CN108463598A - 用于预施加防水膜的辅助细化 - Google Patents
用于预施加防水膜的辅助细化 Download PDFInfo
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- CN108463598A CN108463598A CN201580084933.6A CN201580084933A CN108463598A CN 108463598 A CN108463598 A CN 108463598A CN 201580084933 A CN201580084933 A CN 201580084933A CN 108463598 A CN108463598 A CN 108463598A
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- waterproof membrane
- layer
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- coating
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Abstract
本发明提供防水膜,其不需要可移除的剥离片材,但其仍然粘合至后浇注混凝土并且辅助膜至膜重叠处的水密密封。所述防水膜包含载体和压敏胶粘剂(PSA)层;无机粒子层,其具有部分嵌入PSA中且平均粒度小于PSA层的平均厚度的颗粒体;以及防潜含纳米二氧化硅涂层,其附着至无机粒子的未嵌入部分以便防止在所述膜卷起或展开时完全嵌入PSA中,由此辅助在相邻安装的防水膜的重叠部分之间的水密接缝,且由此优选仅使用细化或防水带而不额外使用液体底漆、胶合辅料或其它涂料来实现水密接缝。
Description
发明领域
本发明涉及粘合至后浇注混凝土(post-cast concrete)上的防水膜,该膜包含载体和压敏胶粘剂(PSA)层、部分嵌入PSA的具有受限粒度的无机粒子层,和包含纳米二氧化硅及成膜聚合物的防潜(anti-submarining)外涂层,其用于防止粒子完全嵌入PSA层、用于提供抗粘连以避免需要剥离衬垫(release liner),并用于在安装时使用细化(detailing)或防水带辅助在重叠的膜之间的水密接缝。
发明背景
Wiercinski等人的美国专利8,453,405和8,713,897(由本申请的共同受让人所有)公开了一种防水膜,其通过将其安装到建筑物、模板(form)或其它表面上并随后对其胶粘剂层侧浇注新鲜混凝土(“后浇注混凝土”)来“预施加”。Wiercinski等人的膜设计涉及使用载体片材、压敏胶粘剂(PSA)以及粒度等于或大于PSA厚度的白水泥粒子,使得在膜卷起和展开时无需剥离片材来防止PSA粘着至载体片材侧。不存在剥离片材意味着在施工现场避免了废弃物。消除剥离衬垫意味着更容易、更快速的施用。
但是,本发明人认为“预施加”膜具有缺点。因为此类膜与载体层一起面对安装表面(例如木材模板、混凝土模具)安装,向外布置的含粒子层面向随后安装的膜(其在末端重叠(侧边用3”PSA镶边密封))的载体层以便与先前安装的(相邻)膜组合实现整体保护。对于施加者,这种粒子至载体重叠在细化过程中需要额外的谨慎、时间和努力。通常需要密封剂胶粘剂或胶合涂料连同合适的细化或防水带(或条带)以确保沿相邻膜的重叠边缘形成水密接缝。
因此,本发明人认为,需要新颖和发明性的预施加型防水膜以确保在重叠处的密封和辅助细化。
发明概述
在克服现有技术的缺点方面,本发明提供了新颖和发明性的预施加防水膜,其借助于在建筑物表面上在相邻膜的重叠边缘处实现水密接缝来辅助细化处理;此外其不需要可移除的剥离衬垫来卷起和展开,这为步行交通提供了耐久性和抗滑性,并且其提供对后浇注混凝土的良好粘合(包括优异的初始粘合强度),即使在膜已经经受UV和潮湿一段延长的时期后也是如此。
本发明的示例性防水膜,包含:包含两个主面的载体层;如限定在两个主面之间的平均厚度为0.05至2.0 mm的压敏胶粘剂(PSA)层,所述两个主面之一附着至载体层主面之一,PSA层进一步具有如根据ASTM D 5-73测得的大于 30 丝米(dmm)的渗透(penetration)(150克,5秒,70℉);包含平均尺寸为70 µm至450 µm的个别颗粒体的无机粒子层,该无机粒子层通过将颗粒体部分嵌入PSA层的第二主面(与附着至载体层的主面相对)来形成,由此颗粒体的一部分相对于PSA保持未浸没;以及平均厚度为0.003至0.011 mm的防潜涂层,其附着至无机颗粒体的未浸没部分以防止在膜卷起或展开时个别颗粒体完全嵌入PSA层内,该涂层通过用包含纳米二氧化硅粒子和至少一种成膜聚合物的乳液涂布无机粒子层并允许该涂层在未浸没的个别颗粒体上干燥来形成,防潜纳米二氧化硅涂层在干燥后具有根据ASTM D 2240-00在23℃下测得的50-90、更优选60-90和最优选70-90的肖氏(Shore)D硬度。
优选地,基于干重量百分比计,防潜涂层中至少一种成膜聚合物与纳米二氧化硅的比率应当优选为1:4至4:1,并且在无机粒子层上的该涂层的干涂层厚度应当为0.004至0.008 mm。
本发明的用于制造整体膜层(course)的示例性方法由此包括:将如上所述的第一防水膜安装到基底(例如模板、墙壁等等)的第一部分上;将第二防水膜安装到基底的第二部分上,同时部分重叠第一防水膜,并在第二防水膜的载体层主面与第一防水膜的防潜含纳米二氧化硅涂层之间进行密封(例如细化),由此在第一和第二(安装的)膜之间生成水密重叠,同时仍提供与后浇注混凝土的优异粘合(包括初始粘合强度)。
与现有技术设计的预施加类型膜相比,本发明注入了高得多的可靠性,即使当单独使用细化或防水带(即具有预先形成的防水压敏胶粘剂层或双面层的条带,无需另外借助液体底漆、密封剂或其它涂布材料)在膜的重叠部分处生成水密接缝时,也能(在重叠处)实现有效的膜至膜密封。
本发明还提供了制造上述膜的方法。示例性膜包含使用包含胶体二氧化硅和至少一种成膜聚合物乳液的水性乳液涂布无机粒子的部分未嵌入部分,并使该涂层干燥,由此形成防潜含纳米二氧化硅涂层。在优选的实施方案中,膜可以卷起和展开而无需使用可移除的剥离衬垫(例如蜡纸或硅化纸)。
如下文中采用显微照相术所解释的那样,使用水性乳液涂层结合尺寸受限的粒子层提供了受控的“更平坦的”向外面部分,其在建筑物或构造体表面上在两个相邻安装的膜之间的重叠处形成防水密封时有利地允许使用防水或细化带(例如在一侧或两侧上具有预先形成的防水压敏胶粘剂层的防水条带,其纵向折叠或纵向平铺);并且这优选在不必使用附加的液体底漆、胶合辅料(mastic)或其它液体涂料组合物的情况下进行。同时,该膜具有足够的抗粘连性质,使得无需剥离片材来卷起膜(在装运前)和展开膜(在施加至表面上之前)。
在下文中详细描述了本发明的其它优点和特征。
附图概述
当结合附图读取优选实施方案的以下详述时,可以更容易地理解本发明的其它优点和特征,其中:
图1是预施加防水膜的横截面的图解说明(未按比例绘制),该防水膜具有载体片材,压敏胶粘剂(PSA)层和平均尺寸等于或大于PSA层的平均厚度的白水泥粒子层;
图2是本发明的示例性预施加防水膜的横截面的图解说明(也未按比例绘制),该防水膜具有载体片材、PSA层、平均尺寸小于PSA层的平均厚度且部分嵌入PSA层中的无机粒子、和附着至未嵌入PSA层中的无机粒子部分的防潜含纳米二氧化硅涂层;
图3是由扫描电子显微镜(SEM)在100×放大倍数下拍摄的现有技术防水膜(其横截面设计图解说明在图1中)的白水泥粒子层的显微照片;和
图4是本发明的示例性防水膜的显微照片,同样由SEM在100×放大倍数下拍摄,其中防潜含纳米二氧化硅涂层在尺寸受限的无机粒子(其部分嵌入PSA层中)上使用包含胶体纳米二氧化硅和成膜聚合物的水性乳液来形成,由此使乳液干燥以形成附着至粒子且用于在卷起和展开膜时最小化或防止尺寸受限的无机粒子完全嵌入(或浸没)到PSA层中的涂层。
优选实施方案详述
图1图解说明了现有技术的预施加防水膜1(例如原始公开在美国专利8,453,405和8,713,897(参见背景部分)中)的横截面,其包含柔性载体片材2、压敏胶粘剂(PSA)层3和在PSA层3表面上的反射性粒子层 4。反射性粒子4具有等于或大于PSA层3的厚度的平均直径。膜1不需要通常用于在膜卷起时防止膜1的胶粘剂部分3粘附至载体片材2或膜1的其它部分的可移除剥离片材。
相比之下,图2图解说明了本发明的示例性预施加防水膜10,其包含具有两个主面的柔性载体层12;具有两个主面的压敏胶粘剂层(PSA)14,其一个主面附着至所述载体层12的主面之一;具有个别颗粒体的无机粒子层16,所述颗粒体的平均尺寸(直径)小于PSA层14的平均厚度并且其部分嵌入PSA层14中(相对于附着至载体层12的主面);和在未嵌入的颗粒体16的部分上形成的防潜涂层18。优选地,防潜涂层18通过将至少一种水性乳液组合物18涂布到无机颗粒层16的暴露的个别颗粒体上并使涂层18干燥来形成,所述水性乳液组合物18由胶体(纳米)二氧化硅和至少一种聚合物成膜材料组成。
如图3(现有技术)中可见的扫描电子显微镜(SEM)照片中所描绘的那样,现有技术防水膜设计(其横截面设计图解说明在图1中)的反射性粒子明显突出在PSA层之外。图3的SEM照片在100×放大倍数下拍摄。容易显现的是,反射性粒子提供了凹凸不平的表面区域,以便在安装膜时耐受步行交通,以及某些抗粘连益处(使得载体侧可以抵靠粒子尺寸卷起,而无需使用可移除的剥离片材以允许展开膜)。
另一方面,图4描绘了本发明的示例性预施加防水膜在相同放大倍数(100×)下拍摄的SEM照片,其中防潜含纳米二氧化硅涂层(在图2中指定为18)显示出具有经涂布的无机颗粒体,其限定了无机粒子层(在图2中指定为16)。如前所述,这种涂层18优选通过将包含胶体(纳米)二氧化硅和至少一种成膜聚合物材料的水性乳液涂布到颗粒体 16的暴露部分上来形成,如将在下文中进一步详细讨论。术语“(纳米)二氧化硅”、“纳米二氧化硅”、“纳米尺寸二氧化硅”和“纳米级二氧化硅”在本文中可互换使用,以指包含在防潜纳米二氧化硅涂层18内的二氧化硅粒子(即具有0.1至100纳米(nm)的平均尺寸)。纳米二氧化硅的水性分散体通常称为胶体二氧化硅。
不欲受理论束缚,本发明人认为,防潜含纳米二氧化硅涂层18有助于防止或最小化无机颗粒体16完全浸没(下沉)和完全嵌入(封装)到PSA层中,特别是在炎热天气中当PSA可能被日光的能量软化时。可以使用平均直径较小(与PSA层的平均厚度相比)的较小粒子16而不会破坏粒子的抗粘连效应,并且不会牺牲耐久性,如对步行交通的耐受性。但是,相当有利且令人惊讶地,防潜纳米二氧化硅涂层18可用于使得良好地初始粘合至后浇注混凝土,并且这种效应可以参考图4的显微照片来或许最好地进行说明,图4显示涂层18附着至许多暴露(未浸没部分)的粒子16,同时仍留下裂缝或开口以便后浇注混凝土嵌入,以用于与膜的良好初始粘合。
如图4所表明的那样,粒子的总表面积的降低(与图3中显示的现有技术的大暴露粒子相比)也表明了当使用单独的细化或防水带(或条带),优选不额外使用液体底漆、胶合辅料或其它液体涂布材料的情况下将在施加位点处在边缘重叠的相邻安装的膜密封在一起时获得的益处。可以以高得多的可靠性和速度实现仅使用细化或防水带生成由两个或更多个本发明的防水膜形成的整体阻隔件。
常规防水、细化或接合带(或条带膜)(如由Grace Construction Products所出售的(参见例如PV100™带、BITUTHENE®带))可用于将相邻的片材膜密封在一起。许多防水制造商出售防水带,这些胶粘剂可以由沥青或合成聚合物防水胶粘剂制成,并且适用于本发明。优选地,防水带是双面的,其中载体膜或织物的两面均带有预先形成的防水压敏胶粘剂层,以使其可以插入相邻膜的重叠边缘之间,而无需纵向折叠该带。
本发明人还认为,本发明的膜设计在层叠体组件的选择方面允许更大的灵活性。
最适于本发明的示例性柔性载体层12应为膜10提供机械强度和防水完整性。载体层12通常将具有大约0.05至2.0 mm且更优选大约0.3至1.0 mm的厚度。载体层12应进一步具有一般性光滑的表面,如通过膜、片材、织物和挤出涂布的织造或非织造织物所提供的那样。适于膜和挤出涂层的材料包括聚丙烯、聚乙烯、乙烯-丙烯共聚物、乙烯-烯烃共聚物、乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚丙烯酸乙酯、聚四氟乙烯(PTFE)、聚偏二氟乙烯(PVDF)、聚对苯二甲酸乙二醇酯(PET)、聚氯乙烯(PVC)、聚酰胺及其组合。聚乙烯和聚丙烯是优选的。优选的载体层12包含高密度聚乙烯(HDPE)的热塑性膜。织物可以是织造或非织造的,并可以包含聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯和聚酰胺。织造的聚丙烯织物是特别合适的。
通常,载体层或片材12未经表面处理以提高表面张力。但是,在一些情况下可能合意的是处理将在其上施加胶粘剂14的载体片材12的表面以增强胶粘剂层14对载体片材12的粘附。表面处理的一个实例是电晕处理。
可以将添加剂并入载体层12材料中以降低表面张力。这些可以在单独的混炼步骤中并入材料主体中。还可以将添加剂在熔体挤出过程期间并入材料主体中以产生片材、膜或挤出涂布的织物。
最适于本发明的示例性压敏胶粘剂(PSA)层14应为防水膜10提供防水完整性。PSA层14用于将无机粒子层16粘合至载体片材 12,并应优选具有大约3至30密耳、更优选大约5至15密耳、最优选大约8至10密耳的厚度。虽然预期使用沥青或橡胶改性的沥青胶粘剂可以令人满意地用在某些防水应用(例如隧道或其它低光应用)中,但本发明人更优选PSA层14中所用防水胶粘剂包含合成(非沥青)压敏胶粘剂。使用沥青压敏胶粘剂对本发明而言并非优选,因为此类材料往往在UV暴露后表现出低劣的耐降解性和快速损失对混凝土的粘合。因此,为了改善对后浇注混凝土的粘附,优选的是压敏胶粘剂包含合成聚合物并具有如根据ASTM D 5-73测得的大于大约30丝米(dmm)的渗透(150克,5秒,70℉)。
据信合适的示例性压敏胶粘剂层14包括基于丁基橡胶的胶粘剂、基于聚异丁烯的胶粘剂、基于丁基的胶粘剂、基于丙烯酸系的胶粘剂、基于苯乙烯-异戊二烯-苯乙烯(SIS)的胶粘剂、基于苯乙烯-乙烯-丁烯-苯乙烯(SEBS)的胶粘剂、基于苯乙烯-丁二烯-苯乙烯(SBS)的胶粘剂、基于苯乙烯-丁二烯橡胶(SBR)的胶粘剂及其组合。优选地,合成胶粘剂是SIS、SBS或SEBS的压敏热熔胶粘剂嵌段共聚物。关于压敏胶粘剂的更详细的说明,参见Satas, Handbook Of Pressure Sensitive Adhesive Technology(Van NostrandReinhold Company, Inc., 1982)。
适用于PSA层14的橡胶或弹性体包括聚异戊二烯、聚丁二烯、天然橡胶、氯丁橡胶、乙烯-丙烯橡胶、乙烯α烯烃、腈橡胶、丙烯酸系橡胶或其混合物。
优选的非沥青合成压敏胶粘剂层14可以任选含有通常用于防水膜的添加剂,包括但不限于光吸收剂(例如炭黑、苯并三唑等等)、光稳定剂(例如受阻胺、二苯甲酮)、抗氧化剂(例如受阻酚)、填料(例如碳酸钙、二氧化硅、二氧化钛等等)、增塑剂、流变添加剂及其混合物。优选的组合是包含光吸收剂、光稳定剂、抗氧化剂或其混合物的合成PSA组合物层。在本发明的其它示例性实施方案中,这些任选添加剂之一还可以包含在防潜纳米二氧化硅涂层18中。
压敏胶粘剂(PSA)14的另一实例包括一种或多种非晶聚烯烃。非晶聚烯烃(APO)定义为如通过差示扫描量热法测得的结晶度小于30%的聚烯烃。这些聚合物可以是丙烯的均聚物,或丙烯与一种或多种α-烯烃共聚单体(例如乙烯、1-丁烯、1-己烯、1-辛烯和1-癸烯)的共聚物。上文所述类型的APO聚合物可以以商品名EASTOFLEX™购自Eastman ChemicalCompany, Kingsport, Tennessee,或以商品名REXTAC™购自Huntsman Corporation,Houston, Texas,或以商品名VESTOPLAST™购自Degussa Corporation, Parsipanny, NewJersey。类似基于橡胶的胶粘剂,也使用增粘剂和增塑剂组合聚合物以产生PSA组合物,其可以涂布到载体层12上,或可以是可经层叠(夹制或挤出)到载体片材12上的预成形层14。参见例如Eastman bulletin “Pressure-Sensitive Adhesives Based on AmorphousPolyolefin From Eastman Chemical Company”。尽管不那么优选,沥青PSA材料,包括用橡胶和/或其它添加剂改性的组合物,也可以热熔涂布或作为预成形层层叠到载体层或片材上。
本发明的无机粒子层16包含一种或多种材料,如部分水化的水泥、水化的水泥、碳酸钙、水玻璃砂、砂、非晶二氧化硅、炉渣、三水合氧化铝、炉底灰、板岩灰、花岗岩灰等等。优选的颗粒包括水泥、部分水化的水泥和水化的水泥;而更优选的颗粒包括白水泥质粒子;且最优选的颗粒是水化的水泥质粒子。
如先前所讨论的那样,个别颗粒体的平均尺寸小于压敏胶粘剂(PSA)层16的平均厚度。微细无机粒子层16具有若干功能和优点,由于其应充分粘合至下方的PSA层14及上方的防潜纳米二氧化硅涂层18二者。此外,这些粒子保持膜10更冷,且阻隔破坏性UV暴露,由此最小化PSA层14的降解速率。粒子16还防止粘连,且消除了对可移除剥离衬垫(例如蜡纸或硅化纸)的需要——在安装期间移除剥离衬垫将生成废弃物以及额外的步骤。粒子(16)还可改善在安装期间膜10的抗滑性以及膜10的通行能力(对步行交通的耐久性)。
虽然在无机粒子层16中最优选使用水化或部分水化的白水泥颗粒,但使用相对于PSA层厚度而言相对较小的粒度并使用纳米二氧化硅涂层18以最小化粒子16的下潜(完全嵌入)对于其中其它无机材料(其并不如水化或部分水化的白水泥颗粒那样反光)可能更易得或更实际可用的区域提供更大的灵活性。
在本发明的其它示例性实施方案中,防潜涂层18可以进一步包含二氧化钛以改善防水膜10的总体反射率。膜表面的反射率可以用NOVO-SHADE™ 45/0反射计来测量。这涉及自45°角的测试表面的照明,以及相对于表面垂直(即0°)的散射光强度的测量。数据记录在其中黑色为0%且白色为100%的灰色标度上。仅测量明暗度而不考虑色彩,且此明暗度的值借助于“白度”来提及。在示例性实施方案中,无机粒子层16应优选具有大于或等于55%、更优选大于65%的光反射率。
根据本发明,无机粒子层16的个别粒子体的平均尺寸应小于PSA层14的平均厚度。典型的PSA层厚度为大约3至80密耳、更优选大约5至15密耳、最优选大约8至10密耳。水泥的粒度应优选为70(以便小于3密耳的最低胶粘剂厚度)至450 µm;而更优选的粒度为100 µm至250 µm;且最优选的粒度范围为120 µm至180 µm。作为实例,如果用于无机粒子层16中的话,则水化白色波特兰水泥粒子优选通过将白色波特兰水泥与水(使用0.22至0.5 W/C的水/水泥(W/C)比率)与聚合物水泥分散剂混合,并通过使水泥固化(优选七天或更多天),接着通过研磨并筛分以实现合适的粒度范围来制得。优选的水泥分散剂是聚羧酸类(polycarboxylate)聚合物水泥分散剂。最优选的是含有环氧乙烷的聚羧酸类,如由W. R.Grace & Co.-Conn.的业务单位Grace Construction Products, 62 Whittemore Avenue,Cambridge, Massachusetts 02140(USA)以ADVA®和ADVA® 120出售的那些。所用分散剂含量可以是基于干水泥计0.1%至1%的活性表面活性剂。
水化白水泥粒子还可以根据所需性质使用一种或多种化学混合物来制备。将该混合物与白水泥和水共混。用于本发明的各种混合物可以包含常规用于实现以下性质的那些:(1)增强膜对混凝土的粘合;(2)加速初凝的时间;(3)加速在早期阶段的强度发展(水泥的固化或硬化)的速率;(4)提高成品材料的强度(压缩强度、抗张强度或挠曲强度);(5)减少水在该材料内的毛细流动;(6)降低材料对液体的渗透性;和/或(7)抑制嵌入金属的腐蚀,如用于保护混凝土基体内的钢筋或其它结构。
最后,如先前所讨论的那样,本发明的防水膜10包含至少一个防潜涂层18,其用于固定或保护微细无机粒子层16以辅助由施加者在相邻防水膜10之间的重叠处建立水密接缝。在一个优选实施方案中,防潜涂层18包含至少一种成膜聚合物乳液粘合剂、纳米级二氧化硅粒子、和任选添加剂(包括光阻隔剂、二氧化钛、光吸收剂、粘度改性剂或其它添加剂)。将通常在水性介质中的胶乳乳液施加至微细颗粒层16的表面以提供乳液涂层,其涂布粒子并至少部分浸渍微细粒子之间的间隙,并在固化时稳定结构。合适的乳液形式的聚合物树脂可以包括丙烯酸系树脂、聚乙酸乙烯酯、丙烯酸酯/苯乙烯共聚物、丙烯酸酯/乙酸乙烯酯共聚物、氯丁二烯(橡胶)、丁基橡胶、苯乙烯-丁二烯共聚物、SEBS及其混合物。聚乙酸乙烯酯和丙烯酸系树脂是优选的。
纳米级二氧化硅溶胶通常具有0.1至100纳米(nm)、优选1至50 nm和更优选5至30nm的粒度。由于其小的粒度,胶体二氧化硅溶胶在水基涂料配制品中可以起到多种作用。已经发现非晶纳米级二氧化硅提供防水膜10与对膜浇注的混凝土之间的良好粘合。
本发明的这种复合益处是预料不到的,因为防潜涂层极硬。由于这样的硬表面的渗透接近0,所以难以精确测量该值;因此,本发明人使用肖氏D硬度作为更适用的测量,代替使用渗透作为硬度的量度。如下文中进一步描述的那样,根据ASTM D 2240-00在环境温度(23℃)下测量肖氏D硬度。浇注防潜涂层的样品。该试样为大约9-10毫米厚,并具有6-7厘米的直径。将该试样置于平坦水平表面上。将硬度计保持在垂直位置处,压头尖端置于距边缘至少12毫米。施加足够的压力以确保压脚与试样之间的接触。在压脚与试样接触一秒后,记录所示读数。进行五次测量,并计算平均硬度值。
粘合强度是优异的,即使在膜已经浸入水中之后也是如此。为了测试这种有利性质,本发明人对本发明的膜10的条带浇注混凝土并使混凝土固化七天。然后将该组装件浸入水中30天。测量一段水浸期之后膜10与混凝土之间的粘合,并与未浸入水中的组装件的粘合进行比较,且发现粘合极好。不受理论的束缚,本发明人相信,非晶纳米级二氧化硅粒子在碱性环境中形成水化产物(如在含有波特兰水泥的混凝土中发现的那样)。非晶纳米级二氧化硅粒子还提高了涂层表面的摩擦系数,这增强了抗粘连性以及抗滑性。
本发明的防水膜10中的优选防潜含纳米二氧化硅涂层18可以通过采用具有小粒度、低粘度且含有100%丙烯酸系聚合物胶乳的丙烯酸系乳液来制得。涂层18由具有以下性质的丙烯酸系胶乳形成:对变色的抗性、对经时膜降解的抗性、对粘性的抗性、10-20℃和更优选10-30℃的玻璃化转变温度。所得涂层是柔性的防水涂层,其往往强化无机粒子层16,保护其免受水、油脂、粗糙处理的侵害。所得涂层应优选在折叠并经受向上延伸至70℃的温度时不会粘合至其自身。低粘度丙烯酸系乳液使其易于通过合适的手段(如喷涂、刷涂、辊轧等等)施加至微细无机粒子16。应当控制所施加的胶乳的量以实现良好的覆盖并同时避免损害涂层品质。
用于膜10的膜涂层18的另一优选聚合物乳液涂料是聚乙酸乙烯酯乳液,其提供了优异的成膜、粘附和粘合能力。使用聚乙酸乙烯酯乳液的其它益处包括良好的颜色稳定性和对氧及紫外线的良好稳定性,其进而导致对外部暴露的良好抗性、对油脂和油的优异抗性、对大多数基底的良好粘附、以及当接触酸性材料或多价离子时良好的乳液稳定性。
如先前所述,本发明的膜10的一个或多个防潜涂层18进一步包含纳米二氧化硅粒子;并且在优选实施方案中,将纳米二氧化硅粒子与一种或多种前述成膜聚合物粘合剂共混。纳米级二氧化硅粒子通常具有0.1至100纳米(nm)、优选1至50 nm和更优选5至30 nm的粒度。由于其小的粒度,纳米二氧化硅粒子在水基涂料配制品中可以起到多种作用。已经发现非晶纳米级二氧化硅提供防水膜10与对膜浇注的混凝土之间的良好粘合,即使在膜已经浸入水中之后也是如此。
本发明的其它示例性防水膜10可以包含两个或更多个按顺序施加的防潜纳米二氧化硅涂层(18),各涂层包含含有纳米二氧化硅的成膜聚合物乳液以便额外易于在相邻膜10之间形成水密重叠。例如,在采用两个或更多个膜涂层18以涂覆膜10的水泥颗粒层16的情况下,优选位于最外层的膜涂层18(即距离无机粒子层16最远的层)具有较高的成膜聚合物:纳米二氧化硅比率(按重量计)。最外层的涂层18应在外涂层表面上具有最少的灰尘(因为灰尘往往会阻碍或破坏膜之间的重叠处的水密接缝)。因此,进一步的实施方案包含至少两个防潜含纳米二氧化硅涂层(18),其中最外一层含有较高的成膜聚合物:纳米二氧化硅比率(按重量计)。
各个膜涂层18中的成膜聚合物:纳米二氧化硅比率以及干膜覆盖物重量取决于成膜聚合物或所用聚合物共混物以及用于制造涂料组合物18的商业纳米二氧化硅产品的性质。本发明的膜10的示例性涂层18的成膜聚合物与纳米二氧化硅的比率(聚合物:纳米二氧化硅)应优选为基于重量百分比(干燥固体)计1:4至4:1,取决于所用聚合物乳液和纳米二氧化硅的性质。干涂层重量应优选为每平方米5-20克,更优选每平方米8-15克。
由此,在一个示例性实施方案中,防水膜具有防潜涂层18,其包含作为至少一种成膜聚合物的聚乙酸乙烯酯(PVAc)和纳米二氧化硅粒子,其中优选的PVAc:纳米二氧化硅比率为1:1至1:4。在另一示例性实施方案中,防水膜具有防潜涂层18,其包含作为至少一种成膜聚合物的丙烯酸系聚合物和纳米二氧化硅粒子,其中优选的丙烯酸系聚合物(acrylic):纳米二氧化硅比率为4:1至1:1,基于干重量固体计。
为了进一步改善防潜涂层18和/或PSA层14的白度和日光阻隔性质,可以添加白色颜料。对于外部涂层18,优选的白色颜料包括二氧化钛、氧化锌、三氧化铝、硫化锌、锌钡白等等。更优选可以使用金红石二氧化钛颜料。优选的金红石二氧化钛颜料可以以商品名Ti-Pure® R-960获自DuPont。为了在膜涂布组合物中分散白色颜料,可以使用分散剂。合适的分散剂可以以商品名Nuosperse™ FN211获自Elementis Specialties。
如先前所述,可以将UV吸收剂添加到防水膜中以提供保护免于UV降解,如在防潜涂层18和/或PSA层14中。此外,一种或多种光稳定剂可以与一种或多种UV吸收剂一起添加以改善防护。市售UV吸收剂的一个实例由Double Bond Chemical Ind. Co. Ltd以商品名Chisorb™ 5392E出售,其据信是一种与HALS(受阻胺光稳定剂)共混的用于涂料的液体UV吸收剂。这是一种不含溶剂的水性UV吸收剂乳液。其在室温下为液体形式,这与苯并三唑UV吸收剂相比有助于处理,并且其提供了宽的UV吸收。另一种优选的水溶性UV吸收剂是由ISPTechnologies, Inc.以商品名Escalol™ 577供应的二苯甲酮-4宽带UV滤光剂。
优选的本发明的防水膜包含:包含两个主面的载体层;如限定在两个主面之间的平均厚度为0.05至2.0 mm的压敏胶粘剂层,所述两个主面之一附着至载体层主面之一,压敏胶粘剂层进一步具有如根据ASTM D 5-73测得的大于 30 丝米(dmm)的渗透(150克,5秒,70℉),所述压敏胶粘剂包含丁基橡胶胶粘剂、聚异丁烯胶粘剂、丁基胶粘剂、丙烯酸系胶粘剂、苯乙烯-异戊二烯-苯乙烯(SIS)胶粘剂、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)胶粘剂、苯乙烯-丁二烯-苯乙烯(SBS)胶粘剂、苯乙烯-丁二烯橡胶(SBR)胶粘剂或其组合;包含平均尺寸为70 µm至450 µm的个别颗粒体的无机粒子层,无机粒子层通过将颗粒体部分嵌入压敏胶粘剂层的第二主面(与附着至载体层的主面相对)来形成,由此颗粒体的一部分保持未浸没,所述个别颗粒体包含部分水化的水泥、水化的水泥、碳酸钙、水玻璃砂、砂、非晶二氧化硅、炉渣、三水合氧化铝、炉底灰、板岩灰、花岗岩灰或其混合物;以及平均厚度为0.003至0.011 mm的防潜涂层,其附着至无机颗粒体的未浸没部分以防止在膜卷起或展开时个别颗粒体完全嵌入压敏胶粘剂层内,该涂层通过用包含纳米二氧化硅粒子和至少一种成膜聚合物的乳液涂布无机粒子层并允许涂层在未浸没的个别颗粒体上干燥来形成,该涂层在干燥后具有根据ASTM D 2240-00在23℃下测得的50-90、更优选60-90和最优选70-90的肖氏D硬度,所述至少一种成膜聚合物材料选自丙烯酸系聚合物、聚乙酸乙烯酯、丙烯酸酯/苯乙烯、丙烯酸酯/乙酸乙烯酯、氯丁二烯(橡胶)、丁基橡胶、苯乙烯-丁二烯、SEBS或其混合物;并且其中至少一种成膜聚合物材料与纳米二氧化硅粒子的比率就干膜涂层重量而言为1:4至4:1(基于干重量固体计)。
本发明提供了制造防水膜的示例性方法。可以使用辊式涂布机、槽模涂布机或幕帘涂布机将PSA热熔涂布到载体上。还可以由载体/PSA层叠体(12/14)开始,并且在PSA变热并软化时,使用平均粒子厚度或粒径小于PSA层14的平均厚度的粒子将无机颗粒体16嵌入PSA层14中以生成无机粒子层16。应当使用重力、真空、拂试或其组合从粒子层16中移除松散粒子,并在部分嵌入的无机粒子层16上形成防潜纳米二氧化硅层,优选通过用包含至少一种成膜聚合物和纳米二氧化硅粒子的水性乳液涂布。在进一步的示例性方法中,将至少一个聚合物涂层干燥,且在不使用可移除的剥离片材的情况下将所得防水膜卷绕成卷。
虽然在本文中使用有限数量的实施方案描述了本发明,这些具体实施方案并非意在限制本文中以其它方式描述和要求保护的本发明的范围。存在所述实施方案的修改和变化。更具体而言,给出以下实施例作为所要求保护的发明的实施方案的具体说明。应当理解的是,本发明不限于实施例中所阐述的具体细节。除非另行规定,否则实施例中以及说明书剩余部分中的所有份数和百分比按重量百分比计。
此外,说明书或权利要求书中所列举的任何数字范围,如代表特定的一组性质、量度单位、条件、物理状态或百分比的数字范围,意欲在字面上通过引用或以其它方式将落在该范围内的任何数字(包括在如此列举的任何范围内的数字的任何子集)明确并入本文中。例如,每当公开具有下限RL和上限RU的数值范围时,均明确公开了落在该范围内的任何数字R。具体而言,明确公开了在该范围内的以下数字R:R = RL + k*(RU -RL),其中k在1%至100%范围内以1%增量可变,例如k为1%、2%、3%、4%、5%……50%、51%、52%……95%、96%、97%、98%、99%或100%。此外,还明确公开了由任何两个R值(如上文中所计算的那样)代表的任何数值范围。
实施例1
本发明的防水膜可以通过以下方式生成:用10密耳厚度的合成压敏(PSA)胶粘剂(如SEBS、SBS、SIS、SBR等等,其用于制造PSA层)的涂层涂布例如包含30密耳高密度聚乙烯(HDPE)的载体片材。包含SIS聚合物的PSA是优选的。
将胶粘剂涂布的片材置于70℃下的空气循环烘箱中一小时以软化PSA层,然后通过使用压辊将微细无机粒子嵌入PSA中,在PSA层的面上生成微细无机颗粒层。
然后将膜放回烘箱中大约30分钟,并在PSA层的面上分散更多微细粒子,并再次使用压辊将粒子嵌入PSA层的面中以确保微细颗粒物质在PSA层上的良好覆盖。可以通过轻轻拂试来移除过量的松散颗粒。
最后,将包含水性聚合物乳液和纳米二氧化硅的防潜纳米二氧化硅涂层喷涂到无机粒子层上至所需的湿涂层重量。使聚合物乳液防潜纳米二氧化硅涂层在环境温度下干燥。
通过遵循这样的过程,制得四层防水膜,其包含HDPE载体片材(12)、防水压敏胶粘剂(14)、微细无机粒子层(16)和至少一个防潜纳米二氧化硅涂层(18)。
实施例2
可以如下使用在防水膜上的各种测试程序。
测试对后施加混凝土的粘合.由于在(对膜)后施加混凝土之前通常使防水膜暴露于日光,因此高度合意的是此类膜在这样的暴露后保持其充分粘附至混凝土的能力。膜对混凝土的粘附通过以下方式来测试:对1.5英寸×6英寸(3.8厘米×15厘米)膜样品的外面浇注混凝土,使混凝土固化七天,然后用Instron™机械测试仪以180°的剥离角和每分钟4英寸(100毫米)的剥离速率测量剥离粘附性。针对未暴露于UV辐射(初始)的样品和针对浇注混凝土之前暴露于UV辐射的样品测量对混凝土的粘合强度,其中UV暴露采用EMMAQUA加速测试,其中暴露相当于一个月UV暴露(28 mj)或两个月UV暴露(56 mj)的当量。
端部搭接粘合性能(初始粘合和长期水浸).使用双面胶带粘合卷末端以形成连续防水(如果纵向折叠的话可以使用单面胶带,但是这在实际构建工作期间需要额外的时间,并且不那么优选)。膜的卷末端重叠最少75毫米。施加双面胶带并将胶粘剂侧固定在底部膜的重叠区域上。紧密地卷起以确保完全粘附而不具有摺痕或空隙。剥离双面胶带另一侧的离型纸,并将第二片膜施加至胶粘带。紧密地卷起以确保完全粘附。T-剥离测试用于测定24小时固化后端部搭接的粘合性能,剥离速度为100毫米/分钟。长期水浸(即一个月)末端搭接粘合样品以检查水是否渗透到末端搭接中并使粘合性能降级。
测试抗粘连性测试.由于防水膜通常卷绕成卷,因此高度合意的是确保膜的一个表面不会强力地粘附至膜的另一表面。否则,将难以展开该卷。为了测试抗粘连性,将一层30密耳(0.75毫米)的HDPE膜置于2.0英寸×6.0英寸膜样品的外表面上,将3磅/平方英寸(psi)的负载置于顶部上;然后将该组装件置于65℃下的烘箱中1周。在冷却至室温后,用T-剥离测试使用Instron™机械测试仪采用每分钟4英寸的十字头速度来测试各样品。粘连经测量为磅/线性英寸(pli)。
测试水浸测试.由于防水膜在对混凝土浇注后可能浸入水中,因此高度合意的是此类膜在这样的水暴露之后保持其粘附至混凝土的能力。已经设计了极为严格的测试来说明本发明的膜的异常性能。通过以下方式测试防水膜至混凝土的粘附:对尺寸为1.5英寸×6英寸(3.8厘米×15厘米)的膜样品的外面浇注混凝土,使混凝土固化七天,将该膜/混凝土组装件浸入水中90天;然后用Instron™机械测试仪以180°的剥离角和每分钟100毫米的剥离速率测量剥离粘附性。水可以在组装件的任何界面之间浸润,包括混凝土/防潜涂层界面、防潜涂层/颗粒层界面、或颗粒层/压敏胶粘剂层界面。该测试被认为是严格的,因为在膜的正常使用中,这些界面将不会暴露于水的浸润。
LT柔性测试.为了测试低温下的柔性,在防水膜上实施以下测试。将样品(50毫米×100毫米)的外面弯曲180度,使得膜样品的边缘沿其宽度尺寸(50毫米)重叠;边缘用平头夹或订书钉或10毫米宽胶带固定。弯曲仪器应当在顶板与底板之间具有试样厚度三倍的距离。在弯曲装置的顶板和底板打开的情况下,将膜样品平坦放置到底板上,经固定的重叠侧朝向轴,并且样品与轴之间的距离为20毫米。将弯曲装置与样品一起放入保持在-25℃温度下的冷室中1小时(或2小时),然后将顶板压向底板1秒至经调整的间距,然后从装置上移除样品。在样品回到室温后,观察弯曲样品以检测其在弯曲区域上是否破损或持续开裂。
抗横向水迁移性测试.抗横向水迁移性是防止水在盲测(blind side)防水系统与混凝土结构之间移动。如果在混凝土安置之前或期间,防水系统被钢筋或其它锋利物体刺穿(这会生成撕裂或空隙),则水可能穿过防水系统。如果水在防水膜系统与混凝土之间自由地横向行进,那么水将寻得其进入建筑物的途径。防止防水膜与地基之间的横向水迁移的防水系统对于保持建筑物内部干燥而言是至关重要的。在样品中心处准备一个10毫米直径的孔以模拟防水膜的破口。将混凝土浇注到膜上并使其固化7天,随后进行静水压头压力测试。将压力在58磅/平方英寸(psi)下保持24小时(h),随后在72 psi下保持4小时,且在87psi下保持4小时。横向水迁移测试结果报告为[通过/失败];通过定义为实现最终压力步骤时;失败定义为水穿过试样漏出,或水存在于膜与混凝土之间。
热老化测试:将三个100毫米×50毫米膜样品垂直悬挂于保持在70℃温度下的烘箱中2小时,样品之间的最小间距大于30毫米。在测试后,取出样品并观察在膜样品上是否出现任何滑移(slip)、凹陷或液滴。
关于本发明的两种示例性防水膜的各种测试结果显示在下表1中。使用SIS制造压敏胶粘剂(PSA)层。在该膜之一者中,膜涂层由包含丙烯酸系聚合物作为成膜聚合物结合纳米二氧化硅的水性乳液制得。在第二膜中,膜涂层由包含聚乙酸乙烯酯作为成膜聚合物结合纳米二氧化硅的水性乳液制得。
表1
两种配制品均表现出优异的对混凝土的初始粘合、在UV暴露后对混凝土的粘合、非常好的防粘连性、且在三个月水浸后良好地保持了对混凝土的粘合。两种配制品均显示出良好的末端搭接粘合强度,且在一个月水浸后保持了末端搭接粘合。将水浸后的末端搭接粘合样品剥离,界面是干燥的。两种配制品均显示出优异的低温和高温稳定性,且在0.6MPa水渗透测试后没有发生水渗透。
实施例3
如上文所述,对包含聚乙酸乙烯酯乳液和纳米二氧化硅的配制品以及对包含丙烯酸系乳液和纳米二氧化硅的配制品进行渗透测量。对于这些实施方案中的每一个,一方面相对于聚乙酸乙烯酯(PVAc)和丙烯酸系聚合物且在另一方面相对于纳米二氧化硅分析干燥聚合物与纳米二氧化硅的比率对肖氏D的影响。结果总结在下表2中。
表2
本发明的原理、优选实施方案和操作模式已经在前述说明书中予以描述。但是,意欲在本文中受保护的本发明不应解释为受限于所公开的特定形式,因为这些应视为说明性的而非限制性的。本领域技术人员可以在不背离本发明的精神的情况下作出变化和改变。
Claims (25)
1.用于后浇注混凝土应用的防水膜,其包含:
包含两个主面的载体层;
如限定在两个主面之间的平均厚度为0.05至2.0 mm的压敏胶粘剂层,所述两个主面之一附着至载体层主面之一,所述压敏胶粘剂层进一步具有如根据ASTM D 5-73测得的大于30 丝米(dmm)的渗透(150克,5秒,70℉);
包含平均尺寸为70 µm至450 µm的个别颗粒体的无机粒子层,所述无机粒子层通过将所述颗粒体部分嵌入所述压敏胶粘剂层的第二主面(与附着至载体层的主面相对)来形成,由此所述颗粒体的一部分保持未浸没;和
平均厚度为0.003至0.011 mm的防潜涂层,其附着至无机颗粒体的未浸没部分以防止在所述膜卷起或展开时个别颗粒体完全嵌入所述压敏胶粘剂层内,所述涂层通过用包含纳米二氧化硅粒子和至少一种成膜聚合物的乳液涂布所述无机粒子层并允许所述涂层在未浸没的个别颗粒体上干燥来形成,所述涂层在干燥后具有根据ASTM D 2240-00在23℃下测得的50-90的肖氏D硬度。
2.权利要求1的防水膜,其中所述载体层包含聚合物膜、织物或二者。
3.权利要求2的防水膜,其中所述载体层包含高密度聚乙烯(HDPE)膜。
4.权利要求2的防水膜,其中所述载体层包含织造或非织造织物,其包含聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚酰胺或其混合物。
5.权利要求2的防水膜,其中所述载体层是织造聚丙烯织物。
6.权利要求2的防水膜,其中所述压敏胶粘剂层包含沥青或合成胶粘剂或其组合。
7.权利要求2的防水膜,其中所述压敏胶粘剂层包含丁基橡胶胶粘剂、聚异丁烯胶粘剂、丁基胶粘剂、丙烯酸系胶粘剂、苯乙烯-异戊二烯-苯乙烯(SIS)胶粘剂、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)胶粘剂、苯乙烯-丁二烯-苯乙烯(SBS)胶粘剂、苯乙烯-丁二烯橡胶(SBR)胶粘剂或其组合。
8.权利要求2的防水膜,其中所述压敏胶粘剂层包含SIS、SBS或SEBS的嵌段共聚物。
9.权利要求2的防水膜,其中所述合成压敏胶粘剂层进一步包含光吸收剂、光稳定剂、抗氧化剂或其混合物。
10.权利要求2的防水膜,其中所述无机颗粒层包含部分水化的水泥、水化的水泥、碳酸钙、水玻璃砂、砂、非晶二氧化硅、炉渣、三水合氧化铝、炉底灰、板岩灰、花岗岩灰或其混合物的个别颗粒体。
11.权利要求10的防水膜,其中所述无机颗粒体包含水化的水泥、部分水化的水泥或其混合物。
12.权利要求10的防水膜,其中水化或部分水化的白水泥粒子通过将白色波特兰水泥与水和聚羧酸类聚合物水泥分散剂混合来制造。
13.权利要求2的防水膜,其中所述防潜纳米二氧化硅涂层通过用水性乳液涂料涂布无机颗粒体的未嵌入部分来形成,所述水性乳液涂料包含(i)胶体二氧化硅和(ii)至少一种选自丙烯酸系聚合物、聚乙酸乙烯酯、丙烯酸酯/苯乙烯、丙烯酸酯/乙酸乙烯酯、氯丁二烯(橡胶)、丁基橡胶、苯乙烯-丁二烯、SEBS或其混合物的成膜聚合物材料。
14.权利要求13的防水膜,其中,在所述防潜纳米二氧化硅涂层中,至少一种成膜聚合物材料与纳米二氧化硅粒子的比率就干膜涂层重量而言为1:4至4:1,基于干重量固体计。
15.权利要求14的防水膜,其中所述载体层包含HDPE膜;所述压敏胶粘剂层选自SEBS、SBS、SIS或其混合物;所述无机粒子层包含水化的白水泥粒子;并且所述防潜纳米二氧化硅涂层包含丙烯酸系聚合物、聚乙酸乙烯酯聚合物或其混合物。
16.权利要求14的防水膜,其中所述防潜纳米二氧化硅涂层包含聚乙酸乙烯酯聚合物,并且聚乙酸乙烯酯聚合物与纳米二氧化硅的比率就干重量固体而言(PVAc:纳米二氧化硅)为1:1至1:4。
17.权利要求14的防水膜,其中所述防潜纳米二氧化硅涂层包含丙烯酸系聚合物,并且丙烯酸系聚合物与纳米二氧化硅的比率就干重量固体而言(丙烯酸系聚合物:纳米二氧化硅)为4:1至1:1。
18.权利要求15的防水膜,其在所述压敏胶粘剂或层、所述防潜纳米二氧化硅涂层、或在两层中,进一步包含二氧化钛、氧化锌、三氧化铝、硫化锌、锌钡白或其混合物中的至少一种。
19.权利要求1的防水膜,其中以卷起形式提供所述膜,其可以展开并施加至建筑物或构造体表面上,而无需剥离片材。
20.权利要求1的防水膜,其与至少一个相同构造的其它防水膜重叠,并仅使用细化或防水带在重叠膜之间形成防水密封,而无需额外使用附加的液体底漆、胶合辅料或其它涂料。
21.权利要求1的防水膜,其中当在与测试表面呈45°角的入射光下使用反射计测量时,所述防水膜具有至少55%的表面反射率。
22.制造整体膜层的方法,其包括:安装根据权利要求1所述的第一防水膜,其载体层相对于基底;和安装根据权利要求1所述的第二防水膜,其载体层相对于先前安装的防水膜的防潜纳米二氧化硅涂层;和在第二防水膜的载体层与第一安装的防水膜的防潜含纳米二氧化硅涂层之间,使用细化或防水带,在第一防水膜与第二防水膜的重叠部分之间防水密封。
23.权利要求22的方法,其中在所述膜之间的防水密封仅使用细化或防水带来实现,而无需额外使用附加的液体底漆、胶合辅料或其它涂料。
24.制造防水膜的方法,其包括:
提供附着至载体层的压敏胶粘剂(PSA)层;
当PSA处于热软化状态时,将平均粒度小于所述PSA层的平均厚度的个别颗粒体部分嵌入所述PSA层中,由此生成部分嵌入的无机粒子层;
借助于重力、真空、拂试或其组合将松散的个别颗粒体从部分嵌入的无机粒子层中移除;和
通过将包含胶体二氧化硅和至少一种成膜聚合物的水性乳液涂布到所述无机粒子层的未嵌入部分上来形成防潜含纳米二氧化硅涂层,所述成膜聚合物选自丙烯酸系聚合物、聚乙酸乙烯酯、丙烯酸酯/苯乙烯、丙烯酸酯/乙酸乙烯酯、氯丁二烯(橡胶)、丁基橡胶、苯乙烯-丁二烯、SEBS及其混合物,当根据ASTM D 2240-00在23℃下测量时,所述防潜层在干燥后具有50-90的肖氏D硬度。
25.权利要求24的方法,其中使防潜含纳米二氧化硅涂层干燥,并且在不使用可移除的剥离片材来允许展开的情况下将所得的防水膜卷绕成卷。
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TW201718799A (zh) | 2017-06-01 |
BR112018006559B1 (pt) | 2021-07-13 |
BR112018006559A2 (pt) | 2018-10-16 |
MX2018003815A (es) | 2018-11-09 |
EP3356612B1 (en) | 2020-12-23 |
WO2017058154A1 (en) | 2017-04-06 |
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