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
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- 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
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- antibacterial
- solid solution
- antibacterial agent
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 64
- 239000006104 solid solution Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 150000003751 zinc Chemical class 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 29
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 28
- 229910052709 silver Inorganic materials 0.000 claims description 28
- 239000004332 silver Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 14
- 239000003973 paint Substances 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229910021645 metal ion Inorganic materials 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 10
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 230000001680 brushing effect Effects 0.000 claims description 9
- 239000004568 cement Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- -1 Schweinfurt green Chemical compound 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000002649 leather substitute Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000004599 antimicrobial Substances 0.000 claims description 3
- 230000003115 biocidal effect Effects 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 244000000010 microbial pathogen Species 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004816 latex Substances 0.000 claims description 2
- 229920000126 latex Polymers 0.000 claims description 2
- 229920002521 macromolecule Polymers 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 108090000623 proteins and genes Proteins 0.000 claims description 2
- 239000008399 tap water Substances 0.000 claims description 2
- 235000020679 tap water Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 235000012255 calcium oxide Nutrition 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 235000012245 magnesium oxide Nutrition 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 229940087373 calcium oxide Drugs 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 239000011214 refractory ceramic Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000001465 calcium Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
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- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
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.
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Cited By (11)
| 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 |
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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 * |
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