技术领域technical field
本发明涉及一种稀土激活载银系无机抗菌剂及其制备方法，属无机化学抗菌剂净化材料技术领域。The invention relates to a rare earth-activated silver-loaded inorganic antibacterial agent and a preparation method thereof, belonging to the technical field of inorganic chemical antibacterial agent purification materials.
背景技术Background technique
众多金属离子，如银离子、铜离子、锌离子等均具有抗菌性能。例如银离子以硝酸银溶液的形态存在，广泛用作消毒剂和抗菌剂，但是以溶液状态使用，不方便，用途也受限。目前已有很多相关的抗菌材料和制备工艺的报道。如抗菌性沸石的制法、银锌组合抗菌剂的制备、复合型银系无机抗菌剂的制备等。Many metal ions, such as silver ions, copper ions, zinc ions, etc., have antibacterial properties. For example, silver ions exist in the form of silver nitrate solution, which is widely used as a disinfectant and antibacterial agent, but it is inconvenient to use in a solution state, and its use is also limited. There have been many reports on related antibacterial materials and preparation techniques. Such as the preparation method of antibacterial zeolite, the preparation of silver-zinc combined antibacterial agent, the preparation of composite silver-based inorganic antibacterial agent, etc.
原有的无机抗菌剂多以沸石、磷酸钙、玻璃等天然或人工合成的具有层状或网状结构的无机材料为载体，以银、铜、锌等金属离子为抗菌有效成分制作而成。此外，也有人采用Al2O3、CaO、SiO2、TiO2等氧化物为载体，以Ag、Cu、Zn等金属离子为抗菌成分，也制备出了具有较好的抗菌特性的无机抗菌剂。将抗菌离子担持在载体上的方法有物理吸附、离子交换等。如利用物理吸附法将抗菌离子担持在活性炭、活性氧化铝、硅胶或硅铝酸盐等上面而获得无机抗菌材料。但因用物理吸附法在这些载体上的抗菌金属容易过度溶出，故不能长久地维持抗菌性。为此开发了离子交换法，利用离子交换法将抗菌金属担持于载体上。如特许等3448530号，提出了利用离子交换法将抗菌金属离子担持在人工合成的羟基磷灰石中而制得无机抗菌剂。又如特开2003-193540公开了利用离子交换法将抗菌金属离子担持在硅酸铝系化合物、二氧化钛系化合物、磷酸盐化合物或二氧化硅系化合物中而获得抗菌材料。Most of the original inorganic antibacterial agents use zeolite, calcium phosphate, glass and other natural or synthetic inorganic materials with layered or network structure as carriers, and metal ions such as silver, copper and zinc as antibacterial active ingredients. In addition, some people use oxides such as Al2 O3 , CaO, SiO2 , TiO2 as carriers, and metal ions such as Ag, Cu, and Zn as antibacterial components to prepare inorganic antibacterial agents with good antibacterial properties. . The methods for carrying antibacterial ions on the carrier include physical adsorption, ion exchange, and the like. For example, the antibacterial ions are supported on activated carbon, activated alumina, silica gel or aluminosilicate by physical adsorption to obtain inorganic antibacterial materials. However, because the antibacterial metals on these carriers by physical adsorption are prone to excessive dissolution, the antibacterial properties cannot be maintained for a long time. To this end, the ion exchange method was developed, and the antibacterial metal is supported on the carrier by ion exchange method. No. 3448530 such as Zhan Zhan proposed to use the ion exchange method to hold antibacterial metal ions in artificially synthesized hydroxyapatite to prepare inorganic antibacterial agents. Another example is JP-A-2003-193540, which discloses that antibacterial metal ions are supported in aluminum silicate-based compounds, titanium dioxide-based compounds, phosphate compounds or silicon dioxide-based compounds by ion exchange to obtain antibacterial materials.
这些种类载有银离子的抗菌剂，存在两个很大的缺点是：其一，贵重金属银作为抗菌性成分会导致抗菌剂的生产成本过高，从而影响它在大范围内的推广使用；其二，载银抗菌剂耐候性差；银离子化学性质比较活泼，对热和光比较敏感，特别是抗菌剂经紫外线照射后易变黑，从而影响白色或浅色制晶的外观；在紫外线照射、偏碱性或加热条件下，其抗菌制品，如各种塑料制品、涂料、陶瓷制品、抗菌建材等容易变色发黑。These types of antibacterial agents loaded with silver ions have two major disadvantages: one, precious metal silver can cause the production cost of antibacterial agents to be too high as an antibacterial component, thereby affecting its popularization and use on a large scale; Second, the weather resistance of silver-loaded antibacterial agents is poor; the chemical properties of silver ions are relatively active, and they are more sensitive to heat and light, especially antibacterial agents are easy to turn black after ultraviolet radiation, thereby affecting the appearance of white or light-colored crystals; Under alkaline or heating conditions, its antibacterial products, such as various plastic products, paints, ceramic products, and antibacterial building materials, are prone to discoloration and blackening.
针对载银无机抗菌剂稳定性差，有些方案提出在抗菌制品中添加各种稳定剂，或者对抗菌剂进行表面改性，以提高其稳定性与耐候性。关于表面改性，有人提出一种组装型抗菌剂粉体，它由载体核及三层包覆层组成，即它以二氧化钛、氧化锌、硫酸钙、高岭土、沸石或硅土为载体核；自内往外的第一层为Ag、Cu、Zn抗菌材料层，第二层为硅酸盐、硅铝酸盐、硼硅酸盐的屏蔽缓释控制层，第三层最外层为增加与基材相容性的表面改性层。这种组装型抗菌粉体也只能在一定程度上改善抗菌剂的耐变色性。In view of the poor stability of silver-loaded inorganic antibacterial agents, some proposals propose to add various stabilizers to antibacterial products, or to modify the surface of antibacterial agents to improve their stability and weather resistance. Regarding surface modification, someone proposed an assembled antimicrobial agent powder, which consists of a carrier core and three coating layers, that is, it uses titanium dioxide, zinc oxide, calcium sulfate, kaolin, zeolite or silica as the carrier core; The first layer from inside to outside is the Ag, Cu, Zn antibacterial material layer, the second layer is the shielding and slow release control layer of silicate, aluminosilicate, borosilicate, and the third outermost layer is the addition and base layer. Surface modification layer for material compatibility. This assembled antibacterial powder can only improve the discoloration resistance of the antibacterial agent to a certain extent.
为降低以银离子作为抗菌离子制备抗菌剂的生产成本，许多相关文献提出了掺杂其他金属抗菌离子，如锌、铜等。锌作为抗菌离子对皮肤有过敏反应，且其抗菌能力较小，需控制其一定用量。铜子作为掺杂的抗菌离子，一则铜离子本身有一定的颜色，其加入量也应受到一定的限制。In order to reduce the production cost of using silver ions as antibacterial ions to prepare antibacterial agents, many related documents have proposed doping with other metal antibacterial ions, such as zinc and copper. As an antibacterial ion, zinc has an allergic reaction to the skin, and its antibacterial ability is small, so its dosage should be controlled. Copper is used as a doped antibacterial ion, and the copper ion itself has a certain color, so its addition should be limited to a certain extent.
经检索，中国专利CN1586202A公开了一种包覆层的多孔结构担载抗菌银离子的复合型无机抗菌剂；CN1256868A和CN1286915A都记载了载银系列复合型无机抗菌剂；还有CN1404732A“无机抗菌剂及其生产工艺”、CN1123291C的“高温无机抗菌剂”、CN1240578A的“长敏无机抗菌剂及其制备和应用”；这些已经公开的专利都涉及载银无机抗菌剂的成本降低和耐变色改进，但是这些方法制备出的无机抗菌剂仍然不能很好地解决银抗菌剂的变色问题。将这些抗菌剂应用于塑料、纤维、陶瓷、涂料中后，经紫外光的照射仍然存在不同层度的变色。After retrieval, Chinese patent CN1586202A discloses a composite inorganic antibacterial agent with a porous structure of the coating layer carrying antibacterial silver ions; CN1256868A and CN1286915A all record silver-loaded series composite inorganic antibacterial agents; and CN1404732A "inorganic antibacterial agent and its production process", CN1123291C's "high-temperature inorganic antibacterial agent", CN1240578A's "long-sensitivity inorganic antibacterial agent and its preparation and application"; these published patents all relate to the cost reduction and discoloration resistance improvement of silver-loaded inorganic antibacterial agents, But the inorganic antibacterial agent prepared by these methods still can't solve the discoloration problem of silver antibacterial agent well. After applying these antibacterial agents in plastics, fibers, ceramics, and coatings, there are still different levels of discoloration after being irradiated by ultraviolet light.
发明内容Contents of the invention
本发明的目的在于提供一种复合型稀土激活载银系无机抗菌剂；将具有激活活性的稀土元素添加入银系无机抗菌剂中以提高和改善银系无机抗菌剂的性能。The object of the present invention is to provide a composite rare earth activated silver-based inorganic antibacterial agent; the active rare earth element is added into the silver-based inorganic antibacterial agent to improve and improve the performance of the silver-based inorganic antibacterial agent.
稀土元素的镧系元素具有光激活活性。光能媒系稀土元素，由于其外层的价电子带存在，当含有紫动线的光照射到该光触媒系抗菌剂时，产生电子(e-)和空穴(h+)，产生的电子一部分跳跃而使其他具有氧化能力的金属形成阴离子；而另一部分则较多地被稀土元素的外层价电子带所俘获，这样便可产生更多的空穴。与此同时，稀土元素价电子带俘获的部分电子也极易被有氧化能力的金属原子所失而形成金属阴离子。上述的金属阳离子具体地说就是本发明中的Ag-离子。由于这种激活效应，它能有效地强化银系抗菌剂的抗菌性能，并且能抑制银系无机抗菌剂的变色。The lanthanides of the rare earth elements are photoactivatable. Due to the existence of the valence electron band in the outer layer of the rare earth element in the photocatalyst system, when the light containing the purple kinetic line irradiates the photocatalyst system antibacterial agent, electrons (e-) and holes (h+) are generated, and part of the generated electrons Jump to make other oxidizing metals form anions; while the other part is more captured by the outer valence electron band of rare earth elements, so that more holes can be generated. At the same time, some of the electrons captured by the valence bands of rare earth elements are easily lost by metal atoms with oxidizing ability to form metal anions. The above-mentioned metal cations are specifically Ag- ions in the present invention. Because of this activation effect, it can effectively strengthen the antibacterial properties of silver-based antibacterial agents, and can inhibit the discoloration of silver-based inorganic antibacterial agents.
本发明的一种稀土激活载银系无机抗菌剂，其特征在于该抗菌剂的化学组成成分及其重量百分比含量为：A rare earth activated silver-loaded inorganic antibacterial agent of the present invention is characterized in that the chemical composition and weight percentage content of the antibacterial agent are:
(1)抗菌离子化合物，如Ag+、Zn2+、Cu2+的硝酸盐或硫酸盐或氮化物，采用Ag+、Zn2+、Cu2+中的一种或两种以上的抗菌离子，其含量为5-10％，优选为6-8％；若采用银和锌两者复合的抗菌离子，则其配比为：Ag+∶Zn2+＝1∶(2～3)；(1) Antibacterial ionic compounds, such as Ag+ , Zn2+ , Cu2+ nitrates or sulfates or nitrides, using one or more antibacterial ions of Ag+ , Zn2+ , Cu2+ , its content is 5-10%, is preferably 6-8%; If adopt the antibacterial ion of both silver and zinc compound, then its proportioning is: Ag+ : Zn2+ =1: (2～3);
(2)稀土激活元素化合物，如硝酸镧、硝酸钇，其含量为0.5-3.0％，优选为1.0-1.5％；(2) Rare earth activating element compounds, such as lanthanum nitrate and yttrium nitrate, the content of which is 0.5-3.0%, preferably 1.0-1.5%;
(3)载体羟基磷酸锆钠，其含有的重量为86-93％。(3) Carrier sodium zirconium hydroxyphosphate, which contains 86-93% by weight.
本发明一种稀土激活载银系无机抗菌剂的制备方法，其特征在于具有以下的工艺过程和步骤：A kind of preparation method of rare earth activated silver-loaded inorganic antibacterial agent of the present invention is characterized in that having following technical process and steps:
a.首先按上述规定配方称重，得一定重量的抗菌离子化合物、稀土元素化合物和载体羟基磷酸锆钠；a. First weigh according to the above-mentioned prescribed formula to obtain a certain weight of antibacterial ionic compound, rare earth element compound and carrier sodium zirconium hydroxyphosphate;
b.将载体羟基磷酸锆钠加水于微观混合反应器中均匀分散成浆液；加入酸或碱溶液，调节载体浆液的PH值至3～7；b. Add water to the carrier sodium zirconium hydroxyphosphate and uniformly disperse it into a slurry in a micro-mixing reactor; add acid or alkali solution to adjust the pH value of the carrier slurry to 3-7;
c.将抗菌离子化合物配制成水溶液，在水浴温度50～80℃下，搅拌机不断搅拌下，将抗菌离子水溶液加入到上述载体羟基磷酸锆钠浆液中，使抗菌离子交换吸附到载体上；c. Prepare the antibacterial ionic compound into an aqueous solution, and add the antibacterial ionic aqueous solution to the above-mentioned carrier sodium zirconium phosphate slurry at a temperature of 50-80° C. in a water bath with a stirrer continuously, so that the antibacterial ion exchange is adsorbed on the carrier;
d.将稀土化合物硝酸镧或硝酸钇用去离子水配制成水溶液，在搅拌机搅拌下，边搅拌边滴入上述载体浆液中；操作温度保持在50～80℃，在此离子反应温度下保持4小时；d. Prepare the rare earth compound lanthanum nitrate or yttrium nitrate into an aqueous solution with deionized water, and drop it into the above-mentioned carrier slurry while stirring under the stirring of a mixer; the operating temperature is kept at 50-80°C, and the ion reaction temperature is maintained at 4 Hour;
e.然后将上述乳液进行真空抽滤，随后用去离子水洗涤3次，将所得的滤饼于700～900℃温度下数煅烧，然后研磨粉碎，制得无机抗菌剂。e. Then carry out vacuum filtration on the above-mentioned emulsion, then wash three times with deionized water, calcinate the obtained filter cake at a temperature of 700-900° C., and then grind and pulverize to obtain an inorganic antibacterial agent.
本发明采用交换吸附抗菌离子的方式，将银、锌离子担持于载体羟基磷酸锆钠晶格中，并且采用稀土元素激活活性，激活银、锌抗菌性离子。本发明制得的抗菌剂具有较好的耐变色性、耐热性和较好的抗菌性；而且是具有抗菌广谱、抗菌持久特性的缓释型长效抗菌剂。The invention adopts the method of exchanging and adsorbing antibacterial ions, supports silver and zinc ions in the lattice of sodium zirconium hydroxyphosphate carrier, and uses rare earth elements to activate activity and activate silver and zinc antibacterial ions. The antibacterial agent prepared by the invention has better discoloration resistance, heat resistance and better antibacterial property; moreover, it is a slow-release long-acting antibacterial agent with broad-spectrum antibacterial and long-lasting antibacterial properties.
具体实施方式Detailed ways
现将本发明结合实施例详细叙述于后。The present invention is described in detail below in conjunction with embodiment now.
实施例1Example 1
将制备好的羟基磷酸锆钠50g置于烧杯中，在电动搅拌下分散2小时；分别称取Zn(NO3)2 2.5g，AgNO3 1.0g，并分别用去离子水配成10wt％的溶液。Put 50 g of the prepared sodium zirconium hydroxyphosphate in a beaker and disperse for 2 hours under electric stirring; weigh 2.5 g of Zn(NO3 )2 and 1.0 g of AgNO3 , and prepare 10 wt % of them with deionized water respectively. solution.
调节水浴箱温度在60℃，将放有载体羟基磷酸锆钠的烧杯放置于该水浴箱中；在继续搅拌下依次加入硝酸银溶液、硝酸锌溶液；随后加入稀硝酸或NaOH溶液，调节其PH值为4。称取稀土元素化合物硝酸镧0.5g，配成1wt％的溶液，将其加入到上述乳液中，保持在60℃温度，进行离子交换反应4小时。然后将乳液进行真空抽滤，用去离子水洗涤3次，将得到的滤饼在800℃温度下煅烧，然后进行研磨粉碎，得到样品1。Adjust the temperature of the water bath at 60°C, place the beaker with the carrier sodium zirconium hydroxyphosphate in the water bath; add silver nitrate solution and zinc nitrate solution in sequence while continuing to stir; then add dilute nitric acid or NaOH solution to adjust its pH The value is 4. Weighed 0.5 g of the rare earth element compound lanthanum nitrate, prepared a 1 wt % solution, added it to the above emulsion, kept the temperature at 60° C., and carried out ion exchange reaction for 4 hours. Then the emulsion was vacuum filtered, washed three times with deionized water, and the obtained filter cake was calcined at 800° C., and then ground and pulverized to obtain Sample 1.
实施例2Example 2
将制备好的羟基磷酸锆钠50g置于烧杯中，在电动搅拌下分散2小时；分别称取Cu(NO3)2 1.0g，Zn(NO3)3.0g，AgNO3 2.0g，并分别用去离子水配成10wt％的溶液。Put 50 g of the prepared sodium zirconium hydroxyphosphate in a beaker and disperse for 2 hours under electric stirring; weigh 1.0 g of Cu(NO3 )2 , 3.0 g of Zn(NO3 ) and 2.0 g of AgNO3 , and use Deionized water was made into a 10wt% solution.
调节水浴箱温度在70℃，将放有载体羟基磷酸锆钠的烧杯放置于该水浴箱中；在继续搅拌下依次加入硝酸银溶液、硝酸铜溶液、硝酸锌溶液；随后加入稀硝酸或NaOH溶液，调节其PH值为3。称取稀土元素化合物硝酸钇0.5g，配成1wt％的溶液，将其加入到上述乳液中，保持在70℃温度，进行离子交换反应5小时。然后将乳液进行真空抽滤，用去离子水洗涤3次，将得到的滤饼在700℃温度下煅烧，然后进行研磨粉碎，得到样品2。Adjust the temperature of the water bath at 70°C, place the beaker with the carrier sodium zirconium hydroxyphosphate in the water bath; add silver nitrate solution, copper nitrate solution, and zinc nitrate solution in sequence while continuing to stir; then add dilute nitric acid or NaOH solution , adjust its pH value to 3. Weigh 0.5 g of the rare earth element compound yttrium nitrate, prepare a 1 wt % solution, add it to the above emulsion, keep the temperature at 70° C., and carry out ion exchange reaction for 5 hours. Then the emulsion was vacuum filtered, washed three times with deionized water, and the obtained filter cake was calcined at 700° C., and then ground and pulverized to obtain sample 2.
实施例3Example 3
将制备好的羟基磷酸锆钠50g置于烧杯中，在电动搅拌下分散2小时；分别称取Cu(NO3)2 1.0g，Zn(NO3) 2.0g，AgNO3 2.0g，并分别用去离子水配成10wt％的溶液。Put 50 g of the prepared sodium zirconium hydroxyphosphate in a beaker and disperse for 2 hours under electric stirring; weigh 1.0 g of Cu(NO3 )2 , 2.0 g of Zn(NO3 ) and 2.0 g of AgNO3 , and use Deionized water was made into a 10wt% solution.
调节水浴箱温度在60℃，将放有载体羟基磷酸锆钠的烧杯放置于该水浴箱中；在继续搅拌下依次加入硝酸银溶液、硝酸锌溶液、硝酸铜溶液；随后加入稀硝酸或NaOH溶液，调节其PH值为4。称取稀土元素化合物硝酸镧0.5g，配成1wt％的溶液，将其加入到上述乳液中，保持在60℃温度，进行离子交换反应4小时。然后将乳液进行真空抽滤，用去离子水洗涤3次，将得到的滤饼在800℃温度下煅烧，然后进行研磨粉碎，得到样品3。Adjust the temperature of the water bath at 60°C, place the beaker with the carrier sodium zirconium hydroxyphosphate in the water bath; add silver nitrate solution, zinc nitrate solution, and copper nitrate solution in sequence while continuing to stir; then add dilute nitric acid or NaOH solution , adjust its pH value to 4. Weighed 0.5 g of the rare earth element compound lanthanum nitrate, made it into a 1 wt % solution, added it to the above emulsion, kept the temperature at 60° C., and carried out the ion exchange reaction for 4 hours. Then the emulsion was vacuum filtered, washed three times with deionized water, and the obtained filter cake was calcined at a temperature of 800° C., and then ground and pulverized to obtain sample 3.
对比例1Comparative example 1
将制备好的羟基磷酸锆钠50g置于烧杯中，在电动搅拌下分散2小时；分别称取Cu(NO3)2 1.0g，Zn(NO3)1.0g，AgNO3 2.0g，并分别用去离子水配成10wt％的溶液。Put 50 g of the prepared sodium zirconium hydroxyphosphate in a beaker and disperse for 2 hours under electric stirring; weigh 1.0 g of Cu(NO3 )2 , 1.0 g of Zn(NO3 ) and 2.0 g of AgNO3 , and use Deionized water was made into a 10wt% solution.
调节水浴箱温度在70℃，将放有载体羟基磷酸锆钠的烧杯放置于该水浴箱中；在继续搅拌下依次加入硝酸银溶液、硝酸锌溶液、硝酸铜溶液；随后加入稀硝酸或NaOH溶液，调节其PH值为3。保持在70℃温度，电动搅拌，进行离子交换反应5小时。然后将乳液进行真空抽滤，用去离子水洗涤3次，将得到的滤饼在700℃温度下煅烧，然后进行研磨粉碎，制得对比例样品1。Adjust the temperature of the water bath at 70°C, place the beaker with the carrier sodium zirconium hydroxyphosphate in the water bath; add silver nitrate solution, zinc nitrate solution, and copper nitrate solution in sequence while continuing to stir; then add dilute nitric acid or NaOH solution , adjust its pH value to 3. Keep the temperature at 70°C, and carry out the ion exchange reaction for 5 hours with electric stirring. Then the emulsion was subjected to vacuum filtration, washed three times with deionized water, and the obtained filter cake was calcined at 700° C., and then ground and pulverized to obtain Comparative Example 1.
将上述实施例1-3制备得到的粉体样品1-3和对比例样品1(未添加稀土元素的载银羟基磷酸锆钠抗菌剂)所作的抑菌性能评价试验结果如下表表1所示：The antimicrobial performance evaluation test results of the powder samples 1-3 prepared by the above-mentioned embodiments 1-3 and comparative sample 1 (the silver-loaded sodium hydroxyzirconium phosphate antibacterial agent without adding rare earth elements) are shown in the following table Table 1 :
表1 样品抑菌性能评价
MIC(ppm)表示枉品的最小抑菌浓度。MIC (ppm) represents the minimum inhibitory concentration of the product.
将上述实施例1-3制备得到的粉体样品1-3和对比例样品1(未添加稀土元素的载银羟基磷酸锆钠抗菌剂)所作的紫外灯光下耐变色性能评价试验结果如下表2所示：With the powder sample 1-3 that above-mentioned embodiment 1-3 prepares and comparative example sample 1 (the silver-loaded hydroxyzirconium hydroxyzirconium phosphate antibacterial agent that does not add rare earth element) the test result of anti-discoloration performance under the ultraviolet lamp light is as follows table 2 Shown:
表2 300瓦紫外光灯下耐变色性能评价
该试验在同一条件下进行，紫外灯选取300W，上海亚明灯具厂制造的紫外灯。The test was carried out under the same conditions, and the ultraviolet lamp was selected as a 300W ultraviolet lamp manufactured by Shanghai Yaming Lamp Factory.
试验结果表明：稀土元素的掺入可以有效提高抗菌剂的杀菌率。抗菌试验所用菌种为大肠杆菌。抗菌离子的掺入量、煅烧温度均对样品的抗菌性能有影响。The test results show that: the incorporation of rare earth elements can effectively improve the bactericidal rate of antibacterial agents. The bacteria used in the antibacterial test was Escherichia coli. The doping amount of antibacterial ions and calcination temperature all have an effect on the antibacterial properties of the samples.
掺入稀土元素激活处理后样品的耐紫外光照性能在不同程度上有所提高。耐变色性能的改善程度与掺入抗菌离子种类和数量、稀土元素种类、制备和后处理工艺等因素的不同而不同。The ultraviolet light resistance performance of the samples after the activation treatment by doping rare earth elements has been improved to varying degrees. The degree of improvement of discoloration resistance varies with the type and quantity of antibacterial ions, the type of rare earth elements, preparation and post-treatment processes and other factors.
本发明方法所制得的抗菌制可以添加在基体材料中，如塑料、涂料、陶瓷、建筑材料中，制成抗菌制品，特别适用于家居用品和住房装潢材料，不但具有抗菌消毒作用，而且使白色器具、白色装潢经久耐用不变黑，具有实际使用效果。The antibacterial product prepared by the method of the present invention can be added to base materials, such as plastics, coatings, ceramics, and building materials, to make antibacterial products, which are especially suitable for household items and housing decoration materials. White utensils and white decorations are durable and will not turn black, and have practical use effects.
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100295954ACN1313005C (en) | 2005-09-13 | 2005-09-13 | Inorganic antiseptic of RE activated silver carrying matter and its prepn |
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100295954ACN1313005C (en) | 2005-09-13 | 2005-09-13 | Inorganic antiseptic of RE activated silver carrying matter and its prepn |
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| CN1739356A CN1739356A (en) | 2006-03-01 |
| CN1313005Ctrue CN1313005C (en) | 2007-05-02 |
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| EE01 | Entry into force of recordation of patent licensing contract | Assignee:Shanghai Huahui Curtain Wall Manufacturing Co.,Ltd. Assignor:Shanghai University Contract fulfillment period:2007.8.1 to 2012.12.31 Contract record no.:2008310000106 Denomination of invention:Inorganic antiseptic of RE activated silver carrying matter and its prepn Granted publication date:20070502 License type:Exclusive License Record date:20081006 | |
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