CN1209971C - Zinc oxide whisker compound germicide composition - Google Patents
Zinc oxide whisker compound germicide composition Download PDFInfo
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- CN1209971C CN1209971C CN 03117502 CN03117502A CN1209971C CN 1209971 C CN1209971 C CN 1209971C CN 03117502 CN03117502 CN 03117502 CN 03117502 A CN03117502 A CN 03117502A CN 1209971 C CN1209971 C CN 1209971C
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Abstract
The present invention discloses a zinc oxide whisker compound germicide composition which contains the components of the following proportion by weight: 50 to 80 portions of tetrapod-shaped zinc oxide whisker, 5 to 25 portions of nanometer zinc oxide, 5 to 25 portions of nanometer titanium oxide and 10 to 40 portions of sodium silicate as carriers. The zinc oxide whisker compound germicide composition has the advantages of strong capacity for sterilization and antisepsis, repeated and persistent process and effect of sterilization and antisepsis, stable function, no color change, no need of photocatalysis, convenient use, etc.
Description
Affiliated technical field:
The present invention relates to a kind of antibacterial agent material, relate in particular to a kind of inorganic complex antimicrobials material.It can be applicable to fields such as packaging for foodstuff, construction material, medical equipment, amenities, articles for daily use, cleaners and polishes, household electrical appliance, Communication Equipment.
Background technology:
Noxious bacteria is present in the various occasions around us, as housing floor, the metope of living, the furniture of use, household electrical appliances, clothing and articles for daily use etc.1996, the national infection incident of 0-157 Escherichia coli of Japanese large tracts of land outburst was not only seized many people's life, and caused that the whole world is panic.According to statistics, the whole world is annual because of bacterial infection causes dead number near 2,000 ten thousand, accounts for more than 30% of dead sum; The intersection bacterial infection rate of each hospital surpasses 10%.Will prevent effectively that bacterium from producing and grow, using anti-biotic material is the most simple and efficient method.Anti-biotic material is meant the class new function material with sterilization and bacteria growing inhibiting function.
Antibacterial agent mainly contains inorganic, organic and natural three major types.Natural antibacterial agent comes from the natural extract material, as shitosan, Hinokitiol etc., natural antibacterial agent toxicity is little, safe, but service life is short, poor heat resistance (150～180 ℃ of charings are decomposed), is mainly used in disposable plastic products such as food pack.The organic antibacterial agent main component is tetravalence amine salt, alcohols, biguanides material, have instant effect, characteristics that sterilizing ability is strong, but easily produce the microorganism drug resistance, and there are deficiencies such as easily migration, poor heat resistance, many organic antibacterial agents are easy decomposition failure under high temperature, high pressure, high shear processing conditions, and catabolite causes secondary pollution.Inorganic antiseptic adopts the physical adsorption ion-exchange process, and metals such as silver, copper, zinc are carried on porous material surface, utilizes the antibacterial action of metal ion, reaches the purpose of long-acting bacteriostatic by slow releasing function.Inorganic antiseptic does not produce drug resistance and safety is good, and particularly its outstanding warm tolerance (＞600 ℃) has very big advantage in the application of multiple antibacterial product.Existing inorganic antiseptic is mainly based on silver and zinc ion, wherein best with the antibacterial effect of silver ion, but silver ion antimicrobial agent exists and easily to be reduced and variable color (being grey black) and cost high two big shortcomings, and simple substance is silver-colored to be lost or weaken its antibacterial effect greatly owing to becoming after reducing.At present, have and report that much nano material has antibiotic property, but simple nano material has very big surface area because particle diameter is too little, be difficult in use fully disperse, even can't disperse.Coat processing so all will carry out the surface before using to it.The result who coats greatly reduces the performance of nano effect and antibacterial action on the one hand, and this on the other hand processing procedure also is very loaded down with trivial details.Moreover, more existing nano-powder materials are (as nano-TiO
2) will rely on photocatalysis just to show certain antibacterial effect.(spy opens flat 5-912 to Japan Patent, Te Kaiping 8-133918) report is compound with four acicular type zinc oxide crystal whisker and silver salt, prepared inorganic antiseptic and in different materials and environment, obtained to use (Te Kaiping-93365 with excellent antibacterial effect, Te Kaiping 5-78498, Te Kaiping 78218, Te Kaiping 6-140731 etc.), the technology of these Japan Patent reports is utilized the spicule activated centre and the point effect of ZnOw, activate airborne water and oxygen, produce hydroxyl radical free radical (OH) and active oxygen ion (O
- 2), destroy bacteria live and multiplication capacity and make bacterium death, and reach antibacterial effect.But owing to use common ZnOw, its whisker length reaches 30-100 μ m, and root diameter (RD) slightly reaches 0.1～10 μ m.Its spicule activated centre is few, and point effect is poor, in order to improve antibacterial effect, add silver ion as one of main antibacterial activity composition, and wherein silver ion still faces discoloration problem.
Summary of the invention:
It is strong to the purpose of this invention is to provide a kind of sterilization antimicrbial power, and it is stable that antibiotic process of sterilization and effect can repeat to continue to carry out, act on, and nondiscolouring, also need not light-catalysed ZnOw complex antimicrobials composition.
The technical solution adopted for the present invention to solve the technical problems is: a kind of ZnOw complex antimicrobials composition, the component and the weight proportion that contain are: length is 1～10 μ m, root diameter (RD) is 50～80 parts of the four acicular type zinc oxide crystal whiskers of 0.1～2 μ m, 5～25 parts of nano zine oxides, 5～25 parts of nano-titanium oxides, 10～40 parts in sodium silicate carrier.
The invention has the beneficial effects as follows: 1, the spicule activated centre and the point effect of ZnOw can produce and discharge active oxygen repeatedly, and have extremely strong and stable oxidation disinfection antibacterial ability; On this basis, the present invention has added nano-ZnO, nano-TiO
2,, antibacterial effect is further strengthened because distinctive skin effect of nanoparticle and small-size effect are given their high catalytic activitys.2, a spot of nanoparticle is a mesoporous material with the sodium silicate inorganic carrier, fixes and adsorbs nano-ZnO and nano-TiO by physical adsorption
2Particulate; Avoided simple nano antibacterial agent, a large amount of nanoparticle difficulties in dispersion easily produce the problem of secondary agglomeration, have both guaranteed the dispersed and stable of nanoparticle, can reach long acting antibiotic by slow releasing function; Simultaneously, the spicule activated centre of ZnOw and point effect effect make nanoparticle need not to rely on photocatalysis just can produce antibacterial action again.3, no silver ion easy to change and expensive in the composition, not easy to change in storage and the use, and reduced manufacturing cost.
Because the length of the pin of the ZnOw (ZnOw) that adopts is 1～10 μ m, length 30～200 μ m much shorters of general ZnOw, can make the antibacterial agent of Unit Weight contain more four spicule activated centres and most advanced and sophisticated nano effect, can make product reach higher fineness simultaneously; ZnOw spicule root diameter (RD) is controlled in 0.1～2 mu m range, and its tip and border show the distinctive high surface effect of nano material; Can activate airborne water and oxygen faster, more repeatedly, produce hydroxyl radical free radical (OH
-) and active oxygen ion (O
- 2), can destroy bacteria live and multiplication capacity in the short time and make bacterium death.So its sterilization antimicrbial power further strengthens, the sterilization antibacterial action is more stable.
Also can contain 1～5 part Li in the lattice of 50～80 parts of four acicular type zinc oxide crystal whiskers of the present invention
+, Na
+, K
+The mixture of one or more in three kind of one valent metal oxide.
Make the ZnOw in the antibacterial agent contain the oxygen content that exceeds the quata like this, improved release active oxygen (O
- 2) ability, further improved antibacterial effect.
Test shows: complex antimicrobials composition of the present invention, the antibiotic longer duration of its sterilization, antibacterial agent can play a role repeatedly, minimum inhibitory concentration (MIC) only is 50～150PPM, the material (plastics, coating etc.) that adds 2% this antibacterial agent to the antibacterial effect of common bacterias such as staphylococcus aureus, Escherichia coli, salmonella and candida albicans all above 90%; And this antibacterial agent all do not have any stimulation to test with eyes and the skin of mouse and rat, and its half lethal dose surpasses 10000mg/Kg, the nontoxic grade of product in true border.
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.
Fig. 1 is electron micrograph (3000X) figure of the four acicular type zinc oxide crystal whisker in the embodiment of the invention component.
Fig. 2 is electron micrograph (100000X) figure of the nano zine oxide in the component of the present invention.
Fig. 3 is electron micrograph (100000X) figure of the nano-titanium oxide in the component of the present invention.
Embodiment
Embodiment 1～4
At first, according to existing four acicular type zinc oxide crystal whisker preparation method (as the method for ZL97107607.3 and ZL98111828.3 two patents), adopt the common chamber type electric resistance furnace preparation four acicular type zinc oxide crystal whisker of heating.But temperature should be controlled between 400～700 ℃, the whisker growth time was controlled at 15～20 minutes.Deal by table 1 illustrated embodiment 1～4 takes by weighing: the zinc band of wide about 5mm, thick about 0.2mm; And press each routine kind shown in the table 1, deal and add Li
+, Na
+Or K
+One or more mixture Deng in the univalent metal salt carries out whisker growth.The length that promptly prepares embodiment 1～4 required deal of special use of the present invention is that 1～10 μ m, root diameter (RD) are 0.1～2 μ m, and contains the four acicular type zinc oxide crystal whisker of a valent metal oxide (oxygen content exceeds the quata) of required deal in lattice.
Its specific operation process is: with the zinc band of wide about 5mm, thick about 0.2mm, put into the refractory ceramics crucible, evenly be sprinkled into LiNO on the zinc band
3Or NaNO
3Or KNO
3(valent metal oxide) or its two or more mixture of powders are put into the chamber type electric resistance furnace that has been warming up to 400～700 ℃ in advance, close fire door, are incubated 15～20 minutes.Open fire door, obtain the white loose sprills, product yield is more than 95%.The product microstructure is four needle-like whiskers as shown in Figure 1, and spicule length is 2～10 μ m, and root diameter (RD) is 0.5～2 μ m, contains a valent metal oxide in the lattice.Certainly, if be not sprinkled into any valent metal oxide, then obtain not containing in the lattice four needle-like whiskers of a valent metal oxide.
Two, can form the sodium silicate of loose structure, water is made as dispersion medium, presses table 1 deal and adds nano-ZnO and nano-TiO
2, leave standstill more than 24 hours the nano-complex that filter, oven dry obtains the mesoporous material coating after stirring.Nano-ZnO and nano-TiO
2Microstructure see Fig. 2, Fig. 3 respectively.
The present invention also can adopt other inorganic carrier materials that can form loose structure to make dispersion, as long as can form loose structure, and can fix and adsorb nano-ZnO and nano-TiO
2Particulate gets final product.
Three, the nano-complex that above-mentioned mesoporous material is coated fully mixes with four needle-like whisker ZnOw, and after sieving with different sieves according to customer requirements, promptly obtains the ZnOw complex antimicrobials composition product of the embodiment of the invention 1～4.
Practical application and test: the complex antimicrobials composition that embodiment 1～4 is made adds in the polyvinyl resin by 1% or 2% part by weight and becomes film article with common process blowing or curtain coating, measures antibacterial effect and sees Table 1.
Do not add any antibacterial agent in the comparative example 1 of table 1, add the common zinc oxide whisker in the comparative example 2.
Table 1 ZnOw composite antibiosis agent prescription (weight portion) and antibacterial effect (%)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | ||
| The special-purpose whisker (ZnOw) of the present invention | 80 | 62 | 50 | 50 | 0 | 0 | |
| Valent metal oxide among the ZnOw | 5(Li +) | 3(Na +) | 1(Li +) | 2(Li +Na +) | |||
| The common zinc oxide whisker | 0 | 0 | 0 | 0 | 0 | 78 | |
| Nano zine oxide | 5 | 8 | 25 | 5 | 0 | 5 | |
| Nano-titanium oxide | 5 | 8 | 5 | 25 | 0 | 5 | |
| Sodium silicate | 10 | 22 | 40 | 40 | 0 | 12 | |
| To the antibacterial effect (%) of staphylococcus aureus (MIC:75PPM) | |||||||
| Add in the blowing PE film (1%) | 98.2 | 92.3 | 80.6 | 76.4 | 0 | 54.6 | |
| Add in the blowing PE film (2%) | 99.9 | 98.4 | 90.5 | 91.9 | 0 | 72.9 | |
| Add in the curtain coating PE film (1%) | 97.8 | 92.6 | 81.5 | 72.0 | 0 | 45.2 | |
| Add in the curtain coating PE film (2%) | 99.8 | 98.8 | 91.9 | 92.4 | 0 | 56.7 | |
| To colibacillary antibacterial effect (%) (MIC:115PPM) | |||||||
| Add in the blowing PE film (1%) | 91.3 | 78.4 | 71.3 | 65.4 | 0 | 43.5 | |
| Add in the blowing PE film (2%) | 99.2 | 96.4 | 97.6 | 97.9 | 0 | 75.3 | |
| Add in the curtain coating PE film (1%) | 93.5 | 94.5 | 82.9 | 62.4 | 0 | 54.2 | |
| Add in the curtain coating PE film (2%) | 99.9 | 95.6 | 95.3 | 95.8 | 0 | 79.8 | |
| To the antibacterial effect (%) of white beads ball (MIC:135PPM) | |||||||
| Add in the blowing PE film (1%) | 81.4 | 82.1 | 65.4 | 67.3 | 0 | 54.2 | |
| Add in the blowing PE film (2%) | 99.9 | 91.6 | 90.9 | 92.3 | 0 | 72.3 | |
| Add in the curtain coating PE film (1%) | 89.2 | 87.3 | 73.2 | 71.2 | 0 | 56.0 | |
| Add in the curtain coating PE film (2%) | 99.6 | 95.2 | 92.1 | 94.4 | 0 | 68.3 | |
Annotate: MIC is a minimum inhibitory concentration.
Antimicrobial composition of the present invention is as function additive, can add in the base materials such as plastics, rubber, fiber, pottery, coating, be widely used in the fields such as packaging for foodstuff, building materials, medical equipment, amenities, articles for daily use, cleaners and polishes, household electrical appliances, Communication Equipment.
Claims (2)
1, a kind of ZnOw complex antimicrobials composition, the component and the weight proportion that contain are: length is 1～10 μ m, and root diameter (RD) is 50～80 parts of the four acicular type zinc oxide crystal whiskers of 0.1～2 μ m, 5～25 parts of nano zine oxides, 5～25 parts of nano-titanium oxides, 10～40 parts in sodium silicate carrier.
2, a kind of ZnOw complex antimicrobials composition according to claim 1 is characterized in that: also contain 1～5 part Li in the lattice of described 50～80 parts of four acicular type zinc oxide crystal whiskers
+, Na
+, K
+The mixture of one or more in three kind of one valent metal oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117502 CN1209971C (en) | 2003-03-21 | 2003-03-21 | Zinc oxide whisker compound germicide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117502 CN1209971C (en) | 2003-03-21 | 2003-03-21 | Zinc oxide whisker compound germicide composition |
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| Publication Number | Publication Date |
|---|---|
| CN1531852A CN1531852A (en) | 2004-09-29 |
| CN1209971C true CN1209971C (en) | 2005-07-13 |
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|---|---|---|---|
| CN 03117502 Expired - Lifetime CN1209971C (en) | 2003-03-21 | 2003-03-21 | Zinc oxide whisker compound germicide composition |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374519C (en) * | 2005-07-29 | 2008-03-12 | 西南交通大学 | Antibacterial surface decorative material and its preparation method |
| CN100467554C (en) * | 2008-03-25 | 2009-03-11 | 中华制漆（深圳）有限公司 | Coating composition with antimicrobial and air purification function |
| CN101705005B (en) * | 2009-11-13 | 2011-10-05 | 中国人民解放军第四军医大学 | Method for modifying performance of compound resin by using tetrapod-like zinc oxide whiskers |
| CN101773147B (en) * | 2010-01-27 | 2012-06-27 | 中南大学 | Modified T-ZnOw antibiotic material and preparation method thereof |
| CN102145276B (en) * | 2011-03-14 | 2013-06-12 | 西南交通大学 | Air-purifying particle composition and preparation method of air-purifying particle composition |
| CN102417220B (en) * | 2011-11-28 | 2013-09-25 | 南京大学 | Application of tantalum-doped zinc oxide nanometer powder photocatalyst in water treatment antisepsis |
| CN102898902A (en) * | 2012-10-26 | 2013-01-30 | 合众（佛山）化工有限公司 | Method for preparing composite multifunctional moisture-adjusting antibacterial interior wall coating |
| CN104054753A (en) * | 2014-06-30 | 2014-09-24 | 南通蛇类治疗研究所 | Antibacterial and sterilization disinfectant for killing avian influenza viruses |
| CN104307471A (en) * | 2014-09-30 | 2015-01-28 | 深圳安吉尔饮水产业集团有限公司 | Nano-whisker activated carbon bar for filter element and preparation method thereof |
| CN105475354B (en) * | 2015-11-25 | 2018-03-02 | 航天神舟生物科技集团有限公司 | A kind of CNT/four acicular type zinc oxide crystal whisker composite antibacterial material and preparation method thereof |
| CN105694176B (en) * | 2016-02-18 | 2019-02-19 | 惠州市环美盛新材料有限公司 | A kind of antibacterial enhancing HDPE function pipeline masterbatch and preparation method thereof |
| CN106883553A (en) * | 2017-04-17 | 2017-06-23 | 成都交大晶宇科技有限公司 | Wear-resisting U.S. vessel of resistance to ware of antibacterial and preparation method thereof |
| CN111286227B (en) * | 2020-01-19 | 2021-09-21 | 成都天佑晶创科技有限公司 | Formaldehyde removal additive for coating and application method thereof |
| CN111925593A (en) * | 2020-08-04 | 2020-11-13 | 日丰企业集团有限公司 | Antibacterial pipe and preparation method thereof |
-
2003
- 2003-03-21 CN CN 03117502 patent/CN1209971C/en not_active Expired - Lifetime
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