CN101176468A - Inorganic complex antimicrobials containing zincium-rare earth as well as preparation method and application thereof - Google Patents
Inorganic complex antimicrobials containing zincium-rare earth as well as preparation method and application thereof Download PDFInfo
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- CN101176468A CN101176468A CNA2007100317492A CN200710031749A CN101176468A CN 101176468 A CN101176468 A CN 101176468A CN A2007100317492 A CNA2007100317492 A CN A2007100317492A CN 200710031749 A CN200710031749 A CN 200710031749A CN 101176468 A CN101176468 A CN 101176468A
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Abstract
The utility model discloses an inorganic composite antimicrobial with zinc - rare earth and a preparation method and applications thereof. The antimicrobial uses natural or chemosynthetic ion exchange material as the carrier, and loads the double active centre of the zinc ions and the rare earth ions by an ion exchange method, wherein, the content of the zinc ions is 6.0 to 8.0wt%, the content of the rare earth ions is 2.0 to 4.0wt%. The antimicrobial exchanges the zinc ions and the rare earth ions into the carrier by means of a liquidoid or a solidoid ion exchange, and then the inorganic composite antimicrobial is prepared after a post treatment. Because having a double antimicrobial active centre of the zinc ions and the rare earth ions which can generate a synergistic effect, the antimicrobial has the advantages of broad antimicrobial spectrum, higher antimicrobial efficiency, good thermal stability and photostability, steady color and low cost; the antimicrobial is an ideal substitute for the silver-loaded inorganic antimicrobial, and can be added in plastic, rubber, fiber, paints, adhesive, paper or ceramic and other material for preparing antimicrobial functional material and products.
Description
Technical field
The invention belongs to the anti-biotic material field, particularly a kind of inorganic complex antimicrobials that contains zincium-rare earth double activity center and its production and application.
Background technology
The high speed development of modern humans social material civilization and science and technology civilization has promoted the rapid development of global economy, but faces more and more severeer environment situation.Environmental pollution and bio-safety problem have become human society and have entered 21 century and seek essence and the strategic problem that sustainable development faces.Because a large amount of uses of chemicalses such as all kinds of antibiotic, disinfectant and bactericide, the incidence of disease of the global infectious disease that once once had been suppressed gos up significantly, and new pathogenic microorganism is found that successively the variation population of known pathogenic microorganism is also more and more.Particularly over past ten years, the global microorganism disaster event that is caused by pathogenic microorganism and mutation thereof takes place again and again, incidents such as " aphthovirus " from the states such as " crazy heifer disease virus ", Korea S and Mongolia of " the O157:H7 Escherichia coli " of " the O139 comma bacillus " of India, Japan, Britain, to also allowing with reverence and awe " dengue fever and the Hemorrhagic fever " incident of people so far, arrive the outburst of epidemic situations such as " atypical pneumonia " and " bird flu " virus and popular again, caused serious casualties and enormous economic loss for respective country or area.
To prevent growth of microorganism effectively, breed, spread and propagate, reduce and reduce the environmental hazard that pathogenic microorganism causes, uses long-acting anti-biotic material be the most simply, safety and effective method.Adopting anti-biotic material is to become passive, large-area environment disinfected for targetedly, initiatively cleaning and the control techniques of sustainable onset, general material or the goods microbial environment in addition of not influencing is the comprehensive utilization of the new and high technology of environmental protection, economy and sustainable development.
The preparation method of most of anti-biotic materials adds antibacterial agent in material.Through taking all factors into consideration the safety of various antibacterial agents, long-lasting and antimicrobial efficiency, silver base inorganic antibacterial agent is the most desirable and most widely used at present antibacterial agent.But have following technical barrier: (1) as active component, cost is too high with silver; (2) discoloration problem can't thoroughly solve, and is therefore selective to the material that is added in application process, limited its range of application; (3) to the weak effect of mould.Therefore, the replacer of searching silver base inorganic antibacterial agent becomes the top priority of current anti-biotic material and goods industry.
Chinese patent application (03127125.1) discloses a kind of Zn molecular sieve anti-biotic material and preparation method thereof that contains.With distilled water is medium, adopts ion-exchange process that the zinc ion in the soluble zinc salt is exchanged to molecular sieve, obtains containing zinc antimicrobial molecule sieve, has that price is low, warm tolerance and light resistance be good, can be added in the various materials such as clothes, decoration, building.But its antibacterial activity also can't satisfy requirement of actual application.
Chinese patent application (200610148306.7) discloses a kind of nanometer bentonite bactericidal materials and its production and application.This material is basic material with the bentonite, becomes the nanoscale bentonite by mechanical agitation, acidification, and load has the rare earth ion (La of antibacterial activity then
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+Deng), the particle diameter of prepared antibacterial agent is 10～100 nanometers, contains rare earth ion 1～30wt% (percentage by weight) and bentonite nano particle 70%～99wt%, can be applicable to fields such as coating.The antibacterial activity that contains the rare earth ion antibacterial agent also can't satisfy requirement of actual application, and rare earth ion itself contains certain color, the too high outward appearance that may influence material and goods of addition.
Summary of the invention
In order to remedy the defective of above-mentioned prior art, primary and foremost purpose of the present invention provides a kind of inorganic complex antimicrobials that contains zinc ion and the two antibacterial activity centers of rare earth ion, because the existence of synergistic effect between two antibacterial activity centers, prepared inorganic complex antimicrobials has warm tolerance and light resistance is good, has a broad antifungal spectrum, antimicrobial efficiency height, colour stable, characteristics that cost is low.
Another object of the present invention is to provide the preparation method of above-mentioned inorganic complex antimicrobials.
A further object of the present invention is to provide the application of above-mentioned inorganic complex antimicrobials in materials such as plastics, rubber, fiber, coating, adhesive, paper, pottery.
Purpose of the present invention realizes by following technical proposals: a kind of inorganic complex antimicrobials that contains zincium-rare earth, be white or light grey powder, and its average grain diameter is less than 5.0 μ m (D
50＜5 μ m, adopt laser particle analyzer to measure), this antibacterial agent is a carrier with the ion exchange material of natural ion exchange material or chemosynthesis, by ion-exchange with zinc ion and rare earth ion exchanged to carrier, zinc ion and rare earth ion are double activity center, the content of zinc ion is 6.0～8.0wt%, and the content of rare earth ion is 2.0～4.0wt%, and described rare earth ion comprises La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+
The present invention adopt earlier liquid phase or solid phase ion-exchange with zinc ion and rare earth ion exchanged to carrier, pass through certain post-processing then, obtain inorganic complex antimicrobials, its processing step and process conditions are as follows:
(1) contains 0.10～0.14mol/l soluble zinc salt and 1.6 * 10 at 100ml
-2～3.2 * 10
-2In the mol/l soluble rare-earth salt mixed aqueous solution, add carrier 10.0g, stirring reaction passes through filtration, washing, drying after 5～7 hours successively in the time of 60～80 ℃;
Perhaps earlier with 1.0 * 10
-2～1.4 * 10
-2Mol soluble zinc salt, 1.6 * 10
-3～3.2 * 10
-3Mol soluble rare-earth salt, carrier 10.0g add in the mortar, and be levigate and mix;
(2) again 400～900 ℃ of roastings 2～4 hours, last ultra-fine grinding to average grain diameter less than 5 microns, to obtain carrying a zinc amount be 6.0～8.0wt%, carry a rare earth content is the inorganic complex antimicrobials that contains zincium-rare earth of 2.0～4.0wt%.
In order to realize the present invention better, preferred zinc nitrate of described soluble zinc salt or zinc acetate etc., the preferred cerous nitrate of described soluble rare-earth salt, cerous acetate, lanthanum nitrate, lanthanum acetate, neodymium nitrate, acetic acid neodymium, samaric nitrate, acetic acid samarium, europium nitrate or acetic acid europium etc.
Described carrier comprises the natural ion exchange material or the ion exchange material of chemosynthesis.
The preferred imvite of described natural ion exchange material, zeolite, rectorite or tourmaline etc.
Ion exchange material preferably phosphoric acid zirconium sodium, lanthanium titanate sodium, titanium phosphate sodium or the hydroxyapatite etc. of described chemosynthesis.
The described application of inorganic complex antimicrobials in materials such as plastics, rubber, fiber, coating, adhesive, paper or pottery that contains zincium-rare earth, this inorganic complex antimicrobials can be added in the materials such as plastics, rubber, fiber, coating, adhesive, paper, pottery and prepare antibiotic functional material.
Because the technical problem that the carrying silver antimicrobials of extensive use now in use exists, purpose of the present invention just provides a kind of substitute of carrying silver antimicrobials.The present invention compares with existing carrying silver antimicrobials, year zinc antibacterial agent or a year rare earth antibacterial agent, except that the good heat resistance with them and long-lasting and tight security, also has following technical advantage:
1, antimicrobial spectrum becomes wide.Because contain the two antibacterial activity centers of zinc ion and rare earth ion, it is wide that its antimicrobial spectrum becomes, and can suppress the microbial growths such as bacterium, mould and spore in the environment effectively.
2, antibacterial activity is higher.Compare with a year zinc antibacterial agent or a year rare earth antibacterial agent, its antibacterial activity increases substantially; Though its antibacterial activity than carrying silver antimicrobials difference, can satisfy requirement of actual application.
3, light fastness is good.Existing carrying silver antimicrobials colour stability is poor, and is easy to change under the irradiation of light; And the colour stability of this antibacterial agent is good, and light fastness is good.
4, cost is low.The cost height of carrying silver antimicrobials; The antibacterial activity that carries zinc antibacterial agent or year rare earth antibacterial agent is poor, need add very high amount in material and just can reach certain antibacterial effect; And can produce synergistic effect between two antibacterial activity centers in this complex antimicrobials, and antibacterial activity is increased substantially, reduced cost.
Embodiment
Below by embodiment the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Contain 0.14mol/l zinc nitrate and 3.2 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add imvite (cation exchange capacity is 100mmol/100g) 10.0g, stirring reaction is after 5 hours in the time of 80 ℃, pass through filtration, washing, drying successively, again 500 ℃ of roastings 3 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 8.0wt%, a year cerium amount are the inorganic complex antimicrobials of 4.0wt%, and result of the test sees Table 1.
Embodiment 2
Contain 0.10mol/l zinc acetate and 1.6 * 10 at 100ml
-2Mol/l cerous acetate [Ce (AC)
3] mixed aqueous solution in, add imvite (cation exchange capacity is 100mmol/100g) 10.0g, stirring reaction is after 7 hours in the time of 60 ℃, pass through filtration, washing, drying successively, again 600 ℃ of roastings 2 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 6.0wt%, a year cerium amount are the inorganic complex antimicrobials of 2.0wt%, and result of the test sees Table 1.
Embodiment 3
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add imvite (cation exchange capacity is 100mmol/100g) 10.0g, stirring reaction is after 6 hours in the time of 70 ℃, pass through filtration, washing, drying successively, again 400 ℃ of roastings 4 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 7.1wt%, a year cerium amount are the inorganic complex antimicrobials of 2.8wt%, and result of the test sees Table 1.
Embodiment 4
Earlier with 1.2 * 10
-2Mol zinc nitrate, 2.4 * 10
-3Mol lanthanum acetate [La (AC)
3], imvite (cation exchange capacity is 100mmol/100g) 10.0g adds in the mortar, and is levigate and mix; Then 500 ℃ of roastings 3 hours; Last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 6.8wt%, a year lanthanum amount are the inorganic complex antimicrobials of 2.5wt%, and result of the test sees Table 1.
Embodiment 5
Contain 0.12mol/l zinc acetate and 2.4 * 10 at 100ml
-2Mol/l lanthanum nitrate [La (NO
3)
3] mixed aqueous solution in, add imvite (cation exchange capacity is 100mmol/100g) 10.0g, stirring reaction is after 5 hours in the time of 70 ℃, pass through filtration, washing, drying successively, again 600 ℃ of roastings 2 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 7.0wt%, a year lanthanum amount are the inorganic complex antimicrobials of 2.9wt%, and result of the test sees Table 1.
Embodiment 6
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l acetic acid neodymium [Nd (AC)
3] mixed aqueous solution in, add imvite (cation exchange capacity is 100mmol/100g) 10.0g, stirring reaction is after 5 hours in the time of 60 ℃, pass through filtration, washing, drying successively, roasting 4 hours under 600 ℃ condition again, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 7.2wt%, a year neodymium amount are the inorganic complex antimicrobials of 2.7wt%, and result of the test sees Table 1.
Embodiment 7
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l samaric nitrate [Sm (NO
3)
3] mixed aqueous solution in, add imvite (cation exchange capacity is 100mmol/100g) 10.0g, stirring reaction is after 7 hours in the time of 60 ℃, pass through filtration, washing, drying successively, roasting 2 hours under 600 ℃ condition again, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 7.3wt%, a year samarium amount are the inorganic complex antimicrobials of 2.5wt%, and result of the test sees Table 1.
Embodiment 8
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l acetic acid europium [Eu (AC)
3] mixed aqueous solution in, add imvite (cation exchange capacity is 100mmol/100g) 10.0g, stirring reaction is after 7 hours in the time of 80 ℃, pass through filtration, washing, drying successively, roasting 2 hours under 400 ℃ condition again, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 7.2wt%, a year europium amount are the inorganic complex antimicrobials of 2.3wt%, and result of the test sees Table 1.
Embodiment 9
Contain 0.12mol/l zinc acetate and 2.4 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add 4A zeolite 10.0g, stirring reaction is after 5 hours in the time of 80 ℃, pass through filtration, washing, drying successively, again 600 ℃ of roastings 4 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 6.9wt%, a year cerium amount are the inorganic complex antimicrobials of 2.6wt%, and result of the test sees Table 1.
Embodiment 10
Contain 0.12mol/l zinc acetate and 2.4 * 10 at 100ml
-2Mol/l lanthanum nitrate [La (NO
3)
3Mixed aqueous solution in, add 4A zeolite 10.0g, stirring reaction is after 7 hours in the time of 60 ℃, pass through filtration, washing, drying successively, again 600 ℃ of roastings 2 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 6.8wt%, a year lanthanum amount are the inorganic complex antimicrobials of 2.8wt%, and result of the test sees Table 1.
Embodiment 11
Earlier with 1.2 * 10
-2Mol zinc nitrate, 2.4 * 10
-2Mol neodymium nitrate [Nd (NO
3)
3], 4A zeolite 10.0g, add in the mortar, levigate and mix; Then 600 ℃ of roastings 4 hours; Last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 6.7wt%, a year neodymium amount are the inorganic complex antimicrobials of 2.5wt%, and result of the test sees Table 1.
Embodiment 12
Contain 0.10mol/l zinc nitrate and 1.6 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add sodium base rectorite 10.0g, stirring reaction is after 5 hours in the time of 80 ℃, pass through filtration, washing, drying successively, again 800 ℃ of roastings 2 hours, last ultra-fine grinding is to the light grey powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 3.1wt%, a year cerium amount are the inorganic complex antimicrobials of 1.2wt%, and result of the test sees Table 1.
Embodiment 13
Contain 0.10mol/l zinc nitrate and 1.6 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add tsilaisite 10.0g, stirring reaction is after 7 hours in the time of 60 ℃, pass through filtration, washing, drying successively, again 800 ℃ of roastings 4 hours, last ultra-fine grinding is to the light grey powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 2.5wt%, a year cerium amount are the inorganic complex antimicrobials of 1.0wt%, and result of the test sees Table 1.
Table 1 is the result of the test of the resulting complex antimicrobials of carrier with natural ion exchange material
| Embodiment | Carrier | The kind of active component and content | Sterilizing rate/% * | Toxicological test | |||
| Escherichia coli/ATCC252 92 | Staphylococcus aureus/ATCC6538 | Acute oral toxicity LD 50(mg/kg) | Mutagenicity | The skin irritatin test | |||
| 1 | Imvite | Zn＝8.0wt％，Ce＝4.0wt％ | 99.9 | 99.9 | ＞5000 | Do not have | Do not have |
| 2 | Imvite | Zn＝6.0wt％，Ce＝2.0wt％ | 97.5 | 96.3 | ＞5000 | Do not have | Do not have |
| 3 | Imvite | Zn＝7.1wt％，Ce＝2.8wt％ | 99.5 | 99.1 | ＞5000 | Do not have | Do not have |
| 4 | Imvite | Zn＝6.8wt％，La＝2.5wt％ | 98.8 | 98.2 | ＞5000 | Do not have | Do not have |
| 5 | Imvite | Zn＝7.0wt％，La＝2.9wt％ | 99.0 | 98.3 | ＞5000 | Do not have | Do not have |
| 6 | Imvite | Zn＝7.2wt％，Nd＝2.7wt％ | 98.5 | 97.8 | ＞5000 | Do not have | Do not have |
| 7 | Imvite | Zn＝7.3wt％，Sm＝2.5wt％ | 99.0 | 98.7 | ＞5000 | Do not have | Do not have |
| 8 | Imvite | Zn＝7.2wt％，Eu＝2.3wt％ | 98.0 | 97.2 | ＞5000 | Do not have | Do not have |
| 9 | The 4A zeolite | Zn＝6.9wt％，Ce＝2.6wt％ | 98.9 | 98.5 | ＞5000 | Do not have | Do not have |
| 10 | The 4A zeolite | Zn＝6.8wt％，La＝2.8wt％ | 97.8 | 97.0 | ＞5000 | Do not have | Do not have |
| 11 | The 4A zeolite | Zn＝6.7wt％，Nd＝2.5wt％ | 97.8 | 97.1 | ＞5000 | Do not have | Do not have |
| 12 | Sodium base rectorite | Zn＝3.1wt％，Ce＝1.2wt％ | 86.4 | 83.1 | ＞5000 | Do not have | Do not have |
| 13 | Tsilaisite | Zn＝2.5wt％，Ce＝1.0wt％ | 82.3 | 80.5 | ＞5000 | Do not have | Do not have |
The concentration of Escherichia coli and staphylococcus aureus starter bacteria liquid is controlled at 10
5Cells/ml, the complex antimicrobials of measuring 1000 μ g/ml and sterilizing rate after bacterium contacts 24h.
Embodiment 14
With basic zirconium chloride (ZrOCl
28H
2O) 0.5mol, oxalic acid 0.5mol, diammonium hydrogen phosphate 0.75mol, deionized water 16mol put into the reactor of 1L, make its dissolving by mechanical agitation and mix at 50 ℃, with sodium hydroxide its pH value is adjusted to 4.0, back flow reaction 16h under 130 ℃, the condition of 0.5Mpa then, again successively through filtration, washing, dry, 800 ℃ of roastings 3 hours, last ultra-fine grinding to average grain diameter less than 5 microns, obtain sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O].
Contain 0.14mol/l zinc acetate and 3.2 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] 10.0g, stirring reaction is after 6 hours in the time of 80 ℃, pass through filtration, washing, drying successively, again 800 ℃ of roastings 2 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 7.8wt%, a year cerium amount are the inorganic complex antimicrobials of 3.9wt%, and result of the test sees Table 2.
Embodiment 15
Sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] preparation with embodiment 14.
Contain 0.10mol/l zinc nitrate and 1.6 * 10 at 100ml
-2Mol/l cerous acetate [Ce (AC)
3] mixed aqueous solution in, add sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] 10.0g, stirring reaction is after 5 hours in the time of 70 ℃, pass through filtration, washing, drying successively, again 700 ℃ of roastings 4 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 6.1wt%, a year cerium amount are the inorganic complex antimicrobials of 2.2wt%, and result of the test sees Table 2.
Embodiment 16
Sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] preparation with embodiment 14.
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] 10.0g, stirring reaction is after 7 hours in the time of 60 ℃, pass through filtration, washing, drying successively, again 800 ℃ of roastings 2 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 7.3wt%, a year cerium amount are the inorganic complex antimicrobials of 3.0wt%, and result of the test sees Table 2.
Embodiment 17
Sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] preparation with embodiment 14.
Earlier with 1.2 * 10
-2Mol zinc nitrate, 2.4 * 10
-3Mol cerous acetate [Ce (AC)
3], sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] 10.0g adds in the mortar, and is levigate and mix; Then 800 ℃ of roastings 3 hours; Last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 7.0wt%, a year cerium amount are the inorganic complex antimicrobials of 2.6wt%, and result of the test sees Table 2.
Embodiment 18
Sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] preparation with embodiment 14.
Contain 0.12mol/l zinc acetate and 2.4 * 10 at 100ml
-2Mol/l lanthanum nitrate [La (NO
3)
3] mixed aqueous solution in, add sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] 10.0g, stirring reaction is after 6 hours in the time of 60 ℃, pass through filtration, washing, drying successively, again 800 ℃ of roastings 2 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 7.2wt%, a year lanthanum amount are the inorganic complex antimicrobials of 3.1wt%, and result of the test sees Table 2.
Embodiment 19
Sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] preparation with embodiment 14.
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l samaric nitrate [Sm (NO
3)
3] mixed aqueous solution in, add sodium zirconium phosphate carrier [NaZr
2(PO
4)
3H
2O] 10.0g, stirring reaction is after 5 hours in the time of 80 ℃, pass through filtration, washing, drying successively, roasting 5 hours under 900 ℃ condition again, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 7.0wt%, a year samarium amount are the inorganic complex antimicrobials of 2.8wt%, and result of the test sees Table 2.
Embodiment 20
With TiO
2, deionized water, La (NO
3)
3And Na
2CO
3Be 1: 50: 0.8 in molar ratio: 0.7 ratio is mixed, earlier grind 3h with planetary mills, dry again and dry grind to average grain diameter less than 5 microns, roasting 12 hours under 900 ℃ condition then, last ultra-fine grinding to average grain diameter less than 5 microns, obtain lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10).
Contain 0.12mol/l zinc acetate and 2.4 * 10 at 100ml
-2Mol/l cerous acetate [Ce (AC)
3] mixed aqueous solution in, add lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10) 10.0g, stirring reaction is after 5 hours in the time of 70 ℃, pass through filtration, washing, drying successively, again 800 ℃ of roastings 4 hours, last ultra-fine grinding is to the light grey powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 6.8wt%, a year cerium amount are the inorganic complex antimicrobials of 2.6wt%, and result of the test sees Table 2.
Embodiment 21
Lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10) preparation with embodiment 20.
Earlier with 1.2 * 10
-2Mol zinc nitrate, 2.4 * 10
-3Mol cerous acetate [Ce (AC)
3], lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10) 10.0g adds in the mortar, and is levigate and mix; Then 900 ℃ of roastings 2 hours; Last ultra-fine grinding is to the light grey powder of average grain diameter less than 5 microns, and obtaining carrying the zinc amount is that 6.5wt%, a year cerium amount are the inorganic complex antimicrobials of 2.4wt%, and result of the test sees Table 2.
Embodiment 22
Lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10) preparation with embodiment 20.
Contain 0.12mol/l zinc acetate and 2.4 * 10 at 100ml
-2Mol/l europium nitrate [Eu (NO
3)
3] mixed aqueous solution in, add lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10) 10.0g, stirring reaction is after 7 hours in the time of 80 ℃, pass through filtration, washing, drying successively, again 700 ℃ of roastings 2 hours, last ultra-fine grinding is to the light grey powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 6.8wt%, a year europium amount are the inorganic complex antimicrobials of 2.7wt%, and result of the test sees Table 2.
Embodiment 23
Lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10) preparation with embodiment 20.
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l acetic acid samarium [Sm (AC)
3] mixed aqueous solution in, add lanthanium titanate sodium carrier (Na
2La
2Ti
3O
10) 10.0g, stirring reaction is after 5 hours in the time of 70 ℃, pass through filtration, washing, drying successively, roasting 3 hours under 900 ℃ condition again, last ultra-fine grinding is to the light grey powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 7.0wt%, a year samarium amount are the inorganic complex antimicrobials of 2.6wt%, and result of the test sees Table 2.
Embodiment 24
In the 1L reactor, the 0.5mol titanyl sulfate is dissolved in the 16mol deionized water is made into the aqueous solution, add the 0.75mol sodium hydrogen phosphate then while stirring, with sodium hydroxide its pH value is adjusted to 5.0, back flow reaction 24h in the time of 98 ℃ then, again successively through washing, filter, dry, at 800 ℃ of roasting 3h, last ultra-fine grinding to average grain diameter less than 5 microns, obtain titanium phosphate sodium carrier [NaTi
2(PO
4)
3H
2O].
Contain 0.12mol/l zinc nitrate and 2.4 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add titanium phosphate sodium carrier [NaTi
2(PO
4)
3H
2O] 10.0g, stirring reaction is after 7 hours in the time of 80 ℃, pass through washing, filtration, drying successively, again 700 ℃ of roastings 4 hours, last ultra-fine grinding is to the white powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 7.1wt%, a year cerium amount are the inorganic complex antimicrobials of 2.7wt%, and result of the test sees Table 2.
Embodiment 25
In the 1L reactor, with the 0.25mol/L Ca (NO of 300mL
3) 4H
2The O aqueous solution fully stirs with magnetic stirring apparatus, and the ammonia spirit with 20% is with pH regulator to 10～11; Drip the 0.15mol/L (NH of 300mL again
4)
2HPO
4The aqueous solution obtains white precipitate, and not open close mistake drips 20% ammonia spirit makes its pH remain on 10～11; Continuous stirring is 2 hours then, and ageing is at normal temperatures and pressures then handled more than the 5h; At last successively through washing, filter, dry, 900 ℃ of roastings 3 hours, ultra-fine grinding to average grain diameter less than 5 microns, obtain hydroxyapatite carrier [Ca
10(PO
4)
6(OH)
2].
Contain 0.10mol/l zinc nitrate and 1.6 * 10 at 100ml
-2Mol/l cerous nitrate [Ce (NO
3)
3] mixed aqueous solution in, add hydroxyapatite carrier [Ca
10(PO
4)
6(OH)
2] 10.0g, stirring reaction is after 7 hours in the time of 60 ℃, pass through washing, filtration, drying successively, again 900 ℃ of roastings 4 hours, last ultra-fine grinding is to the light grey powder of average grain diameter less than 5 microns, obtaining carrying the zinc amount is that 2.0wt%, a year cerium amount are the inorganic complex antimicrobials of 0.8wt%, and result of the test sees Table 2.
Table 2 is the result of the test of the resulting complex antimicrobials of carrier with the ion exchange material of chemosynthesis
| Embodiment | Carrier | The kind of active component and content | Sterilizing rate/% * | Toxicological test | |||
| Escherichia coli/ATCC2 5292 | Staphylococcus aureus/ATCC65 38 | Acute oral toxicity LD 50(mg/kg) | Mutagenicity | The skin irritatin test | |||
| 14 | NaZr 2(PO 4) 3·H 2O | Zn＝7.8wt％，Ce＝3.9wt％ | 99.9 | 99.9 | ＞5000 | Do not have | Do not have |
| 15 | NaZr 2(PO 4) 3·H 2O | Zn＝6.1wt％，Ce＝2.2wt％ | 98.5 | 97.8 | ＞5000 | Do not have | Do not have |
| 16 | NaZr 2(PO 4) 3·H 2O | Zn＝7.3wt％，Ce＝3.0wt％ | 99.3 | 99.0 | ＞5000 | Do not have | Do not have |
| 17 | NaZr 2(PO 4) 3·H 2O | Zn＝7.0wt％，Ce＝2.6wt％ | 99.2 | 98.9 | ＞5000 | Do not have | Do not have |
| 18 | NaZr 2(PO 4) 3·H 2O | Zn＝7.2wt％，La＝3.1wt％ | 98.8 | 98.0 | ＞5000 | Do not have | Do not have |
| 19 | NaZr 2(PO 4) 3·H 2O | Zn＝7.0wt％，Sm＝2.8wt％ | 98.9 | 98.6 | ＞5000 | Do not have | Do not have |
| 20 | Na 2La 2Ti 3O 10 | Zn＝6.8wt％，Ce＝2.6wt％ | 98.7 | 98.2 | ＞5000 | Do not have | Do not have |
| 21 | Na 2La 2Ti 3O 10 | Zn＝6.5wt％，Ce＝2.4wt％ | 98.3 | 97.3 | ＞5000 | Do not have | Do not have |
| 22 | Na 2La 2Ti 3O 10 | Zn＝6.8wt％，La＝2.7wt％ | 98.0 | 96.5 | ＞5000 | Do not have | Do not have |
| 23 | Na 2La 2Ti 3O 10 | Zn＝7.0wt％，Eu＝2.6wt％ | 98.0 | 97.2 | ＞5000 | Do not have | Do not have |
| 24 | NaTi 2(PO 4) 3·H 2O | Zn＝7.1wt％，Ce＝2.7wt％ | 99.3 | 99.2 | ＞5000 | Do not have | Do not have |
| 25 | Ca 2(PO 4) 6(OH) 12 | Zn＝2.8wt％，Ce＝0.8wt％ | 81.7 | 75.2 | ＞5000 | Do not have | Do not have |
*The concentration of Escherichia coli and staphylococcus aureus starter bacteria liquid is controlled at 10
5Cells/ml, the complex antimicrobials of measuring 1000 μ g/ml and sterilizing rate after bacterium contacts 24h.
Embodiment 26
Respectively embodiment 1, embodiment 4, embodiment 6, embodiment 7, embodiment 8, embodiment 9, embodiment 12, embodiment 13, embodiment 14, embodiment 17, embodiment 20, embodiment 22, embodiment 24 and embodiment 25 prepared inorganic complex antimicrobials are passed through surface treatment, be added in polypropylene (PP), acrylonitrile-styrene-butadiene copolymer (ABS) molding powder and extruding pelletization by the amount shown in the table 3 again, be injection molded into PP, ABS plastic plate then.Adopt film adherence method to measure its anti-microbial property; Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 3.
The performance of table 3 antibiotic plastic
| The antibiotic plastic kind | The inorganic complex antimicrobials that adds | Inorganic complex antimicrobials addition/wt% | Anti-microbial property (%) | Aberration | |
| Escherichia coli (ATCC25292) | Staphylococcus aureus (ATCC6538) | ||||
| PP | Embodiment 1 | 3.0 | 99.9 | 99.9 | 0.85 |
| PP | Embodiment 6 | 3.0 | 99.1 | 98.5 | 0.76 |
| PP | Embodiment 7 | 3.0 | 99.6 | 99.0 | 0.72 |
| PP | Embodiment 9 | 3.0 | 98.7 | 97.9 | 0.61 |
| PP | Embodiment 12 | 5.0 | 96.8 | 93.6 | 0.69 |
| PP | Embodiment 14 | 3.0 | 99.9 | 99.9 | 0.70 |
| PP | Embodiment 20 | 3.0 | 98.3 | 97.1 | 0.93 |
| ABS | Embodiment 4 | 3.0 | 98.7 | 98.2 | 1.54 |
| ABS | Embodiment 8 | 3.0 | 98.0 | 97.3 | 1.46 |
| ABS | Embodiment 13 | 5.0 | 95.2 | 92.5 | 1.78 |
| ABS | Embodiment 17 | 3.0 | 99.0 | 98.1 | 1.63 |
| ABS | Embodiment 22 | 3.0 | 98.0 | 96.2 | 1.75 |
| ABS | Embodiment 24 | 3.0 | 98.8 | 98.5 | 1.59 |
| ABS | Embodiment 25 | 5.0 | 96.1 | 93.4 | 1.55 |
Embodiment 27
Respectively with embodiment 2, embodiment 3, embodiment 5, embodiment 10, embodiment 11, embodiment 12, embodiment 13, embodiment 15, embodiment 16, embodiment 18, embodiment 19, embodiment 21, embodiment 23, embodiment 24 and embodiment 25 prepared inorganic complex antimicrobials and emulsifier octyl phenol polyoxyethylene (10) ethers added in the deionized water in 20: 1 in molar ratio, be made into the emulsion that the composite antibiosis agent concentration is 20.0wt%, more than the ball milling 3h, then above-mentioned emulsion is added by a certain percentage in the Silicone acrylic emulsion type interior wall coating and stir, obtain antibacterial inner wall paint, the content of its inorganic complex antimicrobials (solid content with coating is that benchmark calculates) is as shown in table 4.Adopt film adherence method to measure the anti-microbial property of antimicrobial coating; Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 4.
The performance of table 4 antibacterial inner wall paint
| The inorganic complex antimicrobials that adds | Inorganic complex antimicrobials addition/wt% | Anti-microbial property (%) | Aberration | |
| Escherichia coli (ATCC25292) | Staphylococcus aureus (ATCC6538) | |||
| Embodiment 2 | 3.0 | 98.6 | 97.9 | 0.70 |
| Embodiment 3 | 3.0 | 99.9 | 99.9 | 0.83 |
| Embodiment 5 | 3.0 | 99.5 | 99.1 | 0.76 |
| Embodiment 10 | 3.0 | 97.8 | 96.7 | 0.90 |
| Embodiment 11 | 3.0 | 98.2 | 97.3 | 0.92 |
| Embodiment 12 | 5.0 | 96.1 | 94.6 | 0.75 |
| Embodiment 13 | 5.0 | 95.6 | 93.1 | 0.68 |
| Embodiment 15 | 3.0 | 98.8 | 98.2 | 0.65 |
| Embodiment 16 | 3.0 | 99.9 | 99.9 | 0.78 |
| Embodiment 18 | 5.0 | 98.5 | 97.6 | 0.75 |
| Embodiment 19 | 3.0 | 99.0 | 98.5 | 0.81 |
| Embodiment 21 | 3.0 | 98.2 | 97.5 | 0.82 |
| Embodiment 23 | 3.0 | 98.0 | 97.3 | 0.87 |
| Embodiment 24 | 3.0 | 98.7 | 98.2 | 0.70 |
| Embodiment 25 | 5.0 | 94.9 | 92.5 | 0.69 |
Embodiment 28
Respectively embodiment 1, embodiment 7, embodiment 9, embodiment 12, embodiment 13, embodiment 14, embodiment 18, embodiment 23, embodiment 24 and embodiment 25 prepared inorganic complex antimicrobials are added in the sanitary ceramics glaze by the addition shown in the table 5 (solid content with ceramic glaze is that benchmark calculates) earlier, again more than the ball milling 3h, glazing is burnt till antiseptic sanitary at last under＞1250 ℃ to ceramic body then.Adopt film adherence method to measure its anti-microbial property; Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 5.
The performance of table 5 antiseptic sanitary
| The inorganic complex antimicrobials that adds | Inorganic complex antimicrobials addition/wt% | Anti-microbial property (%) | Aberration | |
| Escherichia coli (ATCC25292) | Staphylococcus aureus (ATCC6538) | |||
| Embodiment 1 | 3.0 | 98.1 | 96.5 | 0.61 |
| Embodiment 7 | 3.0 | 97.8 | 96.1 | 0.66 |
| Embodiment 9 | 3.0 | 96.1 | 94.5 | 0.72 |
| Embodiment 12 | 5.0 | 94.3 | 93.0 | 0.56 |
| Embodiment 13 | 5.0 | 92.6 | 90.8 | 0.50 |
| Embodiment 14 | 3.0 | 99.9 | 99.9 | 0.61 |
| Embodiment 18 | 3.0 | 98.2 | 97.5 | 0.54 |
| Embodiment 23 | 3.0 | 97.0 | 96.3 | 0.65 |
| Embodiment 24 | 3.0 | 99.9 | 99.9 | 0.65 |
| Embodiment 25 | 5.0 | 95.1 | 93.7 | 0.42 |
Embodiment 29
Respectively embodiment 2, embodiment 6, embodiment 8, embodiment 10, embodiment 12, embodiment 13, embodiment 15, embodiment 19, embodiment 21, embodiment 24 and embodiment 25 prepared inorganic complex antimicrobials are added in the raw material of silicon rubber by the addition shown in the table 6 and mix, be processed into the antimicrobial silicon rubbery sample then.Adopt film adherence method to measure its anti-microbial property; Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 6.
The performance of table 6 antimicrobial silicon rubber
| The inorganic complex antimicrobials that adds | Inorganic complex antimicrobials addition/wt% | Anti-microbial property (%) | Aberration | |
| Escherichia coli (ATCC25292) | Staphylococcus aureus (ATCC6538) | |||
| Embodiment 2 | 3.0 | 98.7 | 98.0 | 0.86 |
| Embodiment 6 | 3.0 | 99.3 | 98.8 | 0.88 |
| Embodiment 8 | 3.0 | 99.1 | 98.5 | 0.81 |
| Embodiment 10 | 3.0 | 98.9 | 98.3 | 0.79 |
| Embodiment 12 | 5.0 | 97.1 | 95.6 | 0.92 |
| Embodiment 13 | 5.0 | 95.1 | 92.8 | 0.86 |
| Embodiment 15 | 3.0 | 99.9 | 99.9 | 0.95 |
| Embodiment 19 | 3.0 | 99.8 | 99.5 | 0.77 |
| Embodiment 21 | 3.0 | 98.6 | 98.1 | 0.94 |
| Embodiment 24 | 3.0 | 99.7 | 99.2 | 0.85 |
| Embodiment 25 | 5.0 | 94.3 | 93.5 | 0.82 |
Embodiment 30
Respectively embodiment 3, embodiment 11, embodiment 12, embodiment 13, embodiment 16, embodiment 20, embodiment 24 and embodiment 25 prepared inorganic complex antimicrobials are passed through surface treatment, be added in PA (polyamide) the fibre-grade molding powder and extruding pelletization by the addition shown in the table 7 again, obtain antibiotic PA fiber through melt spinning then.Adopt succusion to measure its anti-microbial property; Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 7.
The performance of table 7 anti-bacterial fibre
| The inorganic complex antimicrobials that adds | Inorganic complex antimicrobials addition/wt% | Anti-microbial property (%) | Aberration | |
| Escherichia coli (ATCC25292) | Staphylococcus aureus (ATCC6538) | |||
| Embodiment 3 | 3.0 | 99.0 | 98.5 | 1.21 |
| Embodiment 11 | 3.0 | 97.9 | 96.0 | 1.05 |
| Embodiment 12 | 5.0 | 96.1 | 94.5 | 0.97 |
| Embodiment 13 | 5.0 | 95.4 | 93.6 | 1.26 |
| Embodiment 16 | 3.0 | 98.0 | 97.1 | 1.08 |
| Embodiment 20 | 3.0 | 97.5 | 95.8 | 1.02 |
| Embodiment 24 | 3.0 | 98.6 | 97.7 | 1.13 |
| Embodiment 25 | 5.0 | 94.3 | 91.9 | 1.05 |
Embodiment 31
Respectively embodiment 4, embodiment 9, embodiment 12, embodiment 13, embodiment 17, embodiment 22, embodiment 24 and embodiment 25 prepared inorganic complex antimicrobials are pressed in the raw material of the addition adding white glue with vinyl shown in the table 8, be uniformly dispersed, obtain antibiotic white glue with vinyl.Adopt film adherence method to measure the anti-microbial property of adhesive layer; Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 8.
The performance of the antibiotic white glue with vinyl of table 8
| The inorganic complex antimicrobials that adds | Inorganic complex antimicrobials addition/wt% | Anti-microbial property (%) | Aberration | |
| Escherichia coli (ATCC25292) | Staphylococcus aureus (ATCC6538) | |||
| Embodiment 4 | 3.0 | 98.9 | 98.0 | 0.89 |
| Embodiment 9 | 3.0 | 99.0 | 98.3 | 0.87 |
| Embodiment 12 | 5.0 | 96.1 | 95.4 | 0.96 |
| Embodiment 13 | 5.0 | 95.7 | 94.2 | 0.85 |
| Embodiment 17 | 3.0 | 98.8 | 98.2 | 0.83 |
| Embodiment 22 | 3.0 | 98.5 | 97.1 | 0.90 |
| Embodiment 24 | 3.0 | 98.7 | 97.9 | 0.77 |
| Embodiment 25 | 5.0 | 92.9 | 90.5 | 0.98 |
Embodiment 32
Respectively embodiment 5, embodiment 10, embodiment 12, embodiment 13, embodiment 15, embodiment 23, embodiment 24 and embodiment 25 prepared inorganic complex antimicrobials are pressed in the raw material of the addition adding paper shown in the table 9, after dispersed with stirring is even, copy sheet by hand, obtain antibiotic handmade paper through the squeezing oven dry.Adopt film adherence method to measure its anti-microbial property; Carry out fluorescent ultraviolet lamp exposure test 240h by GB/T 14522-1993, light source is UV-A lamp (351nm), carries out aberration by GB/T 3979-1997, GB/T 7921-1997 and detects.Result of the test sees Table 9.
The performance of the antibiotic handmade paper of table 9
| The inorganic complex antimicrobials that adds | Inorganic complex antimicrobials addition/wt% | Anti-microbial property (%) | Aberration | |
| Escherichia coli (ATCC25292) | Staphylococcus aureus (ATCC6538) | |||
| Embodiment 5 | 3.0 | 99.5 | 99.0 | 0.85 |
| Embodiment 10 | 3.0 | 98.7 | 98.1 | 0.79 |
| Embodiment 12 | 5.0 | 95.2 | 93.7 | 0.92 |
| Embodiment 13 | 5.0 | 93.1 | 91.6 | 0.90 |
| Embodiment 15 | 3.0 | 99.0 | 98.3 | 0.72 |
| Embodiment 23 | 3.0 | 98.5 | 97.0 | 0.78 |
| Embodiment 24 | 3.0 | 99.5 | 98.7 | 0.67 |
| Embodiment 25 | 5.0 | 92.1 | 90.5 | 0.95 |
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. inorganic complex antimicrobials that contains zincium-rare earth, it is characterized in that: described inorganic complex antimicrobials is white or light grey powder, its average grain diameter is less than 5.0 μ m, this antibacterial agent is a carrier with the ion exchange material of natural ion exchange material or chemosynthesis, by ion-exchange with zinc ion and rare earth ion exchanged to carrier, zinc ion and rare earth ion are double activity center, the content of zinc ion is 6.0～8.0wt%, the content of rare earth ion is 2.0～4.0wt%, and described rare earth ion comprises La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+
2. the described preparation method who contains the inorganic complex antimicrobials of zincium-rare earth of claim 1 is characterized in that comprising following processing step and process conditions:
(1) contains 0.10～0.14mol/l soluble zinc salt and 1.6 * 10 at 100ml
-2～3.2 * 10
-2In the mol/l soluble rare-earth salt mixed aqueous solution, add carrier 10.0g, stirring reaction passes through filtration, washing, drying after 5～7 hours successively in the time of 60～80 ℃;
Perhaps earlier with 1.0 * 10
-2～1.4 * 10
-2Mol soluble zinc salt, 1.6 * 10
-3～3.2 * 10
-3Mol soluble rare-earth salt, carrier 10.0g add in the mortar, and be levigate and mix;
(2) again 400～900 ℃ of roastings 2～4 hours, last ultra-fine grinding to average grain diameter less than 5 microns, to obtain carrying a zinc amount be 6.0～8.0wt%, carry a rare earth content is the inorganic complex antimicrobials that contains zincium-rare earth of 2.0～4.0wt%.
3. the preparation method who contains the inorganic complex antimicrobials of zincium-rare earth according to claim 2 is characterized in that: described soluble zinc salt comprises zinc nitrate or zinc acetate.
4. the preparation method who contains the inorganic complex antimicrobials of zincium-rare earth according to claim 2 is characterized in that: described soluble rare-earth salt comprises cerous nitrate, cerous acetate, lanthanum nitrate, lanthanum acetate, neodymium nitrate, acetic acid neodymium, samaric nitrate, acetic acid samarium, europium nitrate or acetic acid europium.
5. the preparation method who contains the inorganic complex antimicrobials of zincium-rare earth according to claim 2 is characterized in that: described carrier comprises the natural ion exchange material or the ion exchange material of chemosynthesis;
Described natural ion exchange material comprises imvite, zeolite, rectorite or tourmaline.
The ion exchange material of described chemosynthesis comprises sodium zirconium phosphate, lanthanium titanate sodium, titanium phosphate sodium or hydroxyapatite.
6. the described application of inorganic complex antimicrobials in plastics, rubber, fiber, coating, adhesive, paper or ceramic material that contains zincium-rare earth of claim 1.
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