CN104206420A - Preparation method and application of silver-free powdery solid solution anti-bacterial agent - Google Patents
Preparation method and application of silver-free powdery solid solution anti-bacterial agent Download PDFInfo
- Publication number
- CN104206420A CN104206420A CN201410387591.2A CN201410387591A CN104206420A CN 104206420 A CN104206420 A CN 104206420A CN 201410387591 A CN201410387591 A CN 201410387591A CN 104206420 A CN104206420 A CN 104206420A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- solid solution
- antibacterial agent
- powdery solid
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a preparation method and application of a silver-free powdery solid solution anti-bacterial agent. The silver-free powdery solid solution anti-bacterial agent is prepared by adding a zinc salt or a copper salt and an oxide or a hydroxide to water, and performing a stirring process, a separating process, a cleaning process and a grinding process. The preparation method is simple and low in cost. The silver-free powdery solid solution anti-bacterial agent is wide in applications, is high-temperature-resistant, is safe and is good in anti-bacterial effect.
Description
Technical field
The present invention relates to a kind of solid solution technique, particularly a kind of preparation method and application's method of non-silver powdery solid solution antibacterial agent.
Background technology
From the last century the eighties, Japan and more domestic mechanisms afterwards, successively develop and produce silver-containing inorganic antibacterial (or claiming ag system antimicrobial agent), be applied to multiple industries such as plastics, make large quantities of unprecedentedly, there is the completely new product automatically killing the pathogenic microorganisms pressing down attachment product surface, receive extensive welcome.
But, all there are some defects in the patent of invention proposed and technical method thereof both at home and abroad.Except the valency of processing raw material is high, process technology method is complicated, and cost improves, and the added value of new product strengthens, and producer and user are difficult to outside acceptance, and in antibacterial agent, silver ion meets light or thermo-color, causes the product employing antibacterial agent cannot present white or bright-coloured colour.After certain hour, antimicrobial product blackening, yellowing, thus make product lose commodity value.
Summary of the invention
The present invention, in order to overcome above-mentioned technological deficiency, the present invention proposes that a kind of cost is low, the preparation method of technique simple non-silver powdery solid solution antibacterial agent.
Solid solution is that occurring in nature extensively exists a kind of chemical phenomenon: can exchange between ion or ion cluster.This process claims solid solution (Solid solution).Namely adopt someway, make in a kind of crystalline texture of material, after having dissolved the ion of another kind of material, still keep this raw-material structure (host lattice).Generate solid solution and can divide two classes: one is substitutional solid solution.Namely the lattice position in raw material, the ion of the material dissolved by another kind replace.The solid solution that metal oxide generates, generally all belongs to metal ion displacement.Such as: MgO-CoO, MgO-CaO, PbTiO
3--PbZrO
3, Al
2o
3-Cr
2o
3, Cu-Zn etc.Another kind is intermittence solid solution.Namely, after the ion of another kind of material enters raw material host lattice, its original interstitial site is occupied.People usually use solid solution principle, prepare or develop various new material, to meet the new demand to material.Such as: if this solid solution having dissolved another material ions, after being heated to uniform temperature, its structure may become even, orderly structure, thus make its mechanical property stronger, this method is called solution strengthening.
Solid solution refers to does solvent with water, pass through hydration process, by metal ions such as zinc, copper, aluminium, repeated multiple timesly, high concentration, be solidly soluted into the crystallization top layer such as oxide or hydroxide, titanium oxide, tricalcium phosphate ubiquitously and form a kind of new composite oxides--spacetabs type solid solution.Use the first diffraction approach of X to show the hydroxide powder after solid solution: suitable with the crystal structure of original slaked lime, illustrate that bivalent metal ion has been solidly soluted into slaked lime and has suffered.Because oxide or hydroxide belong to slightly soluble or micro-indissoluble material in water, if after being solidly soluted into wherein by antibiotic effective ingredient zinc, copper ion, be just provided with significant antibacterial effect.Because oxide or hydroxide belong to solid base, be usually used as heat-resisting, the weather-proof preparation of the materials such as resin, its kick off temperature is more than 300 DEG C.If be used in resin, the phenomenons such as decomposition, foaming would not be there is.
Therefore, based on above-mentioned technology, technical scheme of the present invention is as follows: a kind of preparation method of non-silver powdery solid solution antibacterial agent, comprises the steps:
(1) add water in reactor;
(2) add the metal ion zinc salt with antibacterial functions or mantoquita or the two mixture, stir, dissolve, make its concentration be 0.5 ~ 2mol/L;
(3) add oxide or hydroxide, make its concentration be 1 ~ 3mol/L;
(4) aqueous solution is stirred 10 minutes ~ 2 hours;
(5) make aqueous solution Separation of Solid and Liquid with centrifuge or filter press, obtain filter cake;
(6) filter cake cleaned, grind and obtain non-silver powdery solid solution antibacterial agent.Both can adopt wet grinding, can dry grinding be adopted again.The former can use ball mill etc. directly to grind filter cake, and then is dried into powder; Filter cake first will be dried into powder by the latter, then with grindings such as airflow milling.Wet grinding result, average grain can reach 1 microns, but secondary flocculation can make particle size difference larger; Dry grinding result, average grain is only 10 microns, but particle size is more balanced.
Described zinc or mantoquita be zinc nitrate, copper nitrate, zinc acetate, Schweinfurt green, zinc chloride, copper chloride etc. one or more.
Described oxide or hydroxide are calcium oxide, magnesia, slaked lime or magnesium hydroxide.
Described water is deionized water, pure water or ordinary tap water.
The invention also discloses the application of non-silver powdery solid solution antibacterial agent on pottery utilizing said method to prepare.
The application of described non-silver powdery solid solution antibacterial agent on pottery, one of its application method comprises the steps:
(I) with the temperature of 100 ~ 300 DEG C, antibacterial agent is dried, dewatered;
(II) add water the glaze raw material milling apparatus of pottery grinding, makes common glaze slip;
(III) add after antibacterial agent in the ratio of glaze slip gross weight 3 ~ 5%, then grind, make antibacterial agent and the abundant affinity of glaze, dispersion, obtain antibacterial glaze slip;
(IV) rest, constantly stirs glaze slip in rest process;
(V) dry, and sinter with the temperature higher than former sintering temperature 10 ~ 30 DEG C, make antibacterial ceramic products, described original sintering temperature is generally 800 DEG C ~ 1300 DEG C.
The application of described non-silver powdery solid solution antibacterial agent on pottery, two of its application method comprises the steps:
(I) with the temperature of 100 ~ 300 DEG C, antibacterial agent is dried, dewatered;
(II) in polyvinyl alcohol, add the antibacterial agent of 3 ~ 5%, make antibacterial glaze liquid;
(III) brushing antibacterial glaze liquid at rest and on dry ceramic mold, then carry out drying, sintering, make antibacterial ceramic products.
The invention also discloses that non-silver powdery solid solution antibacterial agent prepared by said method is kept a public place clean at resin, washing powder, cement, printing-ink, paper pulp, paraffin, water body, application in anti-algae.Can keep a public place clean in resin, washing powder, cement, printing-ink, paper pulp, paraffin, water body, the raw material total amount of anti-algae 0.5 ~ 5% ratio directly add.
The invention also discloses non-silver powdery solid solution antibacterial agent prepared by said method to apply in adhesive agent, described adhesive agent refers to can by various antibiotic preparation firmly and be attached on artificial leather, metal, plastics, wood furniture, ceramic sanitary appliance, cement, paper, natural fibre products matrix material for a long time, and the metal ion of energy delivery of antimicrobials, kill the pathogenic microorganisms pressing down attachment.
Described adhesive agent raw material is environmentally-friendly latex paint for interior walls, clean interior wall Polyester Paint, water-fast clean Polyester Paint, organic silicone finishing agent and antibacterial finishing agent.Described organic silicone finishing agent is that active gene introduced by siloxanes side base, and the interpenetrating network copolymer synthesized with specific macromolecule performed polymer, described antibacterial finishing agent is the copolymer of carbimide and acrylic acid fat.
Be specially by non-silver powdery solid solution antibacterial agent by 1 ~ 3% mass ratio add in adhesive agent raw material.
Every new and old object (as artificial leather, metal, plastics, wood furniture, ceramic sanitary appliance, cement, paper, natural fibre products etc.) realizing antibacterial requirement that needs all can adopt the methods such as spraying or brushing, adhesive agent containing antibacterial agent is attached to object surface, form antibacterial film, at any time pathogenic bacteria are killed.As long as antibacterial film does not come off, just play antibacterial action, with relatively accomplishing " putting things right once and for all " antibacterial.And so-called object, both can be the new product just dispatched from the factory, can be again the old product used for many years, and after coating antibacterial film, object also can be repaired sth. old and made it as good as new.
In the present invention, inventor utilizes solid solution technique, with inorganic oxide or hydroxide for conforming to body, with the metal ion such as zinc, copper for active ingredient, adopt solid dissolving method to make brand-new inorganic antiseptic, achieve antibacterial, at a low price, the requirement to antibacterial agent such as high temperature resistant of fine quality.
The zinc-copper ion concentration be solidly soluted in oxide or hydroxide is very low, and the compound made is in white, and toxicity is very low.Usual solid solution concentration is no more than 4%, can not increase antibacterial effect during more than 9%.
Beneficial effect of the present invention is:
(1) the non-silver powdery solid solution antibacterial agent adopting this solid solution legal system standby, prove through test: after the divalence alkaline-earth metals oxide with antibacterial functions is solidly soluted in the alkali metal oxide crystalline solid such as calcium magnesium with atom form, just form a composite quilt coating in the unformed nature of glass, thus inhibit zinc-copper ion wherein, in solid solution, crystallization occurs.Around it, have water, coating will borrow moisture trace to melt, and just can melt gradually and antibacterial metal ions, play antibacterial action in layer.Test proves: the compound formed after zinc, copper ion are solidly soluted in magnesia or calcium or magnesium hydroxide or calcium, has higher antimicrobial acivity than zinc oxide, copper oxide.And then make zinc, copper ion have appropriate melt property to water.In the water of pH=7, stripping quantity can reach 100 ~ 1000 times of common zinc oxide stripping quantity; In the water of pH=8.5, the stripping quantity of zinc ion can reach more than 100 times of common zinc oxide stripping quantity.On the other hand, under normal condition, this metal ion solvability and general glassy phase like or slightly low, approximately pass through tens days to tens months, melt concentration and only have several ppm to tens about ppb.Here it is antibacterial agent can quick-acting again can be long-acting reason.
(2) divalence is moved configuration metal ions Zn by the present invention, Cu is solidly soluted into calcium oxide, after slaked lime, generate brand-new solid solution.It is compared with original slaked lime, more acidproof, and react after the carbonic acid gas in ordinary hydrogen calcium oxide ingress of air and the calcium carbonate become, the slaked lime after solid solution can suppress this phenomenon to occur; Also can not produce bulky grain, easily disperse, thus more stable.Slaked lime dehydration temperaturre after solid solution, also reduces greatly from original 430 DEG C, economic, nontoxic, anti-algae.
(3) be antibacterial metal is solidly soluted in main material calcium and magnesium oxides make brand-new composite oxides with the antibacterial agent that this solid solution legal system is standby.When X-ray diffraction is done to this oxide powder, its crystal structure and original calcium and magnesium oxides or hydroxide almost completely the same.Such as zinc ion is solidly soluted into the anti-bacterial powders made in slaked lime, do X-ray diffraction result and show, its crystal structure is identical with slaked lime.And calcium and magnesium oxides, hydroxide are resistant to elevated temperatures, to antibacterial agent plasma technology of the present invention, after the temperature of instantaneous more than 2000 DEG C sintering, again detect and prove that antibacterial effect is still constant.Thus, can add in the materials such as the refractory ceramics of more than 1000 DEG C and use.
(4) and antibacterial agent of the present invention through solid solution processing after, the decomposition of calcium and magnesium oxides or hydroxide can be covered, added to as in polyvinyl chloride raw material, stabilization can be played; Again because of not silver ion, just there is not antibacterial effect yet and lost efficacy or subtracted effect problem.
(5) antibacterial agent that prepared by the present invention is safe.Toxicity detects to be proved, it is safe to human body.
(6) raw material of antibacterial agent prepared of the present invention not precious materials such as argentiferous, processing method is also easy than processing silver-containing antibacterial agent, and therefore the cost of this non-silver antibacterial agent is very cheap.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
Deionized water is added in reactor, add the zinc nitrate with antibacterial functions, stir, dissolve, make its concentration be 1.0mol/L, add calcium oxide, make its concentration be 1/L, the aqueous solution is stirred 2 hours, make aqueous solution Separation of Solid and Liquid with centrifuge or filter press, obtain filter cake, filter cake is cleaned, grind the particle non-silver powdery solid solution antibacterial agent obtaining average 1.29 μm.
Embodiment 2:
Add water in reactor, add the copper chloride with antibacterial functions, stir, dissolve, make its concentration be 2mol/L, add magnesium hydroxide, make its concentration be 3mol/L, the aqueous solution is stirred 1 hour, make aqueous solution Separation of Solid and Liquid with centrifuge or filter press, obtain filter cake, filter cake is cleaned, grind the particle non-silver powdery solid solution antibacterial agent obtaining average 1.5 μm.
Embodiment 3:
Antibacterial agent in embodiment 1 is applied on pottery, comprises the steps:
(I) with the temperature of 100 ~ 300 DEG C, antibacterial agent is dried, dewatered;
(II) add water the glaze raw material milling apparatus of pottery grinding, makes common glaze slip;
(III) add after antibacterial agent in the ratio of glaze slip gross weight 3%, then grind, make antibacterial agent and the abundant affinity of glaze, dispersion, obtain antibacterial glaze slip;
(IV) rest, constantly stirs glaze slip in rest process;
(V) dry, and sinter with the temperature higher than former sintering temperature more than 1000 DEG C 10-30 DEG C, make antibacterial ceramic products.
Antibacterial effect:
According to " disinfection technology standard ", 0.02ml Escherichia coli and staphylococcus aureus bacterium drop are added in above-mentioned antibacterial refractory ceramics test piece, act on 32 hours.Non-anti-bacteria ceramic test piece is done simultaneously and process product in contrast equally.Wash down with PBS, rapping, cultivation.Test in triplicate.Result is as follows:
The test strain specimen test bacteriostasis rate reference substance of 1 hour 1 hour bacteriostasis rate
Escherichia coli 98.34% 2.46x10
7
Staphylococcus aureus 96.22% 1.66x10
7
Embodiment 4:
The antibacterial agent of preparation in embodiment 2 is applied on pottery, comprises the steps:
(I) with the temperature of 100 ~ 300 DEG C, antibacterial agent is dried, dewatered;
(II) in polyvinyl alcohol, add the antibacterial agent of 3 ~ 5%, make antibacterial glaze liquid;
(III) brushing antibacterial glaze liquid at rest and on dry ceramic mold, then carry out drying, sintering, make antibacterial ceramic products.
Embodiment 5:
Use the PP production of resins antibacterial resin of melt index 60-70, first with 50-100 DEG C, antibacterial agent is dried, dewatered; PP raw material and dispersant, coupling agent and antibacterial agent are fully mixed; Use dual-screw pelletizer granulation, account for the ratio of raw material total amount 2% in antibacterial agent.
Antibacterial effect:
According to " disinfection technology standard ", above-mentioned antibacterial PP fiber is cut into 1.0-3.0cm and drips 0.05ml Escherichia coli and staphylococcus aureus bacterium liquid, act on 1 hour.Non-antibacterial PP fiber is done simultaneously and process product in contrast equally.Wash down with after PBS dilution, get 0.5ml, cultivate 24 hours at 37 DEG C.Test in triplicate.Result is as follows:
The test strain sample bacteriostasis rate reference substance of 1 hour 1 hour bacteriostasis rate
Escherichia coli 82.93% 7.17x10
5
Staphylococcus aureus 76.89% 9.02x10
5
Antibacterial agent the present invention prepared is applied to washing powder, cement, printing-ink, paper pulp, paraffin, water body guarantor in the ratio of 1-5%, possesses good antibacterial effect equally.
Embodiment 6:
Polymerization of epoxy resins is used to react the Polyester Paint of one pack system or the bi-component made.This paint is wear-resisting, water resistance good, in Polyester Paint, adds the antibacterial agent of embodiment 1, more traditionally produce the Polyester Paint with antibacterial functions by 2% of paint vehicle final products consumption.The concrete coating process of this Polyester Paint is very simple.No matter new product or old product, should make object surface smooth, moisture content≤10%, remove surface dust etc.If metal then should do processing of rust removing.Before brushing, resin agitating is even, takes the circumstances into consideration, with thinner dilution, to make it easy to brushing.Above-mentioned various new product or with old product spray once or twice, roller coating or brushing, natural seasoning.
But testing result shows, the above-mentioned new and old goods through the processing of post processing brushing technology, is not only provided with excellent killing the function of attachment pathogenic bacteria, and old product are repaired sth. old and made it as good as new.Some cannot adopt raw material addition manner to realize the natural product of antibacterialization in the past, also can complete antibacterialization simply.With front because of high cost, antibacterial disposable product cannot be realized, also can realize antibacterialization by extremely low cost, simple method.
Therefore, every new and old object (as artificial leather, metal, plastics, wood furniture, ceramic sanitary appliance, cement, paper, natural fibre products etc.) realizing antibacterial requirement that needs all can adopt the methods such as spraying or brushing, adhesive agent containing antibacterial agent is attached to object surface, form antibacterial film, at any time pathogenic bacteria are killed.As long as antibacterial film does not come off, just play antibacterial action, with relatively accomplishing " putting things right once and for all " antibacterial.And so-called object, both can be the new product just dispatched from the factory, can be again the old product used for many years, and after coating antibacterial film, object also can be repaired sth. old and made it as good as new.
In sum; although the specific embodiment of the present invention is to invention has been detailed description; but persons skilled in the art should be understood that; above-described embodiment is only the description to the preferred embodiments of the present invention; but not limiting the scope of the invention; persons skilled in the art are in the technical scope disclosed by the present invention, and the change that can expect easily, all within protection scope of the present invention.
Claims (13)
1. a preparation method for non-silver powdery solid solution antibacterial agent, is characterized in that comprising the steps:
(1) add water in reactor;
(2) add the metal ion zinc salt with antibacterial functions or mantoquita or the two mixture, stir, dissolve, make its concentration be 0.5 ~ 2mol/L;
(3) add oxide or hydroxide, make its concentration be 1 ~ 3mol/L;
(4) aqueous solution is stirred 10 minutes ~ 2 hours;
(5) make aqueous solution Separation of Solid and Liquid with centrifuge or filter press, obtain filter cake;
(6) filter cake cleaned, grind and obtain non-silver powdery solid solution antibacterial agent.
2. the preparation method of non-silver powdery solid solution antibacterial agent as claimed in claim 1, is characterized in that: described zinc salt or mantoquita are one or more in zinc nitrate, copper nitrate, zinc acetate, Schweinfurt green, zinc chloride, copper chloride.
3. the preparation method of non-silver powdery solid solution antibacterial agent as claimed in claim 1, is characterized in that: described oxide or hydroxide are one or more in calcium oxide, magnesia, slaked lime or magnesium hydroxide.
4. the preparation method of non-silver powdery solid solution antibacterial agent as claimed in claim 1, is characterized in that: described water is deionized water, pure water or ordinary tap water.
5. the application of non-silver powdery solid solution antibacterial agent on pottery utilizing claim 1 method to prepare.
6. the application of non-silver powdery solid solution antibacterial agent on pottery as claimed in claim 5, is characterized in that comprising the steps:
(I) with the temperature of 100 ~ 300 DEG C, antibacterial agent is dried, dewatered;
(II) add water the glaze raw material milling apparatus of pottery grinding, makes common glaze slip;
(III) add after antibacterial agent in the ratio of glaze slip gross weight 3 ~ 5%, then grind, make antibacterial agent and the abundant affinity of glaze, dispersion, obtain antibacterial glaze slip;
(IV) rest, constantly stirs glaze slip in rest process;
(V) dry, and sinter with the temperature higher than former sintering temperature 10 ~ 30 DEG C, make antibacterial ceramic products, described original sintering temperature is generally 800 DEG C ~ 1300 DEG C.
7. the application of non-silver powdery solid solution antibacterial agent on pottery as claimed in claim 5, is characterized in that comprising the steps:
(I) with the temperature of 100 ~ 300 DEG C, antibacterial agent is dried, dewatered;
(II) in polyvinyl alcohol, add the antibacterial agent of 3 ~ 5%, make antibacterial glaze liquid;
(III) brushing antibacterial glaze liquid at rest and on dry ceramic mold, then carry out drying, sintering, make antibacterial ceramic products.
8. the non-silver powdery solid solution antibacterial agent utilizing claim 1 method to prepare is kept a public place clean at resin, washing powder, cement, printing-ink, paper pulp, paraffin, water body, application in anti-algae.
9. apply as claimed in claim 8, it is characterized in that: can keep a public place clean in resin, washing powder, cement, printing-ink, paper pulp, paraffin, water body, the raw material total amount of anti-algae 0.5 ~ 5% ratio directly add.
10. the non-silver powdery solid solution antibacterial agent utilizing claim 1 method to prepare is applied in adhesive agent, described adhesive agent refers to can by various antibiotic preparation firmly and be attached on artificial leather, metal, plastics, wood furniture, ceramic sanitary appliance, cement, paper, natural fibre products matrix material for a long time, and the metal ion of energy delivery of antimicrobials, kill the pathogenic microorganisms pressing down attachment.
11. apply as claimed in claim 10, it is characterized in that: described adhesive agent raw material is environmentally-friendly latex paint for interior walls, clean interior wall Polyester Paint, water-fast clean Polyester Paint, organic silicone finishing agent and antibacterial finishing agent.
12. apply as claimed in claim 11, it is characterized in that: described organic silicone finishing agent is that active gene introduced by siloxanes side base, the interpenetrating network copolymer synthesized with specific macromolecule performed polymer, described antibacterial finishing agent is the copolymer of carbimide and acrylic acid fat.
13. utilize the application described in claim 10, it is characterized in that: by non-silver powdery solid solution antibacterial agent by 1 ~ 3% mass ratio add in adhesive agent raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410387591.2A CN104206420A (en) | 2014-08-07 | 2014-08-07 | Preparation method and application of silver-free powdery solid solution anti-bacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410387591.2A CN104206420A (en) | 2014-08-07 | 2014-08-07 | Preparation method and application of silver-free powdery solid solution anti-bacterial agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104206420A true CN104206420A (en) | 2014-12-17 |
Family
ID=52088640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410387591.2A Pending CN104206420A (en) | 2014-08-07 | 2014-08-07 | Preparation method and application of silver-free powdery solid solution anti-bacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104206420A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967642A (en) * | 2016-04-27 | 2016-09-28 | 陈源浩 | Functional active purifying ceramic and preparation method and application thereof |
| CN106621565A (en) * | 2016-11-29 | 2017-05-10 | 浙江水马环保科技有限公司 | Polybasic ion antibacterial carbon fiber filter element |
| CN106633194A (en) * | 2016-11-28 | 2017-05-10 | 浙江水马环保科技有限公司 | Multi-ion antibacterial material |
| CN106719819A (en) * | 2016-11-29 | 2017-05-31 | 浙江水马环保科技有限公司 | A kind of polybasic ion anti-bacteria ceramic base filter core and preparation method thereof |
| CN106832756A (en) * | 2016-12-29 | 2017-06-13 | 浙江水马环保科技有限公司 | A kind of polybasic ion antimicrobial macromolecule material additive |
| CN106938848A (en) * | 2017-01-18 | 2017-07-11 | 浙江水马环保科技有限公司 | A kind of polybasic ion anti-bacteria ceramic filtrate and preparation method thereof |
| CN107723844A (en) * | 2017-10-24 | 2018-02-23 | 安徽亚源印染有限公司 | A kind of preparation method of high temperature resistant PLA fibers |
| CN107723845A (en) * | 2017-10-24 | 2018-02-23 | 安徽亚源印染有限公司 | A kind of antibacterial PLA fabrics and preparation method thereof |
| CN111109291A (en) * | 2019-12-13 | 2020-05-08 | 佛山欧神诺陶瓷有限公司 | Ceramic tile antibacterial agent and preparation method thereof |
| CN111760068A (en) * | 2020-08-21 | 2020-10-13 | 中南大学 | Preparation method and application of pH-responsive controlled-release copper nano material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775032A (en) * | 2005-11-30 | 2006-05-24 | 青岛大学 | Nano TiO2 carrying metal ion antibacterial agent and its preparing method |
-
2014
- 2014-08-07 CN CN201410387591.2A patent/CN104206420A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775032A (en) * | 2005-11-30 | 2006-05-24 | 青岛大学 | Nano TiO2 carrying metal ion antibacterial agent and its preparing method |
Non-Patent Citations (1)
| Title |
|---|
| 金宗哲: "《无机抗菌材料及应用》", 31 August 2004, 化学工业出版社 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967642B (en) * | 2016-04-27 | 2018-04-10 | 陈源浩 | Net porcelain of a kind of feature work and preparation method thereof |
| CN105967642A (en) * | 2016-04-27 | 2016-09-28 | 陈源浩 | Functional active purifying ceramic and preparation method and application thereof |
| CN106633194A (en) * | 2016-11-28 | 2017-05-10 | 浙江水马环保科技有限公司 | Multi-ion antibacterial material |
| CN106621565A (en) * | 2016-11-29 | 2017-05-10 | 浙江水马环保科技有限公司 | Polybasic ion antibacterial carbon fiber filter element |
| CN106719819A (en) * | 2016-11-29 | 2017-05-31 | 浙江水马环保科技有限公司 | A kind of polybasic ion anti-bacteria ceramic base filter core and preparation method thereof |
| CN106621565B (en) * | 2016-11-29 | 2019-06-18 | 浙江水马环保科技有限公司 | A kind of polybasic ion antibiotic carbon fiber filter core |
| CN106832756A (en) * | 2016-12-29 | 2017-06-13 | 浙江水马环保科技有限公司 | A kind of polybasic ion antimicrobial macromolecule material additive |
| CN106938848B (en) * | 2017-01-18 | 2019-01-11 | 浙江水马环保科技有限公司 | A kind of polybasic ion anti-bacteria ceramic filtrate and preparation method thereof |
| CN106938848A (en) * | 2017-01-18 | 2017-07-11 | 浙江水马环保科技有限公司 | A kind of polybasic ion anti-bacteria ceramic filtrate and preparation method thereof |
| CN107723845A (en) * | 2017-10-24 | 2018-02-23 | 安徽亚源印染有限公司 | A kind of antibacterial PLA fabrics and preparation method thereof |
| CN107723844A (en) * | 2017-10-24 | 2018-02-23 | 安徽亚源印染有限公司 | A kind of preparation method of high temperature resistant PLA fibers |
| CN111109291A (en) * | 2019-12-13 | 2020-05-08 | 佛山欧神诺陶瓷有限公司 | Ceramic tile antibacterial agent and preparation method thereof |
| CN111760068A (en) * | 2020-08-21 | 2020-10-13 | 中南大学 | Preparation method and application of pH-responsive controlled-release copper nano material |
| CN111760068B (en) * | 2020-08-21 | 2021-11-12 | 中南大学 | Preparation method and application of pH-responsive controlled-release copper nano material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104206420A (en) | Preparation method and application of silver-free powdery solid solution anti-bacterial agent | |
| CN102763678B (en) | Method for preparing cubic zirconium phosphate silver-carrying antimicrobial powder | |
| CN101176468B (en) | Inorganic complex antimicrobials containing zincium-rare earth as well as preparation method and application thereof | |
| AU690563B2 (en) | Improved antimicrobial composition | |
| US7704903B2 (en) | Antimicrobial phosphate glass with adapted refractive index | |
| US6939820B2 (en) | Antibacterial glass composition and antibacterial polymer composition using the same | |
| CN105494429B (en) | Antibacterial mildew preventive, preparation method thereof and antibacterial mildew preventive method | |
| WO2007004713A1 (en) | Antibacterial agent comprising silver-containing aluminum sulfate hydroxide particle and use thereof | |
| CN103726125A (en) | Anti-mite antibacterial polyester staple fiber and preparation method thereof | |
| US20120064131A1 (en) | Silver-based inorganic antimicrobial agent and method for preparing the same | |
| EP2213173A1 (en) | Silver-containing inorganic antibacterial | |
| CN104206418A (en) | Preparation method and application of discoloration-preventing powdery silver-containing anti-bacterial agent | |
| CN110200013A (en) | A kind of antibacterial mildew inhibitor and the preparation method and application thereof | |
| CN1310589C (en) | Method for preparing superfine composite inorganic antimicrobial agent | |
| CN107641416A (en) | A kind of antibacterial powder paint | |
| JPS6270221A (en) | Amorphous aluminosilicate having antimicrobial and/or germicidal action | |
| CN104161044A (en) | Preparation method and application of organic/inorganic compound antibacterial agent | |
| JP3110963B2 (en) | Durable antimicrobial agent | |
| CN1813539A (en) | Inorganic compound antibacterial agent, and its preparing method and use | |
| CN108558210A (en) | A kind of antibacterial ceramic glaze and preparation method thereof | |
| CN113773049B (en) | Zircon sand whitening emulsion and preparation process thereof | |
| CN105131336A (en) | Antibacterial agent, preparation method and application thereof | |
| CN101182690B (en) | Inorganic silver-impregnated antibiotic zeolite microparticles retention agent, method of producing the same and applications | |
| JPH06263612A (en) | Aqueous suspension of silver-based inorganic antimicrobial agent fine particle and its production | |
| JP4364357B2 (en) | Water reforming parts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160601 Address after: 234300 Wanxing Science Park, Sixian Economic Development Zone, Anhui, Suzhou Applicant after: ANHUI WANXING INDUSTRY LIMITED COMPANY Address before: 100083 No. 8 Garden Road East, Beijing, 12-252, north, Haidian District Applicant before: Cai Huiping |
|
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141217 |
|
| RJ01 | Rejection of invention patent application after publication |