CN101103078A - 可用于在材料表面上提供NOx除去涂层的组合物 - Google Patents
可用于在材料表面上提供NOx除去涂层的组合物 Download PDFInfo
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- CN101103078A CN101103078A CNA2004800439884A CN200480043988A CN101103078A CN 101103078 A CN101103078 A CN 101103078A CN A2004800439884 A CNA2004800439884 A CN A2004800439884A CN 200480043988 A CN200480043988 A CN 200480043988A CN 101103078 A CN101103078 A CN 101103078A
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- titanium dioxide
- hno
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Abstract
本发明涉及用作材料表面的NO除去涂层的具有光催化自清洁性能的组合物，它至少包括：a)具有至少除去NOx活性的光催化的二氧化钛颗粒；b)具有除去-HNO3活性的颗粒；c)不透明剂；和d)所述颗粒在其内分散的硅基材料，其中所述光催化颗粒的晶体尺寸范围为1-50纳米。
Description
技术领域
本发明涉及具有光催化自清洁性能以供用作为在材料表面上的NOx除去涂层的组合物。
背景技术
在建筑和涂料领域中，环境污染产生污染建筑和户外建筑的外部材料的严重问题。在晴朗的天气中，飘浮在空气中的灰尘和颗粒沉积在建筑物的屋顶和外墙上。一旦暴露于雨水下，沉积物与雨水一起流动并且沿着建筑物的外墙向下流动。结果，污染物沿着雨水的路径粘附。当表面干燥时，污物以条状图案形式出现。
为了至少部分解决这一问题，已提出在建筑材料表面上沉积涂层。或者，所述涂层对大气污染物显示出光催化的自清洁性能。因此，在EP0901991、WO97/07069、WO97/10186和WO98/41480中公开了氧化钛光催化涂层。
更具体地，二氧化钛(TiO2)(它是一种半导体)将(例如来自UV光的)UV辐射转化成最终可引发有害有机化合物降解成无害物质的电子和空穴。典型的大气污染物例如是氮氧化物、臭氧和吸附在材料的涂布表面上的有机污染物。在其中特别是在强阳光下，有机污染物的浓度可能相对高，但其中材料可获得的表面积也相对高的堆积(built-up)区域中，例如，在城市街道中，它是尤其有利的。
然而，与如此形成的氧化物种，例如在水和氧气存在下，由NO2和NO与TiO2/UV光反应形成的HNO3有关的一个问题是，它们吸附在材料的涂布表面上，在此它们可引起污点和/或腐蚀问题。
因此，仍需要与现有技术的涂层相比，在除去污染性能、不玷污性能和突出的耐久性方面具有显著改进的涂层。
令人惊奇的是，发明人已发现，这一目的可通过用作涂料的特定组合物来有效地实现。
因此，本发明的目的是提供一种组合物，当作为涂层施加到材料表面上时，显示出改进的NOx和任选地VOCx(即，挥发性有机物含量，例如二甲苯和苯)除去性能。
本发明另一目的是提供一种组合物，当作为涂层施加到材料表面上时，尤其通过雨水或者用水洗涤，可容易地从中释放污染物。具体地说，当施加到基底表面上形成膜时，该组合物能使粘附到表面上的污染物或其衍生物容易通过水洗掉。
根据一个方面，本发明涉及在结构材料表面上用作不透明涂层的NOx除去组合物，它至少包括：
a)具有至少除去NOx活性的光催化的二氧化钛颗粒；
b)具有除去-HNO3活性的颗粒；
c)不透明剂；和
d)所述颗粒在其内分散的硅基材料，
其中所述光催化颗粒的晶体尺寸范围为1-50纳米。
根据另一方面，本发明涉及在材料表面处赋予对大气污染物自清洁性能的方法，所述方法包括至少下述步骤：
-施加本发明的组合物到材料表面上，
-干燥或固化所述组合物，提供不透明的涂层体系。
根据本发明，尤其在暴露于水和UV光之后获得的涂层显示出高的耐久性和除去NO3的效率，正如在下文实施例中所示的。
光催化的二氧化钛颗粒：
本发明的组合物至少包括具有至少除去NOx活性的分散的光催化二氧化钛颗粒，其中NOx是指NO和/或NO2。根据一个具体的实施方案，所述光催化的颗粒还显示出除去VOC的活性。
此处所使用的术语“除去NOx”和/或“除去VOC”活性是指将NOx和/或VOC物质转化成它们各自的氧化物种，例如对于NOx来说，转化成HNO3的能力。
具体地说，在本发明中，此处所使用的术语“光催化的颗粒”是指基于下述材料的颗粒，所述材料当暴露于能量比该晶体的导带和价带之间的能隙高的光(激发光)(即，较短波长)下时，可引起价带内的电子激发(光激发)，产生传导电子和价空穴。
包含在本发明组合物内的光催化二氧化钛颗粒基本上包括二氧化钛的锐钛矿或金红石形式及其混合物。
例如，涂层的二氧化钛颗粒，颗粒的性质可主要是锐钛矿晶体形式。“主要”是指在涂料组合物内二氧化钛颗粒的锐钛矿含量大于50％质量。涂料组合物的颗粒可显示出大于80％的锐钛矿含量。
结晶度和结晶相的性质通过X-射线衍射来测量。
掺入到涂层内的结晶二氧化钛颗粒显示出范围为1-300纳米的平均尺寸，优选范围为2-100纳米，更优选5-50纳米。通过透射电子显微术(TEM)以及XRD测量直径。
优选的光催化剂颗粒每克具有高的表面积，例如大于50m2/g，和优选高于100m2/g，这通过BET方法来测量。
相反，常规TiO2颜料每克的表面积，即光催化性能为约1-30m2/g。光催化剂颗粒中小得多的颗粒和晶体之差得到高得多的表面积。
对于本发明来说，尤其方便的是，例如以S5-300A和B形式由Millennium Inorganic Chemicals Ltd销售的光催化TiO2或者专用中性溶胶。
以所述组合物总重量的0.1-25％，优选0.5-20％，和最优选1-15％重量的用量(以干物质表达)添加具有光催化活性的颗粒。
特别地，本发明的组合物包括至少1％重量的光催化颗粒。
根据一个具体的实施方案，光催化颗粒也可显示出除去VOC的除去性能。
光催化的二氧化钛颗粒可以以通过在水中分散制备的溶胶，以含有水或溶剂的糊剂，或者以粉末形式使用。制备溶胶所使用的分散剂的优选实例包括水、醇，例如甲醇、乙醇、异丙醇、正丁醇和异丁醇，和酮，例如甲乙酮和甲基异丁基酮。
除去HNO3的颗粒
本发明的组合物包括除去由NOx颗粒光催化形成的氧化物种HNO3的分散颗粒。这些第二类颗粒被称为“HNO3除去颗粒”或者除去HNO3的颗粒。
除去HNO3的颗粒的例举实例包括碱性化合物，尤其任何不溶性碳酸盐和例如碳酸钙、碳酸锌、碳酸镁及其混合物。这种化合物特别优选的实例包括碳酸钙。对其用量没有特别限制，所述用量应当足以实现将HNO3转化成其碱性盐，第二，应当与包括它的涂料相容。所述组合物总重量的0.05-50％，尤其0.1-30wt％的用量(以干物质表达)可以是尤其方便的。
除去HNO3的颗粒/光催化的颗粒之比可在0.05-5之间变化，尤其0.1-3，和更尤其0.2-2.0。
所述颗粒，即除去HNO3的颗粒和光催化颗粒包括在本发明的组合物内，其用量大于组合物总重量的1wt％(以干物质表达)，尤其低于50％，和更尤其低于35wt％。
硅基组分：
本发明的组合物含有其中至少前面公开的颗粒捕获在其内的硅基组分。
具体地说，在本发明中，此处所使用的术语“硅基材料”是指基于二氧化硅或其混合物的任何材料，它能提供涂布方便的硅基膜。
硅基材料有利地提供聚硅氧烷聚合物膜。
根据一个实施方案，硅基材料包括至少一种聚硅氧烷衍生物和尤其具有下述化学式：
其中
-n的数值提供固体的重量百分数范围为40-70％的聚硅氧烷含水分散液，和
-R1和R2是1-20个碳原子的烷基，或芳基，例如苯基。
典型地，n的数值范围为约5-2000。
例举的R1和R2基是烷基(例如，甲基、乙基、丙基、丁基、2-乙基丁基、辛基)、环烷基(例如，环己基、环戊基)、链烯基(例如，乙烯基、己烯基、烯丙基)、芳基(例如，苯基、甲苯基、二甲苯基、萘基、二苯基)、芳烷基(例如，苄基、苯乙基)，其中键合到碳上的一些或所有氢被(例如卤素原子或氰基)取代，或者被例如氨基、醚基(-O-)、羰基(-CO-)、羧基(-COOH)或磺酰基(-SO2-)(例如，氯甲基、三氟丙基、2-氰基乙基、3-氰基丙基)取代或者含有它们的任何前述基团。特别地，聚硅氧烷的分子量范围为500-5000，尤其1500-5000。
本发明尤其方便的是以商品名WACKER BS 45由WACKER-ChemieGmbH公司销售的聚硅氧烷。
可合适地确定在本发明组合物内的聚硅氧烷的含量。根据一个具体的实施方案，它的范围可以是组合物总重量的1-60wt％，尤其5-50wt％(以干物质表达)。
根据一个具体的实施方案，本发明的组合物也可含有有机粘合剂。
有机粘合剂：
有机粘合剂可以选自苯乙烯/丁二烯的共聚物，丙烯酸的酯的聚合物与共聚物，尤其聚乙烯基丙烯酸类和苯乙烯/丙烯酸酯的共聚物。
在本发明中，苯乙烯丙烯酸类共聚物包括其苯乙烯/丙烯酸酯的共聚物。
发明人预料不到地发现，这一化合物尤其有利地获得具有高的除去NOx效率的光催化活性的涂层。
在其中这一化合物是苯乙烯/丙烯酸类共聚物和更特别地以光催化TiO2颗粒/有机粘合剂，和尤其苯乙烯/丙烯酸类共聚物的重量比范围为0.3-4.5，尤其0.5-3.6，更尤其1-3.5使用的情况下，尤其注意到这一效果。
特别地，可使用苯乙烯丙烯酸类乳液，例如获自BASF GmbH的ACRONAL 290D。
当组合物包括有机粘合剂时，优选引入它以替代部分硅基材料。
该组合物可具有范围为20-1的硅氧烷基材料/有机粘合剂的重量比。
不透明剂
根据本发明，不透明剂包括能提供涂层遮盖力的任何有机或无机化合物。它包括下文列出的颜料、着色剂和/或填料。更优选，它包括至少一种无机化合物，例如或者金红石或者锐钛矿形式的二氧化钛。
在US6342099(Millennium Inorganic Chemicals Inc.)中公开了非光活性的这种二氧化钛颜料。
特别地，可使用由Millennium Inorganic Chemicals Ltd销售的Tiona 595颗粒和/或Tiona AT-1颗粒。
组合物可含有用量范围为0.5-20wt％，尤其0.5-35wt％的这种不透明剂。
本发明的组合物可包括至少一种溶剂。
此处可用的溶剂的实例包括水、有机溶剂，和由水与有机溶剂组成的混合溶剂，尤其优选水和醇。
本发明的组合物可含有任选的组分，条件是这种添加没有牺牲储存期、UV耐久性、不透明度或非玷污性能。这种额外的化合物的实例包括填料，例如石英、方解石、粘土、滑石、重晶石和/或Na-Al-硅酸盐；颜料，例如TiO2、锌钡白和其它无机颜料；分散剂，例如多聚磷酸盐、聚丙烯酸酯、膦酸盐、萘和木质素磺酸盐；润湿剂，例如阴离子、阳离子、两亲和非离子表面活性剂；消泡剂，例如硅乳液、烃、长链醇；稳定剂，例如大多数阳离子化合物；聚结剂，例如碱稳定的酯、二元醇、烃；流变学添加剂，例如纤维素衍生物(CMC、HEC)、黄原胶、聚氨酯、聚丙烯酸酯、改性淀粉、膨润土和其它层状硅酸盐；防水剂，例如烷基硅化酯(siliconate)、硅氧烷、石蜡乳液、脂肪酸Li盐和常规的杀菌剂或杀虫剂。
可通过任何合适的方法将本发明的组合物施加到材料表面上，和合适的方法的实例包括喷涂、浸涂、流涂、旋涂、辊涂、刷涂和海绵涂布。
然后在施加到基底表面上之后，干燥并固化组合物，形成薄膜。此处所使用的术语“干燥或固化”是指包含在本发明组合物内的硅基材料转化成硅基膜。因此，可通过或者空气干燥或者加热干燥来进行干燥。或者，可进行紫外辐照等等，引起聚合，只要将前体转化成硅膜即可。
本发明的组合物可施加到宽范围的各种材料表面上。
没有特别限制材料，和其实例包括金属、陶瓷、玻璃、塑料、木材、石头、水泥、混凝土、纤维、织造织物和上述材料的结合，以及上述材料的层压体。组合物可施加到其上的具体实例包括房屋、建筑材料；建筑物外部；建筑物内部；窗框；窗玻璃；结构材料；机器和制品的外部；防尘覆盖物和涂层；膜、片材、密封件；隧道和停车场。
在本发明的优选实施方案的制备中，可使用各种替代物以有助于本发明的目的。
列出下述实施例辅助理解本发明，且不打算限制，并决不应当解释为以任何方式限制本发明。对于本领域的技术人员来说，在阅读本发明公开内容的基础上，显而易见的所有替代物、改性和等价物将包括在本发明的精神与范围内。
实施例
通过使用下述材料制备组合物：
-光催化的二氧化钛：获自Millennium Inorganic Chemicals的PC105(在含有1％六偏磷酸钠的水中42wt％的TiO2)，
-二氧化钛颜料：获自Millennium Inorganic Chemicals的Tiona595，
-获自Omya Ltd.的碳酸钙(填料)Snowcal 60，
-获自Hercules Incorporated.的羟乙基纤维素Natrosol 250MR，在水中3％的溶液，
-Wacker BS45：获自Wacker Chemie GmbH的聚硅氧烷聚合物胶乳，
-Texanol：获自Eastman Chemical Company的2，2，4-三甲基-1，3-戊二醇单异丁酸酯，
-聚丙烯酸的钠盐：获自Allied Colloids Ltd.的Dispex N40。
分三部分，称为A、B和C制备油漆。
对于A部分来说，将TiO2加入到水中，然后向其中添加Natrosol250MR、Dipex N40和Snowcal-60。
在高剪切下混合各组分。
对于B部分来说，将聚硅氧烷聚合物加入到A部分中，然后加入到C部分中，将Texanol加入到A和B部分中。
表I中列出了如此制备的油漆的组成。
表I
| F1 | F2 | |
| A部分 | ||
| 光催化TiO2*(wt％) | 23 | 20 |
| CaCO3*(wt％) | 9.8 | 19.9 |
| 不透明剂(TiO2) | 14.6 | 12.6 |
| 聚丙烯酸类的盐(wt％) | 0.7 | 0.6 |
| 羟乙基纤维素(wt％) | 16.6 | 16.7 |
| 水(wt％) | 2.2 | 11.1 |
| B部分 | ||
| 聚硅氧烷(wt％) | 31.5 | 18.2 |
| C部分 | ||
| Texanol(wt％) | 1.6 | 0.9 |
在该表中所述的百分数是以商业产品，即干物质+溶剂表达的百分数。
测定涂层对亚甲基蓝的光活性的方法
用紫外光辐照二氧化钛导致产生空穴和电子，所述空穴和电子然后能形成反应性物种，例如过氧化物、氢过氧化物和羟基离子。这些然后能氧化有机分子，例如亚甲基蓝成水、二氧化碳和含氮物种且相关地损失颜色。通过测量L*(亮度)和b*值(蓝色/黄度)，监控光活性水平。
该方法最适合于用水，例如胶乳或乳液油漆润湿的涂层。涂层的孔隙度将影响膜吸收的污物量，但这通过添加增稠剂到亚甲基蓝溶液中来最小化。由于pH影响导致也可存在蓝色的颜色变化。
制备亚甲基蓝溶液
首先将亚甲基蓝溶解在软化水中成0.05wt％的浓度。然后使用缓慢速度的搅拌，添加1％Natrasol MR(羟乙基纤维素)的当量。为了使Natrosol水化，用稀氨水升高pH到约8.0。这要求仅仅数滴。搅拌溶液另外1小时，使Natrosol完全水合。
漆膜玷污
通过使用螺旋缠绕棒，刮涂膜，用亚甲基蓝溶液的膜罩面涂布待测试的漆膜。通过施加湿的漆膜到30微米厚的Melinex或Mylar片材上，事先制备试验膜。规定螺旋缠绕棒，得到各种膜厚，但通常使用得到25-50微米湿膜的那些。在23℃、50％RH下，使涂层静置至干过夜。
测量
从膜上切割合适尺寸面积的涂层，并使用分光光度计测量L*和b*。漆膜然后暴露于来自Atlas Suntest机器装置的光下，得到250-765nm的551W/m2的光输出。在合适的时间间隔，典型地18-24小时处再测量漆膜。
未曝光和曝光结果之间L*和b*之差是涂层对自清洁的光活性的量度。
下表中提供了数据。
表II
| ΔL* | Δb* | |
| F1 | 2.8 | 3.1 |
| F2 | 3.6 | 3.8 |
测定耐久性的方法
通过在不锈钢板上制备涂层，将它们暴露于在为该应用而设计的机器内的模拟的气候条件下，从而评估涂层的耐久性。在暴露过程中，涂层损失的重量大小是其耐久性的量度。
不锈钢板的大小为75×150mm和厚度为0.75mm。该板在施加漆膜之前和之后称重至0.0001g，以便可计算涂层的重量。
通过任何方便的方式，其中包括刷涂、喷涂、旋涂或者通过螺旋棒涂膜器涂布该板。仅仅涂布待暴露的表面。干燥膜的厚度典型地范围为20-50微米。
在Weatherometer内暴露之前，使涂层静置干燥7天。
暴露所使用的Weatherometer是由Atlas ElectricDevices，Chicago制造的Ci65A。光源是在340纳米下，发射0.5W/m2UV的6.5kW的氙源。黑色面板温度为63℃。每隔120分钟用18分钟喷洒水，且没有暗循环。
图1中提交了如此获得的数值。它们表明在1500小时暴露之后，仅仅损失由本发明的F1和F2获得的涂层起始总重的约15％或38wt％。
测定通过涂层除去的NO/NO2
在进行试验之前，使用滤光的氙灯光源(Atlas WeatherometerCi65A)，在340nm下，用0.5W/m2UV辐照漆膜168小时。这或者活化或者增加未暴露涂层上盖和上部的涂层的活性。对于NOx测量来说，用发射范围为300-400nm的l0W/m2UV的UV荧光管辐照样品。所使用的NOx为氮含量225ppb的NO。
1.设备
氮氧化物分析仪型号ML9841B
-ex Monitor Europe
UV灯型号VL-6LM 365&312纳米波长
-ex BDH
气密样品腔室
3个通道气体混合器
-ex Brooks Instruments，Holland
2.气体
NO一氧化氮
含有水蒸气的压缩空气，在混合气体物流内得到50％相对湿度。
3.方法
1.打开分析仪和排气泵。确保排气管连通大气。
2.允许预热。在分析之前，达到操作温度所需的数个内部组件开始操作。该过程从冷启动起典型地花费60分钟，并显示信号START-UPSEQUENCE ACTIVE，直到满足操作条件。
3.在预热之后，将空气和试验气体供应源接通到气体混合器上。
4.根据制造商的说明书，仅仅在试验气体供应上校正分析仪，(在气体混合器上空气通道接通到0上)。
5.在校正之后，关闭在气体混合器处的试验气体供应。
6.将试样置于试验腔室和密封腔室内。
7.打开空气和试验气体二者并调节每一种气体，直到达到试验气体的所要求含量(这通过分析仪的输出，RECORD水平来显示)。检测相对湿度为50％±5％。
8.当试验气体水平达到所需点时，接通UV灯。
9.允许辐照过的样品值达到平衡，典型地最多3分钟。
10.记录分析仪上所示的数值。
11.报道“起始值”，即没有UV辐照时的数值，和在暴露于UV固定时间段之后的“最终值”。
12.除去的NOx％＝(起始值-最终值)×100/起始值
下表中提供了数据。
| NO除去％ | |
| F1 | 0.5 |
| F2 | 47.0 |
Claims (17)
1.在材料表面上用作涂层的除去NOx组合物，它至少包括：
a)具有至少除去NOx活性的光催化的二氧化钛颗粒；
b)具有除去HNO3活性的颗粒；
c)不透明剂；和
d)所述颗粒在其内分散的硅基材料，
其中所述光催化颗粒的晶体尺寸范围为1-50纳米。
2.权利要求1的组合物，其中光催化颗粒包括至少锐钛矿形式二氧化钛、金红石形式二氧化钛或其混合物。
3.权利要求1至2任一项的组合物，其中二氧化钛颗粒主要为锐钛矿晶体形式。
4.权利要求3的组合物，其中晶体二氧化钛颗粒显示出1-300纳米的平均尺寸，尤其2-100纳米，更尤其5-50纳米。
5.权利要求1-4任何一项的组合物，其中光催化颗粒每克的表面积高于5m2/g。
6.权利要求1-5任何一项的组合物，其中光催化颗粒以所述组合物总重量的0.1-25％，优选0.5-20％，和最优选1-15wt％(以干物质表达)的用量存在。
7.权利要求1-6任何一项的组合物，其中除去HNO3的颗粒包括碱性化合物。
8.权利要求7的组合物，其中除去HNO3的颗粒包括碳酸钙、碳酸锌或其混合物。
9.权利要求8的组合物，其中除去HNO3的颗粒以所述组合物总重量的0.05-50％，尤其0.1-30wt％的用量存在。
10.权利要求1-9任何一项的组合物，其中它包括除去HNO3的颗粒/二氧化钛颗粒之比范围为0.05-5，尤其0.1-3，和更尤其0.2-2的光催化二氧化钛和除去HNO3的颗粒。
11.权利要求1-10任何一项的组合物，其中硅基材料提供聚硅氧烷膜。
12.权利要求1-11任何一项的组合物，其中硅基材料包括至少一种聚硅氧烷聚合物。
13.权利要求1-12任何一项的组合物，其中不透明剂基于锐钛矿或金红石TiO2颗粒。
14.权利要求1-13任何一项的组合物，其中颗粒a)和b)以低于所述组合物总重量的50wt％的用量存在。
15.权利要求1-14任何一项的组合物，进一步包括有机粘合剂。
16.权利要求15的组合物，其中有机粘合剂选自聚乙烯基丙烯酸类和苯乙烯/(甲基)丙烯酸酯的共聚物。
17.赋予材料表面对大气污染物具有自清洁性能的方法，所述方法包括至少下述步骤：
-施加权利要求1-16任何一项的组合物到材料表面上，和
-干燥或固化该组合物，在该材料表面上获得不透明的涂层。
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| PCT/IB2004/002975 WO2006030250A2 (en) | 2004-09-14 | 2004-09-14 | Composition useful for providing nox removing coating on material surface |
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| JP3622585B2 (ja) * | 1999-08-05 | 2005-02-23 | 日本板硝子株式会社 | 光触媒活性を有する物品 |
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| US6695906B2 (en) * | 2000-04-12 | 2004-02-24 | Millennium Inorganic Chemicals, Inc. | Continuous processes for producing titanium dioxide pigments |
| AU2001257372B2 (en) * | 2000-04-27 | 2005-09-01 | E.I. Du Pont De Nemours And Company | Process for making durable titanium dioxide pigment in the chloride process without wet treatment |
| US6342099B1 (en) * | 2000-05-01 | 2002-01-29 | Millennium Inorganic Chemicals, Inc. | Coated titanium dioxide pigments and processes for production and use |
| KR100594225B1 (ko) * | 2000-12-27 | 2006-07-03 | 삼성전자주식회사 | 전자빔 노광 방법 및 이를 이용한 패턴 형성 방법 |
| KR100688108B1 (ko) * | 2001-08-03 | 2007-03-02 | 닛뽕소다 가부시키가이샤 | 금속-산소 함유 분산 성분 |
| JP4116300B2 (ja) * | 2002-01-31 | 2008-07-09 | 富士ゼロックス株式会社 | 酸化チタン光触媒薄膜および該酸化チタン光触媒薄膜の製造方法 |
| FR2838735B1 (fr) * | 2002-04-17 | 2005-04-15 | Saint Gobain | Substrat a revetement auto-nettoyant |
-
2004
- 2004-09-14 MX MX2007003021A patent/MX2007003021A/es unknown
- 2004-09-14 CN CNA2004800439884A patent/CN101103078A/zh active Pending
- 2004-09-14 US US11/662,484 patent/US20080003367A1/en not_active Abandoned
- 2004-09-14 JP JP2007530781A patent/JP2008513188A/ja not_active Withdrawn
- 2004-09-14 BR BRPI0419048-3A patent/BRPI0419048A/pt not_active IP Right Cessation
- 2004-09-14 WO PCT/IB2004/002975 patent/WO2006030250A2/en active Application Filing
- 2004-09-14 AU AU2004323298A patent/AU2004323298A1/en not_active Abandoned
- 2004-09-14 EP EP04769364A patent/EP1805268A2/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101952050A (zh) * | 2008-01-30 | 2011-01-19 | 美礼联无机化工公司 | 光催化涂料组合物 |
| CN105001782A (zh) * | 2008-01-30 | 2015-10-28 | 水晶美国股份公司 | 光催化涂料组合物 |
| CN105001782B (zh) * | 2008-01-30 | 2019-01-11 | 水晶美国股份公司 | 光催化涂料组合物 |
| CN102639657A (zh) * | 2009-09-18 | 2012-08-15 | 美礼联无机化工公司 | 用作去除NOx的半透明涂层的组合物 |
| WO2015131632A1 (zh) * | 2014-03-03 | 2015-09-11 | 福州大学 | 具有TiO2薄膜保护层的催化过滤滤料及其制备方法 |
| CN113683910A (zh) * | 2020-05-18 | 2021-11-23 | 金百利科技(深圳)有限公司 | 一种具有高效光催化功能的光催化涂料及制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0419048A (pt) | 2007-12-11 |
| WO2006030250A3 (en) | 2007-08-16 |
| AU2004323298A1 (en) | 2006-03-23 |
| MX2007003021A (es) | 2007-06-15 |
| US20080003367A1 (en) | 2008-01-03 |
| EP1805268A2 (en) | 2007-07-11 |
| JP2008513188A (ja) | 2008-05-01 |
| WO2006030250A2 (en) | 2006-03-23 |
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