CN100403907C - Inorganic bactericidal agent and its use - Google Patents
Inorganic bactericidal agent and its use Download PDFInfo
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- CN100403907C CN100403907C CNB2004100226771A CN200410022677A CN100403907C CN 100403907 C CN100403907 C CN 100403907C CN B2004100226771 A CNB2004100226771 A CN B2004100226771A CN 200410022677 A CN200410022677 A CN 200410022677A CN 100403907 C CN100403907 C CN 100403907C
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- antibacterial
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Abstract
The present invention relates to an inorganic bactericidal agent and the application thereof, wherein the inorganic bactericidal agent belongs to the technical field of inorganic antibacterial materials. The inorganic bactericidal agent is prepared from apatite or compound ceramics (prepared by mixing apatite with one or above two of natural silicate minerals) as carriers and bactericidal metallic materials with the weight accounting for 3 to 20 wt% of the gross weight of the carriers, wherein the compound ceramics are prepared from 50 to 90 wt% of silicate mineral and 50 to 10 wt% of apatite; the bactericidal metallic materials are selected from metal salts or metal oxides or metal monomers of the metals of Ag, Cu and Zn, the metal salts are hydrochlorides, nitrates, sulfate, arbonates, organic salts or metallic complex salts containing Ag, Cu and Zn, the metal oxides are Ag2O, CuO and ZnO, and the metal monomers are Ag, Cu and Zn. The inorganic bactericidal agent can be used for preparing bactericidal porcelain articles, bactericidal coatings, bactericidal plastic films or antibacterial fibers and antibacterial paper. The inorganic bactericidal agent of the present invention has the advantages of natural materials as the carriers, no need of artificial synthesis, low cost, strong bactericidal power, high temperature resistance, etc.
Description
Technical field:
The present invention relates to a kind of inorganic antiseptic and application thereof, belong to the inorganic antibacterial material technical field.
Background technology:
Original inorganic antiseptic many with synthetic manufacturings such as zeolite, calcium phosphate, glass have stratiform or cancellated inorganic material is a carrier, be that antibiotic effective ingredient is made with metal ions such as silver, copper, zinc.In addition, also there is patent to propose to adopt AL
2O
3, CaO, SiO
2, ZrO
2, TiO
2Deng oxide is carrier, is antimicrobial component with metal ions such as Ag, Cu, Zn, has also prepared the inorganic antibacterial material with good antibacterial characteristics.
It is known that metal ions such as Ag, Cu, Zn have antibacterial action.With what these metal ions load was held in that method on the carrier reports so far physical adsorption, ion-exchange etc. are arranged.Utilize physisorphtion that antibiotic effective ingredients such as Ag, Cu, Zn loads is held in above active carbon, activated alumina, silica gel or the alumino-silicate etc. and obtain inorganic antibacterial material.Because of the antibacterial metal that is adsorbed on physisorphtion on these carriers is understood the transition stripping, and can not keep antibiotic property muchly.Developed ion-exchange for this reason.Utilize ion-exchange that the antibacterial metal load is held on the carrier.As specially permit No. 3448530, invented in the hydroxyapatite that utilizes ion-exchange antibacterial metal ions load to be held in synthetic and made inorganic antiseptic.And for example the spy opens and utilizes for 2003-193540 number ion-exchange that antibacterial metal ions load is held in alumina silicate based compound, titanium dioxide based compound, phosphate-based compound and the silica based compound and obtain anti-biotic material.There are the following problems for ion-exchange: the load amount of holding of antibacterial metal ions is limited, can not control the load of any amount and hold; Simultaneously molten usually in the solution after ion exchange have a certain amount of antibiotic heavy metal ion, for free from environmental pollution, must reclaim, and be uneconomic therefore.For this reason, some inventions have appearred again, open flat 7-315866 as the spy and disclose a kind of mixed sintering body particle surface that utilizes silver mirror reaction the Ag load to be held in calcium phosphate and feldspar, and the pottery that silver is carried on this surface mixed in the common glaze and obtain the method for antibiotic glaze, and for example specially permit No. 3176054 and invented employing bialuminate (A), antibacterial metal salts or metal (B), the direct neutralization reaction of silicate base (C) three and obtain the method for antibiotic property alumina silicate.It is limited that the existence load that said method has is held the antibiotic property metal ion, can not control load and hold the antibacterial metal of any amount, promptly can not carry on a shoulder pole and hold necessary demand, so antibiotic property is low; Have because of poor heat resistance, during sintering by etch in the glassy phase that dissolves to making antibiotic property not high, even lose antibiotic property.Mostly be synthetic about carrier again, the cost height; And the carrier material composition is single, is difficult to bring into play the collaborative synergism of carrier and antibacterial metal ions, and the antibacterial action of antibacterial metal ions can not be given full play to.
The content of invention:
The objective of the invention is to overcome the problem of above-mentioned existence, and propose to adopt natural apatite or natural apatite to mix with in the natural silicate ore deposit one or two or more kinds and the compound pottery be carrier, with metal ions such as Ag, Cu, Zn is antibiotic effective ingredient, adopt to mix again through High temperature diffusion and solid phase reaction and mixed method, effective antibacterial metal ions load is held in the carrier and produces high performance inorganic antiseptic.
Carrier of the present invention is to utilize natural silicate mineral, apatite, and the structure space such as intrinsic stratiform, chain, island, frame shape, all also there be defective, the hole of volume in these materials in structure; Thereby at high temperature antibacterial metal ions can more easily enter in these spaces, defective, the hole, even solid solution or solid phase reaction enter in the lattice of carrier material or mix with it and adhere to; Therefore the controlled carrier can be carried on a shoulder pole the antibacterial metal of holding any amount, and promptly requiring to carry on a shoulder pole the antibacterial metal of holding aequum according to application target is the preparation method of its characteristics.
Inorganic antibacterial of the present invention mix with in the natural silicate mineral one or more by apatite or apatite and compound be carrier, with Ag, Cu, Zn metal ion is antibiotic effective ingredient, the gross weight that all each antibacterial metals that add contain thing weight sum is that the antibacterial metal of the 3-20wt% of total weight of carrier contains material and makes, wherein:
(1) proportioning of composite ceramics is: selected silicate mineral total amount proportion in the composite ceramics total amount is 50-90wt%, and apatite proportion in the composite ceramics total amount is 50-10wt%;
(2) antibacterial metal contains material and is: adopt the slaine or metal oxide or the metal monomer that contain antibacterial metal Ag, Cu, Zn respectively, slaine is respectively the hydrochloride that contains Ag, Cu, Zn, nitrate, sulphate, carbonate, or organic salt or metallic complex salt; Metal oxide is Ag
2O, CuO, ZnO; The metal monomer is Ag, Cu, Zn;
(3) antibacterial metal contain material can choose in the argentiferous thing that satisfies proportioning any one or more than two kinds, its weight of being converted into silver oxide is 3～20wt.% of total weight of carrier; Choose contain in the silver material any one or more than two kinds, it is 0.1～2wt% that its argentiferous amount of substance is converted into behind the silver oxide to vehicle weight, and mix copper-containing substance simultaneously or zinc contains material, or mixing cupric and zinc-containing substance simultaneously, its incorporation is converted into corresponding oxide, and to be converted into the summation of the amount of silver oxide be the 3-20wt% of total weight of carrier with containing silver material.
The said natural silicate of the present invention ore deposit comprises (1) chain silicate mineral (pyroxene: xy[Si
2O
6], x=Ca, Mg, Fe
2+, Mn, Na, Li, y=Mg, Fe
3+, Mn, Al; Wollastonite: Ca
3[Si
3O
9], hornblend class silicate: R
7[Si
4O
11]
2(OH)
2, R=Mg
2+, Ca
2+, Na
+, AI
3+, hornblend: A
0～1X
2Y
5[Si
8O
22] (OH, FCI)
2, A=Na, Ca, K, H, X=Na, Li, K, Ca, Mg, Fe
2+, Y=Mg, Fe
3+, Mn, Al, Ti); (2) layer silicate mineral (kaolinite: Al
4[Si
4O
10] (OH)
8(small amount of Fe, Mg, Cr substitute for Al are often arranged), talcum: Mg
3[Si
4O
10] (OH)
2Shepardite: Mg (OH)
2Mica: [KMg
3(AlSi
3O
10) (OH)
2]; Clay class silicate: comprise kaolinite, montomorillonite, illite; (3) tectosilicate (zeolite: AmXpO
2PnH
2O, A=Na, Ca, K, Ba, Sr, a small amount of Mg, Mn, X=Si, AI; Sodalite: Na
8[AlSiO
4]
6Cl
12, leucite: K[AlSi
2O
6], Partial K can be by Na, the Ca displacement, and scapolite: (Na, Ca)
4[Al
2Si
2O
8]
3(Cl, F, OH, CO
3, SO
4); Feldspar: potassium feldspar, albite, anorthite, baryta fledspar);
(4) nesosilicate mineral (andalusite: Al
2[SiO
4] O, often contain Mn, Fe and carbonaceous, zircon: ZrSiO
4, forsterite: Mg
2[SiO
4], dolomite: CaMg[CO
3]
2); (5) ring silicate mineral (tourmaline: Na[Mg, Fe, Mn, Li, Al]
3Al
6[Si
6O
18] [BO
3]
3(OH)
4)), six classes such as (6) diatomite.Apatite is meant a kind of additional anionic simple island phosphate mineral that has, and empirical formula is Ca
2[PO
4]
3[OH, F] often contains Mn, Fe, and Y, Na, tramp materials such as K are the important source material of extracting phosphorus, making phosphate fertilizer, fluorapatite crystal can be used as laser material.
Inorganic antiseptic of the present invention can be used as the preparation antibacterial ceramic products, or preparation antibiotic paint goods, or the preparation antibacterial plastic film, or the preparation antibacterial fiber product, or the application for preparing antibiotic paper, wherein:
During the preparation antibacterial ceramic products: the addition of antibacterial agent is the 1-35wt% of former glaze solid composition.
During the preparation antibiotic paint: the addition of antibacterial agent is the 0.1-20wt% of former coating solid constituent.
During the preparation antibiotic plastic: the addition of antibacterial agent is the 0.5-5wt%. of former plastics weight
During the preparation anti-bacterial fibre: the addition of antibacterial agent is the 0.5-5wt% of fibrillation weight.
When preparing antibiotic paper: the addition of antibacterial agent is the 0.5-3wt% of the solid composition weight of paper pulp.
Advantages such as inorganic antiseptic of the present invention has carrier and is selected from natural material, need not synthetic, and cost is low, and antimicrbial power is strong, and is high temperature resistant.
Embodiment:
One, the preparation of inorganic antiseptic
1, carrier choose that apatite or apatite mix with in the silicate mine one or two or more kinds and complexes carrier, the proportioning of complexes carrier is: the total amount of selected silicate mineral proportion in the complexes carrier total amount is 50～90wt%, and apatite proportion in the complexes carrier total amount is 50～10wt%.
2, the ratio that adds gross weight that all antibacterial metals in the carrier contain thing and the gross weight of above-mentioned carrier for feature is:
Total weight of carrier: all antibacterial metals that mix contain gross weight=100: 3～20 of thing weight sum
The gross weight that all antibacterial metals that promptly mix contain the thing sum is 3～20wt.% of total weight of carrier;
The antibacterial metal raw material can choose the argentiferous thing that satisfies said ratio (with top described be the salt of feature), in the monomer, oxide any one or more than two kinds, its addition is that the gross weight of being converted into silver oxide is 3～20wt.% of total weight of carrier; Or choose one or two or more kinds that contains silver material, it is 0.1～2wt% that its argentiferous amount of substance is converted into behind the silver oxide with respect to vehicle weight, also mix copper-containing substance simultaneously or mix zinc-containing substance or mix cupric and zinc-containing substance simultaneously, the summation that the amount that this moment, all the other copper-containing substances or zinc-containing substance or cupric, zinc material were converted into oxide and silver oxide are converted into the amount of silver oxide must satisfy 3～20wt% said ratio with respect to the ratio of the weight of carrier.
To put into high temperature furnace through the above-mentioned relevant silicate mine after ore dressing, the removal of impurities (deironing etc.) and apatite and carry out high-temperature heat treatment, treatment temperature is 700～1250 ℃, 1～2 hour constant temperature processing time, when reaching predetermined process after the time, be fetched into room temperature cooling outside the stove immediately from high temperature furnace, heat treated purpose is moisture, the organic matter of removing in the mineral.Suddenly the purpose of reducing to room temperature from high temperature be the defective that will produce the thermal treatment etc. fixedly maintenance get off, be beneficial to the antibacterial metal ions High temperature diffusion and enter carrier.
To press above-mentioned formulated through silicate mineral after the above-mentioned thermal treatment or apatite, the relevant antibacterial metal ions that takes by weighing ormal weight by above-mentioned prescription contains thing again, carrier and antibacterial metal are contained thing to be mixed, after fully mixing and ball milling makes its particle diameter be about 5～50 μ m, pack into and place the high temperature furnace sintering in the crucible, temperature is: 700～1200 ℃, constant temperature time 1～2 hour, after constant temperature time reaches official hour, the crucible that will fill antibiotic bacterium material immediately is taken out to cooling under the room temperature environment from stove, why like this, be to make the antibacterial metals such as Ag that diffuse in the carrier not separate out and be fixed in the carrier.
Anti-microbial property (MIC) value of the antibacterial agent that is obtained after above-mentioned technology is 75～500ppm, shows good antibiotic property.
Specific embodiment and effect see Table 1.
Table 1 examples of implementation list
Two, the application of antibacterial agent
1, above-mentioned antibacterial agent is added in the common ceramic glaze or vitreous enamel, through fully mix get final product antibacterial glaze.After pottery, porcelain, the glazing of enamel base substrate, promptly can be made into anti-bacteria ceramic, antibacterial enamel goods through common sintering process sintering.The goods in these fields have ceramic tile, cleaners and polishes (lavatory, commode, bathtub, bathtub etc.), feeder, vase, hospital with enamel tray etc.Its enameling method is common glaze method or spraying process etc., the addition of above-mentioned anti-biotic material can be with respect to the solid constituent of former glaze former glaze solid constituent 1% or 5% or 10% or 20% or 25% or 30% or 35%, through using proof, its antibacterial effect is good.
2, above-mentioned antibacterial agent is joined (coating for internal and external wall and seven common class) in the common coating, through fully mixing, promptly can be made into antibiotic paint, the addition of above-mentioned antibacterial agent can be 0.1% or 0.5% or 0.9% or 13% or 16% or 20% of former coating solid constituent, through using proof, its antibacterial effect is good.
3, with above-mentioned antibacterial agent, join in plastics or the chemical fibre molten state presoma, mix, can be used for making antibacterial plastic film or anti-bacterial fibre, the addition of above-mentioned antibacterial agent can be 0.5 or 0.8 or 2 or 4 or 5wt% with respect to the weight of plastics or fiber, also can mix with crosslinking agent and bonding agent, spraying or brush dye the surface at hot pressing die again, by hot-forming, antibacterial agent is transferred on the surface of plastic products and obtained antibacterial plastic product, or be sprayed on fiber or be immersed in fiber surface and make anti-bacterial fibre.Through using proof, its antibacterial effect is good.
4, above-mentioned antibacterial agent is joined in the paper pulp, by common system paper technology, can obtain antibiotic paper.The addition of above-mentioned antibacterial agent is for can be 0.5 or 1 or 2 or 3wt.% of the solid composition weight of paper pulp with respect to the solid constituent of paper pulp, through using proof, its antibacterial effect is good.
Claims (5)
1. inorganic antiseptic, it is characterized in that this inorganic antiseptic mixes the compound that forms with natural apatite with natural silicate be carrier, to be selected from Ag or Cu or the Zn metal ion one or more is that antibiotic effective ingredient constitutes, each antibiotic effective ingredient is provided by slaine or the oxide that it contains respective metal, and the gross weight that the various antibiotic effective ingredient in the adding carrier contains the weight sum of thing is the 3-20wt.% of total weight of carrier; Wherein:
(1) natural apatite mixes the proportioning of the compound that forms and is with natural silicate: selected silicate proportion in the compound gross weight is 50-90wt.%, and apatite proportion in the compound gross weight is 50-10wt.%;
(2) antibacterial metal contains material and is: adopt the corresponding metal salt that contains antibacterial metal effective ingredient Ag or Cu or Zn, or metal oxide, slaine is respectively hydrochloride, nitrate, sulphate, the carbonate that contains Ag or Cu or Zn; Oxide is respectively Ag
2O, CuO, ZnO;
(3) antibacterial metal contains material to choose with (2) is in the silver salt of feature one or two or more kinds, its gross weight is the 3-20wt.% of total weight of carrier, or choose one or two or more kinds in (2) described silver salt and mix copper-containing substance or zinc-containing substance simultaneously, or mix cupric and zinc-containing substance simultaneously, the gross weight of its selected various argentiferous substance weight sums is the 0.1-2wt.% of total weight of carrier.
2. be the application of the inorganic antiseptic of feature as the preparation antibacterial ceramic products with claim 1, the addition that it is characterized in that antibacterial agent is the 1-35wt% of former glaze solid composition.
3. be the application of the inorganic antiseptic of feature as the preparation antibacterial plastic film with claim 1, the addition that it is characterized in that antibacterial agent is the 0.5-5wt% of former plastics weight.
4. be the application of the inorganic antiseptic of feature as the preparation anti-bacterial fibre with claim 1, the addition that it is characterized in that antibacterial agent is the 0.5-5wt% of fibrillation weight.
5. be the application of the inorganic antiseptic of feature as the antibiotic paper of preparation with claim 1, the addition that it is characterized in that antibacterial agent is the 0.5-3wt% of former paper pulp solid composition weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100226771A CN100403907C (en) | 2004-05-30 | 2004-05-30 | Inorganic bactericidal agent and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100226771A CN100403907C (en) | 2004-05-30 | 2004-05-30 | Inorganic bactericidal agent and its use |
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|---|---|
| CN1582663A CN1582663A (en) | 2005-02-23 |
| CN100403907C true CN100403907C (en) | 2008-07-23 |
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Families Citing this family (12)
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| CN100413811C (en) * | 2005-09-16 | 2008-08-27 | 广东三水大鸿制釉有限公司 | Nanometer clay modified silide composition for filming on polished brick and its prepn process |
| CN100439597C (en) * | 2006-11-21 | 2008-12-03 | 朱运彬 | Process for preparing fruit and vegetable fresh-keeping paper made from tourmaline |
| CN101182689B (en) * | 2007-12-14 | 2010-09-29 | 华南理工大学 | Inorganic silver-impregnated zeolite antibiotic papers and method of producing the same |
| CN102504615B (en) * | 2011-11-17 | 2013-08-07 | 中国科学院宁波材料技术与工程研究所 | Antibacterial agent preparation method for antibacterial plastic product |
| CN104017409B (en) * | 2014-06-18 | 2017-02-15 | 杜一挺 | Antibacterial coating and preparation method thereof |
| CN105482510A (en) * | 2015-12-20 | 2016-04-13 | 高大元 | Preparing method for nanometer illite platinum-loaded plastic antibacterial agent |
| CN106433245A (en) * | 2016-06-25 | 2017-02-22 | 佛山市三水金大田门业有限公司 | Antibacterial coating of intelligent door |
| CN107021630A (en) * | 2017-03-17 | 2017-08-08 | 界首市伟盛古窑彩陶制作发展有限公司 | A kind of high-temperature environmental-protection antibacterial glaze |
| CN107933017A (en) * | 2017-11-10 | 2018-04-20 | 宁波市恩迪卫浴有限公司 | A kind of anti-bacteria stainless steel composite plate and preparation method thereof |
| CN109097856B (en) * | 2018-08-15 | 2020-11-06 | 晋大纳米科技（厦门）有限公司 | Copper-based antibacterial master batch and preparation method thereof |
| CN110547302B (en) * | 2019-09-04 | 2021-03-23 | 晋大纳米科技（厦门）有限公司 | Antibacterial powder and preparation method and application thereof |
| CN112409026B (en) * | 2020-10-12 | 2022-09-02 | 华能国际电力股份有限公司海门电厂 | Novel antifouling porcelain plate for coastal engineering |
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