CN100439271C - 有自洁式涂层的基材 - Google Patents

有自洁式涂层的基材 Download PDF

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CN100439271C
CN100439271C CNB038142031A CN03814203A CN100439271C CN 100439271 C CN100439271 C CN 100439271C CN B038142031 A CNB038142031 A CN B038142031A CN 03814203 A CN03814203 A CN 03814203A CN 100439271 C CN100439271 C CN 100439271C
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base material
glass
coating
mesoporous structure
application
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CN1662465A (zh
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L·盖诺
M·龙代特
T·加科因
J-P·布瓦洛
S·贝松
C·杜兰德
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Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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    • C03C17/25—Oxides by deposition from the liquid phase
    • C03C17/256—Coating containing TiO2
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
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    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
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    • C03C25/42—Coatings containing inorganic materials
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    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
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    • C03C25/52—Coatings containing inorganic materials only
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
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    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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    • C03C2217/00—Coatings on glass
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    • C03—GLASS; MINERAL OR SLAG WOOL
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    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
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    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
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    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
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Abstract

本发明涉及玻璃或一种或多种聚合物基的透明基材，或陶瓷或玻璃-陶瓷基材，或包括墙灰浆、混凝土砖或块、建筑混凝土、瓦、胶结组合物材料、琉璃砖、石板瓦、石料、金属面类建筑材料制得的基材，或绝缘矿棉或增强玻璃丝类玻璃基的纤维基材。这种基材的特征在于它在其至少一部分表面上有涂层，该涂层的中孔性结构具有光催化的性质，它含有至少部分结晶的二氧化钛。生产这种基材的方法，它在玻璃窗、作为建筑材料或作为绝缘矿棉的应用。

Description

有自洁式涂层的基材
本发明涉及在建筑物、车辆、城市设施或家用电器等中可以见到的各种类型的材料，即具体地是：
-用玻璃或聚合物制成的透明基材，它们例如可用作玻璃窗，显示屏，
-用陶瓷或玻璃陶瓷制成的基材，例如在家用电器中可以使用这些基材，
-建筑材料，例如瓦、地面砖、石料、胶结组合物、金属面，
-无机纤维材料，例如绝缘玻璃棉或织物玻璃丝，这些材料可以用作过滤材料，为了制造吊顶，可以使用石英纤维、二氧化硅纤维等。
近来的研究试图改善人们使用这些材料的舒适性，特别是有利于清洁这些材料。
特别地，曾研制一些具有光催化性能的功能涂料。特别涉及含有至少部分结晶TiO2，尤其是锐钛矿型TiO2的涂料，在专利WO 97/10185、WO 97/10186、WO 99/44954和WO 01/66271中具体描述过这些涂料。这类任选掺杂的(还有其它可以是光催化的氧化物，例如ZnO等)金属氧化物基半导体材料，在适当波长的辐射作用下能引发自由基反应，使有机化合物氧化：如果这类涂料充分暴露在特别辐射(一般是紫外光，任选地可见光区)下，它因此会非常有效地使有机污染物降解。另外曾发现，特别是氧化钛基涂料，如果它们足够长时间暴露于所述的辐射下，则它们还具有某些亲水特性。这种涂料能使有机污染物降解，并且因其亲水性还能除去无机污染物，因此它的性能非常好。然而，它的活性与它暴露(足够长的时间)在特定的波长辐射(足够的辐射强度)下相关。这类涂料在户外暴露时，它的性能因此高度依赖于环境的气候条件，尤其是阳光照射和雨水条件。同样地，没有适当的照明，它在晚上的活性不如白天的活性。
因此，本发明的目的是改善由这类“自洁式”或“污染延缓式”涂料赋予的功能性。本发明的目的具体地是获得可具有高效率的涂料，它们在不同方面还可是“多种性能的”：首先对于暴露于辐射的条件，其次对于机械应力(耐磨损等)，最后对于其它功能结合。更具体地，本发明的目的是甚至在通常的阳光照射条件下，甚至在夜晚或在户内，尤其在通常照明灯具的残余紫外辐射或透过玻璃窗的紫外辐射下，都可具有一定抗污染活性的涂料。本发明的目的还是与紫外灯具结合的产品，特别是自洁过滤器。
本发明的主题首先是一种基材，它可以是基本透明的基材，特别是玻璃或一种或多种聚合物基的基材，或它可以用陶瓷或玻璃-陶瓷制得，或它还可以用建筑材料(墙灰浆、混凝土砖或块、建筑混凝土、瓦、胶结组合物材料、琉璃砖、石板瓦、石料类的建筑材料，或它还可以是绝缘矿棉或增强玻璃丝类玻璃基的纤维基材，或是含有石英或二氧化硅纤维的产品)制得。这种基材的特征在于它在其至少一部分表面上有涂层，该涂层的中孔性结构具有光催化性质，它含有至少部分结晶的二氧化钛，特别是锐钛矿和/或金红石型的二氧化钛。术语“中孔性的”是指直径2-50nm的孔。以下面将要描述的方式得到的中孔性结构特别是元素Si、W、Sb、Ti、Zr、Ta、V、B、Pb、Mg、Al、Mn、Co、Ni、Sn、Zn、In、Fe和Mo中至少一种的至少一种化合物基的，任选地，它们与像O、S、N、C等元素共价键键合。至少部分结晶的二氧化钛(oxyde de titane)例如以充分可辩别的微粒形式加到该中孔性结构中。加入二氧化钛的整个中孔性结构基本上是固体，具有优异的附着性、机械强度和耐磨性。这种中孔性结构可以专门由钛或钛化合物组成，例如由氧化物，特别地锐钛矿、金红石型结晶氧化物等组成。已被证实，如此加入的二氧化钛使其具有格外高度的光催化活性。因此，通过单层、双层等玻璃窗后的残余紫外辐射，或来自室内电照明的残余紫外辐射足以使本发明基材上的有机残留物降解，然后将它们带到相对均匀的液膜中，任选地，这种辐射可使在该基材上形成的液膜变成亲水的。本发明的涂料将光催化降解有机残留物的功能与在任何液体(例如冷凝液作用)作用下除去有机和无机残留物(具有亲水/亲油特性)的功能结合起来。本发明达到的高性能或许可至少部分地归因于孔的网状结构相互连接，因此能使污染物很易接近二氧化钛颗粒，同时能使在这些颗粒表面上的光生粒子很好地扩散到该涂料中。
此外，达到如此高度的耐磨性和光催化活性的耐久性是极佳的(参见下面的实施例)。本发明因此还能在磨损后保持其孔隙度，而更确切地说，人们可以预料磨损结果是表层变得密实，因此最后失去防污性能。
另外，这种基材的中孔性性质可以预料在生成中孔性结构后被除臭的、抗菌的或任何其它性质的功能剂浸渍。
有利地，本发明的基材基本上是玻璃板类的平或弯曲的透明基材，因为正是在这类应用中，积累的污物降低能见度，这令人很不舒服，为了保证其能见度，需要经常擦洗。可能涉及宏观凹凸不平的玻璃窗，例如深度约几毫米的锥体状图案(刻痕玻璃)，或表面极小不均度的玻璃窗，例如用氢氟酸化学蚀刻得到的玻璃窗(磨砂玻璃，不透明玻璃)。
优选地，形成的本发明涂层插入了至少部分氧化的硅衍生物基内层，所述至少部分氧化的硅衍生物选自二氧化硅、亚化学计量硅氧化物、硅氧碳化物、硅氧氮化物或硅氧碳氮化物。下层表面是用玻璃制成的时，该内层被证明是有效的，因为本发明涂层中玻璃的碱金属离子(钠)迁移在某些条件下可改变其光催化性质；或该内层构成了碱金属的阻挡层。该内层可以是在上述专利WO 01/32578中描述的内层。它的折射指数1.45-1.80，特别地1.50-1.75，例如1.55-1.68是很有利的。这样一种折射指数相对来讲不太高，因此在玻璃类透明基材上可以避免被认为不美观的反射作用。
这个内层因此有利地含有Si、O，任选地碳和氮。但是，它还可以含有与硅相比较少的物质，例如金属，像Al、Zn或Zr。可以采用溶胶-凝胶法或采用热解法，特别地采用气相热解法(CVD)沉积该内层。其后一种技术能够相对容易地获得SiOxCy或SiO2涂层，在玻璃基材情况下在浮法玻璃条板上采用直接沉积尤其如此。然而，还可以采用真空技术进行沉积，例如使用Si靶(任选地掺杂的)或低氧化硅靶(例如在氧化性和/或渗氮活性气氛下)采用阴极溅射法进行沉积。
这个内层的厚度优选地是至少5nm，该厚度尤其是10-200nm，例如80-120nm。
根据本发明基材的其它有利特征：
-采用溶胶-凝胶法沉积具有中孔性结构的涂层；
-其厚度是30-800nm；
-任选地掺杂加入中孔性结构中的二氧化钛，如在申请WO97/10185和WO 97/10186中所解释的，本文将该申请作为参考文献加以引用，该二氧化钛含有直径0.5-100nm，特别1-80nm的纳米微粒，它们本身由直径0.5-10nm的基本颗粒或微晶簇组成。术语“直径”本文取其广义，更多的涉及计算纳米微粒或微晶的尺寸。它的形状接近于球形，或稻粒的伸长形状或完全随机形状。
本发明的另一个目的是如前面描述基材的生产方法，该方法相继地包括：
-制备液体组合物，该组合物含有至少一种构成涂层中孔性结构的材料的前体和至少一种有机结构剂，
-该前体在该有机结构剂周围沉淀，与由该前体衍生的分子生长，
-往液体组合物中添加任选掺杂的二氧化钛纳米微粒或微晶(根据前面定义的)，其直径是0.5-100nm，
-将该组合物涂布到待涂敷表面上，
-除去有机结构剂。
这些二氧化钛基本微粒或微晶加到中孔性结构中，同时基本上保持其完整性，其中多个二氧化钛基本微粒或微晶可能聚集成簇。根据这些操作条件(含量、pH、温度等)，在这样一种基材生产过程中不排除二氧化钛微粒或微晶彼此聚集和/或生长，特别是最小二氧化钛微粒或微晶彼此聚集和/或生长。
为了生产本发明的基材，有利地，该液体组合物的制备方法包括下述步骤：
-制备氧化物(特别是二氧化硅)前体的溶胶，
-该溶胶熟化，然后
-与结构剂混合。
事实上，溶胶熟化有可能使氧化物前体初步缩合，这样有利于在支承表面上在大尺寸范围内缩合氧化物涂层结构化。有利的熟化条件包括让溶胶在温度40-60℃下保持30分钟至24小时，熟化温度越高，熟化时间就越短。
在这种情况下，该氧化物前体为可水解化合物很有利，例如卤化物或醇盐，该结构剂有利地选自阳离子表面活性剂，优选地季铵类阳离子表面活性剂，像溴化鲸蜡基三甲基铵，或非离子表面活性剂，其中包括例如环氧乙烷或环氧丙烷基的二嵌段或三嵌段共聚物。
本发明还有一个目的是本发明基材，特别是基本透明基材在生产“自洁式”玻璃窗中的应用，这些玻璃窗能够同时防污、防雾和防凝结水。可涉及双玻璃窗类的建筑物用玻璃窗，风挡玻璃、后窗玻璃、遮阳篷顶、侧窗类车辆用玻璃窗。还可能涉及火车、飞机、轮船用玻璃窗。还可能涉及实用玻璃板，例如养鱼缸玻璃、商店橱窗玻璃、温室玻璃，或室内陈设品、城市设施中使用的玻璃或镜子。还可能涉及用作电视机、计算机、电话屏幕类显示屏的玻璃板。这类涂料还可以涂在电控玻璃板上，例如电线或层类加热玻璃板、电致变色玻璃板、液晶薄膜玻璃板、电致发光的玻璃板、光电玻璃板。
在本发明基材作为玻璃板(透明塑料或玻璃基的)的应用中，除上述内层外，一个或多个至少部分氧化的硅衍生物基的薄层可以插入支承表面与具有中孔性结构的涂层之间。特别涉及具有抗静电功能层、热功能(加热、用电线提供热低-发射率功能、防晒功能等)层、光学功能(降低光反射和/或使反射时基材颜色变得更中性等)层，抗反射叠层等。关于在玻璃板上这样一些以已知方式应用的功能层，任选地为叠层形式的功能层，本文将已经提到的申请WO 97/10186和WO 02/02472作为参考文献加以引用。
除作为玻璃窗的应用外，本发明的基材还可以用任何建筑材料制成，它们可用于生产室内外的隔墙、建筑物面、屋面、地面(金属、木料、石料、水泥、混凝土、琉璃砖、陶瓷、墙灰浆等)。
这种基材如果更确切地说是绝缘矿棉基的，和增强玻璃纤维基的织物，可以用作过滤材料，或用作吊顶，它们是易于清洁的。
本发明还有一个目的是机织基材、非机织基材(针刺垫、毡、羊毛等)、针织基材、编织基材、以直径为1-20μm熔融二氧化硅纤维、根据权利要求1所述的洗涤玻璃纤维(90％以上二氧化硅)、氧化铝和莫来石纤维为基的烧结纤维块(以硬质二氧化硅名称为人们所知)，应用于生产防臭过滤器、工业排放物除污过滤器、抗菌过滤器、室内除污过滤器、家庭空气净化过滤器、运输车辆(汽车、铁路、航空、船舶等)乘客室净化过滤器、吸烟室过滤器、家用电器(电冰箱等)净化过滤器。
通过下述非限制性实施例说明本发明。
实施例1
在浮法玻璃条板形状的玻璃上沉积氧碳化硅(为方便起见记为SiOC)基内层(无须预料在该涂层中氧和碳的实际比)，该玻璃是厚度4mm的钙钠硅透明玻璃，例如Saint-Gobain Glass France以商品名Planilux销售的玻璃。借助置于其上的喷嘴，使用Si前体，特别地使用用氮气稀释的SiH4和乙烯混合物，采用CVD方法沉积这个内层，并当该玻璃还是温度约550-600℃时就在平板玻璃生产线的浮法玻璃带上横向通过浮室。得到涂层厚度约50nm，折射指数约1.55。从如此得到的有SiOC碱金属阻挡内层的浮法玻璃切割10cm×10cm试样；这些试样进行洗涤、漂洗、干燥，再进行UV/臭氧处理45min。
在该内层上形成具有中孔结构的涂层。
第一步将22.3ml四乙氧基硅烷、22.1ml无水乙醇、9ml HCl放到软化水(pH 1.25)中进行混合，直到该溶液变成透明的，然后把瓶放在60℃水浴中达1小时，这样得到处理的液体组合物。
第二步，往前面得到的溶胶中添加溴化鲸蜡基三甲基铵(CTAB)溶液和聚氧化亚乙基-聚氧化亚丙基嵌段共聚物溶液(它是BASF公司以登记商标Pluronic PE6800(分子量8000)销售的商品)，其摩尔比分别是CTAB/Si＝0.1，PE6800/Si＝0.01。这是将下述化合物混合得到的：
-0.686g CTAB，20ml乙醇和10ml该溶胶；
-3.78gPE6800，50ml乙醇和25ml该溶胶。
锐钛矿型结晶TiO2纳米微粒的尺寸约50nm，把这种纳米微粒按不同比例加到如此得到两种组合物中的一种或另一种组合物中，然后立刻沉积到试样上。每个试样的起始量为3ml，采用旋涂方法进行沉积。(其它等效沉积技术是蘸涂、喷涂、层涂、辊涂、流涂等)。
这些试样再进行下述淬灭(recuit)处理：
-100℃30分钟，保持2小时；
-150℃15分钟，保持2小时；
-175℃15分钟，保持2小时；
-200℃10分钟，不保持；
-300℃3小时20分钟，保持1小时；
-450℃2小时30分钟，保持1小时。
阳离子表面活性剂CTAB用作结构剂时，如此生成涂层孔尺寸是2-3nm，共聚物PE6800用作结构剂时，这个尺寸是4-5nm。
采用SIMS分析证明了这种具有中孔性结构的涂层，其Ti/Si原子比与开始液体组合物的Ti/Si原子比完全相同。SIMS分析还能证明，纳米微粒沿其涂层三维方向均匀地分布。
下表列出了涂层在生成时与在500个Opel摩擦试验循环后(在这后一情况下，其值用括号表示)的不同特性。Opel试验(2001年1月的标准
Figure C0381420300111
En 1096-2)是在长度9.4cm的部分涂敷表面(这部分称之道)上贴直径14mm、厚度10mm和密度0.52g/cm2的毡，在负载400g/cm2下，再让这种毡同时进行平移运动(沿其整个毡长度每分钟往返平移运动50次)与6转/分旋转运动(1个循环＝1个往返)。
使用SIMS剖面和MEB显微照片测量了以nm表示的涂层厚度E。
采用X射线荧光法分析了以μg/cm2表示的TiO2量。
以下述方式测定了光催化活性：
1-用约15cm2涂层进行试验；
2-称取试样，测量基材厚度、光透射TL和混浊度Td(两者都以％表示)；
3-在垂直的基材上，采用喷涂棕榈酸溶液(1升氯仿8克酸)涂敷，玻璃/喷涂距离为20cm，相继喷涂3-4次；
4-棕榈酸沉积后称量试样，分析以纳米表示的涂敷棕榈酸厚度；
5-涂敷后测量光透射TL和混浊度Td；
6-测量在强度约50W/m2的UVA作用下混浊度随着辐照时间的变化；
7-图形测定混浊度降低50％时的时间：这个时间称之T1/2(消失)；
8-以棕榈酸减少速率v(以nm/h表示)评价涂层的光催化活性，该速率定义如下：
v(nm/h)＝(棕榈酸厚度(nm))/(2×T1/2(消失(h))
在下表中还列出用该涂层中TiO2量除以光催化活性的值。最后，列出了光反射RL和混浊度Td(以％表示)的光学性能。
试验序号定义如下：
-1和2：CTAB作为结构剂；Ti/Si分别为0.1和0.25；
-3-7：PE6800作为结构剂；Ti/Si分别为0.1、0.25、0.5、1、2。
  试验序号  Enm   TiO<sub>2</sub>μg/cm<sup>2</sup>   Vnm/h   V/TiO<sub>2</sub>   Ri％   Td％
  1  214(220)   2.2(1.9)   43(21)   20(11)   6.5(10.2)   0.8(0.5)
  2  208(247)   7.5(5.7)   117(114)   16(20)   8.7(7.9)   1.1(1.2)
  3  274(209)   4.7(3.4)   47(31)   10(9)   10.2(7.8)   0.2(0.4)
  4  308(299)   8.0(10.2)   209(123)   26(12)   12.8(10.2)   0.2(0.3)
  5  336(294)   17.3{14.8)   349(181)   20(12)   9.7(11.4)   0.4(0.4)
  6  454(184-320)   33.3(28.7)   620(354)   18(12)   9.7(14.3)   0.3(0.8)
  7  515(209-268)   66.0(46.7)   684(...)   10(...)   9.4(17.7)   0.8(1.1)
根据加入TiO2纳米微粒量，这些层厚度可以从200nm到500nm。在500个Opel循环后，只是最厚涂层(450和500nm)受到压实，其厚度减少超过其开始厚度的一半以上。然而还是试验了这些涂层的光活性。
这些涂层的光活性是，从用阳离子表面活性剂结构化，并且TiO2浓度最低(2.2μg/cm2)的涂层为43nm/h，到用该共聚物结构化，并且TiO2浓度最高(66μg/cm2)的涂层为648nm/h。V/TiO2比总是至少等于9。
观察到，在500个Opel循环后保持其部分或全部的功能性，另外，只是改变了最厚层和最高TiO2浓度(Ti/Si＝1和2)层的光学性能，而其它层的RL和Td值分别低于11.4和1.2％。
使用1.5W/m2通常照明灯的低UVA辐射重复进行了试验3-7(试验3′-7′)；第N次试验的V(nm/h)和V/TiO2值如下：
-3′：0和0；
-4′：0和0；
-5′：13和0.75；
-6′：19和0.57以及
-7′：28和0.42。
有本发明涂层的基材在低UVA辐射下对棕榈酸降解因此还是有光活性的。
实施例2
另外，Saint-Gobain Quartz公司以商品名针刺Quartzel毡(7-16μm纤维)销售的针刺二氧化硅纤维毡，将其直径47mm、厚度8mm和表面密度1000g/m2毡片浸渍在上述第6号试验组合物中，进行如前面所述的热处理。如此得到毡片的质量增加达到10％。
在UV照明(190-350nm)与以62.5ml/mm流量过滤的条件下，测试了这些毡片分解在氮气中的甲醇(以体积计，浓度350ppm)的能力。
在照明功率48mW/cm2的条件下，效率(即分解甲醇的比例)是100％。在照明功率25.6mW/cm2的条件下，效率是约96％，而照明功率低到8.22mW/cm2时，其效率还达到约58％。
因此，本发明能获得一种基材，它在室外大气气候与腐蚀条件下可以达到在玻璃窗应用中要求的透明光学质量和持久的自洁性功能。这种显著高度的光催化功能还可以考虑在夜晚或室内利用低强度辐射的应用，例如利用通常照明、通过窗玻璃的太阳辐射产生的低强度辐射的应用，以及排放物或大气净化的应用、过滤等。

Claims (23)

1、基本透明的基材，或陶瓷或玻璃-陶瓷基材，或用墙灰浆、混凝土砖或块、建筑混凝土、瓦、胶结组合物材料、琉璃砖、石板瓦、石料、金属面类建筑材料制得的基材，或绝缘矿棉或增强玻璃丝类玻璃基的纤维基材，其特征在于它在其至少一部分表面上有涂层，该涂层的中孔性结构具有光催化的性质，它含有至少部分结晶的二氧化钛，它以充分可辩别的微粒形式加到该中孔性结构中。
2、根据权利要求1所述的基材，其特征在于基本透明的基材是玻璃或一种或多种聚合物基的基材。
3、根据权利要求1所述的基材，其特征在于所述基材是玻璃板类的平或弯曲的基本透明基材。
4、根据权利要求1-3任一项所述的基材，其特征在于形成的所述涂层插入了至少部分氧化的硅衍生物基的内层，所述至少部分氧化的硅衍生物选自二氧化硅、亚化学计量的硅氧化物、硅的氧碳化物、氧氮化物或氧碳氮化物。
5、根据权利要求4所述的基材，其特征在于所述的内层厚度至少5nm。
6.根据权利要求5所述的基材，其特征在于所述的内层厚度是10-200nm。
7.根据权利要求6所述的基材，其特征在于所述的内层厚度是30-120nm。
8、根据权利要求1-3任一项所述的基材，其特征在于采用溶胶-凝胶法沉积该涂层。
9、根据权利要求1-3任一项所述的基材，其特征在于该涂层的厚度是30-800nm。
10、根据权利要求1-3任一项所述的基材，其特征在于任选地掺杂了二氧化钛，它含有直径0.5-100nm的纳米微粒，其微粒本身由直径0.5-10nm的基本微粒或微晶簇组成。
11.根据权利要求10所述的基材，其特征在于所述直径是1-80nm。
12、根据上述权利要求中任一权利要求所述基材的生产方法，该方法包括：
-制备液体组合物，该组合物含有至少一种构成涂层中孔性结构的材料前体和至少一种有机结构剂，
-该前体在该有机结构剂周围沉淀，与由该前体衍生的分子生长，
-往液体组合物中添加任选掺杂的二氧化钛基本纳米微粒或微晶，其直径是0.5-100nm，
-将该组合物涂布到待涂敷表面上，
-除去有机结构剂，
这些二氧化钛微晶加到中孔性结构中，同时基本上保持其完整性。
13.根据权利要求12的生产方法，其中这些二氧化钛微晶加到中孔性结构中，同时基本上保持其完整性，其中多个微晶聚集成纳米微粒。
14、根据权利要求1-11中任一权利要求所述的基本透明基材的应用，该应用为用于生产自洁式玻璃窗。
15.根据权利要求14的应用，其中自洁式玻璃窗是防雾、防污和防凝结水的玻璃窗。
16.根据权利要求15的应用，其中所述玻璃窗是双玻璃窗类的建筑物用玻璃窗，风挡玻璃、后窗玻璃、遮阳篷顶、侧窗类车辆用玻璃窗，火车、飞机、轮船用玻璃窗，实用玻璃板，或室内陈设品、城市设施或镜子使用的玻璃，用作电视机、计算机、电话屏幕类显示系统屏或电控玻璃板。
17.根据权利要求16的应用，其中实用玻璃板是养鱼缸玻璃、商店橱窗玻璃或温室玻璃。
18.根据权利要求16的应用，其中电控玻璃板是电致变色玻璃板、液晶玻璃板、电致发光玻璃板或光电玻璃板。
19、根据权利要求1-11中任一权利要求所述的用建筑材料制成的基材在生产室内外的隔墙、建筑物面、屋面或地面中的应用。
20、根据权利要求1-11中任一权利要求所述的绝缘矿棉基的基材或增强玻璃纤维基的织物基材在生产吊顶或过滤材料中的应用。
21、根据权利要求1所述的基材用于生产防臭过滤器、工业排放物除污过滤器、抗菌过滤器、室内除污过滤器、家庭空气净化过滤器、运输车辆乘客室净化过滤器、吸烟室过滤器、家用电器净化过滤器的用途。
22.根据权利要求21的用途，其中所述的基材为机织基材、非机织基材、针织基材、编织基材、以直径为1-20μm熔融二氧化硅纤维、洗涤玻璃和氧化铝和莫来石纤维为基的烧结纤维块。
23、根据权利要求1-3中任一权利要求所述的透明塑料或玻璃基的基本透明基材，其特征在于抗反射叠层插入在支承表面与具有中孔性结构涂层之间。
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WO2003087002A1 (fr) 2003-10-23
BR0309276B1 (pt) 2012-08-07
BR0309276A (pt) 2005-02-22
AU2003262137A1 (en) 2003-10-27
ATE486825T1 (de) 2010-11-15
PL218194B1 (pl) 2014-10-31
JP2005528312A (ja) 2005-09-22
PL372454A1 (en) 2005-07-25
US20060014050A1 (en) 2006-01-19
DE60334788D1 (de) 2010-12-16
CA2482630C (fr) 2012-08-07
EP1497234B1 (fr) 2010-11-03
CN1662465A (zh) 2005-08-31
CA2482630A1 (fr) 2003-10-23
MXPA04010162A (es) 2005-02-03
ES2355553T3 (es) 2011-03-28
FR2838734A1 (fr) 2003-10-24
EP1497234A1 (fr) 2005-01-19
KR100973747B1 (ko) 2010-08-04
PT1497234E (pt) 2011-02-09
US7510763B2 (en) 2009-03-31

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