid salt, polyacrylic, polyacrylate, polyesters, polyester salt, polyamide-based, polyamide salt, polyurethanes, polyurethane salt, polyethers, polyethers salt, polyanhydrides, polysiloxane-based, polyoxyethylene, polyoxypropylene class, maleic anhydride class, gather ε-one or more compounds in oneself in ketone, polyalcohols, the alcohols.
Solvent wherein is one or more compounds in fat hydrocarbon, alicyclic hydrocarbon type, arene, alcohols, ketone, ester class, terpene, alcohol ether and ether-ether class, replacement hydro carbons, the water.
Among the present invention, the antibiotic mechanism of nano-inorganic substance is following:
(1) nano magnesia
Magnesia is hydration very easily, and forms one deck magnesium hydroxide on the surface, and the oxygen that is dissolved in the solution generates active oxygen ion through the single electron reduction reaction.Magnesian surface coats one deck hydroxide ion, because oxygen has chemical stability in alkaline environment, so the active oxygen ion of high concentration is able to exist at mgo surface.And active oxygen ion has strong oxidisability, can destroy the peptide bond structure of the cell membrane walls of bacterium, thus rapid killing bacteria.In addition, nano oxidized magnesium particle can produce destructive absorption, also maybe the cell membrane of bacterium be destroyed.Antibiotic mechanism like this can overcome the deficiency that slow, the easy to change and titanium dioxide series antibacterial agent of silver-series antibacterial agent effect needs ultraviolet irradiation.
(2) nano zine oxide
Under illumination condition; The antibiotic of nano zine oxide is photocatalysis and the coefficient result of metal ion stripping; Nano zine oxide is better than Escherichia coli to the antibiotic property of staphylococcus aureus, and reason is that staphylococcus aureus has more negative electrical charge in nearly neutrality or weakly alkaline environment; Positively charged nano zine oxide is adsorbed onto its surface more easily, thereby it is killed; Unglazed according to the time, just metal ion stripping mechanism in action, the particle diameter of nano particle is more little, photocatalytic effect is strong more.
(3) nano-titanium oxide
Because TiO 2The characteristics that electronic structure had make it receive the light time to generate very strong superoxide anion free radical and the hydroxyl free radical of chemical activity, attack organic matter, reach the effect of degradable organic pollutant.When running into bacterium, the cell of directtissima bacterium causes the organic matter degradation in the bacterial cell, with this kill bacteria, and makes it to decompose.General commonly used bactericide silver, copper etc. can make bacterial cell lose activity, but after bacterium kills, and corpse discharges the component that endotoxin etc. is harmful to.Nano titanium oxide can not only influence bacterial reproduction power, and can destroy the membrane structure of bacterium, reaches thorough bacterium for degrading; Prevent the secondary pollution that endotoxin causes; Nano titanium oxide belongs to non-dissolution type material, and at degradable organic pollutant with when killing bacterium, self does not decompose, not stripping; Photocatalysis is lasting, and has lasting sterilization, degradation of contaminant effect.
(4) nano cupric oxide
But nano cupric oxide antibacterium and fungi; Nano cupric oxide can mix the people in plastics, synthetic fibers, adhesive and coating etc. easily; Even in rigorous environment, also can keep high activity for a long time, nano cupric oxide all has antibacterial action preferably to staphylococcus aureus and hay bacillus.
(5) nano cuprous oxide
Cuprous oxide is as a kind of hypotoxic broad spectrum antimicrobicide; Mainly by discharge in copper ion and fungi or the bacterial body internal protein-SH ,-N2H ,-COOH ,-groups such as OH work and cause bacterial death; Be insoluble to organic solvent and water, be dissolved in diluted mineral acid (hydrochloric acid, sulfuric acid, nitric acid) and the ammonia.In malaria, be prone to slowly be oxidized to copper oxide, stable in the air of drying.
(6) nano phase ag_2 o
Nano phase ag_2 o discharges sulfydryl electronegative in positively charged silver ion and the bacterialprotease and reacts, and protease loses activity rapidly because of the forfeiture of sulfydryl, thereby causes bacterium to carry out schizogamy and be killed.After thalline lost activity, silver ion can dissociate out from thalline again, repeats fungicidal property, so its antibacterial effect is lasting.In addition, silver ion also has photocatalysis.Under the effect of light; Silver ion can play the effect of catalytic active center, activates the oxygen in the water and air, produces hydroxyl radical free radical and active oxygen ion; Active oxygen ion has very strong oxidability, can destroy the multiplication capacity of bacterium at short notice and makes cell death.
(7) nano-zinc sulfide
The antibiotic mechanism of nano-zinc sulfide is that when nano-zinc sulfide contacted with bacterium, zinc ion slowly released; Because zinc ion tool oxidation-reduction quality; And can react with organic matter (thio group, carboxyl, hydroxyl), can combine with bacterial cell membrane and memebrane protein, destroy its structure; Get into and to combine with enzyme behind the cell and react, reach antibiotic purpose with DNA.
(8) nano zircite
Nano zircite is a lotus positive electricity nano particle, and it has strong suction-operated to bacterium, so that other have the antibacterial action particle and bacterium fully acts on, strengthens antibacterial effect.
(9) nano yttrium oxide
Nano yttrium oxide is a lotus positive electricity nano particle, and it has strong suction-operated to bacterium, so that other have the antibacterial action particle and bacterium fully acts on, strengthens antibacterial effect.
(10) nano aluminium oxide
Nano yttrium oxide is a lotus positive electricity nano particle, and it has strong suction-operated to bacterium, so that other have the antibacterial action particle and bacterium fully acts on, strengthens antibacterial effect.
(11) nano calcium oxide
Nano calcium oxide can be through its local strong basicity performance antibacterial action.
Advantage of the present invention is:
1, the antibacterial and mouldproof performance is strong.Adopt the inorganic composite nano powder slurry of the inventive method preparation to possess the Synergistic antimicrobial fungicidal properties of multiple inorganic matter, and have synergistic effect, its antibacterial effect is far above the single nano powder slurry of planting with concentration.
2, technology is simple, and cost is low.The method that the present invention adopts dispersion and ball milling to combine prepares inorganic composite nano powder slurry, and Processes and apparatus is all very ripe, simple.
3, the dispersiveness that has height.The inorganic composite nano powder slurry that utilizes technology of the present invention to prepare has formed the system of high degree of dispersion; Can be distributed in other systems equably; This nano composite powder is starched storage period more than 1 year, and antibiotic anti-fungi performance is excellent, meets or exceeds international most advanced level; Thereby potential wide application prospect is arranged at aspects such as antibiotic paint, deodorant, textile, paper products, plastics, rubber, water treatment agent, boats and ships protectants, be a kind of inorganic antiseptic that has very big use to be worth.
4, inorganic antiseptic of the present invention has excellent properties such as long-acting, environmental protection, bacteriostasis rate height; Inorganic matter antibacterial antiplaque agent mechanism such as nano level zinc oxide, titanium oxide, copper oxide, cuprous oxide, silver oxide, zinc sulphide, zirconia, yittrium oxide, aluminium oxide, calcium oxide are different, will bring into play the special effect of antibacterial and mouldproof after compound.
Embodiment
Through instance the present invention is detailed below; Among the present invention except that specializing; Related ratio is weight ratio, and the powder anti-microbial property identifies that according to standard GB/T 21510-2008 method coating antibacterium and mould ability are pressed HG/T 3950-2007 industry standard and identified.
Embodiment 1
In the 2000ml beaker, take by weighing deionized water 840g; With high speed dispersor high-speed stirred under the 1000rpm condition, add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 60g, add magnesia powder 70g, oxide powder and zinc 20g and the titanium oxide powder 10g of average particle size particle size 50nm respectively; Disperse 60min; Mixture is through planetary type ball-milling 5h, and drum's speed of rotation is 300rpm, forms the inorganic composite nano powder slurry of high degree of dispersion.According to original proportioning, wherein the nano magnesia weight ratio is 7%, and the nano zine oxide weight ratio is 2%, and the weight ratio of nano-titanium oxide is 1%, and composite powder gross weight ratio is 10%, and the macromolecule dispersing agent weight ratio is 6%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.2%, and 24h Escherichia coli sterilizing rate reaches 99.96%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.93%, is the I level, and the mildew grade is 1 grade.
Embodiment 2
In the 2000ml beaker, take by weighing deionized water 700g; With high speed dispersor high-speed stirred under the 2000rpm condition, add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 100g, add magnesia powder 40g, oxide powder and zinc 120g and the titanium oxide powder 40g of average particle size particle size 60nm respectively; Disperse 120min; Mixture is through planetary type ball-milling 10h, and drum's speed of rotation is 500rpm, forms the inorganic composite nano powder slurry of high degree of dispersion.According to original proportioning, wherein the nano magnesia weight ratio is 4%, and the nano zine oxide weight ratio is 12%, and the weight ratio of nano-titanium oxide is 4%, and composite powder gross weight ratio is 20%, and the macromolecule dispersing agent weight ratio is 10%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.3%, and 24h Escherichia coli sterilizing rate reaches 99.99%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.96%, is the I level, and the mildew grade is 0 grade.
Embodiment 3
In the 2000ml beaker, take by weighing deionized water 890g; With high speed dispersor high-speed stirred under the 500rpm condition; Add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 30g, add magnesia powder 40g and the oxide powder and zinc 40g of average particle size particle size 30nm respectively, dispersion 10min; Mixture forms the inorganic composite nano powder slurry of high degree of dispersion through oscillatory type ball milling 2h.According to original proportioning, wherein the nano magnesia weight ratio is 4%, and the nano zine oxide weight ratio is 4%, and composite powder gross weight ratio is 8%, and the macromolecule dispersing agent weight ratio is 3%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.5%, and 24h Escherichia coli sterilizing rate reaches 99.94%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.93%, is the I level, and the mildew grade is 1 grade.
Embodiment 4
In the 2000ml beaker, take by weighing deionized water 900g; With high speed dispersor high-speed stirred under the 700rpm condition; Add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 50g, add magnesia powder 45g and the titanium oxide powder 5g of average particle size particle size 80nm respectively, dispersion 40min; Mixture forms the inorganic composite nano powder slurry of high degree of dispersion through roller milling 15h.According to original proportioning, wherein the nano magnesia weight ratio is 4.5%, and the nano-titanium oxide weight ratio is 0.5%, and composite powder gross weight ratio is 5%, and the macromolecule dispersing agent weight ratio is 5%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.0%, and 24h Escherichia coli sterilizing rate reaches 99.5%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.2%, is the I level, and the mildew grade is 1 grade.
Embodiment 5
In the 2000ml beaker, take by weighing deionized water 800g; With high speed dispersor high-speed stirred under the 2500rpm condition, add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 80g, add magnesia powder 84g, oxide powder and zinc 24g, titanium oxide powder 10.8g and the cupric oxide powder 1.2g of average particle size particle size 40nm respectively; Disperse 100min; Mixture is through planetary type ball-milling 8h, and drum's speed of rotation is 600rpm, forms the inorganic composite nano powder slurry of high degree of dispersion.According to original proportioning, wherein the nano magnesia weight ratio is 8.4%, and the nano zine oxide weight ratio is 2.4%; The weight ratio of nano-titanium oxide is 1.08%; The weight ratio of nano cupric oxide is 0.12%, and composite powder gross weight ratio is 12%, and the macromolecule dispersing agent weight ratio is 8%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.6%, and 24h Escherichia coli sterilizing rate reaches 99.97%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.98%, is the I level, and the mildew grade is 0 grade.
Embodiment 6
In the 2000ml beaker, take by weighing deionized water 630g; With high speed dispersor high-speed stirred under the 3000rpm condition; Add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 120g, add magnesia powder 75g, zinc sulphide 100g, titanium oxide 73.75g and the cuprous oxide 1.25g of average particle size particle size 20nm respectively, disperse 110min; Mixture forms the inorganic composite nano powder slurry of high degree of dispersion through oscillatory type ball milling 6h.According to original proportioning, wherein the nano magnesia weight ratio is 7.5%, and the nano-zinc sulfide weight ratio is 10%; The weight ratio of nano-titanium oxide is 7.375%; The weight ratio of nano cuprous oxide is 0.125%, and composite powder gross weight ratio is 25%, and the macromolecule dispersing agent weight ratio is 12%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.7%, and 24h Escherichia coli sterilizing rate reaches 99.98%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.98%, is the I level, and the mildew grade is 0 grade.
Embodiment 7
In the 2000ml beaker, take by weighing deionized water 780g; With high speed dispersor high-speed stirred under the 1500rpm condition; Add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 70g, add magnesia powder 148.5g and the oxidation silver powder 1.5g of average particle size particle size 45nm respectively, dispersion 80min; Mixture forms the inorganic composite nano powder slurry of high degree of dispersion through roller milling 13h.According to original proportioning, wherein the nano magnesia weight ratio is 14.85%, and the nano phase ag_2 o weight ratio is 0.15%, and composite powder gross weight ratio is 15%, and the macromolecule dispersing agent weight ratio is 7%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 98.9%, and 24h Escherichia coli sterilizing rate reaches 99.96%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.94%, is the I level, and the mildew grade is 0 grade.
Embodiment 8
In the 2000ml beaker, take by weighing deionized water 730g; With high speed dispersor high-speed stirred under the 1800rpm condition, add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 90g, add magnesia powder 140g, zinc sulphide powder 25g, alumina powder 10g and the calcium oxide powder 10g of average particle size particle size 85nm respectively; Disperse 30min; Mixture is through planetary type ball-milling 7h, and drum's speed of rotation is 450rpm, forms the inorganic composite nano powder slurry of high degree of dispersion.According to original proportioning, wherein the nano magnesia weight ratio is 13.9%, and the nano-zinc sulfide weight ratio is 2.49%; The nano aluminium oxide weight ratio is 1%; The nano calcium oxide weight ratio is 1%, and composite powder gross weight ratio is 18.4%, and the macromolecule dispersing agent weight ratio is 8.96%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 98.3%, and 24h Escherichia coli sterilizing rate reaches 99.90%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.8%, is the I level, and the mildew grade is 1 grade.
Embodiment 9
In the 2000ml beaker, take by weighing deionized water 490g; With high speed dispersor high-speed stirred under the 1300rpm condition, add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 110g, add magnesia powder 40g, zinc oxide 320g, zirconia 20g, yittrium oxide 20g and the silver oxide 8g of average particle size particle size 70nm respectively; Disperse 90min; Mixture is through planetary type ball-milling 12h, and drum's speed of rotation is 350rpm, forms the inorganic composite nano powder slurry of high degree of dispersion.According to original proportioning; Wherein the nano magnesia weight ratio is 3.97%, and the nano zine oxide weight ratio is 31.7%, and the weight ratio of nano zircite is 1.98%; The weight ratio of nano yttrium oxide is 1.98%; The weight ratio of nano phase ag_2 o is 7.94%, and composite powder gross weight ratio is 40.5%, and the macromolecule dispersing agent weight ratio is 10.9%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.4%, and 24h Escherichia coli sterilizing rate reaches 99.98%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.99%, is the I level, and the mildew grade is 0 grade.
Embodiment 10
In the 2000ml beaker, take by weighing deionized water 780g; With high speed dispersor high-speed stirred under the 400rpm condition, add the macromolecule dispersing agent Disperbyk192 of chemical company (German Bi Ke) 60g, add magnesia powder 96g, zinc oxide 48g, calcium oxide 12.8g, silver oxide 1.6g and the copper oxide 1.6g of average particle size particle size 25nm respectively; Disperse 120min; Mixture is through planetary type ball-milling 20min, and drum's speed of rotation is 800rpm, forms the inorganic composite nano powder slurry of high degree of dispersion.According to original proportioning; Wherein the nano magnesia weight ratio is 9.6%, and the nano zine oxide weight ratio is 4.8%, and the weight ratio of nano calcium oxide is 1.28%; The weight ratio of nano phase ag_2 o is 0.16%; The weight ratio of nano cupric oxide is 0.16%, and composite powder gross weight ratio is 16%, and the macromolecule dispersing agent weight ratio is 6%.
This inorganic composite nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 99.3%, and 24h Escherichia coli sterilizing rate reaches 99.96%.This inorganic composite nano powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.98%, is the I level, and the mildew grade is 0 grade.
Embodiment 11
Change the solvent among the embodiment 1 into 672g benzinum and 168g trichloroethanes by 840g water; Dispersant adopts the Anti-Terra-202 of German Bi Ke chemical company; But it is constant that institute adds weight ratio, and other amount of substances and technological parameter are constant, preparation inorganic composite nano powder slurry.
This inorganic composite nano powder slurry adds in the coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.80%, is the I level, and the mildew grade is 1 grade.
Embodiment 12
Change the solvent among the embodiment 2 into 380g xylol and 320g toluene by 700g water; Dispersant adopts TEXAPHOR
Figure BDA0000116756410000081
963S of Henkel Henkel company; But it is constant that institute adds weight ratio; Other amount of substances and technological parameter are constant, preparation inorganic composite nano powder slurry.
This inorganic composite nano powder slurry adds in the coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.93%, is the I level, and the mildew grade is 0 grade.
Embodiment 13
Change the solvent among the embodiment 3 into 840g isohexane and 50g turpentine oil by 890g water, dispersant adopts the Hypersol L4708 of Denmark KVK company, but that institute adds weight ratio is constant, and other amount of substances and technological parameter are constant, preparation inorganic composite nano powder slurry.
This inorganic composite nano powder slurry adds in the coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.88%, is the I level, and the mildew grade is 1 grade.
Embodiment 14
Change the solvent among the embodiment 4 into the 900g isopropyl alcohol by 900g water; The Solsperse41090 of German Avecia company is adopted in the also corresponding change of dispersant, dispersant, but that institute adds weight ratio is constant; Other amount of substances and technological parameter are constant, preparation inorganic composite nano powder slurry.
This inorganic composite nano powder slurry adds in the coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.30%, is the I level, and the mildew grade is 1 grade.
Embodiment 15
Change the solvent among the embodiment 5 into the 800g cyclohexanone by 800g water; Dispersant adopts the TEXAPHOR
Figure BDA0000116756410000091
3250 of Henkel Henkel company; But it is constant that institute adds weight ratio; Other amount of substances and technological parameter are constant, preparation inorganic composite nano powder slurry.
This inorganic composite nano powder slurry adds in the coating with powder content 1% weight, and 24h composite nano anti-biotic coating antibiosis rate reaches 99.95%, is the I level, and the mildew grade is 0 grade.
Comparative example 1
Adopt with embodiment 1 identical technological parameter to have prepared pure nano magnesia water-based powder slurry, its final nano magnesia weight ratio is 10%.
This nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 62.2%, and 24h Escherichia coli sterilizing rate reaches 93.6%.This inorganic nanometer-powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h nano antibacterial coating antibiotic rate reaches 95%, is the II level, and the mildew grade is 2 grades.
Comparative example 2
Adopt with embodiment 1 identical technological parameter to have prepared pure zirconia magnesium water-based powder slurry, magnesium oxide granularity is at 1 μ m~100 μ m, and its final magnesia weight ratio is 10%.
This powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 22%, and 24h Escherichia coli sterilizing rate reaches 28%.This inorganic powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h antibiotic paint antibiotic rate reaches 31%, does not have fungus resistance basically.
Comparative example 3
Adopt with embodiment 11 identical technological parameters to have prepared pure nano magnesia powder slurry, its final nano magnesia weight ratio is 10%.
This inorganic nanometer-powder slurry adds in the coating with powder content 1% weight, and 24h nano antibacterial coating antibiotic rate reaches 94.4%, is the II level, and the mildew grade is 2 grades.
Comparative example 4
Adopt with embodiment 1 identical technological parameter to have prepared pure nano zine oxide water-based powder slurry, its final nano zine oxide weight ratio is 10%.
This nano powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 88.0%, and 24h Escherichia coli sterilizing rate reaches 95.1%.This inorganic nanometer-powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h nano antibacterial coating antibiotic rate reaches 96.5%, is the II level, and the mildew grade is 2 grades.
Comparative example 5
Adopt with embodiment 1 identical technological parameter to have prepared pure zinc oxide water-based powder slurry, the zinc oxide granularity is at 1 μ m~100 μ m, and its final zinc oxide weight ratio is 10%.
This powder slurry adds in the nutrient broth medium (NB) with powder content 0.5% weight, and 1h Escherichia coli sterilizing rate reaches 25%, and 24h Escherichia coli sterilizing rate reaches 31%.This inorganic powder slurry adds in the acrylic acid aqueous coating with powder content 1% weight, and 24h antibiotic paint antibiotic rate reaches 33%, does not have fungus resistance basically.
Comparative example 6
Adopt with embodiment 11 identical technological parameters to have prepared pure nano zinc oxide powder slurry, its final nano zine oxide weight ratio is 10%.
This inorganic nanometer-powder slurry adds in the coating with powder content 1% weight, and 24h nano antibacterial coating antibiotic rate reaches 96.0%, is the II level, and the mildew grade is 2 grades.
Visible by embodiment and comparative example, the inorganic composite nano powder slurry of the inventive method preparation has fabulous antibacterial and mouldproof effect.

Claims (10)

1.一种高效环保抗菌防霉无机复合纳米粉浆,其特征在于:所述无机复合纳米粉浆为由纳米无机物、高分子分散剂和溶剂组成的悬浮液,经过分散和研磨后形成均匀的分散体系;以纳米氧化镁为主体,其与纳米氧化锌、纳米氧化钛、纳米氧化铜、纳米氧化亚铜、纳米氧化银、纳米硫化锌、纳米氧化锆、纳米氧化钇、纳米氧化铝、纳米氧化钙中的一种或一种以上无机物复合组成纳米粉浆;按重量百分比计,纳米粉浆中纳米氧化镁的含量为0.1~40%,其它无机物含量为0.01~40%,高分子分散剂含量为0.5~12%,余量为溶剂。1. A highly efficient, environmentally friendly, antibacterial, mildew-proof inorganic composite nano-powder slurry is characterized in that: the inorganic composite nano-powder slurry is a suspension composed of nano-inorganic matter, a polymer dispersant and a solvent, and forms a uniform after dispersion and grinding. nano-magnesium oxide, nano-zinc oxide, nano-titanium oxide, nano-copper oxide, nano-cuprous oxide, nano-silver oxide, nano-zinc sulfide, nano-zirconia, nano-yttrium oxide, nano-alumina, One or more inorganic substances in nano-calcium oxide are compounded to form nano-powder paste; by weight percentage, the content of nano-magnesium oxide in nano-powder paste is 0.1-40%, and the content of other inorganic substances is 0.01-40%. The molecular dispersant content is 0.5-12%, and the balance is solvent. 2.按照权利要求1所述的高效环保抗菌防霉无机复合纳米粉浆,其特征在于:按重量百分比计,所述无机复合纳米粉浆的优选组成为:纳米粉浆中纳米氧化镁的含量优选为1~30%,其它无机物含量优选为0.03~30%,高分子分散剂含量优选为1~8%,余量为溶剂。2. according to the described high-efficiency environmental protection antimicrobial mildew-proof inorganic composite nano-powder slurry of claim 1, it is characterized in that: by weight percentage, the preferred composition of described inorganic composite nano-powder slurry is: the content of nano magnesium oxide in the nano-powder slurry It is preferably 1-30%, the content of other inorganic substances is preferably 0.03-30%, the content of polymer dispersant is preferably 1-8%, and the balance is solvent. 3.按照权利要求1或2所述的高效环保抗菌防霉无机复合纳米粉浆,其特征在于:以纳米氧化镁为主体,其与纳米氧化锌、纳米氧化钛、纳米氧化铜、纳米氧化亚铜、纳米氧化银、纳米硫化锌、纳米氧化锆、纳米氧化钇、纳米氧化铝、纳米氧化钙中的三种或三种以上无机物复合组成纳米粉浆。3. according to claim 1 or 2 described high-efficiency environmental protection antimicrobial mildew-proof inorganic composite nano-powder slurry, it is characterized in that: take nano-magnesium oxide as main body, it and nano-zinc oxide, nano-titanium oxide, nano-copper oxide, nano-suboxide Three or more inorganic substances in copper, nano-silver oxide, nano-zinc sulfide, nano-zirconia, nano-yttrium oxide, nano-alumina, and nano-calcium oxide are composited to form a nano-powder. 4.按照权利要求1或2所述的高效环保抗菌防霉无机复合纳米粉浆,其特征在于:以纳米氧化镁为主体,其与纳米氧化锌、纳米氧化钛、纳米氧化铜、纳米氧化亚铜、纳米氧化银、纳米硫化锌、纳米氧化锆、纳米氧化钇、纳米氧化铝、纳米氧化钙中的五种或五种以上无机物复合组成纳米粉浆。4. according to claim 1 or 2 described high-efficiency environmental protection antibacterial mildew proof inorganic composite nano-powder slurry, it is characterized in that: take nano-magnesium oxide as main body, it and nano-zinc oxide, nano-titanium oxide, nano-copper oxide, nano-suboxide Five or more inorganic substances among copper, nano-silver oxide, nano-zinc sulfide, nano-zirconia, nano-yttrium oxide, nano-alumina, and nano-calcium oxide are composited to form a nano-powder. 5.按照权利要求1所述的高效环保抗菌防霉无机复合纳米粉浆,其特征在于:所述纳米氧化镁的平均颗粒尺寸小于100nm,纳米氧化锌的平均颗粒尺寸小于100nm,纳米氧化钛的平均颗粒尺寸小于100nm,纳米氧化铜的平均颗粒尺寸小于100nm,纳米氧化亚铜的平均颗粒尺寸小于100nm,纳米氧化银的平均颗粒尺寸小于100nm,纳米硫化锌的平均颗粒尺寸小于100nm,纳米氧化锆的平均颗粒尺寸小于100nm,纳米氧化钇的平均颗粒尺寸小于100nm,纳米氧化铝的平均颗粒尺寸小于100nm,纳米氧化钙的平均颗粒尺寸小于100nm。5. according to the described high-efficiency environmental protection antimicrobial mildew-proof inorganic composite nano powder slurry of claim 1, it is characterized in that: the average particle size of described nano-magnesia is less than 100nm, the average particle size of nano-zinc oxide is less than 100nm, and the average particle size of nano-titanium oxide is less than 100nm. The average particle size is less than 100nm, the average particle size of nano-copper oxide is less than 100nm, the average particle size of nano-cuprous oxide is less than 100nm, the average particle size of nano-silver oxide is less than 100nm, the average particle size of nano-zinc sulfide is less than 100nm, nano-zirconia The average particle size of nano-yttrium oxide is less than 100nm, the average particle size of nano-alumina is less than 100nm, and the average particle size of nano-calcium oxide is less than 100nm. 6.按照权利要求1所述的高效环保抗菌防霉无机复合纳米粉浆,其特征在于:所述的高分子分散剂是聚烯烃类、聚羧酸类、聚羧酸盐类、聚丙烯酸类、聚丙烯酸盐类、聚酯类、聚酯盐类、聚酰胺类、聚酰胺盐类、聚氨酯类、聚氨酯盐类、聚醚类、聚醚盐类、聚酐类、聚硅氧烷类、聚氧乙烯类、聚氧丙烯类、马来酸酐类、聚ε-己内酮类、聚醇类、醇类中的一种或一种以上化合物。6. According to the high-efficiency, environment-friendly, antibacterial, mildew-proof, inorganic composite nano-powder slurry according to claim 1, it is characterized in that: the polymer dispersant is polyolefins, polycarboxylic acids, polycarboxylates, polyacrylic acid , polyacrylates, polyesters, polyester salts, polyamides, polyamide salts, polyurethanes, polyurethane salts, polyethers, polyether salts, polyanhydrides, polysiloxanes, One or more compounds of polyoxyethylenes, polyoxypropylenes, maleic anhydrides, polyε-caprolactones, polyalcohols, and alcohols. 7.按照权利要求1所述的高效环保抗菌防霉无机复合纳米粉浆,其特征在于:所述的溶剂是脂肪烃类、脂环烃类、芳香烃类、醇类、酮类、酯类、萜类、醇醚及醚酯类、取代烃类、水中的一种或一种以上化合物。7. According to the high-efficiency, environment-friendly, antibacterial, mildew-proof, inorganic composite nano-powder slurry according to claim 1, it is characterized in that: the solvent is aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, ketones, esters , terpenoids, alcohol ethers and ether esters, substituted hydrocarbons, and one or more compounds in water. 8.按照权利要求1或2所述的高效环保抗菌防霉无机复合纳米粉浆的制备方法,其特征在于:利用纳米氧化镁和所述的一种或一种以上纳米无机物在高分子分散剂和溶剂组成的溶液中形成的分散体系,制备一系列成分的无机复合纳米粉浆;以平均颗粒尺寸小于100nm的氧化镁粉和平均颗粒尺寸小于100nm的所述的一种或一种以上纳米无机物为原料,按预定比例将其高速分散进入高分子分散剂和溶剂组成的溶液中,分散速度为400~3000rpm,分散时间为2~120min,混合物经球磨20min~20h,形成高度分散的无机复合纳米粉浆。8. According to the preparation method of the high-efficiency, environment-friendly, antibacterial and mildew-proof inorganic composite nano-powder slurry according to claim 1 or 2, it is characterized in that: utilize nano-magnesium oxide and the described one or more nano-inorganic substances to disperse in the macromolecule A dispersion system formed in a solution composed of an agent and a solvent to prepare a series of inorganic composite nano-powder slurry; magnesium oxide powder with an average particle size of less than 100nm and one or more of the above-mentioned nano Inorganic substances are used as raw materials, and they are dispersed into a solution composed of polymer dispersants and solvents at a high speed according to a predetermined ratio. The dispersion speed is 400-3000rpm, and the dispersion time is 2-120min. Composite nano powder paste. 9.按照权利要求8所述的高效环保抗菌防霉无机复合纳米粉浆的制备方法,其特征在于:分散速度优选为500~2500rpm,分散时间优选为5~60min,混合物经优选球磨时间为40min~15h,形成高度分散的无机复合纳米粉浆。9. According to the preparation method of the high-efficiency, environment-friendly, antibacterial and mildew-proof inorganic composite nano powder slurry according to claim 8, it is characterized in that: the dispersion speed is preferably 500~2500rpm, the dispersion time is preferably 5~60min, and the mixture is preferably ball milled for 40min ~15h, a highly dispersed inorganic composite nano-powder slurry is formed. 10.按照权利要求8所述高效环保抗菌防霉无机复合纳米粉浆的制备方法,其特征在于:所述混合物的球磨方式为行星式、滚筒式或振动式球磨方法。10. The method for preparing the high-efficiency, environment-friendly, antibacterial, mildew-proof and inorganic composite nano-powder slurry according to claim 8, characterized in that: the ball milling method of the mixture is a planetary, roller or vibratory ball milling method.
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