CN101133110B - 透汽性液体涂布膜 - Google Patents

透汽性液体涂布膜 Download PDF

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CN101133110B
CN101133110B CN2006800021092A CN200680002109A CN101133110B CN 101133110 B CN101133110 B CN 101133110B CN 2006800021092 A CN2006800021092 A CN 2006800021092A CN 200680002109 A CN200680002109 A CN 200680002109A CN 101133110 B CN101133110 B CN 101133110B
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R·A·维尔钦斯基
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Abstract

本发明的典型膜、液体组合物和方法涉及使用疏水丙烯酸系聚合物和至少一种水溶性聚合物(例如PVOH)在建筑物表面提供水蒸汽渗透性气密层。不像现有技术的蒸汽阻挡层，本发明提供了具有良好裂纹桥接和不吸水特征的膜。

Description

透汽性液体涂布膜
发明领域
本发明涉及防水的可渗透水蒸汽的膜，并更具体地涉及由具有疏水丙烯酸系聚合物相和作为水蒸汽通过管道的连续水溶性聚合物相的液体涂布组合物制成的膜。
背景技术
在建筑结构表面使用液体涂料组合物形成可渗透水蒸汽的气密膜是公知的。这种组合物可从Henry Company，California以商品名AIR-BLOC31获得。该组合物可喷涂并固化形成阻隔空气和漏气的膜，并声称实现了ASTM E-96下为12.3perm(或704ng/Pa.m2.s)的水蒸汽透过率(2002年7月15日的Henry Technical Data Sheet)。
相信由该组合物形成的膜具有微孔结构。微孔性通过装载填料或硬质颗粒材料至超过临界“颜料体积浓度”(“PVC”)的水平来实现。在该临界点以上，填料数量破坏了聚合物基质的连续性，从而形成可透过水蒸汽的管道。
相信Henry公司的组合物含有约15份碳酸钙(一种典型填料)、35份烃蜡(认为起到填料作用，因为它不形成膜)和50份乙酸乙烯酯-丙烯酸酯共聚物，从而超过了临界颜料体积浓度(PVC)。
PVC值由填料(包括不形成膜的材料)体积乘以100并除以固体总体积确定。PVC计算如下：PVC＝100×((wt％蜡/蜡密度)+(wt％填料/填料密度))/((wt％蜡/蜡密度)+(wt％填料/填料密度)+(wt％聚合物/聚合物密度))＝(35+(15/2.6))×100/(35+(15/2.6)+50)＝45％。相信该值超过了临界PVC。虽然由该组合物获得的膜可透过蒸汽而不能透过液态水，但本发明人相信该膜具有低伸长率和差的裂纹桥接性能。此外，该膜还吸收大量水。
鉴于上述缺点，本发明人相信需要新颖的液体涂布蒸汽阻挡组合物及方法。
发明概述
为了克服现有技术的缺点，本发明提供了可透过水蒸汽并阻挡空气和液态水的膜，其使建筑结构中的冷凝和最终的霉菌生长最小化。
除气密性和水密性以及透汽性外，该膜还具有低吸水率、高伸长率，以及足够的用于桥接在温湿度循环下会膨胀和收缩的板接头和裂纹的本体(湿涂层厚度)。该膜可喷射涂布。干燥后，该膜完全附着在基材表面。
不使用会导致微孔但会弱化基质结构的超出临界颜料体积浓度(PVC)装载的无机填料，本发明的组合物包含疏水丙烯酸系聚合物相以提供液态水不透性，和连续的水溶性聚合物相以提供水蒸汽渗透性。作为选择，填料可以不超过临界PVC的水平掺入。
因此，用于在建筑物表面提供透汽性气密膜的本发明的典型液体组合物包含具有至少一种带有式-(CH2-CH2COOR)-表示的重复基团的疏水丙烯酸系聚合物的乳液，其中R表示C2-C8烷基，该至少一种丙烯酸系聚合物具有-55℃至0℃的玻璃化温度，且含量以总干固体计为50-97wt％。
如上所述，典型的液体组合物可进一步含有以总固体计含量为0-50wt％的选自碳酸钙、滑石、粘土、二氧化硅和二氧化钛的无机填料。填料和其它硬质非成膜成分的体积乘以100除以固体总体积计算得到的PVC可为0-25％。填料用量优选应小于超出临界PVC所需的量。换句话说，所得膜不是微孔的。
该液体组合物还含有占总重量30-50％的水和占固体总干重3-17wt％的至少一种水溶性聚合物。水中的4wt％水溶性聚合物应具有2-50厘泊的溶液粘度。水溶性聚合物优选选自数均分子量为5,000-50,000的聚乙烯醇；平均分子量为5,000-200,000的聚环氧乙烷；和数均分子量为3,000-20,000的纤维素甲基醚或乙基醚。
通过在基材表面上喷涂组合物形成的本发明典型膜优选干膜厚为20-60密耳，并具有1-20perms，更优选2-10perms的水蒸汽渗透率。在这种厚度下，由本发明的涂料组合物形成的膜表现出高伸长率，从而赋予优异的裂纹桥接能力。
本发明提供了诸如石膏板，水泥、砖石或混凝土制成的结构，或木制结构的基材表面的涂布方法。本发明还涉及通过用上述涂料组合物涂布这种基材表面形成的复合材料结构。
本发明的其它优点和特征将在下面进一步详细描述。
附图简述
通过以下典型实施方案的详细描述，结合附图，可更好地理解本发明。
图1是本发明的组合物形成连续的水蒸汽渗透相的机理的示意图；
图2是分别由薄膜涂层和本发明典型厚膜涂层提供的裂纹桥接性能的比较图；
图3和4是聚乙烯醇(PVOH)浓度对本发明典型组合物渗透率、强度和伸长率的影响的图；
图5是本发明典型膜的渗透率的图；
图6是本发明典型膜的伸长的图；
图7是本发明典型膜的强度的图；和
图8是本发明典型膜的颜料体积浓度(PVC)的图。
典型实施方案详述
本发明的水蒸汽渗透性气密膜通过在基材表面上流延液体组合物制备，该组合物优选含有阴离子或非离子丙烯酸系乳液，至少一种水溶性聚合物，和任选的诸如碳酸钙、滑石、砂子或其它颗粒(且优选无机的)材料的填料，或这种任选的填料的组合。
其它任选的成分包括着色剂(通常意义上指赋予膜颜色的“颜料”)、流变学改性剂、抗氧化剂、紫外稳定剂、消泡剂和生物杀伤剂。
本发明典型液体组合物的成分数量除非另外指明，均用基于总固体的百分比干重表示。
适用于本发明的典型液体组合物包含含有至少一种式-(-CH2-CH2COOR-)-表示的重复基团的疏水丙烯酸系聚合物的乳液，其中R代表C2-C8烷基，该至少一种丙烯酸系聚合物具有-55℃至0℃的玻璃化温度，且含量以总干固体计为50-97wt％。该聚合物可含有包括但不限于苯乙烯、乙酸乙烯酯和氯乙烯的其它单体。
适用于本发明的典型液体组合物包含含有丙烯酸丁酯和苯乙烯的乳液。丙烯酸丁酯/苯乙烯的摩尔比大于1。优选的丙烯酸丁酯/苯乙烯摩尔比大于1.5。
优选R代表乙基、丙基、丁基、辛基或乙基己基聚合物。更优选疏水丙烯酸系聚合物是丙烯酸丁酯。其它典型组合物可进一步包括甲基(丙烯酸)系聚合物。丙烯酸系聚合物的含量以组合物中总固体计优选为50-97％，更优选60-90％。
典型液体组合物进一步含有至少一种水溶性聚合物。该水溶性聚合物在液体组合物中的存在量以总干重固体计应为3-17wt％。该水溶性聚合物在4wt％的水溶性聚合物水溶液情况下还应具有约2-50厘泊(cps)的溶液粘度。
优选的水溶性聚合物选自数均分子量为5,000-50,000的聚乙烯醇；平均分子量为5,000-200,000的聚环氧乙烷；和数均分子量为3,000-20,000的纤维素甲基醚或乙基醚。甲基纤维素醚可从Dow Chemical以商品名METHOCEL A获得，据称含有27.5-31.5％甲氧基或1.64-1.92的甲氧基取代度。其它水溶性聚合物包括羟丙基甲基纤维素、羟乙基纤维素、含有乙烯基甲基醚的聚合物、包括水解马来酸酐聚合物和共聚物的聚合物，以及具有乙烯基醚、苯乙烯、乙烯和其它烯烃的共聚物，聚乙烯吡咯烷酮、磺化聚苯乙烯、polysulfethyl丙烯酸酯、聚(丙烯酸2-羟乙酯)、聚丙烯酰胺、聚(丙烯酸)及其碱金属盐、天然或合成改性的聚糖、蛋白质、藻酸盐、黄原胶和瓜耳胶。
可以采用冷水溶性和热水溶性两种级别的聚乙烯醇。冷水溶性级具有80％-90％的水解度。热水溶性级具有90％-100％的水解度。
然而，如上所述，聚乙烯醇、聚环氧乙烷和甲基纤维素是最优选的水溶性聚合物。采用这些聚合物的低MW版本保证液体组合物具有能喷涂该液体组合物的足够低粘度，而水溶性聚合物的重量分数高到足以保证高的水蒸汽渗透率。
本发明的典型液体组合物任选地进一步含有选自碳酸钙、滑石、粘土、二氧化硅和二氧化钛的无机填料，该至少一种填料的存在量以组合物中总固体计为0-50wt％。颜料体积浓度可为0-25％。PVC＝100×填料(和其它非成膜成分)的体积％/所有固体成分(丙烯酸系和水溶性聚合物是成膜成分)的体积％(当用背景部分所述公式计算时，此处参考引用)，且应小于临界颜料体积浓度(高于该值时，由该液体组合物提供的干膜涂层将变为多孔的)。优选填料材料具有不小于0.1μm且不大于50μm的平均粒度。
以组合物中总固体重量，填料含量更优选计为2-40％，且更优选5-30％。
该组合物可喷涂、刷涂、抹涂或以另外方式涂布在目标基材上。基材包括粘结性表面(例如水泥、灰浆、砌筑体、混凝土、喷浆混凝土、石膏)和石膏板，以及诸如木材或胶合板等可用于构筑建筑物和人类或动物居住的其它腔室的其它多孔结构。
因此，本发明涉及基材的防水方法，包括在基材表面，以及用该组合物和上述方法处理的复合材料(例如建筑板、墙面、地基面、上承面、屋顶面)上涂布该组合物的步骤。
通过在基材表面上涂布组合物形成的膜优选具有10-100密耳的平均干厚，更优选20-80密耳的平均干厚，最优选40-60密耳的平均干厚。
由该组合物形成的典型膜还优选具有不小于2 perm且不大于20perm的根据ASTM E-96的透汽率；不小于200％且不大于1,000％的伸长率；在水中浸没1天(24小时)后小于50％的吸水率值；以及0-25％的颜料体积浓度(PVC)。
在本发明的典型组合物中，以液体组合物的总重量计，连续水溶性聚合物相的重量分数应为3％-17％，更优选5％-10％。水溶性聚合物的含量还有可用作丙烯酸系乳液中的保护性胶体的任何水溶性聚合物(如果乳液制造商供应乳液的话)。
如图1所示，形成两相组合物的机理如下。将水溶性聚合物溶解在预制的阴离子或非离子丙烯酸系乳液的含水相中。将该液体组合物流延在基材上，并使水份蒸发。蒸发掉大部分水后，形成两相组合物。水溶性聚合物(例如溶液中溶解的PVOH)随着水份蒸发而从溶液析出，构成所得膜涂层中的连续相。
因此，由组合物的液体涂层形成的膜因由水溶性聚合物相建立的亲水管道的存在而非微孔性而具有蒸汽渗透性。由于颜料体积浓度(PVC)通过填料(无机物和非成膜的不挥发材料)体积乘以100并除以固体总体积确定，因此可以理解的是，在高PVC值下，成膜材料(例如丙烯酸系聚合物)的量不足以润湿所有非成膜成分，从而导致微孔性。CPVC(临界颜料体积浓度)是从非孔性过渡到微孔性的填料材料固体的浓度。
本发明的组合物不是微孔性的，但表现出低PVC。该PVC优选小于或等于25％。优选本发明组合物的PVC小于或等于16％。
本发明组合物通过高伸长率与高膜厚能力的结合提供了良好的裂纹桥接特征。如图2所示，诸如混凝土或石膏板墙壁的基材表面30中的裂纹33随着温度和湿度波动而膨胀和收缩。当裂纹33发生膨胀时，存在应力分布梯度存在。涂层顶部的应力对于薄涂层32比对于厚涂层31要大。因此，对于给定裂纹尺寸，薄涂层32要比厚涂层31更快地失效。
从图2可见本发明的液体涂布组合物与简单的油漆涂层之间的重要差别。油漆往往以薄涂层涂布，得到的干燥厚度小于10密耳。相反，本发明的膜具有大于20密耳，更优选大于40密耳的平均干膜厚。
以下实施例出于举例说明的目的提供。
实施例1
证明了仅包含丙烯酸系聚合物和PVOH(聚乙烯醇)的体系中，聚乙烯醇(PVOH)浓度对渗透率、强度和伸长率的影响。丙烯酸系聚合物从BASF以商品名ACRONAL S400获得。PVOH从Dupont以商品名ELVANOL51-05获得。重复渗透率结果，两组数据分别示于图3和4。注意渗透率与PVOH含量成正比。拉伸强度也与PVOH含量成正比。然而，低PVOH含量下伸长率相对不受影响。
实施例2
测试了丙烯酸系聚合物含量、填料含量和聚乙烯醇含量对由液体组合物形成的膜的渗透率、强度和伸长率的影响。为了配制液体组合物，丙烯酸系聚合物从BASF(ACRONAL S400)获得，而PVOH从Celanese Corporation获得。各种膜组合物示于表1。
膜的渗透率、伸长率和强度分别绘制在图5、6和7中。注意渗透率最依赖于PVOH浓度，并且对于分别含有6％-23％PVOH的配方在8-27perm间变化。由含有高聚合物含量和低PVOH和填料含量的组合物形成的膜的伸长率最大。发现由组合物7和9形成的膜具有良好的渗透率和高伸长率。渗透率分别为12perm和8perm。伸长率值分别为460％和680％。
                           表1
序号    聚合物        填料          PVOH
5       0.33          0.49         0.18
4       0.38          0.50         0.13
1       0.77          0.00         0.23
10      0.42          0.51         0.06
11      0.58          0.28         0.14
7       0.64          0.29         0.07
1       0.77          0.00         0.23
9       0.92          0.00         0.08
3       0.84          0.00         0.16
5       0.33          0.49         0.18
2       0.53          0.27         0.20
3       0.84          0.00         0.16
1       0.77          0.00         0.23
2       0.53          0.27         0.20
实施例3
测试了由采用Henry Company以商品名AIR-BOC31销售的丙烯酸系聚合物的组合物制备的膜的丙烯酸系聚合物、填料和PVOH含量对吸水率的影响。成分类型与实施例2相同。对每种试样流延平均干厚60密耳的膜。将干膜在自来水中浸泡24小时。用各种组合物制成的膜的结果示于下表2中。吸水率以百分数测量(表中示出了膜由于脆弱而破坏(“破裂”)的情况)。注意吸水率大致正比于PVOH含量。较低PVOH含量是优选的以使吸水率最小。
                 表2
组分
                          膜的吸水率
聚合物     填料      PVOH      (％)
0.33       0.49     0.18      28.5
0.38       0.50     0.13      32.1
0.77       0.00     0.23      破裂
0.42       0.51     0.06      39.1
0.58       0.28     0.14      52.1
0.64       0.29     0.07      15.5
0.77       0.00     0.23      破裂
0.92       0.00     0.08      19.1
0.84       0.00     0.16      63.5
0.33       0.49     0.18      破裂
0.53       0.27     0.20      44
0.84       0.00     0.16      75.5
0.77       0.00     0.23      破裂
0.53       0.27     0.20      破裂
测定Henry组合物的吸水率为102％。对于其它试样，流延商购产品的60密耳干膜，并在水中浸泡24小时。测量基于重量百分比的吸水率。
实施例4
计算本发明组合物的颜料体积浓度并示于图8中。注意到本发明组合物的颜料体积浓度最高为25％。相反，Henry组合物的PVC测定为45％。
实施例5
评价PVOH分子量对配方粘度的影响。必须有足够的PVOH来获得目标渗透率，但PVOH分子量必须足够低，以允许喷涂该液体组合物。表3示出用于所有试验的配方。PVOH分子量和液体组合物粘度示于表4。
注意到液体组合物粘度与PVOH分子量成正比。配方1不容易喷涂，但其它配方很容易喷涂。
              表3
          粘度
丙烯酸系乳液          56.5
水                    24
聚乙烯醇              3.75
CaCO3                 15
颜料                  0.5
消泡剂                0.25
合计                  100
                                表4
序号    PVO HMW        4％水溶液粘度      组合物粘度(cps)
                       (cps)              0.5RPM  5RPM    50RPM
1       80,000         18                 35200   17360   ND
2       10,000-13,000  5                  1600    480     272
3       15,000-23,000  6                  2400    960     640
4       7,000-10,000   3                  800     320     168
以上实施例和实施方案仅用于举例说明目的，并不拟限制本发明的范围。

Claims (22)

1.通过喷涂涂布到建筑物表面上提供透汽性气密膜的液体组合物，包含：
含有至少一种带有式-(-CH2-CH2COOR-)-代表的重复基团的疏水丙烯酸系聚合物的乳液，其中R表示C2-C8烷基，所述至少一种丙烯酸系聚合物具有-55℃至0℃的玻璃化温度，且含量以组合物中总固体计不小于50％和不大于97wt％；
所述液体组合物进一步含有选自碳酸钙、滑石、粘土、二氧化硅和二氧化钛的至少一种无机填料，所述至少一种无机填料的含量以所述液体组合物的总固体计为5-30wt％；所述液体组合物中含有的所有无机填料的总量为使得颜料体积浓度为不大于16％的量；
所述液体组合物进一步含有以所述液体组合物总重量计不小于30％且不大于50wt％的水；和
所述液体组合物进一步含有以所述液体组合物中总固体计不小于5％且不大于17wt％的至少一种水溶性聚合物，并且所述至少一种水溶性聚合物在4wt％水中具有不小于2厘泊且不大于50厘泊的溶液粘度。
2.权利要求1的组合物，其中所述至少一种水溶性聚合物选自：
数均分子量不小于5,000且不大于50,000的聚乙烯醇；
平均分子量不小于5,000且不大于200,000的聚环氧乙烷；和
数均分子量不小于3,000且不大于20,000的纤维素甲基醚或乙基醚。
3.权利要求1的组合物，其中所述至少一种水溶性聚合物是数均分子量不小于5,000且不大于50,000的聚乙烯醇。
4.权利要求1的组合物，其中所述至少一种水溶性聚合物是平均分子量不小于5,000且不大于200,000的聚环氧乙烷。
5.权利要求1的组合物，其中所述至少一种水溶性聚合物是数均分子量不小于3,000且不大于20,000的纤维素甲基醚或乙基醚。
6.权利要求1的组合物，其中在所述至少一种疏水丙烯酸系聚合物中，R代表乙基、丙基、丁基、辛基或乙基己基。
7.权利要求1的组合物，进一步含有疏水甲基(丙烯酸)系聚合物。
8.权利要求1的组合物，其中所述至少一种疏水丙烯酸系聚合物是丙烯酸丁酯聚合物。
9.权利要求1的组合物，其中至少一种疏水聚合物是丙烯酸丁酯与苯乙烯的共聚物。
10.权利要求9的组合物，其中丙烯酸丁酯/苯乙烯摩尔比大于1.5。
11.权利要求1的组合物，其中所述无机填料是碳酸钙。
12.权利要求1的组合物，其中所述无机填料具有不小于0.1μm且不大于50μm的平均粒度。
13.权利要求3的组合物，其中所述聚乙烯醇具有80-90％的水解度。
14.权利要求3的组合物，其中所述聚乙烯醇具有90-100％的水解度。
15.通过用权利要求1的组合物喷涂涂布基材表面并使所述组合物干燥而制备的膜。
16.权利要求15的膜，其平均厚度不小于20密耳且不大于100密耳厚。
17.权利要求15的膜，其平均厚度不小于40密耳。
18.权利要求15的膜，其平均厚度不小于40密耳且不大于100密耳厚，根据ASTM E-96的透汽率不小于2perm且不大于20perm，且伸长率不小于200％且不大于1000％；水中浸泡1天后吸水率值小于50％。
19.一种形成水蒸汽渗透膜的方法，包括在粘结性基材、木材或石膏基材上喷涂涂布权利要求1的组合物，以及使所述组合物干燥。
20.权利要求19的方法，其中所述水蒸汽渗透膜的平均厚度为20密耳至100密耳。
21.一种复合材料，其包含涂布了权利要求1的组合物的建筑板或粘结体。
22.权利要求21的复合材料，其中在干燥后，经涂布的组合物形成平均厚度为20密耳至100密耳的水蒸汽渗透膜。
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US20060155031A1 (en) 2006-07-13
KR20070095917A (ko) 2007-10-01
WO2006076186A2 (en) 2006-07-20
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JP2008527107A (ja) 2008-07-24

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