CN101454522A - 涂布聚合物分散体的砖瓦及其制备方法 - Google Patents
涂布聚合物分散体的砖瓦及其制备方法 Download PDFInfo
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- CN101454522A CN101454522A CNA2007800191914A CN200780019191A CN101454522A CN 101454522 A CN101454522 A CN 101454522A CN A2007800191914 A CNA2007800191914 A CN A2007800191914A CN 200780019191 A CN200780019191 A CN 200780019191A CN 101454522 A CN101454522 A CN 101454522A
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- tile
- copolymer
- acrylate
- brick
- monomer
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- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
- E04F13/14—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements stone or stone-like materials, e.g. ceramics concrete; of glass or with an outer layer of stone or stone-like materials or glass
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- 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
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C04B41/46—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 organic materials
- C04B41/48—Macromolecular compounds
- C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B41/4869—Polyvinylalcohols, polyvinylacetates
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- C—CHEMISTRY; METALLURGY
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- 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
- C04B41/46—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 organic materials
- C04B41/48—Macromolecular compounds
- C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B41/4876—Polystyrene
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- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
本发明涉及背面涂布聚合物膜的瓷砖或玻璃瓦，其中涂层通过施用聚合物水分散体形式、或水溶液形式、或聚合物粉末再分散至水中的水性再分散体形式的均聚物或共聚物并随后干燥得到，本发明还涉及所述瓷砖或玻璃瓦的制备和它们用于衬里表面的用途。
Description
本发明涉及背面涂布聚合物膜的瓷砖和玻璃瓦，也涉及它们的制备和用途。
瓷砖和玻璃瓦用作各种基材的衬里。取决于砖瓦的类型、基材的本质、所铺设砖瓦的载荷或砖瓦复合材料的应力，使用不同的铺设方式。
如今普遍的方法是通过薄层工艺粘结砖瓦。本文将砖瓦铺设至砂浆的薄层。在同样惯用的厚层工艺(“背涂-镘涂法”)中，在将砖瓦以反面接触砂浆应用至砂浆层并固定之前，另外用含水泥的粘合砂浆润湿砖瓦的背面。
此外，也已知自粘砖瓦无需进一步的粘合砂浆而能使用。这些自粘砖瓦，例如，在背面涂布压敏胶(例如EP 1044797 A1)。然而，EP1044797 A1中描述的体系的特征在于砖瓦和基材之间具有局限的粘合，从而能无破坏地从基材移除粘结的砖瓦。这些体系的缺点也为压敏胶的高反应活性，即在应用所述砖瓦后，砖瓦位置的校正非常困难。
为了抵抗这个缺点，EP 0001881 A1描述了包含聚合粘合剂和水硬性材料的混合物的砖瓦涂层。然而，这种方式得到具有相对较厚(通常1至5mm)的涂层的砖瓦。此外，当在这种涂层的制备中使用不足够水溶性的粘合剂时，有必要加入有机溶剂。这个要求是对于工业规模使用的经济和环境的缺点。
鉴于此背景，本发明的一个目标是增加粘结砖瓦或玻璃瓦在各种基材上的粘合而避免涂层砖瓦的上述不利性质。
本发明提供了背面涂布聚合物膜的瓷砖和玻璃瓦，其中涂层通过施用聚合物水分散体形式、或水溶液形式、或聚合物粉末再分散至水中的水性再分散体形式的均聚物或共聚物，以及随后的干燥分散体得到。
合适的砖瓦尤其为陶质砖、炻质砖，和优选的细炻砖，也为玻璃瓦。术语玻璃瓦也包括片状玻璃制品或玻璃板。
用于涂布砖瓦背面的合适的聚合物为基于一种或多种单体的那些聚合物，所述单体选自具有1至15个碳原子的羧酸的乙烯酯、羧酸与具有1至15个碳原子的非分枝的或分枝的醇的甲基丙烯酸酯或丙烯酸酯、烯烃和二烯烃、乙烯基芳香烃或卤乙烯。
优选的乙烯酯为醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、乙烯基-2-己酸乙酯、月桂酸乙烯酯、醋酸异丙烯酯、新戊酸乙烯酯和具有9至13个碳原子的α-分枝的单羧酸的乙烯酯(例如VeoVa9R或VeoVa10R(Shell的商品名))。特别优选为醋酸乙烯酯。
优选的甲基丙烯酸酯或丙烯酸酯为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸冰片酯。优选为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯和丙烯酸2-乙基己酯。
优选的烯烃和二烯烃为乙烯、丙烯和1，3-丁二烯。优选的乙烯基芳香烃为苯乙烯和乙烯基甲苯。合适的卤乙烯为氯乙烯。
若适当，可共聚辅助单体，该辅助单体的含量以基础聚合物的总重量计为0.05重量％至50重量％，优选为1重量％至10重量％。辅助单体的例子为烯属不饱和单羧酸和二羧酸(优选为丙烯酸、甲基丙烯酸、富马酸和马来酸)、烯属不饱和羧酰胺和羧酸腈(优选为丙烯酰胺和丙烯腈)、富马酸和马来酸的单酯和双酯(例如二乙酯和二异丙酯，以及马来酐)、烯属不饱和磺酸或烯属不饱和磺酸盐(优选乙烯基磺酸、2-丙烯酰胺-2-甲基丙磺酸)。进一步的例子为预交联的共聚单体，如多烯属不饱和共聚单体(例如己二酸二乙烯酯、马来酸二烯丙酯、甲基丙烯酸烯丙酯或氰尿酸三烯丙酯)，或后交联共聚单体(例如丙烯酰胺羟基乙酸(AGA)、甲基丙烯酰胺羟乙酸甲酯(MAGME)、N-羟甲基丙烯酰胺(NMA)、N-羟甲基甲基丙烯酰胺(NMMA)、N-羟甲基烯丙基氨基甲酸、如异丁醚的烷基醚或N-羟甲基丙烯酰胺酯、N-羟甲基甲基丙烯酰胺酯和N-羟甲基烯丙基氨基甲酸酯)。如甲基丙烯酸环氧丙酯和丙烯酸环氧丙酯的环氧官能化共聚单体也合适。进一步的例子为如丙烯酰氧基-丙基三(烷氧基)硅烷和甲基丙烯酰氧基丙基-三(烷氧基)硅烷、乙烯基三烷氧基硅烷和乙烯基甲基二烷氧基硅烷的硅官能化共聚单体，其中，例如甲氧基、乙氧基和乙氧基丙二醇醚基作为烷氧基。也提到具有羟基或CO基团的单体，例如羟烷基甲基丙烯酸酯和羟烷基丙烯酸酯(例如羟乙基、羟丙基或羟丁基丙烯酸酯或者羟乙基、羟丙基或羟丁基甲基丙烯酸酯)，以及如双丙酮丙烯酰胺和乙酰基乙酰氧乙基丙烯酸酯或乙酰基乙酰氧乙基甲基丙烯酸酯化合物。进一步的例子为如甲基乙烯醚、乙基乙烯醚或异丁基乙烯醚的乙烯醚。
合适的均聚物和共聚物的例子为醋酸乙烯酯均聚物、醋酸乙酯和乙烯的共聚物、醋酸乙烯酯与乙烯和一种或多种另外的乙烯酯的共聚物、醋酸乙烯酯与乙烯和丙烯酸酯的共聚物、醋酸乙烯酯与乙烯和氯乙烯的共聚物、苯乙烯-丙烯酸酯共聚物、苯乙烯-1，3-丁二烯共聚物。
优选聚乙烯醇或聚乙烯醇缩醛的水溶液。合适的聚乙烯醇为部分水解的聚醋酸乙烯酯或部分水解的醋酸乙烯酯共聚物以及完全水解的聚醋酸乙烯酯。水解度一般为75摩尔％至100摩尔％。部分水解的醋酸乙烯酯共聚物的例子为具有乙烯共聚单体单元和/或羧基官能化、环氧基官能化或硅醇官能化的共聚单体单元的那些。合适的聚乙烯醇缩醛为聚乙烯醇乙酰缩醛(polyvinyl acetacetal)、聚乙烯醇缩丁醛，若合适，所述聚乙烯醇乙酰缩醛和聚乙烯醇缩丁醛可由羧基官能化或环氧基官能化或硅醇官能化的共聚单体单元改性。
优选醋酸乙烯酯均聚物；醋酸乙烯酯与1重量％至40重量％的乙烯的共聚物；醋酸乙烯酯与1重量％至40重量％的乙烯和1重量％至50重量％的一种或多种另外的共聚单体的共聚物，其中另外的共聚单体选自在羧酸基中具有1至12个碳原子的乙烯酯(例如丙酸乙烯酯、月桂酸乙烯酯)、具有9至13个碳原子的α-分枝的羧酸的乙烯酯(例如VeoVa9R、VeoVa10R、VeoVa11R)；醋酸乙烯酯、1重量％至40重量％的乙烯和优选1重量％至60重量％的具有1至15个碳原子的非分枝的或分枝的醇的丙烯酸酯(特别是丙烯酸正丁酯或丙烯酸2-乙基己酯)的共聚物；包含30重量％至75重量％的醋酸乙烯酯、1重量％至30重量％的月桂酸乙烯酯或具有9至11个碳原子的α-分枝的羧酸的乙烯酯，以及1重量％至30重量％的具有1至15个碳原子的非分枝的或分枝的醇的丙烯酸酯(特别是丙烯酸正丁酯或丙烯酸2-乙基己酯)的共聚物，该共聚物可另外含有1重量％至40重量％的乙烯；包含醋酸乙烯酯、1重量％至40重量％的乙烯和1重量％至60重量％的氯乙烯的共聚物；其中所述聚合物能另外含有上述指定量的辅助单体，且在每种情况下重量％的数值总和为100重量％。
也优选(甲基)丙烯酸酯聚合物(如丙烯酸正丁酯或丙烯酸2-乙基己酯的共聚物或者甲基丙烯酸甲酯与丙烯酸正丁酯和/或丙烯酸2-乙基己酯和(若适当)乙烯的共聚物)；包含一种或多种单体的苯乙烯-丙烯酸酯共聚物，所述单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯；包含一种或多种单体的醋酸乙烯酯-丙烯酸酯共聚物，所述单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯或(若适当)乙烯；苯乙烯-1，3-丁二烯共聚物；其中所述聚合物能另外含有上述指定量的辅助单体，在每种情况下重量％的数值总和为100重量％。
选择单体和单体的重量比例从而得到通常-50℃至+50℃，优选为-30℃至+40℃的玻璃化转变温度Tg。能利用差示扫描量热法(DSC)以已知的方式测定聚合物的玻璃化转变温度Tg。也能预先利用Fox方程近似计算Tg。根据Fox T.G.，Bull.Am.Physics Soc.1，3，第123页(1956)：
1/Tg＝x1/Tg1+x2/Tg2+...+xn/Tgn，其中xn为单体n的质量分数(重量/100的％)，Tgn为单体n的均聚物的玻璃化转变温度(以开尔文计)。Polymer Handbook第二版，J.Wiley & Sons，New York(1975)给出了均聚物的Tg值。
通过乳液聚合工艺或通过悬浮聚合工艺(优选通过乳液聚合工艺)在通常40℃至100℃，优选60℃至90℃的聚合温度下进行均聚物和共聚物的制备。也能在通常5巴至100巴的超大气压力下进行如乙烯、1，3-丁二烯或氯乙烯的气态共聚单体的共聚合。
利用水溶性或单体可溶性的引发剂或常用于乳液聚合或悬浮聚合的氧化还原引发剂组合来引发聚合。水溶性引发剂的例子为过硫酸的钠盐、钾盐和铵盐、过氧化氢、叔丁基过氧化物、叔丁基过氧化氢、过氧二磷酸钾、过新戊酸叔丁酯、异丙苯过氧化氢、单异丙苯过氧化氢、偶氮二异丁腈。单体可溶性的引发剂的例子为过氧化二碳酸联十六烷酯、过氧化二碳酸二环己酯、过氧化二苯甲酰。通常以0.001重量％至0.02重量％，优选0.001重量％至0.01重量％的含量(在每种情况下以单体总重量计)使用所述的引发剂。
使用上述引发剂和还原剂的结合作为氧化还原引发剂。合适的还原剂为碱金属和铵的亚硫酸盐和酸式亚硫酸盐(例如亚硫酸钠)、次硫酸衍生物(例如甲醛次硫酸的锌盐或碱金属盐，如甲醛次硫酸氢钠)，和抗坏血酸。还原剂的含量在每种情况下以单体总重量计通常为0.001重量％至0.03重量％，优选为0.001重量％至0.015重量％。
在聚合期间能使用调节物质以控制分子量。若使用调节剂，则一般使用调节剂的含量以聚合的单体计为0.01重量％至5.0重量％，而且这些调节剂分别加入或与反应组分预混合。这种物质的例子为正十二碳硫醇、叔十二碳硫醇、巯基丙酸、巯基丙酸甲酯、异丙醇和乙醛。
合适的用于聚合的保护胶体为聚乙烯醇；聚乙烯醇缩醛；聚乙烯吡咯烷酮；水溶性形式的多糖(例如淀粉(直链淀粉和支链淀粉)、纤维素及其羧甲基、甲基、羟乙基、羟丙基衍生物、糊精和环糊精)；蛋白质(如干酪素或酪蛋白酸盐、大豆蛋白、明胶、木素磺酸盐)；合成聚合物(如聚(甲基)丙烯酸、(甲基)丙烯酸与羧基官能化共聚单体单元的共聚物、聚(甲基)丙烯酰胺、聚乙烯基磺酸及其水溶性共聚物)；三聚氰胺甲醛磺酸酯、萘甲醛磺酸酯、苯乙烯-马来酸和乙烯醚-马来酸的共聚物。
优选部分水解或完全水解的水解度为80摩尔％至100摩尔％的聚乙烯醇，特别是水解度为80摩尔％至95摩尔％以及在4％强度水溶液中的
粘度(20℃下的
法，DIN 53015)为1mPas至30mPas的部分水解的聚乙烯醇。也优选水解度为80摩尔％至95摩尔％以及在4％强度水溶液中的
粘度为1mPas至30mPas的部分水解的、疏水改性的聚乙烯醇。例子为醋酸乙烯酯与疏水共聚单体的部分水解的共聚物，所述疏水共聚单体如醋酸异丙烯酯、新戊酸乙烯酯、乙烯基己酸乙酯、具有5个或9至11个碳原子的饱和α-分枝的单羧酸的乙烯酯、马来酸二烷酯和富马酸二烷酯(例如马来酸二异丙酯和富马酸二异丙酯)、氯乙烯、烷基乙烯基醚(如丁基乙烯基醚)、烯烃(如乙烯和癸烯)。疏水单元的比例以部分水解的聚乙烯醇的总重量计优选为0.1重量％至10重量％。也可能使用上述聚乙烯醇的混合物。
最优选水解度为85摩尔％至94摩尔％以及在4％强度水溶液中的
粘度(20℃下的
法，DIN 53015)为3mPas至15mPas的聚乙烯醇。所述保护胶体能通过本领域技术人员已知的方法获得，且所述保护胶体通常以1重量％至20重量％的总量(以单体总重量计)加入聚合。
若在乳化剂存在下进行聚合，则乳化剂的含量以单体含量计为1重量％至5重量％。合适的乳化剂包括阴离子型、阳离子型和非离子型乳化剂，例如，阴离子型表面活性剂(如具有8至18个碳原子的链长的烷基硫酸盐、具有在疏水基中的8至18个碳原子，且具有多达40个环氧乙烷或环氧丙烷单元的烷醚硫酸盐或烷芳醚硫酸盐、具有8至18个碳原子的烷基磺酸盐或烷基芳基磺酸盐、硫代琥珀酸与一元醇或烷基酚的酯或半酯)，或者非离子型表面活性剂(如具有8至40个环氧乙烷单元的烷基聚乙二醇醚或烷基芳基聚乙二醇醚)。
聚合结束之后，能使用已知方法进行后聚合以去除剩余的单体，一般通过使用氧化还原催化剂引发的后聚合的方法。也能通过蒸馏，优选在减压下去除挥发性剩余单体，且若适当，用如空气、氮气或蒸汽的惰性共沸气体穿过或越过聚合混合物。以这种方式获得的水分散体具有30重量％至75重量％，优选50重量％至60重量％的固体含量。
通过干燥相应的水分散体制备可再分散于水中的聚合物粉末。例如，通过流化床干燥、冷冻干燥或喷雾干燥进行干燥。分散体优选进行喷雾干燥。在能够利用单流体、双流体或多流体喷嘴或利用旋转盘进行雾化的常规喷雾干燥元件上进行喷雾干燥。取决于所述元件和所需的干燥度，出口温度一般为45℃至120℃，优选为60℃至90℃。
为了制备可再分散于水中的聚合物粉末，在加入作为干燥助剂的保护胶体之后干燥水分散体。适用于此目的的保护胶体为上述适用于聚合的保护胶体。
为了通过改进粘连稳定性从而增加储存稳定性，特别是对于具有低玻璃化转变温度的粉末的情况，所得的粉末能与抗粘连剂(防结块剂)混合，所述抗粘连剂的含量以聚合组分总重量计优选高达30重量％。抗粘连剂的例子为碳酸钙或碳酸镁、滑石、石膏、硅石、高岭土、偏高领土、粒子尺寸优选为10nm至100μm的硅酸盐。
本发明进一步提供制备背面涂布聚合物膜的瓷砖或玻璃瓦的方法。在该方法中，将均聚物或共聚物以其聚合物水分散体的形式通过喷雾或涂装或其他施用方法(滚涂)施用至砖瓦的背面。在随后的分散介质水的蒸发的干燥中发生膜的形成。
不同于聚合物分散体，也可能将可再分散于水中的聚合物粉末的水性再分散体或聚合物水溶液施用至砖瓦的背面。
施用至砖瓦背面的聚合物粉末的总量优选为1g/m2至1000g/m2且特别优选为10g/m2至100g/m2。
取决于所用砖瓦的多孔性，在使用前能适当稀释分散体或再分散体溶液。优选分散体(再分散体)的固体含量或溶液的浓度为3重量％(高度多孔砖瓦)至60重量％(低多孔性)。取决于施用的方法，优选的层厚为100μm至500μm。
通过铺设砖瓦的标准方法，例如薄层工艺或“背涂-镘涂法”，能将本发明的砖瓦施用和固定至各种基材。
本发明的砖瓦能用于内部或外部施用中的衬里表面。特别地，当铺设的砖瓦暴露于湿气或湿环境或冻融循环时，本发明的砖瓦也适用。
在铺设于各种基材之后，本发明的砖瓦(表1，实施例1-4)意外地显示与未处理的砖瓦(表1，比较实施例1-2)相比显著增加的拉伸粘结强度。无论使用何种砖瓦粘合剂，都发生该效果，而且该效果的发生也独立于铺设的砖瓦所暴露的温度和湿度条件(表1)。
当本发明铺设砖瓦经受湿储存(表1，第4列)或冻融循环的湿储存(表1，第6列)时，即在对砖瓦粘合具有特别极端要求的温度和湿度条件下，本发明铺设砖瓦的增加的拉伸粘结强度的效果特别明显。
在细炻砖，即具有低吸水性的砖瓦(表1，实施例2或4以及第4或6列)的情况中，所述效果尤其显著。由于这种砖瓦的低多孔性，一般难以利用粘合剂粘结这种砖瓦。
相比于不用含水泥的砂浆而铺设的自粘合砖瓦，本发明铺设砖瓦的进一步的优势为有机会在置于基材上之后对本发明砖瓦的位置进行校正，这由于固定于砂浆层需要短时间，且不会在将砖瓦压至基材上之时立即发生。
由于无需有机溶剂而仅仅使用水作为溶剂或分散介质，用于制备本发明砖瓦的本发明的方法在经济上有利。此外，对有机溶剂排放的避免也使得本发明的方法环境友好。
此外，用于制备本发明砖瓦的本发明方法的使用使得制备具有低涂层厚度的涂层砖瓦成为可能。由于制备产品仅需要相应少量的材料，这也与可观的经济优势有关。
下述实施例用于详细说明本发明，且不构成任何限制。
实施例：
使用如下砖瓦进行测试：
F1：炻质砖
F2：细炻砖
以25％强度的水分散体的形式使用如下聚合物进行测试：
D1：乙烯-醋酸乙烯酯共聚物，Tg＝5℃，聚乙烯醇稳定化
D2：具有硅烷官能团的苯乙烯-丙烯酸丁酯共聚物，Tg＝10℃，乳化剂稳定化
在单次施用中利用刷子将分散体涂装至砖瓦的背面并干燥。
实施例1：具有D1分散膜的F1
实施例2：具有D1分散膜的F2
实施例3：具有D2分散膜的F1
实施例4：具有D2分散膜的F2
比较实施例1：未处理的F1
比较实施例2：未处理的F2
为了进行测试，使用具有如下组成的砖瓦粘合剂粘结得自实施例1-4或比较实施例1-2的砖瓦。
砖瓦粘合剂：
使用含水泥的砖瓦粘合剂(其中含有不同含量的分散粉末)粘结砖瓦，并测试粘结强度。
砖瓦粘合剂测试配方：
水泥 40份
石英砂 53-59份
纤维素醚 0.5份
另外的添加剂 0.5份
分散粉末Vac/VeoVa/E，Tg＝5℃ 0-6份
水 每100份干混料21-26份
砖瓦粘合剂FK1 0％的分散粉末
砖瓦粘合剂FK2 2.8％的分散粉末
砖瓦粘合剂FK3 4.5％的分散粉末
砖瓦粘合剂FK4 6％的分散粉末
借助于实施例1-4和比较实施例1-2检验铺设砖瓦的粘结强度(以N/mm2计)对砖瓦粘合剂和储存条件的依赖性。根据EN 12004(测试标准EN 1348)进行以N/mm2计的粘结强度的测定。
28d StdC： 标准的温度和湿度条件下28天
7d StdC/21d水： 标准条件下7天/湿储存21天
14d StdC/14d70℃/1d StdC：标准条件下14天/70℃下14天/标准条件下1天
冻融： 标准条件下7天/湿储存21天/25个冻融循环
OZ 15分钟： 施用砖瓦粘合剂后铺设砖瓦15分钟，在标准条
件下28天
粘结强度测试结果总结于表1中。
表1：
Claims (7)
1、一种具有在砖瓦背面的聚合物膜涂层的瓷砖或玻璃瓦，其特征在于所述涂层通过施用聚合物水分散体形式、或水溶液形式、或聚合物粉末再分散至水中的水性再分散体形式的均聚物或共聚物，以及随后的干燥分散体得到。
2、根据权利要求1所述的瓷砖或玻璃瓦，其特征在于使用一种单体或多种单体制备聚合物分散体或聚合物粉末或溶液，其中所述单体选自具有1至15个碳原子的羧酸的乙烯酯、羧酸与具有1至15个碳原子的非分枝或分枝的醇的甲基丙烯酸酯或丙烯酸酯、烯烃和二烯烃、乙烯基芳香烃或卤乙烯。
3、根据权利要求1或2所述的瓷砖或玻璃瓦，其特征在于使用一种单体或多种单体制备聚合物分散体或聚合物粉末或溶液，其中所述单体选自醋酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、乙烯基-2-己酸乙酯、月桂酸乙烯酯、醋酸异丙烯酯、新戊酸乙烯酯或具有9至13个碳原子的α-分枝的单羧酸的乙烯酯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸2-乙基己酯、丙烯酸冰片酯、乙烯、丙烯或1，3-丁二烯、苯乙烯或乙烯基甲苯、氯乙烯。
4、根据权利要求1至3任一项所述的瓷砖或玻璃瓦，其特征在于共聚物用作聚合物，所述共聚物包含
醋酸乙烯酯与乙烯和，若适当，一种或多种另外的乙烯酯的共聚物
或醋酸乙烯酯与乙烯和丙烯酸酯的共聚物
或醋酸乙烯酯与乙烯和氯乙烯的共聚物，
或苯乙烯和1，3-丁二烯的共聚物，
或如甲基丙烯酸甲酯的各种丙烯酸酯与丙烯酸正丁酯和/或丙烯酸2-乙基己酯和，若适当，乙烯的共聚物，
苯乙烯与丙烯酸酯和一种或多种单体的共聚物，其中所述单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯，
或包含醋酸乙烯酯和丙烯酸酯以及一种或多种单体的共聚物，其中所述单体选自丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸2-乙基己酯或，若适当，乙烯，
其中所述共聚物可另外含有辅助单体。
5、根据权利要求1至4任一项所述的瓷砖或玻璃瓦，其特征在于部分水解的聚醋酸乙烯酯或部分水解的醋酸乙烯酯共聚物或完全水解的聚醋酸乙烯酯或聚乙烯醇缩醛用作均聚物或共聚物。
6、一种制备如权利要求1-5任一项所述的瓷砖或玻璃瓦的方法，其特征在于特别通过喷雾、涂装或滚涂将聚合物水分散体形式、或水溶液形式、或可再分散至水中的聚合物粉末的水性再分散体形式的均聚物或共聚物施用至砖瓦背面，且通过随后的干燥形成膜。
7、如权利要求1-5任一项所述的瓷砖或玻璃瓦作为墙砖或地砖的用途，所述墙砖或地砖用于内部和外部施用中的衬里表面。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102006026699.4 | 2006-06-08 | ||
| DE102006026699A DE102006026699A1 (de) | 2006-06-08 | 2006-06-08 | Mit Polymerdispersionen beschichtete Fliesen sowie Verfahren zu deren Herstellung |
| PCT/EP2007/055406 WO2007141211A1 (de) | 2006-06-08 | 2007-06-01 | Mit polymerdispersionen beschichtete fliesen sowie verfahren zu deren herstellung |
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| Publication Number | Publication Date |
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| CN101454522A true CN101454522A (zh) | 2009-06-10 |
| CN101454522B CN101454522B (zh) | 2012-04-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2007800191914A Expired - Fee Related CN101454522B (zh) | 2006-06-08 | 2007-06-01 | 涂布聚合物分散体的砖瓦及其制备方法 |
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| Country | Link |
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| EP (1) | EP2024584B8 (zh) |
| CN (1) | CN101454522B (zh) |
| BR (1) | BRPI0712425A2 (zh) |
| DE (1) | DE102006026699A1 (zh) |
| ES (1) | ES2465667T3 (zh) |
| MX (1) | MX2008015668A (zh) |
| PL (1) | PL2024584T3 (zh) |
| PT (1) | PT2024584E (zh) |
| RU (1) | RU2439007C2 (zh) |
| WO (1) | WO2007141211A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109971367A (zh) * | 2017-12-28 | 2019-07-05 | 东莞市广信知识产权服务有限公司 | 一种强力瓷砖粘结剂 |
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| RU2464179C1 (ru) * | 2011-04-29 | 2012-10-20 | Общество с ограниченной ответственностью "Мауэр Бюро" | Способ получения защитно-декоративного покрытия (варианты) |
| EP2809629B1 (en) | 2012-02-01 | 2019-11-13 | Sika Technology AG | Covering material for flooring and walls |
| WO2021023366A1 (de) | 2019-08-05 | 2021-02-11 | Wacker Chemie Ag | Zementäre bindemittel-zusammensetzungen |
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| CA1120792A (en) | 1977-09-13 | 1982-03-30 | Easy-Do Products Limited | Tiles |
| GB2155944B (en) * | 1984-03-16 | 1988-04-27 | Building Adhesives Ltd | Powder compositions for producing tile adhesives and grouts |
| EP1044797A1 (en) | 1999-04-13 | 2000-10-18 | 3M Innovative Properties Company | Method for mounting ceramic tiles by means of an acrylic foam pressure sensitive adhesive |
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2006
- 2006-06-08 DE DE102006026699A patent/DE102006026699A1/de not_active Withdrawn
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2007
- 2007-06-01 MX MX2008015668A patent/MX2008015668A/es not_active Application Discontinuation
- 2007-06-01 EP EP07729803.2A patent/EP2024584B8/de not_active Not-in-force
- 2007-06-01 PL PL07729803T patent/PL2024584T3/pl unknown
- 2007-06-01 RU RU2008151517/03A patent/RU2439007C2/ru not_active IP Right Cessation
- 2007-06-01 PT PT77298032T patent/PT2024584E/pt unknown
- 2007-06-01 ES ES07729803.2T patent/ES2465667T3/es active Active
- 2007-06-01 CN CN2007800191914A patent/CN101454522B/zh not_active Expired - Fee Related
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109971367A (zh) * | 2017-12-28 | 2019-07-05 | 东莞市广信知识产权服务有限公司 | 一种强力瓷砖粘结剂 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX2008015668A (es) | 2009-01-09 |
| BRPI0712425A2 (pt) | 2012-07-10 |
| ES2465667T3 (es) | 2014-06-06 |
| CN101454522B (zh) | 2012-04-04 |
| EP2024584B1 (de) | 2014-03-19 |
| RU2008151517A (ru) | 2010-07-20 |
| WO2007141211A1 (de) | 2007-12-13 |
| RU2439007C2 (ru) | 2012-01-10 |
| PL2024584T3 (pl) | 2014-11-28 |
| EP2024584A1 (de) | 2009-02-18 |
| DE102006026699A1 (de) | 2007-12-13 |
| EP2024584B8 (de) | 2014-09-03 |
| PT2024584E (pt) | 2014-06-04 |
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