CN1426683A - High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method - Google Patents
High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method Download PDFInfo
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- CN1426683A CN1426683A CN01144357A CN01144357A CN1426683A CN 1426683 A CN1426683 A CN 1426683A CN 01144357 A CN01144357 A CN 01144357A CN 01144357 A CN01144357 A CN 01144357A CN 1426683 A CN1426683 A CN 1426683A
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Abstract
A high-temp. resistant non-allochronic inorganic antibacterial mildew inhibitor is prepared from Ag or Ag-Zn mixture as active component and hydroxy apatite or calcium oxide-calcium phosphate mixture as carrier through mixing disperser, diluent and calcium solution, mixing with phosphorus solution, refluxing, adding Zn, filtering, washing, baking or pulping, infiltrating Ag, filtering, washing, baking, high-temp. treating and airflow pulverizing. Its advantages are broad spectrum, high effect and high speed.
Description
Technical field
The present invention designs a kind of high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent and preparation method thereof.
Background technology
Along with the raising of people's living standard, human beings'health consciousness strengthens day by day, thereby clothing, food, lodging and transportion--basic necessities of life, daily electrical home appliance and living environment have been proposed lasting aseptic requirement.Organic antibacterial agent easily decomposes, and can not stand high temperature, can cause secondary pollution to environment again, and antibiotic persistence is poor, and antibacterial range is narrow.For this reason, inorganic antiseptic is developed.But general inorganic antiseptic also has shortcoming: 1. the speed of kill bacteria is slower, and 100% sterilization needs 24 hours; 2. the variable color tendency is arranged, and is the inorganic antiseptic of active component with silver, owing to silver-colored reaction sensibility to light can make the product variable color; 3. price is higher, and general price is 10000～25000 yen/kilogram, closes RMB 720-1800 unit/kilogram.
Summary of the invention
The objective of the invention is to realize a kind of high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent.This inorganic antimicrobial mildew preventive agent is that the mixture with hydroxyapatite and its small amounts calcium that decomposites is a carrier, is the inorganic antimicrobial mildew preventive agent of active component with silver or silver-colored zinc.This antibacterial mildew inhibitor can remedy the shortcoming of general inorganic antiseptic, and have high temperature resistant, fastness, wide spectrum, lastingly, advantage fast and efficiently.This antibacterial agent low price, grain diameter is little, and this helps its interpolation and application in plastics, fiber, glass, coating, pottery, building materials, metal etc. very much.
Another object of the present invention is to realize the preparation method of this high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent.
For achieving the above object, the present invention takes following technical scheme: this high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent is to be active component with silver or to be active component with silver-colored zinc mixture, and this antibacterial mildew inhibitor be with the hydroxyapatite be carrier or with hydroxyapatite and its decomposite calcium oxide or the mixture of calcium phosphate be carrier.
At high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent of the present invention is that nanoscale is to micron-sized powder particle
Preparation of the present invention is that the method for the high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent of active component may further comprise the steps with silver:
(1) be that the calcium solution of 0.01M-20M mixes with dispersant dilution and calcium concentration, adjust pH is 7-14, and the content of dispersant is controlled to be 0.1 weight %-30 weight % to account for the calcium ion mass percent;
(2) add in above-mentioned solution and contain the phosphorus solution that phosphorus concentration is 0.01M-20M, 20-100 ℃ of mixing, and to keep the pH value be 7-14, and wherein calcium phosphorus mole ratio is 1-8 in the solution: 1;
(3) above-mentioned solution is refluxed, return time is 0.5h-24h;
(4) above-mentioned solution is carried out suction filtration and cleaning;
(5) above-mentioned solid particle is dried, or size mixing;
(6) to oven dry or the solid particle after sizing mixing ooze silver, wherein the addition of silver ion is 0.01 weight %-40 weight % to account for the calcium ion mass percent, it is 0.001M-10M that silver ion adds concentration, the reaction time that adds silver ion is 0.5h-36h;
(7) solution that oozes behind the silver is carried out suction filtration and cleaning;
(8) above-mentioned solid particle is dried;
(9) solid particle after the oven dry being carried out temperature is 600-1500 ℃ high temperature treatment, and the time is 0.5h-24h;
(10) solid particle after the high temperature treatment is carried out comminution by gas stream, promptly make high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent.
Made antibacterial mildew inhibitor is active component with silver in the said method.The method that preparation is the antibacterial mildew inhibitor of active component with silver-colored zinc mixture is on the said method basis, between above-mentioned steps (3) and (4), be added with following step: in above-mentioned solution, add zinc ion, the addition of zinc ion is to account for the calcium ion mass percent, be 0.01 weight %-60 weight %, the reaction that adds zinc ion keeps the pH value to be 7-14, reaction temperature is 10-200 ℃, and the reaction time is 0.5h-36h.
In the method for the invention, used calcium solution is meant the solution by calcium salt or slaked lime or calcium oxide preparation; Calcium salt is meant the nitrate of calcium, or sulphate, or phosphate, or carbonate, or silicate, or acetate, or perchlorate, or halide.
In the method for the invention, used phosphorus solution is meant the solution that the various oxides of phosphate or phosphoric acid or phosphorus are prepared; Phosphate is meant a kind of phosphate in following argent, zinc, copper, calcium, iron, sodium, potassium, magnesium, lead and the manganese, or hydrophosphate, or dihydric phosphate, or the phosphate of phosphite and ammonium, or hydrophosphate, or dihydric phosphate, or phosphite.
In the method for the present invention's antibacterial mildew inhibitor that to prepare silver-colored zinc mixture be active component, used zinc ion is meant from zinc salt, or zinc hydroxide, or the zinc ion of zinc oxide; Zinc salt is meant the nitrate of zinc, or sulphate, or phosphate, or carbonate, or silicate, or acetate, or perchlorate, or halide, or sulphide.
In the method for the invention, used silver ion is meant from silver salt, or silver hydroxide, or the silver ion of silver oxide; Silver salt is meant the nitrate of silver, or sulphate, or phosphate, or carbonate, or silicate, or acetate, or perchlorate, or halide, or sulphide.
The advantage of high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent of the present invention is:
1, has heat-resisting quantity
The active component of antibacterial agent (metallic elements such as silver, zinc, copper) is resistant to elevated temperatures, so heat resisting temperature depends primarily on bearer type.The carrier series of calcium phosphate hydroxyapatite of this antibacterial agent can stand 1500 ℃ high temperature.High-temperature stable processing in the production technology of antibacterial mildew inhibitor has guaranteed the high-temperature stability of antibacterial agent again.
2. has good anti-discoloration
The nontoxic active component of inorganic antiseptic has only silver, copper, three kinds of metallic elements of zinc to select.And the antibiotic vigor of silver is the manyfold of copper, is 100 times of zinc.But silver is subject to sulfuration or oxidation and variable color.In the hydroxyapatite dot matrix, there is the tunnel, just in time hold silver ion, make it stable to light.This antibacterial agent is heated to 1500 ℃ from room temperature, or is placed on for a long time in the air, and visual do not have a change in color, illustrates that this antibacterial agent has good anti-tarnishing ability.
3. antibiotic persistence
One of antibiotic mechanism of silver ion: Ag+ can attract sulfydryl, the amino of zymoprotein in the bacterium body consumingly, makes enzyme deactivation, thus kill bacteria.After thalline death, it is separated from thalline again, combines again with the bacterium mould on its next door, and it is killed.Go round and begin again the sterilization that same Ag+ can be lasting.Hydroxyapatite is water-soluble hardly, and the low 0.01mg/L magnitude that reaches of the concentration of silver ions that discharges in water is 1 * 10
-6%.The silver ion of this concentration both can have been killed the microorganism of wide spectrum, satisfied the sanitary standard of drinking-water again.And silver ion accounts for 2% in the antibacterial agent, is 2 * 10 of the concentration of silver ions that discharges of hydroxyapatite
6Doubly
The antibiotic persistence of the silver in the antibacterial mildew inhibitor of the present invention adds the low rate of release of carrier hydroxyapatite to silver, makes that antibacterial mildew inhibitor of the present invention has lasting characteristic.
4 high antimicrobial efficiency
The hydroxyapatite that under condition of the present invention, prepares, in phase transition process, will decomposite small amounts calcium, these calcium oxide can discharge the active ion that is solid-solubilized in wherein more rapidly, thereby accelerate the sterilization speed of inorganic antimicrobial mildew preventive agent of the present invention in the starting stage.Adopt the working condition of antibacterial mildew inhibitor of the present invention can make nanometer, will improve its antimicrobial efficiency greatly to submicron order antibacterial agent powder (see figure 1).
Description of drawings
Fig. 1 is the powder diameter photograph (SEM) of inorganic antimicrobial mildew preventive agent of the present invention
Fig. 2 is present embodiment 1 technological process of production figure
Fig. 3 is present embodiment 2 technological process of production figure
Embodiment
Embodiment 1
As shown in Figure 2, get dispersant 0.26 gram, be diluted to 25 milliliters; Get calcium chloride 53.1 grams, be diluted to 380 milliliters; The dilution of dispersant dilution and calcium chloride is mixed, keep pH in the scope of 7-14.Get phosphoric acid 24 grams, be diluted to 90 milliliters, be added in the aforementioned mixed solution, stir, keep pH=7-14, form slurry solution.Above-mentioned reaction slurry liquid solution is heated to fluidized state, refluxed 0.5 hour; Zinc nitrate 1.45 grams dilute 25 milliliters.Zinc nitrate solution is added in the slurry solution, stirred 0.5 hour.To above-mentioned slurry solution suction filtration, and clean.Filter cake behind the suction filtration is sized mixing, transfer to 200 milliliters.Get silver nitrate 0.6 gram, rare to 25 milliliters, add in the slurry and ooze silver, fully stirred 0.5 hour.To ooze the slurry suction filtration behind the silver, and clean, the filter cake oven dry that suction filtration is obtained.Powder was inserted in 1300 ℃ of high temperature furnaces high temperature treatment after 0.5 hour, take out.Powder after the high temperature treatment is carried out comminution by gas stream, obtain high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent finished product.
Embodiment 2
As shown in Figure 3, get dispersant 0.13 gram, be diluted to 25 milliliters; Get slaked lime 40 grams, add 350 ml deionized water; Dispersant dilution and lime water are mixed.Get phosphoric acid 24 grams, be diluted to 100 milliliters, be added to aforementioned mixed solution, stir, keep pH=7-14, form slurry solution.Above-mentioned reaction slurry liquid solution is heated to fluidized state, refluxed 20 hours; To above-mentioned slurry solution suction filtration, and clean.With the oven dry of the filter cake behind the suction filtration, add deionized water after the preliminary pulverizing of the solid after will drying again and make slurry for 200 milliliters.Get silver nitrate 0.6 gram, rare to 25 milliliters, add in the slurry and ooze silver, fully stirred 0.5 hour.To ooze the slurry suction filtration behind the silver, and clean, the filter cake oven dry that suction filtration is obtained.Powder was inserted in 800 ℃ of high temperature furnaces high temperature treatment after 0.5 hour, take out.Powder after the high temperature treatment is carried out comminution by gas stream, obtain high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent finished product.
High temperature resistant colour fastness inorganic antimicrobial mildew preventive agent of the present invention is carried out anti-microbial property detect, its testing result is as follows.Antibacterial mildew inhibitor of the present invention is hereinafter to be referred as antibacterial agent.Here show two kinds of model antibacterial agents: active component has only argent, is numbered LA certainly; Active component is argent and metallic zinc, is numbered LM certainly.
1, detects bacterial classification
The bacterium that anti-microbial property detects has following three kinds: (1) pseudomonad (Pseudomonasaeruginsa), (2) Escherichia coli (Escherichia Coli), (3) staphylococcus aureus (Staphylococcus aureus).These three kinds of bacteriums are the close representative bacteriums of hygiene co-relation.
2, assay method
Above three kinds of bacterium are made bacteria suspension (cell age 24 hours) respectively.Bacteria suspension concentration: pseudomonad is 3.3 * 10
6/ cc, Escherichia coli are 3.0 * 10
6/ cc, staphylococcus aureus is 2.8 * 10
6/ cc.In bacteria suspension, add the variable concentrations antibacterial agent, after placing 4 hours and 24 hours under 30 ± 1 ℃ of constant temperature, carry out the nutrient agar plate count, and calculate sterilizing rate according to survival bacterium amount with dilution method.
3, result of the test
Antibacterial agent shows that with result's (table 1) of 4 hours of test organisms contact antibacterial agent all has obvious bactericidal action to these several bacteriums, and especially the LM sterilizing rate all reaches more than 97%.In order to measure the sterilizing rate of longer time of contact, carried out medicament with 24 hours bactericidal assay of bacterium contact, the results are shown in Table 2, from this result, prolong time of contact, the antibacterial agent sterilizing rate improves greatly, and LA is to reaching 99.99～100% sterilizing rates under Escherichia coli, staphylococcus aureus 0.5% concentration.The sterilizing rate of LM all reaches 100%.
Table 1 antibacterial agent keeps in touch after 4 hours pseudomonad, Escherichia coli and staphylococcic killing
Effect
| The antibacterial agent model | The antibacterial agent type | Antibacterial agent concentration (ppm) | Antibiotic rate (%) | ||
| Pseudomonad | Escherichia coli | Staphylococcus aureus | |||
| ????LA | Hydroxyapatite+argent | ????10000 | ????99.99 | ????96.94 | ????93.93 |
| ????LM | Hydroxyapatite+argent, zinc | ????1000 | ????97.82 | ????99.90 | ????99.78 |
| Hydroxyapatite+argent, zinc | ????5000 | ????99.99 | ????99.99 | ????99.99 | |
| Hydroxyapatite+argent, zinc | ????10000 | ????100 | ????100 | ????100 | |
| No medicine contrast | ????0 | ????0 | ????0 | ????0 | |
Table 2 medicament keeps in touch after 24 hours Escherichia coli, staphylococcic killing action
| The antibacterial agent model | The antibacterial agent type | Antibacterial agent concentration (ppm) | Antibiotic rate (%) | |
| Escherichia coli | Staphylococcus aureus | |||
| ????LA | Hydroxyapatite+argent | ????1000 | ????86.70 | ????99.50 |
| ????LM | Hydroxyapatite+argent, zinc | ????1000 | ????100 | ????100 |
| Hydroxyapatite+argent, zinc | ????5000 | ????100 | ????100 | |
| Hydroxyapatite+argent, zinc | ????10000 | ????100 | ????100 | |
| No medicine contrast | ????0 | ????0 | ????0 | |
4, test result
To the close pseudomonad of hygiene co-relation, Escherichia coli, staphylococcus, LA, LM have the obvious sterilization effect in 0.5% above concentration, and be especially more remarkable after reaching 24 hours time of contact.Therefore, no matter be that LA or LM bactericide can both reach 99.99～100% sterilizing rate through contact in 24 hours.
Claims (8)
1, a kind of high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent, this antibacterial agent is to be active component with silver or to be active component with silver-colored zinc mixture, it is characterized in that be all be with the hydroxyapatite carrier or with hydroxyapatite and its decomposite calcium oxide or the mixture of calcium phosphate be carrier.
2, high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent according to claim 1 is characterized in that: described antibacterial mildew inhibitor is that nanoscale is to micron-sized powder particle.
3, a kind of preparation claim 1 or 2 described high temperature resistant colour fastness inorganic antimicrobial mildew preventive agents and preparation method thereof, it is characterized in that: this method comprises the steps:
(1) be that the solution of 0.01M-20M mixes with dispersant dilution and calcium concentration, adjust pH is 7-14, and the content of dispersant is controlled to be 0.1 weight %-30 weight % to account for calcium ion mass percent ratio;
(2) adding phosphorus concentration in above-mentioned solution is the solution of 0.01M-20M, and 20-100 ℃ of mixing, and to keep the pH value be 7-14, and wherein calcium phosphorus mole ratio is 1-8 in the solution: 1;
(3) above-mentioned solution is refluxed, return time is 0.5h-24h;
(4) above-mentioned solution is carried out suction filtration and cleaning;
(5) above-mentioned solid particle is dried, or size mixing;
(6) to oven dry or the solid particle after sizing mixing ooze silver, wherein the addition of silver ion is 0.01 weight %-40 weight % to account for the calcium ion mass percent, it is 0.001M-10M that silver ion adds concentration, the reaction time that adds silver ion is 0.5h-36h;
(7) solution that oozes behind the silver is carried out suction filtration and cleaning;
(8) above-mentioned solid particle is dried;
(9) solid particle after the oven dry being carried out temperature is 600-1500 ℃ high temperature treatment, and the time is 0.5h-24h;
(10) solid particle after the high temperature treatment is carried out comminution by gas stream, promptly make high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent.
4, high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent preparation method according to claim 3, it is characterized in that: following step is arranged: in above-mentioned solution, add zinc ion between above-mentioned steps (3) and (4), the addition of zinc ion is to account for the calcium ion mass percent, be 0.01 weight %-60 weight %, the reaction that adds zinc ion keeps the pH value to be 7-14, reaction temperature is 10-200 ℃, and the reaction time is 0.5h-36h.
5, according to claim 3 or 4 described high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent preparation methods, it is characterized in that: used calcium solution is meant the solution by calcium salt or slaked lime or calcium oxide preparation; Calcium salt is meant the nitrate of calcium, or sulphate, or phosphate, or carbonate, or silicate, or acetate, or perchlorate, or halide.
6, according to claim 3 or 4 described high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent preparation methods, it is characterized in that: used phosphorus solution is meant the solution of the various oxide preparations of phosphate or phosphoric acid or phosphorus; Phosphate is meant a kind of phosphate in following argent, zinc, copper, calcium, iron, sodium, potassium, magnesium, lead and the manganese, or hydrophosphate, or dihydric phosphate, or the phosphate of phosphite and ammonium, or hydrophosphate, or dihydric phosphate, or phosphite.
7, according to claim 3 or 4 described high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent preparation methods, it is characterized in that: used zinc ion is meant from zinc salt, or zinc hydroxide, or the zinc ion of zinc oxide; Zinc salt is meant the nitrate of zinc, or sulphate, or phosphate, or carbonate, or silicate, or acetate, or perchlorate, or halide, or sulphide.
8, according to claim 3 or 4 described high temperature resistant colour fastness inorganic antimicrobial mildew preventive agent preparation methods, it is characterized in that: used silver ion is meant from silver salt, or silver hydroxide, or the silver ion of silver oxide; Silver salt is meant the nitrate of silver, or sulphate, or phosphate, or carbonate, or silicate, or acetate, or perchlorate, or halide, or sulphide.
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| CNB01144357XA CN1230078C (en) | 2001-12-17 | 2001-12-17 | High temp. resistant, colour fastness inorganic antimicrobial mildew preventive agent and its preparing method |
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| CN1230078C CN1230078C (en) | 2005-12-07 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450365C (en) * | 2004-06-23 | 2009-01-14 | 北京圣鑫泽房地产经纪有限公司 | Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions |
| CN101327340B (en) * | 2008-07-11 | 2012-09-05 | 西安交通大学 | Method for preparing bacterial inhibition-resistance petal-shaped or sheet-shaped Ag/Cu/HAP nano compound powder |
| CN101677530B (en) * | 2007-04-04 | 2014-03-26 | 佩伦转化股份公司 | Antimicrobial material |
| CN109896754A (en) * | 2019-03-21 | 2019-06-18 | 南京汉旗新材料股份有限公司 | A kind of glass fungus-proof liquid |
| CN114680107A (en) * | 2022-03-24 | 2022-07-01 | 成都天佑晶创科技有限公司 | Slow-release antibacterial agent and preparation method and application thereof |
-
2001
- 2001-12-17 CN CNB01144357XA patent/CN1230078C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100450365C (en) * | 2004-06-23 | 2009-01-14 | 北京圣鑫泽房地产经纪有限公司 | Hydroxyl apatite inorganic antibacterial agent containing silver and zinc ions |
| CN101677530B (en) * | 2007-04-04 | 2014-03-26 | 佩伦转化股份公司 | Antimicrobial material |
| CN101327340B (en) * | 2008-07-11 | 2012-09-05 | 西安交通大学 | Method for preparing bacterial inhibition-resistance petal-shaped or sheet-shaped Ag/Cu/HAP nano compound powder |
| CN109896754A (en) * | 2019-03-21 | 2019-06-18 | 南京汉旗新材料股份有限公司 | A kind of glass fungus-proof liquid |
| CN109896754B (en) * | 2019-03-21 | 2021-07-27 | 南京汉旗新材料股份有限公司 | Glass mildew-proof liquid |
| CN114680107A (en) * | 2022-03-24 | 2022-07-01 | 成都天佑晶创科技有限公司 | Slow-release antibacterial agent and preparation method and application thereof |
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| CN1230078C (en) | 2005-12-07 |
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Effective date of registration: 20190625 Address after: 101407 No. 11 Xingke East Street, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Research Institute of engineering and Technology Co., Ltd. Address before: 100088, 2, Xinjie street, Beijing Patentee before: General Research Institute for Nonferrous Metals |
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