CN101528832A - 改进的除污染涂料组合物 - Google Patents
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Abstract
本发明是含光催化的二氧化钛颗粒,遮光剂、硅酮化合物、除-HNO3颗粒、苯乙烯树脂空心微球和溶剂的涂料组合物。与常规涂料相比,在除污染的涂料组合物中硅酮化合物和苯乙烯树脂空心微球的结合物导致改进的遮光性和耐久性。
Description
本申请要求2006年10月18日提交的美国专利申请序列号11/582763的优先权,其内容在此通过参考全文引入。
发明领域
本发明涉及可用于在基底表面上形成除污染和/或防垢涂层的改进的涂料组合物。
发明背景
使材料表面污物清洁的常规方法包括处理表面,以提供除去在表面上沉积的污点或污物的能力。在其它方法中,固定在表面上的光催化剂的优良氧化降解活性被用于降解在表面上沉积的有机物或污点或污物以及与该表面接触的任何气体污染。
特别地,非均相光催化剂有效地用于氧化并进而从流体,其中包括水和空气中除去不想要的化合物。因此,UV发光(UV-illuminated)催化剂,例如二氧化钛吸收紫外光,产生迁移到催化剂表面上的电子和空穴。在该表面处,电子还原所吸收的氧气,而空穴氧化有机化合物或所吸收的水分子。
然而,仅仅采用这种单一的光催化涂料组合物,不可能长寿命,即超过5年以上提供满意的除污染性能。
因此,本发明的目的是提供一种涂料组合物,与环境,例如户内或户外环境无关,该涂料组合物可半永久地和在单一的涂层内显示出优良的表面除污染性能,尤其对油脂污物,其中包括霉菌(mildew)、霉菌(mold)、藻类或污点具有优良的污物清洁活性。
对于各种原因来说,包括成本和所需特性,总希望开发出新的更好的除污涂料组合物。
发明概述
本发明是一种涂料组合物,它包括光催化的二氧化钛颗粒,遮光剂、硅酮化合物、除-HNO3颗粒、苯乙烯树脂空心微球和溶剂。与不含硅酮化合物和苯乙烯树脂空心微球的结合物的涂料相比,该涂料组合物显示出预料不到的改进的遮光性和耐久性。
发明详述
本发明的涂料组合物包括光催化的二氧化钛颗粒。在本发明中,此处所使用的术语“光催化的二氧化钛颗粒”是指当暴露于任何波长的光下时,可引起价带内的电子激发(光激发)产生导带电子并在价带内留下空穴的二氧化钛颗粒。
光催化二氧化钛颗粒可以是任何类型的二氧化钛。优选地,光催化的二氧化钛颗粒是锐钛矿、金红石或其混合物。最优选,光催化二氧化钛颗粒主要是锐钛矿,这通过X-射线衍射图案来测定。所谓主要是锐钛矿是指纳米颗粒至少80%为锐钛矿,和最优选大于95%是锐钛矿。二氧化钛的锐钛矿形式因其较高的光活性是特别优选的。可优选通过添加周期表中的其它元素来改性光催化二氧化钛颗粒,以提高在较长波长下以及在光谱的可见光部分内的光活性。
结晶锐钛矿二氧化钛颗粒优选平均粒度为2-100纳米,更优选5-50纳米,和最优选5-40纳米。可通过透射式电子显微术(TEM)以及X-射线颜色(XRD)来测量直径。
优选地,光催化颗粒具有大于30m2/g,更优选大于50m2/g,和最优选大于约100m2/g的高表面积,这通过BET法来测量。
合适的光催化二氧化钛颗粒可购自Millennium InorganicChemicals Ltd.(PC系列产品)、Degussa Corporation(例如,)、Sachtleben Chemie GmbH(例如,Hombikat UV 100)、Tayca Corporation(例如,AMT-600),或Ishihara Corporation(ST系列产品)。也可通过本领域已知的任何方法制备光催化二氧化钛颗粒。制备光催化二氧化钛颗粒的方法是本领域众所周知的,参见例如,美国专利No.4012338,在此通过参考将其引入。
光催化二氧化钛颗粒的存在量优选为组合物总重量的0.5-20%,更优选1-15%,和最优选1-12%。
可将光催化二氧化钛颗粒以通过在分散剂内分散制备的溶胶形式,以含水或含溶剂的糊剂形式,或者以粉末形式引入到组合物中。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。
本发明的涂料组合物还包括遮光剂。适合于本发明的遮光剂包括能提供涂层遮盖力的任何有机或无机化合物,其中包括颜料、着色剂和/或填料。更优选,遮光剂是二氧化钛。颜料级二氧化钛优选粒度范围为0.2-0.5微米,因此与光催化二氧化钛颗粒的粒度相比显著要大。在例如美国专利No.6342099中公开了通过表面处理降低其光活性的二氧化钛颜料。合适的可商购的二氧化钛颜料包括595(Millennium Inorganic Chemicals Ltd的产品),或在胶乳或乳液油漆应用中被推荐的任何颜料级二氧化钛。
颜料级二氧化钛可以是未处理的二氧化钛。然而,优选是用至少一种无机氧化物涂料,例如氧化铝、二氧化硅、氧化锆和类似物处理过的涂布的二氧化钛。在二氧化钛上沉积金属氧化物的方法是本领域的技术人员众所周知的。优选地,通过湿法处理或者通过气相沉积,添加金属氧化物。在美国专利Nos.3767455、4052223和6695906中教导了合适的湿法处理技术,其教导在此通过参考引入。在美国专利Nos.5562764和6852306中教导了合适的气相沉积技术,其教导在此引入作为参考。
通过添加二氧化硅化合物形成在颜料级二氧化钛表面上的二氧化硅涂层。合适的二氧化硅化合物包括水溶性碱金属硅酸盐。优选的碱金属硅酸盐包括硅酸钠、硅酸钾和类似物。最优选,二氧化硅化合物是硅酸钠。通过添加氧化锆化合物,形成二氧化锆涂层。适合于在本发明中使用的氧化锆化合物包括氧化锆的酸性盐,例如氯氧化锆、硫酸氧锆和类似物。最优选,氧化锆化合物是氯氧化锆或硫酸氧锆。类似地,可由范围典型地为0.5-10%的盐,例如硫酸铝或铝酸钠来沉淀氧化铝的水合形式或氢氧化铝。
另外,可用多元醇,例如三羟甲基乙醇和三羟甲基丙烷、烷醇胺,例如三乙醇胺、磷酸盐及其混合物处理涂布的二氧化钛颜料。优选地,由水溶性磷酸盐化合物,例如焦磷酸四钾、多聚磷酸钠、焦磷酸四钠(Tetron)、三聚磷酸钠、三聚磷酸钾、六偏磷酸钠(Calgon)、磷酸和类似物形成磷酸盐化合物。最优选水溶性磷酸盐化合物是六偏磷酸钠。
在一个实例中,可首先用磷酸盐化合物的沉积物处理二氧化钛,在基础TiO2上形成邻接层,接着通过沉积与磷酸盐沉积物邻接的致密的二氧化硅化合物,任选地第二次沉积与致密的二氧化硅化合物邻接的磷酸盐化合物,和最后沉积氧化铝化合物。或者,可用氧化锆化合物替代二氧化硅化合物涂布二氧化钛。
磷酸盐的重量百分数可随在二氧化钛基础材料上沉积的层而变化。若磷酸盐以在二氧化钛上的第一层形式沉积,则基于二氧化钛基础材料的重量,磷酸盐的沉积量为约0.05%-约1.0%,更优选约0.05%-约0.75%,和最优选约0.05%-约0.5%。基于二氧化钛基础材料的总重量,所沉积的二氧化硅的重量百分数优选用量为约0.5%-约15wt%的二氧化硅。优选地,基于二氧化钛基础材料的总重量,二氧化锆的沉积量为约0.1%-约5.0wt%二氧化锆。
涂料组合物中遮光剂的用量优选为涂料组合物总重量的0.05-25%,和更优选0.1-15wt%(以干物质表示)。
本发明的涂料组合物还包括硅酮化合物。该硅酮化合物是基于二氧化硅或其混合物的任何材料,它能提供方便涂布的硅酮基膜。
优选地,硅酮化合物包括至少一种聚硅氧烷衍生物。优选的聚硅氧烷的化学式为:
其中n为约10-2000,和R1与R2是C1-10烷基或芳基,例举的R1与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、联苯基)、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)取代的任何前述基团,或者被例如下述基团取代,或者含有例如下述基团的基团: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-氰乙基、3-氰丙基)。
基于涂料组合物的总重量,以干重计,涂料组合物中的硅酮化合物用量优选为0.05-20%,和更优选0.1-16%。除了硅酮化合物以外,还可任选地添加有机聚合物。合适的有机聚合物包括丙烯酸聚合物、聚乙酸乙烯酯和苯乙烯-丁二烯。丙烯酸聚合物包括丙烯酸、甲基丙烯酸、丙烯酸酯和甲基丙烯酸酯,和丙烯腈的聚合物与共聚物,其中包括苯乙烯-丙烯酸树脂。
本发明的涂料组合物还包括除-HNO3颗粒。除-HNO3颗粒是能除去由NOx通过光催化形成的氧化物种-HNO3的任何材料。
合适的除-HNO3颗粒包括碱性化合物,尤其任何不溶的碳酸盐,例如碳酸钙、碳酸锌、碳酸镁及其混合物。优选地,除-HNO3颗粒包括碳酸钙。基于涂料组合物的总重量,以干重(以干物质表达)计,除-HNO3颗粒在涂料组合物内的用量优选为0.05-40%,和更优选0.1-15%。
除-HNO3颗粒/光催化颗粒之比优选为0.01-50,更优选0.1-20,和最优选0.2-5。
本发明的涂料组合物还包括苯乙烯树脂空心微球。空心树脂微球在内部具有空腔且外径典型地小于10微米。优选地,该微球的外径范围为约0.1微米-约2微米,更优选约0.2微米-约1微米。用于空心树脂微球的合适的苯乙烯树脂包括聚苯乙烯、聚α-甲基苯乙烯和苯乙烯-丙烯酸共聚物树脂。尤其优选苯乙烯-丙烯酸共聚物树脂。
以重量计(以干物质表达),在组合物中苯乙烯树脂空心微球的用量优选为涂料组合物总重量的0.1%-20%,和更优选2-15%。
本发明的涂料组合物还包括溶剂。合适的溶剂包括水、有机溶剂,和由水与有机溶剂组成的混合溶剂。尤其优选水和高沸点酯、醚或二醇,后面的有机溶剂被称为聚结剂或聚结溶剂。
本发明的涂料组合物可任选地包括其它化合物,条件是这种添加没有牺牲所得涂层的寿命、UV耐久性或除污染性能。
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;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、两性和非离子的表面活性剂;消泡剂,例如硅乳液、烃和长链醇;稳定剂,例如大多数阳离子化合物;聚结剂,例如碱稳定的酯、多元醇、烃;流变学添加剂,例如纤维素衍生物(羧甲基纤维素CMC、羟乙基纤维素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;拒水剂,例如硅酸烷酯、硅氧烷、蜡乳液、脂肪酸Li盐和常规的杀菌剂或杀生物剂。
当然,这些添加剂不应当能皂化或者对最终的涂料的碱度(pH值约7.5-10)不稳定。
通过下述方法形成光催化活性的涂布基底,所述方法包括通过接触基底材料表面与涂料组合物,在基底材料上沉积涂料组合物。可通过任何合适的方法,将本发明的涂料组合物施加到基底材料表面上。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。
然后通常通过干燥或固化,固定在施加到基底表面上之后的涂料组合物,形成有机/无机层,通常薄膜形式的层。此处所使用的术语“干燥或固化”是指根据本发明,在组合物内包含的粘合剂转化成膜。优选地,通过空干进行干燥。有利地,形成涂层不要求在高温,例如50-450℃下热处理数小时。
可将本发明的涂料组合物施加到各种基底材料表面上。合适的基底材料包括,但不限于,金属、陶瓷、玻璃、木材、石头、水泥、混凝土,和上述材料的结合物以及上述材料的层压体。可施加到其上的具体实例包括住房和建筑材料;建筑物的外部;建筑物的内部;窗框;玻璃;结构材料;机器和制品外部;防尘覆盖层和涂层;和薄膜、片材与密封件。
下述实施例仅仅阐述本发明,本领域的技术人员要意识到许多变化在本发明的范围和权利要求的范围内。
实施例1:涂料组合物
使用下述材料,制备各种涂料组合物:(a)获自MillenniumInorganic Chemicals的PC105M光催化二氧化钛;(b)获自MillenniumInorganic Chemicals的595颜料级二氧化钛;(c)获自OmyaLtd.的碳酸钙-Snowcal 60;(d)获自Hercules Incorporated的羟乙基纤维素-250MR;(e)获自Cognis Corp.的消泡剂-NXZ;(f)获自Ciba Speciality Chemicals的聚丙烯酸的钠盐-Adiprex N40;(g)获自Wacker Chemie GmbH的聚硅氧烷聚合物胶乳-BS45;(h)获自BASF AG的苯乙烯-丙烯酸乳液聚合物-290D;(i)获自Rohm Haas Company的苯乙烯-丙烯酸树脂空心微球-(j)获自Eastman Chemical Company的2,2,4-三甲基-1,3-戊二醇单异丁酸酯-(k)获自ThorSpecialities的杀菌剂-
在低速搅拌下,在500rpm下,将Foamaster NXZ消泡剂和AdiprexN40加入到Natrosol 250MR的水溶液(在水中3%溶液)中。然后,在最大到3000rpm的增加速度下添加PC105M、Tiona 595和Snowcal 60。分散颜料10分钟,然后降低速度到1000RPM,之后添加水,接着添加Acronal 290D乳液聚合物或Silres BS45聚硅氧烷聚合物、Texanol和Acticide SPX。对于含有苯乙烯-丙烯酸树脂空心微球的油漆来说,最后添加Ropaque Ultra E。在1000RPM下进一步搅拌油漆5分钟,然后转移到合适的密封容器内。
表1中示出了涂料组合物1-8。
对比涂料#1是含有聚硅氧烷,但不含Ropaque Ultra E苯乙烯树脂空心微球的40%颜料体积浓度(PVC)涂料。涂料#2是含有聚硅氧烷和Ropaque Ultra E的40%PVC涂料。
对比涂料#3是含有聚硅氧烷,但没有Ropaque Ultra E的60%PVC涂料。涂料#4是含有聚硅氧烷和Ropaque Ultra E的60%PVC涂料。
对比涂料#5是含有Arconal 290D(一种苯乙烯丙烯酸胶乳聚合物)替代聚硅氧烷,但不含Ropaque Ultra E的40%PVC涂料。对比涂料#6是含有Arconal 290D替代聚硅氧烷,且还含有Ropaque Ultra E的40%PVC涂料。
对比涂料#7是含有Arconal 290D替代聚硅氧烷,但不含RopaqueUltra E的60%PVC涂料。对比涂料#8是含有Arconal 290D替代聚硅氧烷,且还含有Ropaque Ultra E的60%PVC涂料。
实施例2:涂层的耐久性试验
通过在不锈钢板上制备涂层,并在老化试验机内将其暴露于模拟的气候条件下,测试涂层1-8的耐久性。在暴露期间涂层损失的重量值是其耐久性的量度。
在施加漆膜之前和之后,称取不锈钢板(75×150mm;厚度0.75mm)到0.0001g精度,以便计算涂层的重量。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施涂器涂布该面板。仅仅涂布待暴露的表面。干燥膜厚范围典型地为20-50微米。
让涂层静置干燥7天,之后在由Atlas Electric Devices,Chicago制造的老化试验机Atlas C165A内暴露。光源为在340nm下发射0.5W/m2UV的6.5kW氙灯源。黑色面板的温度为63℃,每隔120分钟,施加水的喷洒18分钟,且不存在暗的循环。表2中示出了结果。
结果证明基于聚硅氧烷的涂层比基于常规的苯乙烯丙烯酸聚合物(Arconal 290D)的那些更加耐久。还表明,与常规的苯乙烯丙烯酸聚合物基树脂相比,对随着时间流逝,添加苯乙烯树脂空心微球(RopaqueUltra E)导致聚硅氧烷基涂层低得多的重量百分数损失。事实上,在40%PVC下,涂料#2显示出低于或最差等于不含苯乙烯树脂空心微球的涂料#1的重量损失。
实施例3:遮光性试验
通过测量散射系数(以mil-1为单位测量),测定涂料1-8的遮光性。通过用螺旋缠绕施涂器,在透明聚酯膜(其厚度为30-40微米)上刮涂涂层成约25微米的干燥膜厚,制备漆膜。使用Byk-Gardner分光光度计,首先采用与白瓷砖接触的膜,第二采用与黑瓷砖接触的膜,测量涂层的反射率。通过施加具有与聚酯膜相同折射指数的液体涂层,例如Shellsol T(Shell Chemicals的产品),在漆膜和瓷砖之间制造良好的光学接触。
然后通过切割出约15cm2的漆膜面积(它对应于在其上测定反射率的相同面积),测定涂层的膜厚。然后称取涂层和聚酯基底的重量到0.1mg以内。然后通过浸渍,从基底上取下涂层,并在丙酮内清洁,和测定聚酯膜的重量。两次重量之差是漆膜的重量。根据其重量,其已知面积和涂层的密度,测定涂层的膜厚。然后使用Kubela-Monk方程式,计算散射系数。表3中示出了结果。
结果证明,与常规的苯乙烯丙烯酸聚合物基树脂相比,聚硅氧烷和苯乙烯树脂空心微球的结合物预料不到地导致遮光度显著增加。
实施例4:除NOx试验
通过下述工序,测试涂层1-4除去NOx的能力。在进行试验之前,首先使用滤光过的氙灯源(Atlas Weather-Ometer C165A),用0.5W/m2UV在340nm下辐照根据实施例3制备的漆膜7天。这或者活化或者增加涂层的活性超过未曝光的涂层。
试验中使用的NOx是与等体积的50%湿度的空气混合的氮气内450ppb的NO,以得到225ppb NO。使用Monitor Europe9841Nitrogen Oxide Analyzer,测量NOx。对于NOx的测量来说,用发射300-400nm范围内的10W/m2UV的UV荧光管辐照样品。
将漆膜样品置于氮氧化物分析仪的试验腔室内并密封该腔室。NO试验气体流入到试验腔室内,并分析腔室内NOx的起始值。然后打开UV灯,并允许辐照过的样品达到平衡(典型地最多3分钟),之后分析腔室内NOx的最终值。通过(起始值-最终值)/起始值×100,计算NOx%除去率。表4中示出了结果。
结果表明,含有Ropaque的涂层对NOx具有活性,尽管与不含Ropaque的涂层相比,其效率下降。
表1:涂料配方
*对比例
1聚合物是涂料1、2、3和4的聚硅氧烷聚合物胶乳(Silres BS45)和涂料5、6、7和9的苯乙烯-丙烯酸乳液聚合物(Acronal 290D)。
表2:耐久性结果
*对比例
表3:遮光性结果
涂料 | 散射系数(mil-1) |
1* | 5.7 |
2 | 11.1 |
3* | 7.9 |
4 | 11.2 |
5* | 4.1 |
6* | 4.6 |
7* | 3.9 |
8* | 9.6 |
*对比例
表4:除NOx结果-NO下降百分数
涂料 | 7天Atlas曝光 |
1* | 44.6 |
2 | 8.8 |
3* | 85.5 |
4 | 45.6 |
*对比例
Claims (14)
1.一种涂料组合物,它包括:(a)光催化的二氧化钛颗粒,(b)遮光剂,(c)硅酮化合物,(d)除-HNO3颗粒,(e)苯乙烯树脂空心微球和(f)溶剂。
2.权利要求1的涂料组合物,其中光催化的二氧化钛颗粒是锐钛矿、金红石或其混合物。
3.权利要求1的涂料组合物,其中光催化的二氧化钛颗粒主要是锐钛矿。
4.权利要求3的涂料组合物,其中光催化的二氧化钛颗粒的平均粒度为2-100纳米。
5.权利要求1的涂料组合物,其中光催化的二氧化钛颗粒的存在量在全部组合物重量的0.5-20%范围内。
6.权利要求1的涂料组合物,其中遮光剂是颜料级二氧化钛。
7.权利要求1的涂料组合物,其中硅酮化合物是聚硅氧烷。
8.权利要求1的涂料组合物,其中除-HNO3颗粒选自碳酸钙、碳酸锌、碳酸镁及其混合物。
9.权利要求1的涂料组合物,其中除-HNO3颗粒是碳酸钙。
10.权利要求1的涂料组合物,其中苯乙烯树脂空心微球选自聚苯乙烯、聚α-甲基苯乙烯和苯乙烯-丙烯酸共聚物树脂。
11.权利要求1的涂料组合物,其中苯乙烯树脂空心微球是苯乙烯-丙烯酸共聚物树脂。
12.权利要求1的涂料组合物,其中溶剂包括水。
13.权利要求1的涂料组合物,进一步包括有机聚合物。
14.权利要求13的涂料组合物,其中有机聚合物选自丙烯酸聚合物、聚乙酸乙烯酯,和苯乙烯-丁二烯。
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CN2011102203505A Pending CN102352185A (zh) | 2006-10-18 | 2007-09-26 | 涂覆基体用的光催化活性聚硅氧烷组合物 |
Country Status (11)
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US (4) | US20080097018A1 (zh) |
EP (1) | EP2066741A4 (zh) |
KR (1) | KR101158779B1 (zh) |
CN (2) | CN101528832A (zh) |
AU (1) | AU2007313072B2 (zh) |
BR (1) | BRPI0717606A2 (zh) |
CA (1) | CA2666335C (zh) |
MX (1) | MX2009003540A (zh) |
MY (1) | MY183055A (zh) |
SG (1) | SG175646A1 (zh) |
WO (1) | WO2008048765A2 (zh) |
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CN103740106A (zh) * | 2012-10-16 | 2014-04-23 | 瓦克化学(中国)有限公司 | 水性硅树脂乳液及其应用 |
CN109609029A (zh) * | 2018-12-05 | 2019-04-12 | 杭州师范大学 | 一种具有延缓低分子量润滑剂释放作用的低表面能海洋防污涂料及其制备方法 |
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-
2006
- 2006-10-18 US US11/582,763 patent/US20080097018A1/en not_active Abandoned
-
2007
- 2007-09-26 KR KR1020097006569A patent/KR101158779B1/ko active IP Right Grant
- 2007-09-26 BR BRPI0717606-6A2A patent/BRPI0717606A2/pt not_active Application Discontinuation
- 2007-09-26 CN CNA2007800388316A patent/CN101528832A/zh active Pending
- 2007-09-26 WO PCT/US2007/079526 patent/WO2008048765A2/en active Application Filing
- 2007-09-26 EP EP20070853635 patent/EP2066741A4/en not_active Withdrawn
- 2007-09-26 MX MX2009003540A patent/MX2009003540A/es active IP Right Grant
- 2007-09-26 MY MYPI20091224A patent/MY183055A/en unknown
- 2007-09-26 AU AU2007313072A patent/AU2007313072B2/en not_active Ceased
- 2007-09-26 CA CA 2666335 patent/CA2666335C/en not_active Expired - Fee Related
- 2007-09-26 CN CN2011102203505A patent/CN102352185A/zh active Pending
- 2007-09-26 SG SG2011075876A patent/SG175646A1/en unknown
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2010
- 2010-11-17 US US12/948,436 patent/US8840718B2/en not_active Expired - Fee Related
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2014
- 2014-08-15 US US14/460,785 patent/US9228095B2/en not_active Expired - Fee Related
-
2015
- 2015-10-20 US US14/887,665 patent/US20160040018A1/en not_active Abandoned
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102464932A (zh) * | 2010-11-16 | 2012-05-23 | 罗门哈斯公司 | 红外反射涂料组合物 |
CN102464932B (zh) * | 2010-11-16 | 2016-03-30 | 罗门哈斯公司 | 红外反射涂料组合物 |
CN103740106A (zh) * | 2012-10-16 | 2014-04-23 | 瓦克化学(中国)有限公司 | 水性硅树脂乳液及其应用 |
CN109609029A (zh) * | 2018-12-05 | 2019-04-12 | 杭州师范大学 | 一种具有延缓低分子量润滑剂释放作用的低表面能海洋防污涂料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
SG175646A1 (en) | 2011-11-28 |
KR101158779B1 (ko) | 2012-06-22 |
MY183055A (en) | 2021-02-09 |
US8840718B2 (en) | 2014-09-23 |
MX2009003540A (es) | 2009-07-17 |
BRPI0717606A2 (pt) | 2013-10-22 |
AU2007313072A1 (en) | 2008-04-24 |
US20140357751A1 (en) | 2014-12-04 |
CN102352185A (zh) | 2012-02-15 |
EP2066741A4 (en) | 2010-11-17 |
US20110059841A1 (en) | 2011-03-10 |
EP2066741A2 (en) | 2009-06-10 |
WO2008048765A2 (en) | 2008-04-24 |
CA2666335A1 (en) | 2008-04-24 |
AU2007313072B2 (en) | 2013-02-21 |
US9228095B2 (en) | 2016-01-05 |
US20080097018A1 (en) | 2008-04-24 |
WO2008048765A3 (en) | 2008-11-06 |
KR20090079880A (ko) | 2009-07-22 |
US20160040018A1 (en) | 2016-02-11 |
CA2666335C (en) | 2012-04-10 |
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