CN1481342A - 具有自清洁表面的基材及其制备方法和用途 - Google Patents
具有自清洁表面的基材及其制备方法和用途 Download PDFInfo
- Publication number
- CN1481342A CN1481342A CNA018207944A CN01820794A CN1481342A CN 1481342 A CN1481342 A CN 1481342A CN A018207944 A CNA018207944 A CN A018207944A CN 01820794 A CN01820794 A CN 01820794A CN 1481342 A CN1481342 A CN 1481342A
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- Prior art keywords
- base material
- particle
- glass
- self
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000853 adhesive Substances 0.000 claims description 7
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- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052728 basic metal Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
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- BKQMNPVDJIHLPD-UHFFFAOYSA-N OS(=O)(=O)[Se]S(O)(=O)=O Chemical compound OS(=O)(=O)[Se]S(O)(=O)=O BKQMNPVDJIHLPD-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
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- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
- C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
- C03C2205/04—Compositions applicable for the manufacture of vitreous enamels or glazes for self-cleaning enamels or glazes
-
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Abstract
具有自清洁表面的基材，所述基材具体指玻璃、陶瓷、塑料或金属基材，或者是釉面或搪瓷基材，所述基材包括位于其上的至少部分表面疏水化和结构化(突起和凹陷)的涂层。根据本发明的基材含有用来形成涂层结构的平均粒径小于100nm，特别是5nm到小于50nm的颗粒。根据本发明的用来形成本发明基材的结构化涂层的组合物含有重量比为100∶1到1∶2的，特别是20∶1到1∶1的形成结构的颗粒和成层材料。所述涂层不但具有良好的自清洁性，而且具有优良的透明度。所述基材的用途特别针对各种不同的玻璃物件。
Description
技术领域
本发明涉及具有至少一个自清洁表面的基材，具体而言，所述基材为玻璃、陶瓷、塑料或金属基材，或者是釉面或搪瓷基材。所述基材上的自清洁表面基于一种具有形成结构的颗粒的涂料，所述形成结构的颗粒位于所述基材上，从而形成凸凹不平的表面结构；至少部分所述表面是疏水的。本发明还涉及用来制备所述具有至少一个自清洁表面的基材的组合物。本发明还涉及所述具有至少一个自清洁表面的基材的制备方法，所述方法包括用所述组合物涂敷所述基材的步骤。最后，本发明还涉及根据本发明的具有自清洁表面的基材的用途。
背景技术
已经知道，为了使表面获得良好的自清洁性，除了使表面具有良好的疏水性之外，还必需使表面具有微糙的表面结构。有些物体天然具有这两个特性，例如莲叶。莲叶的表面由疏水性物质形成，该表面上具有彼此相距数个微米的金字塔形突起。水滴实际上只接触到金字塔尖，所以接触面积很小，从而导致附着力很低。A.A.Abramzo在Khimiai Zhizu(1982)第11期第38-40页提出了上述机理以及“莲叶效应”在人工表面上的应用。
US 3,354,022公开了斥水表面，但没有提及莲叶效应。所述斥水表面具有由疏水性材料形成的凸凹不平的微糙结构，具体来说，所述疏水性材料是一种含氟的聚合物。根据一个实施方式，可在瓷砖或玻璃上形成具有自清洁性的表面，其形成方法是用一种悬浮液涂敷基材，所述悬浮液含有粒径为3μm到12μm的玻璃珠和基于乙氧甲基丙烯酸氟代烷基酯聚合物的碳氟蜡。这种涂层的缺陷是耐磨性差，自清洁性一般。
EP 0 909 747 A1教导了一种使表面产生自清洁性的方法，具体来说，所述的表面是屋瓦。该表面具有高度为5μm到200μm的疏水性突起。该表面的形成方法是，在其上涂敷由惰性材料的粉末颗粒在硅氧烷溶液中形成的悬浮液，随后使涂层固化。在上述方法中，形成结构的颗粒没有以耐磨的方式被固定在基材的表面。
欧洲专利0 772 514教导了物体的自清洁表面，该表面具有人造的凸凹不平的表面结构，其突起之间相距5μm到200μm，突起的高度为5μm到100μm，所述结构含有疏水性聚合物或经过了稳定的疏水化处理的材料。可以采用蚀刻、浮雕以及涂敷的方法来形成这种结构。如果必要的话，在形成这种结构之后进行疏水化处理，例如所谓的硅烷化处理。
EP 0 933 388 A2教导了具有类似结构的疏水表面。这种表面具有平均高度为50nm到10μm，平均间距为50nm到10μm的突起，未经构造的原料的表面能为10到20mN/m。为了获得特别低的表面能，以便使其具有疏水性和疏油性，使所构造的表面含有含氟的聚合物，或者用烷基氟硅烷处理该表面。对于构成的表面，该文献公开了成形方法，但不能从中得到也采用涂敷方法的暗示。
德国专利申请100 16 485.4教导了具有自清洁表面的玻璃、陶瓷和金属基材，所述自清洁表面基于经过构造的并且至少部分疏水化的涂层。所述涂层含有玻璃熔剂和平均粒径为0.1μm到50μm的形成结构的颗粒。所述玻璃熔剂和形成结构的颗粒的体积比为0.1到5，在这种微糙表面结构中，突起的平均高度与相邻突起的平均间距之比为0.3到10。与上述EP 0 909 747 A1中屋瓦的自清洁表面相比，该自清洁表面具有较高的耐磨性。
发明内容
本发明的目的是提供具有至少一个自清洁表面的基材，所述基材具体为玻璃、陶瓷、塑料或金属基材，或者是釉面或搪瓷基材，所述自清洁表面不但因具有小的滚动角或大的接触角而具有良好的自清洁性，而且所述自清洁表面是透明的。所述自清洁表面对于水应当具有很大的接触角，所述接触角优选接近或大于150°。应当尽可能不降低透明基材例如玻璃或塑料的透明度。处于所述自清洁表面之下的装饰应当保持清晰可见。根据本发明的另一个目的，本发明的玻璃、陶瓷、塑料或金属基材，或者是釉面或搪瓷基材应当比已知的基材具有更高的耐磨性，而且在本发明的上述基材上，由有机聚合物形成结构化表面，或者结构化表面包含结合在有机聚合物材料中的形成结构的颗粒。根据本发明的又一个目的，本发明的具有自清洁表面的基材应当由简单方法获得，优选由用于玻璃和陶瓷工业或金属加工工业中的表面装饰方法获得。本发明的所有实施方式并非均必须同时实现上述及由其后的描述所导出的目的。
因此，本发明提供了具有至少一个自清洁表面的基材，所述基材具体指玻璃、陶瓷、塑料或金属基材，或者是釉面或搪瓷基材，所述基材上分布有涂层，所述涂层含有用来形成表面结构的颗粒，而且至少部分表面是疏水的，其特征在于，所述形成结构的颗粒的平均粒径小于100nm。本发明的从属权利要求涉及优选的实施方式。
我们发现，如果涂层含有平均粒径小于100nm的形成结构的颗粒，则基材表面的疏水性涂层具有“纳米级”表面结构，该基材具有优异的自清洁性。所述颗粒的粒径优选从5nm到小于50nm。应当理解，此处的术语“平均粒径”指初级颗粒的直径，而不是其聚集体的直径。通常，平均粒径小于100nm的，特别优选小于50nm的初级颗粒至少为90％，优选约100％。术语“纳米级”指，与具有微米范围的形成结构的颗粒的表面相比，所述结构具有明显较低的突起高度和突起峰间距——不考虑聚集体时，所述突起高度和突起峰间距小于所述粒径。
所述形成结构的颗粒可以是有机或无机材料。可以举出的无机材料的例子有：金属氧化物、混合氧化物、硅酸盐、硫酸盐、磷酸盐、硼酸盐、金属硫化物、氧代硫化物、硒化物和硫硒化物、金属氮化物和氧化物-氮化物以及金属粉末。可以举出的有机形成结构的颗粒的例子有：碳黑和纳米级有机聚合物颗粒，其中包括含氟的聚合物。可以购得多种形成结构的颗粒，例如，根据本发明的权利要求，具体是平均粒径为5nm到小于50nm的形成结构的颗粒。也可通过本身已知的沉淀法，或者通过高温法将气态起始物质转化为粉体。所述形成结构的颗粒特别优选自由二氧化硅(SiO2)、二氧化钛(TiO2)、氧化铝(Al2O3)、氧化锆(ZrO2)和氧化锡(SnO2)组成的组中的金属氧化物。这些氧化物特别优选煅制的氧化物，其中特别优选二氧化硅。可以购得初级颗粒的平均粒径为约7nm到40nm的煅制二氧化硅。
除形成结构的颗粒之外，根据本发明的基材的自清洁表面含有无机或有机成层材料。所述成层材料形成均一的层，所述的形成结构的颗粒以初级颗粒和/或聚集体的形式被固定在所述的层内，或者所述的形成结构的颗粒被成层材料固定在所述基材上。有些初级颗粒和/或其聚集体至少部分突出表面，从而形成突起和凹陷，这些突起和凹陷与疏水化作用共同促成了本发明的效果。
成层材料特别优选无机材料。所述无机材料有利地是玻璃质材料。这种材料可以煅烧陶瓷的方式由一种或多种玻璃料或形成玻璃的生料形成。在煅烧过程中，玻璃质材料裹夹了形成结构的颗粒，从而使得一些形成结构的颗粒从其表面上突出。用来制备根据本发明的自清洁表面的玻璃料为这样的组合物，所述组合物的熔点低于所述形成结构的颗粒的熔点，且低于被涂敷的基材的变形温度。
根据一个替代的实施方式，所述的玻璃质材料是这样一种物质，在煅烧一种或多种形成玻璃的生料的过程中，具体来说，所述生料是低熔点的氧化性生料或具有足够反应性的生料，该物质与所述基材的成分和/或一些形成结构的颗粒形成了玻璃键。这些玻璃键是具有通式Me-O-Me’的结构单元，其中，Me和Me’可以相同或不同，并代表基材中的硼、硅、磷、铝、钛、锡、锆或其他金属。
例如，含有Me-O-Me’结构单元且其中嵌有形成结构的颗粒的材料是这样一种体系，所述体系的形成途径是，用含有硼酸和/或碱金属磷酸盐和形成结构的颗粒的组合物来涂敷玻璃或玻璃质或搪瓷基材，随后进行煅烧，从而得到所述体系。因此在该煅烧过程中，所述硼酸和/或磷酸盐与玻璃基材或釉面/搪瓷层的反应性基团形成化学键，而且选择性地，与形成结构的颗粒上的反应性基团形成化学键。
根据另一个替代的实施方式，具有Me-O-Me’结构单元的涂层材料是这样一些体系，例如，使具有至少两个可水解基团的元素硼、硅、铝、钛和锆的有机金属化合物水解/醇解，随后进行缩合反应，以及选择性地随后进行煅烧，从而形成上述的涂层材料体系。
根据本发明的具有自清洁表面的基材的一个优选实施方式，所述结构化涂层含有平均粒径小于100nm的，特别是从5nm到小于50nm的形成结构的颗粒，并含有成层的无机或有机材料，所述形成结构的颗粒与所述成层的无机或有机材料的重量比为从100∶1到1∶2，特别是20∶1到1∶1。上述比例实际上也可能在上述范围之外，但如果成层材料的含量太低，则结果可能会导致形成结构的颗粒不能被充分固定。当成层材料的含量太高时，由于形成结构的颗粒可能被成层材料包埋得太深而减弱自清洁效果。
优选的基材具有基本上含有形成结构的颗粒和成层的无机材料的涂层，但所述涂层还可另外含有粘合促进剂或其他一些化合物，所述化合物例如是，由所存在的辅助成分和/或成层材料的前体在制备所述涂层的过程中形成的化合物，所述制备涂层的过程包括可能是必须的加热步骤，或者包括煅烧步骤。
为了给结构化表面赋予必须的疏水性以及所需的大的接触角，具体说是接近或大于150°的接触角，或小的滚动角，具体说是接近或小于1°的滚动角，该结构化层通常为疏水层，例如经硅烷化所得到的疏水层。
根据另一个实施方式，除了由形成结构的颗粒所形成的纳米级凸起和凹陷之外，根据本发明的自清洁表面还包括一个上层结构，由规则分布的或随机分布的突起或凹陷形成微糙结构。“微糙”一词指突起峰的高度及其间距在0.1μm到50μm的范围内，特别是0.5μm到15μm的范围内。本发明的这种具有纳米级和微米级表面粗糙度的基材可具有一个或两个用来形成结构的涂层。在第一种情形下，纳米级或微米级颗粒分布在成层材料之内。在第二种情形下，在事先涂敷的含有微米级颗粒的涂层之上，有一含有纳米级颗粒的涂层。
根据一个特别优选的实施方式，所述基材是玻璃或上釉的玻璃，根据本发明的用来获得自清洁性的涂层基本上是透明的。
根据本发明的具有自清洁表面的基材具有表面疏水的涂层。如果涂层本身不具有疏水性，则通过在该结构化的表面上涂敷具有疏水化作用的物质来实现其疏水性。有机硅烷，在本发明中特别是含氟的有机硅烷特别有利于疏水化。如果结构化表面的涂层材料是玻璃质材料，则还可通过采用具有疏水化作用的有机硅烷来形成Si-O-Si结构单元，结果使得具有疏水化作用的物质被牢牢地固定在结构化基材上，从而使其永久地保持自清洁性。
本发明另外涉及所述基材的制备方法，还涉及例如在所述基材的制备中所用的组合物。
用于制备本发明的具有自清洁表面的基材的组合物为这样一些物质的混合物，所述混合物含有平均粒径小于100nm的，特别是5nm到小于50nm的形成结构的颗粒，还含有粒子或液态成层材料。如上所述，所述粒径指初级颗粒的粒径，而且至少90％的，优选基本上全部颗粒的粒径优选小于100nm，或小于50nm。
所述粒子或液态成层材料可以是有机或无机材料。应当理解，术语“成层材料”指这样一种物质，即，当其通过物理或化学途径被涂敷到所述基材上时，该物质能够形成均一的层，并可将形成结构的颗粒固定在该层内和/或所述基材上。如果该材料是有机聚合物材料或聚合物的前体，则该材料以在有机溶剂、水性溶剂或溶混合物中的溶液形式存在于所述组合物中，或者以在有机溶剂或水性溶剂中的悬浮液形式存在于所述组合物中。通过蒸发溶剂和/或在随后的热处理过程中，通过熔合热塑性粒子或通过缩合、聚加成或缩聚而形成所述的均一的层。
根据所述组合物的优选实施方式，所述组合物含有无机成层材料或至少含有其前体。特别适合的成层无机材料是玻璃料或氧化的生料(即前体)，这两种材料可以与其他物质形成玻璃，所述的其他物质具体为，例如，硼酸(B2O3)、氧化铋(Bi2O3)、碱金属和碱土金属的氧化物、氧化锌和氧化铅，以及碱土金属的硅酸盐、磷酸盐和硼酸盐。大多数形成玻璃的物质被包含在颗粒形式的组合物之内。碱金属的水性溶液形式的组合物或水玻璃(硅酸钠溶液)形式的组合物中有利地含有碱金属氧化物和碱金属硅酸盐。
根据另一个替代实施方式，根据本发明的组合物含有作为成层材料的一种或多种元素硼、硅、铝、钛和锆的有机金属化合物。所述有机金属化合物优选那些含有烷氧基、乙酰基或乙酰丙酮酸基团的化合物，以便通过缩合反应形成Me-O-Me’结构单元，其中，Me和Me’可以相同或不同，它们代表如上所述的元素。
根据本发明的组合物所含的形成结构的颗粒与成层材料的重量比通常为100∶1到1∶2，所述重量比优选在20∶1到1∶1的范围内。
可以通过敷粉法或静电涂敷法将本发明的粉体组合物涂敷到所述基材上。
除了成层材料和形成结构的颗粒之外，本发明的组合物的一个优选实施方式还含有液体介质。所述组合物的稠度可以在大范围内变化，例如，当采用喷涂或浸渍方法来涂敷时，所用的粘度显著低于通过传统的印刷方法涂敷该组合物时所用的粘度。当采用印刷法，例如丝网印刷法来涂敷所述组合物时，所述组合物的稠度优选为浆状。
适于在玻璃、陶瓷、金属基材或者釉面或搪瓷基材上形成结构化表面的组合物特别优选为，其含有作为成层材料的一种或多种玻璃料作为主成份，这些玻璃料的软化点足够地低于被涂敷基材的变形温度。如果该组合物含有能够形成玻璃的生料(即前体)，则选择那些在常规的煅烧条件下能够彼此形成化学键的物质，和/或那些能够与所述基材和/或纳米级颗粒的结构单元形成化学键的物质。硼酸和碱金属磷酸盐是特别适合的成层材料或其前体。
当采用从液态到浆状的含有硼酸或碱金属磷酸二氢盐的组合物作为成层材料或其前体，以及采用煅制二氧化物作为结构形成材料时，经过有机硅烷特别是含氟的有机硅烷疏水化处理之后，可以在玻璃上形成牢固地附着的结构化表面，从而获得特别优异的自清洁性。用这种方法涂敷的玻璃的接触角大于150°。
所述液体介质可以是有机或有机-水性介质，或者是水性介质，该介质中除了所含的必要成分外，还可含有加工助剂，例如用来调节粘度的助剂。
微糙层的表面至少部分是疏水的，特别是突起峰和突起是疏水的。然而，优选整个表面是疏水的。疏水化基本上包括一个很薄的层，例如厚度为1到10nm的层，该层紧密地附着到其下面的表面上。通过将涂料组合物涂敷后形成薄膜来实现附着。疏水剂优选与基材化学键合，例如通过Si-O-Si桥的化学键合。这种桥由结构化涂层中的硅酸盐类物质的硅醇基团与烷氧基硅烷或烷氧基硅氧烷反应所形成。本发明优选的具有自清洁表面的基材具有仅为数个原子层厚的涂层，该涂层基于烷基三烷氧基硅烷，优选长链的氟代烷基三烷氧基硅烷或这类硅烷的低聚体。
本发明具有自清洁表面的基材可采用简单的方法制备，所述的制备方法包括以下步骤：
1.用一种组合物涂敷基材的表面，所述组合物含有形成结构的颗粒和无机或有机成层材料，该组合物是粉体，或者优选从液体到浆状物，
2.形成粘着层，所述粘着层固定了形成结构的颗粒并牢固地附着在所述基材上，和
3.采用疏水化剂特别是有机硅烷来使结构化表面疏水化，所述疏水化剂牢固地附着在所述结构化表面上，或者与所述结构化表面形成化学键。
该方法的一个具体特点是所用的形成结构的颗粒的平均粒径小于100nm，优选小于50nm，但至少为5nm。在没有由微米级的颗粒形成上层结构的情况下，该突起的剖面高度小于100nm，特别是小于50nm。上文已经提到了所述形成结构的颗粒和成层材料。
采用传统涂敷方法涂敷的组合物优选含有本发明的必要组分，也即，含量为上文所述比例的所述形成结构的颗粒和所述成层材料。如果涂层采用粉体组合物，则可采用敷粉法或静电涂敷法来涂敷基材。优选采用液体到浆状的组合物进行涂敷，所述组合物中所含的液体介质为例如本领域的技术人员已知的体系，特别是玻璃和陶瓷工业领域的装饰技术人员已知的体系。采用液体到浆状组合物涂敷时，可以采用喷涂、刷涂、浇注或浸渍，或者可以采用传统的印刷方法，例如丝网印刷或贴花转印法。
“形成粘着层，所述粘着层固定了形成结构的颗粒并牢固地附着在所述基材上”这一特征可根据待涂敷的基材以及涂料组合物的组成而变化。如果所述组合物含有粉体或在液体介质中悬浮的有机聚合物，附着层的形成可以是，通过将涂敷后的基材经过热处理，蒸发掉选择性地存在的溶剂，使聚合物颗粒熔合，或者当附着层为多组分体系时，使该体系反应生成聚合物材料。
涂敷到可煅烧的基材上的组合物经热处理可被转化为附着的结构化层，所述基材为玻璃、陶瓷或金属基材，或者是釉面或搪瓷基材，而且所述基材含有玻璃料或可与基材表面和/或颗粒形成玻璃的成分，此处所述的热处理指煅烧。在煅烧过程中，玻璃料熔化为均一的层；所述组合物中能够形成玻璃的组分与基材和/或形成结构的颗粒的反应性基团发生化学反应，形成具有Me-O-Me’结构单元的玻璃结构，其中Me和Me’的含义同上。对所述组合物中含有的玻璃料和/或可形成玻璃的成分的选择应当是，选择那些可以在低于所述基材的变形温度下进行热处理的材料，此处所述的热处理指煅烧。于是，在玻璃的涂层中，组合物所含有的成层材料为可在650℃以下，特别是在450℃到600℃的范围内熔化，并可形成所需结构的组分。
涂敷到基材上的纳米结构的涂层可以具有不同的厚度。这些涂层的厚度优选为5nm到1000nm，所述的涂层排他地含有本发明的形成结构的颗粒，所述颗粒的平均粒径小于100nm，特别是小于50nm但至少为5nm。如果该组合物还含有较大的形成结构的颗粒，例如粒径为0.5μm到15μm的颗粒，则该层的最大厚度当然会更大。在后一种情形下，根据本发明的纳米结构位于微糙的上层结构之上。作为替代的方法，也可以在具有微糙表面结构的基材上涂敷本发明的组合物，然后焙烧，再进行疏水化处理，所述微糙表面结构例如根据德国专利申请100 16 485.4的基材的表面结构，所述组合物所含有的形成结构的颗粒的粒径基本上均小于100nm，优选小于50nm。
形成结构化表面之后，疏水化步处理骤如下：
通过涂敷疏水漆或在微糙表面上进行单体的聚合来进行疏水化。适当的聚合性漆为例如聚偏二氟乙烯的溶液或分散液。还可通过全氟代或部分氟代的乙烯基化合物的等离子聚合来进行疏水化处理。
采用具有反应性的烷基硅烷来进行疏水化特别有利，或者优选采用氟代烷基硅烷和低聚烷基硅氧烷或低聚氟代烷基硅氧烷。所述硅烷或硅氧烷优选含有作为反应基团的一个或多个烷氧基或乙酰基，例如乙氧基。通过这些官能团有可能使疏水化剂交联，并使之与含有硅醇基的硅酸盐表面发生化学键合。特别优选采用十三氟代辛基三乙氧基硅烷及其低聚体作为硅烷化剂。可以稀释的有机溶液、水-有机溶液和水性溶液的形式将这类物质涂敷到需要进行疏水化处理的基材上，所述的有机溶液具体为醇，涂敷的方法为例如浸渍、喷涂或刷涂。
将含有含氟的硅烷或硅氧烷的溶液涂敷到基材上之后，使之干燥固化，干燥温度优选为高达500℃，例如在约150℃下干燥30到60分钟，在250-300℃下干燥10到15分钟，或者在约500℃下干燥1分钟。为了获得最大的耐磨性，最适宜的后处理是在200℃到300℃下的热处理。
采用所述的硅烷或硅氧烷的稀释溶液得到了数个纳米厚的层，该层具有很高的化学耐性和机械耐性，并且呈二维和三维硅氧烷网状结构。
采用反应性氟代硅烷或氟代硅氧烷所得到的疏水层的显著特点是，其疏水性和疏油性一样良好，因此，根据本发明的基材沾染了疏水性污物颗粒之后，可用水容易地将其清除。
本发明还涉及所述具有自清洁表面的基材的用途。所述的用途例如车辆和窗户的玻璃、建筑物用的玻璃、瓷砖、屋瓦、太阳能光电池的盖板、金属框架和上漆的基材，所述的漆例如汽车漆。
本发明的具有自清洁表面的基材具有高度的自清洁性。根据本发明的优选的基材对水的接触角通常大约为150°，而且常常大于150°。
本发明的基材的特别突出的特点是其纳米结构涂层具有透明性。因此，特别适合在塑料和玻璃的透明基材上以及在釉面或搪瓷基材上涂敷本发明的透明涂料，从而得到优质的自清洁表面，这些自清洁表面本身是透明的，因此可以清楚地看到其下面的装饰。
本发明的组合物的重要优点是，它们不但易于制备，而且其组成具有多种变化。因此，这些组合物可用来涂敷各种基材并取得良好的自清洁性。
根据本发明的方法的步骤紧紧围绕所采用的处理步骤，例如，在玻璃和陶瓷工业中的装饰步骤，以及采用烤漆给金属基材上漆的传统方法。因此，可以采用本领域的技术人员所已知的设备和技术。
具体实施方式
实施例
具有透明的自清洁表面的浮法玻璃或高级钢的制备
1.采用本发明的组合物通过丝网印刷来涂敷4mm的浮法玻璃。所述组合物含有占丝网印刷介质(80858号，来自dmc2有限公司)0.5重量％的硼酸(B2O3)和4重量％的煅制二氧化硅。该煅制二氧化硅初级颗粒的平均粒径为12nm。所述的印刷介质是与水相容的介质。采用100T的丝网进行丝网印刷。干燥后，将涂层在660℃下骤热4分钟。采用氟代烷基硅烷组合物对烘干后的结构化表面进行疏水化处理，所述的氟代烷基硅烷组合物即十三氟代辛基三乙氧基硅烷的乙醇溶液。将该溶液涂敷到所述基材上，然后在高温下使其固化。
用该法涂敷的浮法玻璃是透明的，其接触角大于150°。
2.重复实施例1，不同之处仅在于所述组合物含有0.5重量％的磷酸氢二铵((NH)2HPO4)作为成层材料，而不含有硼酸。疏水化之后，玻璃涂层显示出优异的自清洁性。
据推断，在煅烧过程中，在硼酸或磷酸盐与玻璃或金属以及二氧化硅形成结构的颗粒的反应性中心之间形成了Si-O-B或Si-O-P或金属-O-P的结构单元。
3.基材为除去油污的V4A高级钢。涂敷时采用的组合物为，在80858丝网印刷介质中含有4重量％的煅制二氧化硅(d＝12nm)以及(a)0.25重量％、(b)0.5重量％和(c)1.0重量％的磷酸氢二铵。经过丝网印刷方法涂敷后，在660℃下煅烧6分钟。上述三种情形下均得到了耐刻划的自清洁表面。
Claims (19)
1.具有至少一个自清洁表面的基材，所述基材具体指玻璃、陶瓷、塑料或金属基材，或者是釉面或搪瓷基材，所述基材上分布有涂层，所述涂层含有用来形成表面结构的颗粒，而且至少部分表面是疏水的，其特征在于，所述形成结构的颗粒的平均粒径小于100nm。
2.根据权利要求1所述的具有自清洁表面的基材，其特征在于，所述形成结构的颗粒的平均粒径小于50nm且至少为5nm。
3.根据权利要求1或2所述的具有自清洁表面的基材，其特征在于，所述形成结构的颗粒选自由金属氧化物、混合氧化物、硅酸盐、硫酸盐、磷酸盐、硼酸盐、碳黑、金属粉末、金属硫化物、硒化物、硫硒化物、氧代硫化物、金属氮化物、氧化物-氮化物和有机聚合物组成的组。
4.根据权利要求1到3任一项所述的具有自清洁表面的基材，其特征在于，所述形成结构的颗粒是选自由SiO2、TiO2、Al2O3、ZrO2和SnO2组成的组中的金属氧化物，特别是高温煅制的上述氧化物。
5.根据权利要求1到4任一项所述的具有自清洁表面的基材，其特征在于，所述涂层包含所述形成结构的颗粒，所述形成结构的颗粒被固定在无机或有机成层材料中，或者通过无机或有机成层材料而被固定。
6.根据权利要求5所述的具有自清洁表面的基材，其特征在于，所述的成层材料是玻璃或能够形成Me-O-Me’的结构单元的材料，其中，Me和Me’相同或不同，代表硼、硅、铝、磷、钛、锡或锆。
7.根据权利要求1到6任一项所述的具有自清洁表面的基材，其特征在于，除了根据本发明的平均粒径小于100nm的、特别是小于50nm的形成结构的颗粒之外，在根据本发明的涂层中，或者在其下涂敷有微米级表面结构的涂层中，还含有形成上层结构的颗粒，所述颗粒的平均粒径为0.1μm到50μm，特别是0.5μm到15μm。
8.根据权利要求1到7任一项所述的具有自清洁表面的基材，其特征在于，所述涂层不但含有平均粒径小于100nm的、特别是小于50nm的形成结构的颗粒，而且含有一种或多种成层的无机或有机材料，所述形成结构的颗粒与所述成层材料的重量比为100∶1到1∶2，特别是20∶1到1∶1。
9.根据权利要求1到8任一项所述的具有自清洁表面的基材，其特征在于，所述基材为玻璃或塑料，或者为釉面或搪瓷基材。
10.根据权利要求9所述的基材，其特征在于，所述的基材是玻璃，而且根据本发明的方法涂敷的所述基材基本上是透明的。
11.用来制备根据权利要求1到10任一项所述的具有自清洁表面的基材的组合物，其特征在于，所述组合物不但含有平均粒径小于100nm的、特别是小于50nm但至少为5nm的形成结构的颗粒，而且含有粒子或液态成层材料，所述形成结构的颗粒与所述成层材料的重量比为100∶1到1∶2。
12.根据权利要求11所述的组合物，其特征在于，所述成层材料含有作为主成份的一种或多种玻璃料和/或一种或多种玻璃生料，在煅烧时，该玻璃料和/或玻璃生料彼此形成玻璃或玻璃质结构，和/或该玻璃料和/或玻璃生料与所述基材的基团形成玻璃或玻璃质结构，和/或该玻璃料和/或玻璃生料与能够形成玻璃的所述形成结构的颗粒的基团形成玻璃或玻璃质结构。
13.根据权利要求12所述的组合物，其特征在于，所述组合物基本上含有形成结构的颗粒和成层材料，特别是可悬浮于液体介质中粒子材料。
14.根据权利要求11到13任一项所述的组合物，其特征在于，所述组合物不但含有根据本发明的粒径小于50nm但至少为5nm的形成结构的颗粒，而且含有一种或多种作为成层材料的氧化物，所述形成结构的颗粒特别是二氧化硅，所述氧化物选自由在650℃以下熔化的B2O3、Bi2O3、碱金属氧化物、锌的氧化物、铅的氧化物、硼酸盐、硅酸盐、磷酸盐或玻璃料组成的组。
15.根据权利要求14所述的组合物，其特征在于，所述组合物基本上含有以该组合物的重量计，1重量％到10重量％的煅制二氧化硅(SiO2)和0.1重量％到2重量％的硼酸(B2O3)、碱金属磷酸二氢盐或磷酸二氢铵或者磷酸氢二碱金属盐或磷酸氢二铵或者在600℃以下熔化的玻璃料，以及一种印刷介质。
16.根据权利要求1到10任一项所述的具有自清洁表面的基材的制备方法，所述方法包括(i)用一种组合物涂敷基材的表面，所述组合物含有形成结构的颗粒和无机或有机成层材料，(ii)形成粘着层，所述粘着层固定了所述形成结构的颗粒并牢固地附着在所述基材上，和(iii)使所形成的结构化表面疏水化，其特征在于，所述形成结构的颗粒的平均粒径小于100nm，优选小于50nm，并至少为5nm。
17.根据权利要求16所述的方法，其特征在于，用根据权利要求11到15任一项所述的组合物涂敷基材，所述基材选自由玻璃、陶瓷、塑料和金属和釉面或搪瓷基材组成的组，所述基材在涂敷之前就已具有微糙表面，所述组合物含有玻璃料或形成玻璃的生料，将所述经过涂敷的基材进行煅烧，以便形成牢固附着的粘着层，然后用有机硅烷，特别是氟代有机硅烷涂敷所述结构化表面，从而使之疏水化。
18.根据权利要求16或17所述的方法，其特征在于，采用印刷方法或采用喷涂、刷涂、浇注或浸渍的方法，以液体到浆状的稠度来涂敷用来形成表面结构的所述组合物。
19.根据权利要求1到10任一项所述的具有自清洁表面的基材的用途，或根据权利要求16到18任一项所述的方法所得到的基材的用途，所述用途为车辆和窗户的玻璃、建筑物用的玻璃、瓷砖、屋瓦、太阳能光电池的盖板、金属框架和上漆的基材。
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| DE19941753A1 (de) | 1999-09-02 | 2001-05-10 | Nanogate Gmbh | Verfahren und Stoffe |
| DE19958336A1 (de) | 1999-12-03 | 2001-06-07 | Inst Neue Mat Gemein Gmbh | Selbstvernetzende Beschichtungszusammensetzungen auf Basis anorganischer fluorhaltiger Polykondensate |
| DE10016485A1 (de) * | 2000-04-01 | 2001-10-11 | Dmc2 Degussa Metals Catalysts | Glas-, Keramik- und Metall-Substrate mit selbstreinigender Oberfläche, Verfahren zu deren Herstellung und deren Verwendung |
| EP1276824A4 (en) | 2000-04-21 | 2005-03-16 | Stc Unm | PROTOTYPING OF STRUCTURED, FUNCTIONAL NANOSTRUCTURES |
| DE10059487A1 (de) | 2000-11-30 | 2002-06-06 | Inst Neue Mat Gemein Gmbh | Metallische Substrate mit einer glasartigen Oberflächenschicht |
| DE10063739B4 (de) | 2000-12-21 | 2009-04-02 | Ferro Gmbh | Substrate mit selbstreinigender Oberfläche, Verfahren zu deren Herstellung und deren Verwendung |
| DE10106213A1 (de) | 2001-02-10 | 2002-08-22 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Selbstreinigende Lackbeschichtungen und Verfahren und Mittel zur Herstellung derselben |
| DE10110589A1 (de) | 2001-03-06 | 2002-09-12 | Creavis Tech & Innovation Gmbh | Geometrische Formgebung von Oberflächen mit Lotus-Effekt |
| DE10118351A1 (de) | 2001-04-12 | 2002-10-17 | Creavis Tech & Innovation Gmbh | Selbstreinigende Oberflächen durch hydrophobe Strukturen und Verfahren zu deren Herstellung |
| DE10138036A1 (de) | 2001-08-03 | 2003-02-20 | Creavis Tech & Innovation Gmbh | Strukturierte Oberflächen mit Lotus-Effekt |
-
2000
- 2000-12-21 DE DE10063739A patent/DE10063739B4/de not_active Expired - Fee Related
-
2001
- 2001-12-04 CA CA002429866A patent/CA2429866A1/en not_active Abandoned
- 2001-12-04 KR KR20037008037A patent/KR20030069186A/ko not_active Application Discontinuation
- 2001-12-04 CN CNA018207944A patent/CN1481342A/zh active Pending
- 2001-12-04 WO PCT/EP2001/014168 patent/WO2002049980A1/en active Application Filing
- 2001-12-04 JP JP2002551485A patent/JP2004516216A/ja not_active Withdrawn
- 2001-12-04 EP EP01985843A patent/EP1347948A1/en not_active Ceased
- 2001-12-04 AU AU2002235752A patent/AU2002235752A1/en not_active Abandoned
- 2001-12-12 US US10/021,558 patent/US6800354B2/en not_active Expired - Fee Related
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| CN101092289B (zh) * | 2007-05-18 | 2010-09-01 | 华东理工大学 | 一种超疏水粗糙表面材料 |
| CN102625784A (zh) * | 2009-05-06 | 2012-08-01 | 康宁股份有限公司 | 防指印玻璃基材 |
| CN101891397A (zh) * | 2010-07-07 | 2010-11-24 | 东华大学 | 一种太阳能电池自清洁防护膜的制备方法 |
| CN101891397B (zh) * | 2010-07-07 | 2012-07-18 | 东华大学 | 一种太阳能电池自清洁防护膜的制备方法 |
| CN103154400B (zh) * | 2010-10-18 | 2015-12-16 | Usg内部有限责任公司 | 天花板瓷砖和制造防水天花板瓷砖的方法 |
| CN103154400A (zh) * | 2010-10-18 | 2013-06-12 | Usg内部有限责任公司 | 耐水天花板瓷砖 |
| CN102102168B (zh) * | 2011-03-30 | 2012-06-27 | 北京矿冶研究总院 | 一种利用热喷涂技术制备憎水涂层的方法 |
| CN102102168A (zh) * | 2011-03-30 | 2011-06-22 | 北京矿冶研究总院 | 一种利用热喷涂技术制备憎水涂层的方法 |
| CN103765599A (zh) * | 2011-08-29 | 2014-04-30 | 法国圣戈班玻璃厂 | 具有疏水背面涂层的薄层光伏组件 |
| TWI594963B (zh) * | 2011-11-09 | 2017-08-11 | 康寧公司 | 奈米粒子與玻璃結合的方法 |
| TWI644877B (zh) * | 2011-11-09 | 2018-12-21 | 美商康寧公司 | 奈米粒子與玻璃結合的方法 |
| US10155361B2 (en) | 2011-11-09 | 2018-12-18 | Corning Incorporated | Method of binding nanoparticles to glass |
| CN104105675A (zh) * | 2011-11-09 | 2014-10-15 | 康宁股份有限公司 | 把纳米颗粒粘合到玻璃上的方法 |
| CN107500565A (zh) * | 2011-11-09 | 2017-12-22 | 康宁股份有限公司 | 把纳米颗粒粘合到玻璃上的方法 |
| CN104105675B (zh) * | 2011-11-09 | 2017-11-17 | 康宁股份有限公司 | 把纳米颗粒粘合到玻璃上的方法 |
| CN102746718A (zh) * | 2012-05-08 | 2012-10-24 | 金季平 | 常温干燥型高透光抗静电自清洁玻璃的涂料及制备方法 |
| CN103232168A (zh) * | 2013-02-19 | 2013-08-07 | 冯益安 | 利用疏水或疏油的纳米颗粒实现玻璃表面自清洁的方法 |
| CN103337524B (zh) * | 2013-05-17 | 2015-09-16 | 宁夏东旭太阳能科技有限公司 | 自洁高效太阳能电池 |
| CN103337524A (zh) * | 2013-05-17 | 2013-10-02 | 宁夏东旭太阳能科技有限公司 | 自洁高效太阳能电池 |
| CN105507061A (zh) * | 2015-11-27 | 2016-04-20 | 湖北大学 | 一种超疏水涂层及其制备方法 |
| CN106700675A (zh) * | 2016-12-26 | 2017-05-24 | 广州碧然环保有限公司 | 外墙基材防静电防污涂膜剂及其制备方法 |
| CN108249961A (zh) * | 2018-01-19 | 2018-07-06 | 段艳玲 | 一种基于3d打印和表面涂覆微米/纳米颗粒制备超疏水高强度陶瓷釉薄层的方法 |
| CN108641415A (zh) * | 2018-03-29 | 2018-10-12 | 广州碧然环保有限公司 | 一种有机和无机相结合的自清洁涂层材料及其制备方法 |
| CN110606773A (zh) * | 2019-11-01 | 2019-12-24 | 湖南天欣科技股份有限公司 | 一种自洁陶瓷瓦及其制备方法 |
| CN113173805A (zh) * | 2021-04-30 | 2021-07-27 | 萍乡学院 | 在釉面上构建陶瓷基荷叶仿生疏水微纳乳突结构的方法 |
| CN116355471A (zh) * | 2023-03-31 | 2023-06-30 | 广东晟毅新材料科技有限公司 | 一种超疏水涂料、超疏水玻璃以及超疏水钢化玻璃及其制备方法 |
| CN116355471B (zh) * | 2023-03-31 | 2024-03-29 | 广东晟毅新材料科技有限公司 | 一种超疏水涂料、超疏水玻璃以及超疏水钢化玻璃及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030069186A (ko) | 2003-08-25 |
| DE10063739A1 (de) | 2002-06-27 |
| WO2002049980A1 (en) | 2002-06-27 |
| JP2004516216A (ja) | 2004-06-03 |
| EP1347948A1 (en) | 2003-10-01 |
| CA2429866A1 (en) | 2002-06-27 |
| AU2002235752A1 (en) | 2002-07-01 |
| DE10063739B4 (de) | 2009-04-02 |
| US6800354B2 (en) | 2004-10-05 |
| US20020142150A1 (en) | 2002-10-03 |
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