CN1313005C - Inorganic antiseptic of RE activated silver carrying matter and its prepn - Google Patents
Inorganic antiseptic of RE activated silver carrying matter and its prepn Download PDFInfo
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- CN1313005C CN1313005C CNB2005100295954A CN200510029595A CN1313005C CN 1313005 C CN1313005 C CN 1313005C CN B2005100295954 A CNB2005100295954 A CN B2005100295954A CN 200510029595 A CN200510029595 A CN 200510029595A CN 1313005 C CN1313005 C CN 1313005C
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- antibiotic
- antibacterial agent
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Abstract
The present invention relates to a rare earth activated silver carrier series inorganic antibacterial agent and a preparation method thereof, and belongs to the technical field of inorganic chemical antibacterial agent purification materials. The present invention takes composite phosphate as the carrier of the silver series inorganic antibacterial agent, utilizes porous carriers to simultaneously carry several kinds of antibacterial ion, such as silver ion, zinc ion and copper ion, and utilizes the activation characteristics of rare earth elements to improve antibacterial performance and discoloration resistance. The rare earth elements adopt the elements of lanthanum, yttrium, etc. The antibacterial agent of the present invention has high antibacterial ability and high ultraviolet radiation resistance, and is not easy to be discolored and blackened. The antibacterial agent can be added in various plastics, paint and ceramic building materials, is made into antibacterial products, is suitable for various household articles and house decorative materials, and has actual effect.
Description
Technical field
The present invention relates to a kind of Rare Earth Activated Silver Group Inorganic Anti-bacterial Agent And Its Preparation Method of Year, belong to inorganic chemistry antibacterial agent scavenging material technical field.
Background technology
Numerous metal ions all have anti-microbial property as silver ion, copper ion, zinc ion etc.For example silver ion exists with the form of liquor argenti nitratis ophthalmicus, is widely used as disinfectant and antibacterial agent, but uses with solution state, and inconvenience, purposes are also limited.Existing at present a lot of relevant anti-biotic materials and preparation technology's report.As the method for making of antibacterial zeolite, the preparation of silver zinc combined antimicrobial agent, the preparation of compound silver series inorganic germifuge etc.
Original inorganic antiseptic many with zeolite, calcium phosphate, glass etc. natural or synthetic have stratiform or cancellated inorganic material is a carrier, be that antibiotic effective ingredient is made with metal ions such as silver, copper, zinc.In addition, also the someone adopts Al
2O
3, CaO, SiO
2, TiO
2Deng oxide is carrier, is antimicrobial component with metal ions such as Ag, Cu, Zn, has also prepared to have the inorganic antiseptic of antibacterial characteristics preferably.The method that antibiotic ion load is held on the carrier has physical adsorption, ion exchange etc.As utilize physisorphtion that antibiotic ion load is held in above active carbon, activated alumina, silica gel or the alumino-silicate etc. and obtain inorganic antibacterial material.But because of using the excessively stripping easily of the antibacterial metal of physisorphtion on these carriers, so can not keep antibiotic property muchly.Develop ion-exchange for this reason, utilized ion-exchange that the antibacterial metal load is held on the carrier.As specially permit etc. No. 3448530, in the hydroxyapatite that has proposed to utilize ion-exchange the antibacterial metal ions load to be held in synthetic and make inorganic antiseptic.And for example the spy opens 2003-193540 and discloses and utilize ion-exchange that antibacterial metal ions load is held in alumina silicate based compound, titanium dioxide based compound, phosphate compounds or the silica based compound and obtain anti-biotic material.
The antibacterial agent of these kind Ag-bearing ions exists two very big shortcomings to be: one, and precious metals silver becomes branch to cause the production cost of antibacterial agent too high as antibiotic property, thereby influences its interior promoting the use of on a large scale; Its two, the carrying silver antimicrobials weather resistance is poor; Silver ion chemistry character is more active, and is relatively more responsive to light and heat, particularly antibacterial agent easily blackening after ultraviolet irradiation, thereby the outward appearance of influence white or light combinations; Under ultraviolet irradiation, meta-alkalescence or heating condition, its antibacterial product is as easy variable color blackout such as various plastic products, coating, ceramic, antibiotic building materials.
At the silver base inorganic antibacterial agent poor stability, some scheme proposes to add various stabilizing agents in antibacterial product, perhaps antibacterial agent is carried out surface modification, to improve its stability and weather resistance.About surface modification, the someone proposes a kind of packaging antibacterial agent powder, and it is made up of carrier core and three layers of clad, and promptly it is a carrier core with titanium dioxide, zinc oxide, calcium sulphate, kaolin, zeolite or tripoli; From interior ground floor outward is Ag, Cu, Zn anti-biotic material layer, and the second layer is the shielding slowly-releasing key-course of silicate, alumino-silicate, borosilicate, and the 3rd layer of outermost layer is the surface reforming layer of increase with the base material compatibility.This packaging antimicrobial powder also can only improve the discoloration-resistant of antibacterial agent to a certain extent.
Prepare the production cost of antibacterial agent for reducing with silver ion as antibiotic ion, many pertinent literatures have proposed other metal antibacterial ions that mix, as zinc, copper etc.Zinc has allergy as antibiotic ion pair skin, and its antibacterial ability is less, needs its certain consumption of control.Copper is as the antibiotic ion that mixes, and copper ion itself has certain color first, and its addition also should be subjected to certain restriction.
By retrieval, the Chinese patent CN1586202A loose structure that discloses a kind of clad supports the composite inorganic antibacterial agent of antimicrobial silver ion; CN1256868A and CN1286915A have put down in writing a year silver-colored serial composite inorganic antibacterial agent; Also have " high-temp inorganic antibacterial agent " of CN1404732A " inorganic antiseptic and production technology thereof ", CN1123291C, " long quick inorganic antiseptic and preparation and the application " of CN1240578A; The cost that these disclosed patents all relate to silver base inorganic antibacterial agent reduces and anti-variable color improvement, but the inorganic antiseptic that these methods are prepared still can not solve the discoloration problem of silver antibacterial agent well.After being applied to these antibacterial agents in plastics, fiber, pottery, the coating, still there is the variable color of different depths through the irradiation of ultraviolet light.
Summary of the invention
The object of the present invention is to provide a kind of compound inorganic antiseptic of RE activated silver carrying matter; The rare earth element that will have the activity of activating is added in the silver-based inorganic antibacterial agent to improve and to improve the performance of silver-based inorganic antibacterial agent.
The lanthanide series of rare earth element has the photoactivation activity.Luminous energy matchmaker series rare earth element, because its outer field valence band exists, when the illumination that contains purple moving-wire is mapped to this photocatalyst series antibacterial agent, produce electronics (e-) and hole (h+), the electronics part of generation is jumped and is made other metals with oxidability form anion; Another part is captured by the outer valence band of rare earth element then morely, so just can produce more hole.Meanwhile, the rare earth element valence band portions of electronics of capturing is also very easily had the metallic atom of oxidability to lose and is formed anionic metal.Above-mentioned metal cation specifically is exactly the Ag-ion among the present invention.Because this activation effect, it can strengthen the anti-microbial property of silver-series antibacterial agent effectively, and can suppress the variable color of silver-based inorganic antibacterial agent.
A kind of inorganic antiseptic of RE activated silver carrying matter of the present invention is characterized in that the chemical composition of this antibacterial agent and weight percent content thereof are:
(1) antibiotic ionic compound is as Ag
+, Zn
2+, Cu
2+Nitrate or sulphate or nitride, adopt Ag
+, Zn
2+, Cu
2+In one or more antibiotic ion, its content is 5-10%, is preferably 6-8%; If adopt silver and the compound antibiotic ion of zinc, then its proportioning is: Ag
+: Zn
2+=1: (2～3);
(2) rare-earth activated element compound, as lanthanum nitrate, yttrium nitrate, its content is 0.5-3.0%, is preferably 1.0-1.5%;
(3) carrier hydroxyl sodium zirconium phosphate, its weight that contains is 86-93%.
The preparation method of a kind of inorganic antiseptic of RE activated silver carrying matter of the present invention is characterized in that having following technical process and step:
A. at first weigh, get antibiotic ionic compound, rare-earth compound and the carrier hydroxyl sodium zirconium phosphate of constant weight by the afore mentioned rules prescription;
B. carrier hydroxyl sodium zirconium phosphate is added water and in the microcosmic mixing reactor, evenly be dispersed into slurries; Add acid or aqueous slkali, regulate pH value to 3～7 of carrier pulp;
C. antibiotic ionic compound is mixed with the aqueous solution, under 50～80 ℃ of bath temperatures, agitator constantly stirs down, and antibiotic deionized water solution is joined in the above-mentioned carrier hydroxyl sodium zirconium phosphate slurries, and antibiotic ion exchange is adsorbed onto on the carrier;
D. rare earth compound lanthanum nitrate or yttrium nitrate are mixed with the aqueous solution with deionized water, under agitator stirs, splash into while stirring in the above-mentioned carrier pulp; Operating temperature remains on 50～80 ℃, keeps 4 hours under this ionic reaction temperature;
E. then above-mentioned emulsion is carried out vacuum filtration, spend deionised water subsequently 3 times, the filter cake number calcining under 700～900 ℃ of temperature with gained grinds then, makes inorganic antiseptic.
The present invention adopts the mode of the antibiotic ion of exchange absorption, silver, zinc ion load is held in the carrier hydroxyl sodium zirconium phosphate lattice, and adopts the activated by rare earth elements activity, activates silver, zinc antibiotic property ion.The antibacterial agent that the present invention makes has preferably discoloration-resistant, warm tolerance and antibiotic property preferably; And be spacetabs type long-acting antibiotic agent with antibiotic wide spectrum, antibiotic persistent characteristic.
Embodiment
Now the present invention is described in detail in conjunction with the embodiments in after.
Embodiment 1
The hydroxyl sodium zirconium phosphate 50g for preparing is placed beaker, under electronic stirring, disperseed 2 hours; Take by weighing Zn (NO respectively
3)
22.5g, AgNO
31.0g, and be made into the solution of 10wt% respectively with deionized water.
Regulate the water bath temperature at 60 ℃, the beaker that is placed with carrier hydroxyl sodium zirconium phosphate is positioned in this water bath; Continuing to add liquor argenti nitratis ophthalmicus, zinc nitrate solution successively under the stirring; Add rare nitric acid or NaOH solution subsequently, regulating its pH value is 4.Take by weighing rare-earth compound lanthanum nitrate 0.5g, be made into the solution of 1wt%, it is joined in the above-mentioned emulsion, remain on 60 ℃ of temperature, carried out ion-exchange reactions 4 hours.Then emulsion is carried out vacuum filtration, spend deionised water 3 times, the filter cake that obtains at 800 ℃ of temperature lower calcinations, is ground then, obtain sample 1.
Embodiment 2
The hydroxyl sodium zirconium phosphate 50g for preparing is placed beaker, under electronic stirring, disperseed 2 hours; Take by weighing Cu (NO respectively
3)
21.0g, Zn (NO
3) 3.0g, AgNO
32.0g, and be made into the solution of 10wt% respectively with deionized water.
Regulate the water bath temperature at 70 ℃, the beaker that is placed with carrier hydroxyl sodium zirconium phosphate is positioned in this water bath; Continuing to add liquor argenti nitratis ophthalmicus, copper nitrate solution, zinc nitrate solution successively under the stirring; Add rare nitric acid or NaOH solution subsequently, regulating its pH value is 3.Take by weighing rare-earth compound yttrium nitrate 0.5g, be made into the solution of 1wt%, it is joined in the above-mentioned emulsion, remain on 70 ℃ of temperature, carried out ion-exchange reactions 5 hours.Then emulsion is carried out vacuum filtration, spend deionised water 3 times, the filter cake that obtains at 700 ℃ of temperature lower calcinations, is ground then, obtain sample 2.
Embodiment 3
The hydroxyl sodium zirconium phosphate 50g for preparing is placed beaker, under electronic stirring, disperseed 2 hours; Take by weighing Cu (NO respectively
3)
21.0g, Zn (NO
3) 2.0g, AgNO
32.0g, and be made into the solution of 10wt% respectively with deionized water.
Regulate the water bath temperature at 60 ℃, the beaker that is placed with carrier hydroxyl sodium zirconium phosphate is positioned in this water bath; Continuing to add liquor argenti nitratis ophthalmicus, zinc nitrate solution, copper nitrate solution successively under the stirring; Add rare nitric acid or NaOH solution subsequently, regulating its pH value is 4.Take by weighing rare-earth compound lanthanum nitrate 0.5g, be made into the solution of 1wt%, it is joined in the above-mentioned emulsion, remain on 60 ℃ of temperature, carried out ion-exchange reactions 4 hours.Then emulsion is carried out vacuum filtration, spend deionised water 3 times, the filter cake that obtains at 800 ℃ of temperature lower calcinations, is ground then, obtain sample 3.
Comparative Examples 1
The hydroxyl sodium zirconium phosphate 50g for preparing is placed beaker, under electronic stirring, disperseed 2 hours; Take by weighing Cu (NO respectively
3)
21.0g, Zn (NO
3) 1.0g, AgNO
32.0g, and be made into the solution of 10wt% respectively with deionized water.
Regulate the water bath temperature at 70 ℃, the beaker that is placed with carrier hydroxyl sodium zirconium phosphate is positioned in this water bath; Continuing to add liquor argenti nitratis ophthalmicus, zinc nitrate solution, copper nitrate solution successively under the stirring; Add rare nitric acid or NaOH solution subsequently, regulating its pH value is 3.Remain on 70 ℃ of temperature, electronic stirring was carried out ion-exchange reactions 5 hours.Then emulsion is carried out vacuum filtration, spend deionised water 3 times, the filter cake that obtains at 700 ℃ of temperature lower calcinations, is ground then, make comparative example 1.
The bacteriostasis property evaluation test result that powder sample 1-3 that the foregoing description 1-3 is prepared and comparative example 1 (not adding the silver-colored hydroxyl sodium zirconium phosphate antibacterial agent that carries of rare earth element) are done is shown in following table table 1:
Table 1 sample bacteriostasis property is estimated
| The sample name | Sample 1 | Sample 2 | Sample 3 | Comparative Examples 1 |
| MIC(ppm) | 100 | 150 | 165 | 220 |
MIC (ppm) expression is the minimal inhibitory concentration of product in vain.
Discoloration-resistant performance evaluation test result is as shown in table 2 below under the ultraviolet light that powder sample 1-3 that the foregoing description 1-3 is prepared and comparative example 1 (not adding the silver-colored hydroxyl sodium zirconium phosphate antibacterial agent that carries of rare earth element) are done:
Discoloration-resistant performance evaluation under 300 watts of ultraviolet lamps of table 2
| The sample name | Sample 1 | Sample 2 | Sample 3 | Comparative Examples 1 |
| Anti-variable color elapsed-time standards | 28 hours | 50 hours | 50 hours | 15 hours |
This test is carried out under identical conditions, and uviol lamp is chosen 300W, the uviol lamp that Ya Ming lamps ﹠ lanterns factory in Shanghai makes.
Result of the test shows: rare earth element mix the sterilizing rate that can effectively improve antibacterial agent.The used bacterial classification of antibacterial tests is Escherichia coli.The incorporation of antibiotic ion, calcining heat are all influential to the anti-microbial property of sample.
The ultraviolet resistance that mixes activated by rare earth elements processing back sample is increasing in varying degrees according to performance.The improvement degree of discoloration-resistant performance with mix the different and different of factors such as antibiotic ionic species and quantity, rare earth element kind, preparation and aftertreatment technology.
The prepared antibiotic system of the inventive method can be added in the matrix material, in plastics, coating, pottery, construction material, make antibacterial product, be specially adapted to household articles and house art work, not only has the antibiotic and sterilizing effect, and make white utensil, white decoration not blackening durable in use, have practical effect.
Claims (3)
1. inorganic antiseptic of RE activated silver carrying matter is characterized in that the chemical composition of this antibacterial agent and weight percent content thereof are:
(1) antibiotic ionic compound is for containing Ag
+, Zn
2+, Cu
2+Nitrate or sulphate or nitride; Adopt Ag
+, Zn
2+, Cu
2+In one or more antibiotic ion, its content 5-10%;
(2) rare-earth activated element compound is lanthanum nitrate or yttrium nitrate, and its content is 0.5-3.0%;
(3) carrier hydroxyl sodium zirconium phosphate, its weight that contains is 86-93%;
Each components contents percentage sum of this antibacterial agent is 100%.
2. a kind of inorganic antiseptic of RE activated silver carrying matter according to claim 1, when it is characterized in that adopting the compound antibiotic ion of silver and zinc, then its proportioning is: Ag
+: Zn
2+=1: (2～3).
3. the preparation method of a kind of inorganic antiseptic of RE activated silver carrying matter according to claim 1 is characterized in that having following technical process and step:
A. at first weigh, get antibiotic ionic compound, rare-earth compound and the carrier hydroxyl sodium zirconium phosphate of constant weight by the afore mentioned rules prescription;
B. carrier hydroxyl sodium zirconium phosphate is added water and in the microcosmic mixing reactor, evenly be dispersed into slurries; Add acid or aqueous slkali, regulate pH value to 3～7 of carrier pulp;
C. antibiotic ionic compound is mixed with the aqueous solution, under 50～80 ℃ of bath temperatures, agitator constantly stirs down, and antibiotic deionized water solution is joined in the above-mentioned carrier hydroxyl sodium zirconium phosphate slurries, and antibiotic ion exchange is adsorbed onto on the carrier;
D. rare earth compound lanthanum nitrate or yttrium nitrate are mixed with the aqueous solution with deionized water, under agitator stirs, splash into while stirring in the above-mentioned carrier pulp; Operating temperature remains on 50～80 ℃, keeps 4 hours under this ionic reaction temperature;
E. then above-mentioned emulsion is carried out vacuum filtration, spend deionised water subsequently 3 times, the filter cake of gained in 700～900 ℃ of temperature lower calcinations, is ground then, make inorganic antiseptic.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100295954A CN1313005C (en) | 2005-09-13 | 2005-09-13 | Inorganic antiseptic of RE activated silver carrying matter and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100295954A CN1313005C (en) | 2005-09-13 | 2005-09-13 | Inorganic antiseptic of RE activated silver carrying matter and its prepn |
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| CN1739356A CN1739356A (en) | 2006-03-01 |
| CN1313005C true CN1313005C (en) | 2007-05-02 |
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ID=36092002
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| CN101543228B (en) * | 2009-04-30 | 2012-01-25 | 广东迪美生物技术有限公司 | Copper-rare earth compound antimicrobial agent and preparation method and application thereof |
| CN103229783B (en) * | 2013-05-16 | 2015-01-07 | 西南大学 | Silver-loaded zirconium phosphonate synergetic antibacterial agent as well as preparation method and application thereof |
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| CN113396902B (en) * | 2021-08-04 | 2021-12-03 | 广东迪美生物技术有限公司 | Silver-rare earth composite antibacterial agent and preparation method thereof |
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| CN115925388B (en) * | 2022-07-28 | 2023-07-25 | 西安理工大学 | Preparation method of long-acting antibacterial domestic ceramic |
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Assignee: Shanghai Huahui Curtain Wall Manufacturing Co., Ltd. Assignor: Shanghai University Contract fulfillment period: 2007.8.1 to 2012.12.31 contract change Contract record no.: 2008310000106 Denomination of invention: Inorganic antiseptic of RE activated silver carrying matter and its prepn Granted publication date: 20070502 License type: Exclusive license Record date: 2008.10.6 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.8.1 TO 2012.12.31; CHANGE OF CONTRACT Name of requester: SHANGHAI HUAHUI WALL MAKING ENGINEERING CO., LTD. Effective date: 20081006 |