CN102763678A - Method for preparing cubic zirconium phosphate silver-carrying antimicrobial powder - Google Patents
Method for preparing cubic zirconium phosphate silver-carrying antimicrobial powder Download PDFInfo
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Abstract
The invention relates to a method for preparing a zirconium phosphate silver-carrying antimicrobial powder, particularly a cubic zirconium phosphate silver containing antimicrobial powder. The cubic zirconium phosphate silver-carrying antimicrobial powder is in the microstructure of a cube, the silver is carried by the cube, and the side of the cube has a length of 400-1,000nm. The method comprises the following steps: preparing a cubic zirconium phosphate carrier, mixing the cubic zirconium phosphate carrier with the aqueous solution of zinc nitrate, stirring to generate a zinc-carrying intermediate; preparing the zinc-carrying intermediate into an aqueous dispersion solution, adding the silver nitrate solution so that the carrier contains 1.5-3.5% of silver ions, stirring, washing, filtering, drying and forging to obtain the final product. The carrier is prepared by adopting the atmospheric-pressure hydrothermal synthesis method, and the hydrofluoric acid used as the template agent in the old process is replaced by the sodium oxalate. The process is simple and convenient to operate, and the equipment has high selectivity. The product and the product producing process are truly safe and nontoxic, the enamel equipment can be used as the production equipment, and the production cost can be saved.
Description
Technical field
The present invention relates to a kind of basic zirconium phosphate carrying silver antimicrobials, especially relate to a kind of preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder.
Background technology
Silver-ion antibiotic comes from Ancient Chinese generation, and is accompanied by human civilization advance and progressively improves and grow up.The existing important component part that improves human lives's quality that become also is countries in the world scientist's a research focus.Silver-based inorganic antibacterial agent be main in the inorganic antibacterial material also be a most important veriety.
Inorganic silver to be antibiotic powder can be divided into from the carrier silicate system (comprise zeolite, hold in the palm vigorous mullite, silica gel glass, bentonite etc.), phosphate-based (comprising basic zirconium phosphate, calcium phosphate etc.), oxide basedly (comprise TiO
2, ZrO
2, Al
2O
3Deng) and other (like activated carbon, carbon fiber, complex compounds etc.).But because the chemical property of silver is active, the easy variable color of silver-series antibacterial agent under the irradiation of ultraviolet light, thus had a strong impact on its application.Silver-series antibacterial agent is easy to change to be because a little less than the adhesion of silver ion and carrier, silver ion is easy to the result of stripping oxidation.Cube sodium zirconium phosphate surface is the porous type structure, and not only specific surface area is big, high adsorption capacity, and chemical stability is good, high temperature resistant, and the antibacterial metal ions that load is held produces good slow releasing function.Can effectively strengthen the adhesion between carrier and the silver ion as carrier, thereby make antibacterial agent have ultraviolet resistance according to, high temperature resistant, advantage such as antimicrbial power is lasting.
Chinese patent CN102239887A discloses the preparation method that a kind of nanoscale basic zirconium phosphate carries silver-colored composite inorganic antimicrobial agent, and it comprises the steps: a, preparation nanometer basic zirconium phosphate carrier: the sodium dihydrogen phosphate reactant aqueous solution that in zirconium oxychloride aqueous solution, adds capacity obtains nanoscale basic zirconium phosphate carrier; B, ultrafiltration: nanometer basic zirconium phosphate carrier is inserted in the ultrafiltration membrane system, to the filtrating during with the no chlorion of silver ion check, the completion ultrafiltration; C, antibacterial metal ions absorption, displacement: the colloidal sol deposition of nanometer basic zirconium phosphate carrier is added the pure water dissolving, then add the antibacterial metal ions aqueous solution, fully absorption, displacement reaction; The preparation of d, inorganic antibiosis powder: suction filtration, the cleaning reaction product, oven dry filter cake, the filter cake after the oven dry are pulverized the back calcining a little, obtain product.This preparation method adopts milipore filter to remove the by-product inorganic salts that produces in the synthesizing zirconium phosphate process, just can directly not be used for absorption, displacement metal ion so that the basic zirconium phosphate carrier need not pass through high-temperature calcination.
Chinese patent CN1600536 discloses a kind of nano lamellar basic zirconium phosphate and carries silver-colored inorganic antibacterial powder and novel preparation method thereof.It is a carrier with the nano lamellar basic zirconium phosphate, and its pH is between 1～2, and less than 50nm, its preparation process is controlled the pattern and size of powder to the major diameter of disk through template and grain growth inhibitor less than 600nm, thickness.The exchange of silver ion is to adopt zinc ion transition method, and this method makes the availability of silver ion bring up to 100%, through excessive slightly zinc ion, at high temperature can form the micronucleus structure of zinc oxide coated with silver ion.That the inorganic antibiosis powder that this method makes has is nontoxic, uniform particles, have excellent weather resistance, characteristics such as processing stability is excellent, antibacterial effect is lasting.Can be widely used in fields such as chemical fibre, plastics, water treatment, back arrangement.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder.
Said cube basic zirconium phosphate Ag-carried antibacterial powder, its powder microstructure is a cubic shaped, and silver loads on the cube, and the cube length of side is 400～1000nm.
The present invention includes following steps:
1) preparation of cube basic zirconium phosphate carrier: with zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate water-soluble in agitated reactor heated and stirred, cube basic zirconium phosphate carrier;
2) step 1) gained cube basic zirconium phosphate carrier is mixed with zinc nitrate aqueous solution, stir the back and generate a year zinc intermediate;
3) will carry the zinc intermediate and be mixed with 6%～10% aqueous dispersions, and add liquor argenti nitratis ophthalmicus, and make that the content of silver ion in carrier will be 1.5%～3.5%, and stir, washing is filtered, drying, and calcination gets end product cube basic zirconium phosphate Ag-carried antibacterial powder.
In step 1), the mol ratio of said zirconium oxychloride, sodium dihydrogen phosphate, sodium oxalate is 1: (1.5～2.1): (0.7～1), the temperature of said heating can be 90 ℃, and the time of heating can be 28h; Wherein zirconium oxychloride and sodium dihydrogen phosphate are reaction raw materials, are the sources of zr element and phosphate radical in the product, and sodium oxalate is a template, is used to control the pattern of carrier; The mol ratio of said zirconium oxychloride, sodium dihydrogen phosphate, sodium oxalate is preferably 1: 1.9: 0.9; In the said cube basic zirconium phosphate carrier by mass percentage moisture content can be 40%～50%.
In step 2) in, said stirring condition can be at 90 ℃ and stirs 2h down; The mass ratio of said cube basic zirconium phosphate carrier and zinc nitrate aqueous solution can be 1: (0.3～0.4), the concentration of said zinc nitrate aqueous solution can be 40%～50%.
In step 3), said stirring condition is to be 60～70 ℃ in temperature to stir 3h down.
The constant pressure hydro-thermal synthetic method is adopted in the preparation of cube basic zirconium phosphate carrier of the present invention, and its technology is simple, and is easy to operate, and choice of equipment property is big.
It is the hydrofluoric acid that template replaces old technology that the present invention selects sodium oxalate for use, prepares the basic zirconium phosphate carrier of cubic shaped, thereby makes product and production process thereof really accomplish safety non-toxic, and on production equipment, can select enamel equipment, saves production cost.
The present invention adopts zinc ion transition overload silver, receives ion with the zinc ion exchange earlier, uses the Ag ion exchange zinc ion again, and the availability that the zinc ion amount improves silver ion of carrying through the control powder makes the availability of silver ion almost reach 100%, practices thrift cost.
Description of drawings
The sem photograph of the cube basic zirconium phosphate Ag-carried antibacterial powder that Fig. 1 makes for the embodiment of the invention.In Fig. 1, scale is 0.2 μ m.
The sem photograph of the cube basic zirconium phosphate Ag-carried antibacterial powder that Fig. 2 makes for the embodiment of the invention.In Fig. 2, scale is 100nm.
Fig. 3 is the weather resisteant trial curve of the prepared serial antibacterial agent of basic zirconium phosphate silver of the embodiment of the invention.In Fig. 3, abscissa be the time (hour), ordinate is aberration (Δ E); Curve a is 1% interpolation, and b is blank.
Embodiment
The preparation method of cube basic zirconium phosphate carrying silver antimicrobials of the present invention, one is divided into following three steps:
Synthesizing of 1 cube basic zirconium phosphate carrier
The color constant pressure hydro-thermal synthetic method of cube basic zirconium phosphate carrier.The raw materials for production of cube basic zirconium phosphate carrier are zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate.Sodium oxalate is as the structure and the pattern of template control carrier.
The 180kg zirconium oxychloride is dissolved in 1 ton of water, and the 100kg sodium dihydrogen phosphate is dissolved in 0.5 ton of water, and the 68kg sodium oxalate is dissolved in 0.5 ton of water; Fully join simultaneously in the same agitated reactor after the dissolving, under the normal pressure, temperature is controlled at 90 ℃; Reaction time obtains cube basic zirconium phosphate slurry after being controlled at 28h.Zirconates molar yield 83.5%.
The 180kg zirconium oxychloride is dissolved in 1 ton of water, and the 114kg sodium dihydrogen phosphate is dissolved in 0.5 ton of water, and the 68kg sodium oxalate is dissolved in 0.5 ton of water; Fully join simultaneously in the same agitated reactor after the dissolving, under the normal pressure, temperature is controlled at 90 ℃; Reaction time obtains cube basic zirconium phosphate slurry after being controlled at 28h.Zirconates molar yield 91.2%.
The 180kg zirconium oxychloride is dissolved in 1 ton of water, and the 128kg sodium dihydrogen phosphate is dissolved in 0.5 ton of water, and the 68kg sodium oxalate is dissolved in 0.5 ton of water; Fully join simultaneously in the same agitated reactor after the dissolving, under the normal pressure, temperature is controlled at 90 ℃; Reaction time obtains cube basic zirconium phosphate slurry after being controlled at 28h.Zirconates molar yield 95.5%.
Embodiment 4
The 180kg zirconium oxychloride is dissolved in 1 ton of water, and the 128kg sodium dihydrogen phosphate is dissolved in 0.5 ton of water, and the 52kg sodium oxalate is dissolved in 0.5 ton of water; Fully join simultaneously in the same agitated reactor after the dissolving, under the normal pressure, temperature is controlled at 90 ℃; Reaction time obtains cube basic zirconium phosphate slurry after being controlled at 28h.Zirconates molar yield 90.0%.
Embodiment 5
The 180kg zirconium oxychloride is dissolved in 1 ton of water, and the 128kg sodium dihydrogen phosphate is dissolved in 0.5 ton of water, and the 60kg sodium oxalate is dissolved in 0.5 ton of water; Fully join simultaneously in the same agitated reactor after the dissolving, under the normal pressure, temperature is controlled at 90 ℃; Reaction time obtains cube basic zirconium phosphate slurry after being controlled at 28h.Zirconates molar yield 94.0%.
Embodiment 6
The 180kg zirconium oxychloride is dissolved in 1 ton of water, and the 128kg sodium dihydrogen phosphate is dissolved in 0.5 ton of water, and the 76kg sodium oxalate is dissolved in 0.5 ton of water; Fully join simultaneously in the same agitated reactor after the dissolving, under the normal pressure, temperature is controlled at 90 ℃; Reaction time obtains cube basic zirconium phosphate slurry after being controlled at 28h.Zirconates molar yield 95.0%.
2, the cube basic zirconium phosphate carries the preparation of zinc
Gained cube basic zirconium phosphate carrier slurry (moisture content 40 ~ 50%) in the step 1 is mixed with zinc nitrate aqueous solution, and 90 ℃ are stirred 2h down, generate and carry the zinc intermediate; The proportioning mass ratio of said cube basic zirconium phosphate carrier slurry and zinc nitrate aqueous solution is 1:0.3 ~ 0.4, and the concentration of said zinc nitrate aqueous solution is 40%～50%.
3, the cube basic zirconium phosphate carries the preparation of silver
The cube basic zirconium phosphate that makes in the step 2 is mixed with 6% ~ 10% aqueous dispersions with deionized water, adds the liquor argenti nitratis ophthalmicus that quantitatively is dissolved in 100kg water, the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 7
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6%～10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 4.7kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 1.5% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 8
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6%～10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 5.6kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 1.5% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 9
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6% ~ 10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 6.2kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 2% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 10
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6% ~ 10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 7.1kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 2.3% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 11
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6% ~ 10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 7.8kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 2.5% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 12
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6%～10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 8.7kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 2.8% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 13
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6%～10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 9.6kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 3.1% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Embodiment 14
The 200kg cube basic zirconium phosphate that makes in the step 2 is mixed with 6%～10% aqueous dispersions with deionized water, adds 100kg liquor argenti nitratis ophthalmicus (wherein containing silver nitrate 10.9kg), the control temperature is 60 ~ 70 ℃; Constant temperature stirs 2h, behind the washing and filtering, and 120 ℃ of oven dry; And the control moisture content is below 8%; 450 ℃ of calcination 6h again after the fragmentation of solid after oven dry hammer powder to be cooledly carry out comminution by gas stream to room temperature, just make that to contain concentration of silver ions be 3.5% the silver-colored antibiotic powder of cube basic zirconium phosphate.
Fig. 1 and 2 provides the sem photograph of the cube basic zirconium phosphate Ag-carried antibacterial powder that the embodiment of the invention makes.
Fig. 3 provides the weather resisteant trial curve of the prepared serial antibacterial agent of basic zirconium phosphate silver of the embodiment of the invention.
Table 1 provides the impact analysis of basic zirconium phosphate carrier silver carrying amount to the antibacterial effect and the anti-tarnishing ability of antibiotic powder.
Table 1
| Silver carrying amount (%) | Staphylococcus aureus (MIC) | Anti-tarnishing ability |
| 1.5 | 266 | By force |
| 1.8 | 180 | By force |
| 2.0 | 120 | By force |
| 2.3 | 112 | By force |
| 2.5 | 106 | By force |
| 2.8 | 103 | Generally |
| 3.1 | 98 | Slightly |
| 3.5 | 96 | A little less than |
Visible by table 1, along with the increase of silver carrying amount, the antibacterial effect of antibiotic powder can rise thereupon; But after surpassing saturation value, antibacterial effect changes little, and anti-tarnishing ability descends to some extent; Explain that excessive silver ion can accumulate in the surface of cube basic zirconium phosphate carrier, variable color easily.
Below provide key technology of the present invention and industrial analysis:
(1) adopt the constant pressure hydro-thermal synthetic method to prepare cube basic zirconium phosphate carrier, technology is simple, and is easy to operate, and choice of equipment property is big.
(2) new preparation technology controls the structure and the pattern of basic zirconium phosphate through template; We select the hydrofluoric acid of sodium oxalate replace old technology for use; Removed of the harm of poisonous ocratation, thereby made product and production process thereof really accomplish safety non-toxic, greening and environmental protection human body and environment; And on production equipment, can select enamel equipment, avoid the corrosion of hydrofluoric acid enamel.
(3) the correct judgement of solubility, temperature, time and reaction end through the control synthetic reaction, the average grain diameter and the D of control antimicrobial powder
50(meso-position radius), D
90(particle size range of 90% particle) thus reduce the bulky grain in the powder.
(4) wash the electrical conductivity≤50 μ s/cm of purifying and the electrical conductivity≤30 μ s/cm of powder washing through control basic zirconium phosphate carrier, thereby effectively control the impurity content and the whiteness of antibiotic powder, improve the antibacterial effect of antimicrobial product.
(5) in the selection of antibiotic ion; New technology has been selected the silver ion of strong antibacterial ability and high security for use, carries the silver technology and adopts zinc ion transition method, receives ion with the zinc ion exchange earlier; Exchange zinc ion with silver ion again; The availability that the zinc ion amount improves silver ion of carrying through the control powder make the availability of silver ion reach 100%, and excessive zinc ion can form the micronucleus structure of zinc oxide coated with silver ion after high-temperature calcination.Reduce the probability that silver ion and raw materials such as plastics, resin, chemical fibre directly contact, thereby improved the anti-tarnishing ability of antibiotic powder.
(6) adopted 700～900 ℃ of antimicrobial powder high-temperature calcinations in the new technology of preparing, time 5～8h can increase heat endurance, photostability and the processing stability of antibiotic powder behind the high-temperature shaping.
Below provide the performance test of the antibiotic powder of cube basic zirconium phosphate:
1. particle diameter and structure
The submicron of cubic shaped structure, the narrow range of size distribution uses quite high safety.
Through laser particle size analyzer the carrier particle diameter being carried out measurement result is: D
50≤1.0um, D
90≤2.0um.Antibiotic powder behind year silver is carried out the particle diameter test result is: D
50≤1.5um, D
90≤2.5um.
2. anti-microbial property test
2.1 the test of minimal inhibitory concentration (MIC)
According to the test of the minimal inhibitory concentration in " disinfection technology standard ", use the distilled water diluting antimicrobial powder, be made into the suspension of variable concentrations, inoculation 0.1ml bacterial concentration is 1.0 * 10 in each suspension of 5ml
8Behind the bacterium liquid of CFU/ml, cultivate 48h down at 36 ℃, the turbidity of the suspension that detects by an unaided eye, the least concentration that the suspension turbidity keeps not increasing is MIC.According to Japanese inorganic antiseptic standard, the powder that MIC is not more than 800 μ g/ml is that anti-microbial property is qualified.And we develop the basic zirconium phosphate antimicrobial powder minimal inhibitory concentration of Escherichia coli, staphylococcus aureus, Candida albicans are respectively 120 (mg/kg), 110 (mg/kg), 130 (mg/kg).
2.2 quantitative test---GB/T21510-2008 powder anti-microbial property test method succusion
Get basic zirconium phosphate and carry aluminium powder 0.5g and put into conical flask, add the phosphate buffer that 95mL contains 0.1% Tween-80 again, behind the mixing, add the prefabricated bacteria suspension of 5.0mL (bacterial concentration about 1.0 * 10 again
5CFU/ml), under 37 ℃ of conditions of operative temperature, with 150r/min speed, test sample need be diluted the material vibration contact 1h-4h that uses the back, and bacterium colony is cultivated again.The basic zirconium phosphate antimicrobial powder that we develop to the antibiotic rate of Escherichia coli, staphylococcus aureus, Candida albicans all greater than 90%.
3. safety in utilization
Various safety testing results are as shown in table 2. from table 2, can find out the high safety in utilization of the basic zirconium phosphate serial antibacterial agent of silver.
Table 2
4. warm tolerance and drug resistance
The serial antibacterial agent of basic zirconium phosphate silver is the pottery property material of highly crystallineization, and physico chemical property are highly stable.Even the serial antibacterial agent of cube basic zirconium phosphate silver also has no volatile matter (comprising water) volatilization when being heated to 1000 ℃, and its antibacterial ability does not have any variation.
5. weather resisteant
The various resins that added the serial antibacterial agent of basic zirconium phosphate silver are owing to deterioration and discoloration test that light and heat causes are as shown in Figure 3.
It is quite high causing the stability of silver ion in the serial antibacterial agent of cube basic zirconium phosphate silver of variable color, so the suffered influence of the basic zirconium phosphate serial antibacterial agent of silver is quite little.
The product surface of the present invention's preparation is cube structure, has very stiff stability, strong antibacterial ability, high-fire resistance, durability and safety.Can be widely used in industries such as plastics, building materials, weaving, medicine, pottery, commodity.
1. textile industry
The antibacterial fabric main technique for back arrangement with before spin dual mode, antibacterial textile adopts afterfinish method, be characterized in showing antibiotic, the short-term good anti-bacterial effect, cost is low.Shortcomings such as but the textile washing fastness of back arrangement is relatively poor, and antibacterial effect is not lasting, and feel is bad.In order to address this problem; Jinda Nanotechnology's independent research in 2008 silver-colored antibiotic odourproof fiber (FreeCooL); Be to process the terylene antibacterial matrices, in spinning, directly add and the anti-bacterial wet-absorbing sweat-repellent fiber processed by spinning level basic zirconium phosphate Ag-carried antibacterial powder.Owing to spin interpolation before belonging to; Made lining has long-lasting antibacterial effect; And washing fastness is good, safety non-toxic, the design of fiber cross profiled-cross-section in addition; Have stronger moisture pick-up properties and lead the sweat performance, be widely used in back boxing, gym suit, towel, socks, underwear pants, interior decoration etc. in the footwear at present.
Inorganic silver is that the terylene antibacterial matrices also can be made into silver-colored antibacterial deodourizing short fiber in addition, is mainly used in antibacterial nonwoven cloth made, antimicrobial socks, antibiotic facing material etc.
2. household electric appliances
The antibiotic family of mandatory enforcement on September 15 electric standard in 2011 means that the household electrical appliances healthy functions of having propagandized hotly over more than 10 year on the market at home will step into " product standard configuration epoch " from " concept hype epoch ".These standards have played landmark effect to standard and the development that promotes the antibacterial functions household electrical appliances.Antibiotic household electrical appliances are become " there are laws to abide by ", antibiotic household electric appliances are played good standardization role, can protect consumer's rights and interests simultaneously effectively.Antibiotic household electrical appliances be unable to do without antibiotic plastic; According to the correlative study address prediction, by 2015, the commercial Application market scale of global antibiotic plastic will reach 1,400,000,000 pounds; The value of the product that is used for the consumer goods is 10.3 hundred million pounds, and the whole world will have antibacterial functions up to 20% plastic products.The cube basic zirconium phosphate Ag-carried antibacterial powder of this explained hereafter can add in the various types of resins, is processed into the antibacterial matrices of all size, processes various antibacterial products, is widely used.
3. anti-bacteria ceramic
To the raising of people's living standard nowadays, the reinforcement of health of people consciousness, environment-friendly materials have become current theme.Sanitary ceramics such as toilet seat, bathtub, porcelain basin and ceramic tile etc. often contact with human body, if above grow germ, will communicate illness, the serious harm health.Therefore, antiseptic sanitary possesses sterilizing function, effectively kill the colibacillus and other noxious bacteria of harmful to human, thereby the protection people's is healthy.Cube Ag-carried antibacterial powder can directly add in the glaze in the pottery, and employing secondary dispersion technology can make anti-bacteria ceramic have the excellent antibiotic performance and not influence the presentation quality of original glaze.Because the temperature of ceramic kiln is very high, the silver ion in the antibiotic powder has part and runs off, and normal antibiotic powder adds ratio and often do not reach national antibiotic standard, shows through a large amount of experiments:
A, along with the rising of kiln temperature, the addition of antibiotic powder in glaze rises thereupon just can reach good antibacterial effect.
B, when kiln temperature is constant, the increase of the addition of antibiotic powder in glaze can make the antibiotic rate of anti-bacteria ceramic rise.
Table 3 provides the influence of 1250 ℃ of antibiotic powder additions to the 24h antibiotic rate.
Table 3
| Antibiotic powder addition (%) in the |
2 | 4 | 6 | 8 | 10 |
| Antibiotic rate (%) | 71.62 | 82.5 | 91.51 | 94.86 | 98.50 |
Can find out by table 3:
(1) addition of antibiotic powder in glaze reaches at 6% o'clock, and the antibiotic rate on anti-bacteria ceramic surface can reach more than 90%, has good antibacterial performance.
(2) the high-temperature calcination meeting makes silver have part to run off for a long time, and anti-microbial property is descended, so in anti-bacteria ceramic is made, add the also corresponding increase of ratio of antimicrobial powder.
4, foaming EVA uses
Characteristics such as the EVA expanded material has light weight, softness is good, electrical insulating property is excellent, heat resistance and resistance to corrosive chemicals are widely used in goods fields such as toy for children, medical equipment backing plate, motion backing plate.Yet these goods in use often receive the pollution of bacterium, mould, to people's live and work environment structure threat.Because the EVA expanded material is temperature higher (molding temperature is 165～175 ℃) in process of production, natural antibacterial agent and organic antibacterial agent all are difficult to satisfy the requirement of processing technology.And the cube basic zirconium phosphate carries aluminium powder and has advantages such as good, the antibiotic lasting timeliness length of heat resistance, safety height, can use in the EVA foaming.
Claims (9)
1. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder is characterized in that,
Said cube basic zirconium phosphate Ag-carried antibacterial powder, its powder microstructure is a cubic shaped, and silver loads on the cube, and the cube length of side is 400～1000nm;
Said preparation method may further comprise the steps:
1) preparation of cube basic zirconium phosphate carrier: with zirconium oxychloride, sodium dihydrogen phosphate and sodium oxalate water-soluble in agitated reactor heated and stirred, cube basic zirconium phosphate carrier;
2) step 1) gained cube basic zirconium phosphate carrier is mixed with zinc nitrate aqueous solution, stir the back and generate a year zinc intermediate;
3) will carry the zinc intermediate and be mixed with 6%～10% aqueous dispersions, and add liquor argenti nitratis ophthalmicus, and make that the content of silver ion in carrier will be 1.5%～3.5%, and stir, washing is filtered, drying, and calcination gets end product cube basic zirconium phosphate Ag-carried antibacterial powder.
2. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 1 is characterized in that,
In step 1), the mol ratio of said zirconium oxychloride, sodium dihydrogen phosphate, sodium oxalate is 1: (1.5～2.1): (0.7～1).
3. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 1 is characterized in that,
In step 1), the temperature of said heating is 90 ℃, and the time of heating is 28h.
4. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 2 is characterized in that,
The mol ratio of said zirconium oxychloride, sodium dihydrogen phosphate, sodium oxalate is 1: 1.9: 0.9.
5. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 1 is characterized in that,
In step 1), in the said cube basic zirconium phosphate carrier by mass percentage moisture content be 40%～50%.
6. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 1 is characterized in that,
In step 2) in, said stirring condition is to stir 2h down at 90 ℃.
7. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 1 is characterized in that,
In step 2) in, the mass ratio of said cube basic zirconium phosphate carrier and zinc nitrate aqueous solution is 1: 0.3～0.4.
8. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 1 is characterized in that,
In step 2) in, the concentration of said zinc nitrate aqueous solution is 40%～50%.
9. the preparation method of cube basic zirconium phosphate Ag-carried antibacterial powder as claimed in claim 1 is characterized in that,
In step 3), said stirring condition is to be 60～70 ℃ in temperature to stir 3h down.
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