CN114728494A - 具有高表面粗糙度的密封装置 - Google Patents
具有高表面粗糙度的密封装置 Download PDFInfo
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- CN114728494A CN114728494A CN202080078144.2A CN202080078144A CN114728494A CN 114728494 A CN114728494 A CN 114728494A CN 202080078144 A CN202080078144 A CN 202080078144A CN 114728494 A CN114728494 A CN 114728494A
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- functional layer
- sealing device
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- waviness
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Abstract
本发明涉及包含具有第一主表面和第二主表面的功能层(2)和与功能层(2)的第二主表面直接或间接连接的阻挡层(3)的密封装置,其中功能层(2)具有由波度因子Wf表征的表面粗糙度。本发明还涉及生产密封装置的方法和密封装置用于基材防水的用途。
Description
技术领域
本发明涉及用于在建筑工业中使用的密封装置,用于地下或地上建筑结构的防水。特别地,本发明涉及密封装置,其可用于使地下室、屋顶和隧道结构免受水渗透。
背景技术
在建筑领域中,使用常被称作膜或板的聚合物片材来使地下和地上建筑例如地下室、隧道和屋顶免受水渗透。应用防水膜例如来防止水通过由于建筑沉降、载荷挠曲或混凝土收缩所致在混凝土结构中逐渐形成的裂纹侵入。屋顶膜用于平的和低斜坡屋顶结构的防水。现有技术的防水和屋顶膜是包含至少一个基于聚合物的阻挡层来提供水密性的单层或多层系统。
阻挡层常使用的材料包括塑料,特别是热塑性塑料例如增塑的聚氯乙烯(p-PVC)、热塑性聚烯烃(TPO)和弹性体例如乙烯-丙烯二烯单体(EPDM)。热塑性聚烯烃是含有高结晶度基础聚烯烃和低结晶度或无定形的聚烯烃改性剂的多相聚烯烃组合物。基于交联的EPDM的膜是非常柔性的并耐候的,但它们由于化学交联的结构所致不可热焊接。由TPO组成的膜可热焊接并比EPDM-膜更昂贵,但是它们还稍微更具刚性,这在一些应用中会是缺点。基于增塑PVC的膜比TPO膜更具柔性,但是它们含有环境有害的增塑剂和重金属添加剂例如阻燃剂,这会限制它们在一些应用中的使用。
在防水应用中,可将膜后施加至现有的混凝土结构或在建筑待防水的混凝土结构之前预先施加。在第一种情况下,将膜通过胶黏剂层或通过使用密封带粘附至待防水的混凝土结构的表面。在预先施加的防水应用中,将膜放置成它的阻挡层面向在下面的结构或模板的表面,然后将新鲜混凝土浇注在膜的相对表面的表面上,从而使膜完全且永久地与硬化混凝土的表面结合。
基于聚合物的阻挡层的众所周知的缺点之一是它们的差的结合性质;它们通常显示与在建筑工业中常使用的胶黏剂例如环氧胶黏剂、聚氨酯胶黏剂和水泥基组合物的低结合强度。因此,通常使用接触层例如羊毛毡以改进基于聚合物的阻挡层与待防水结构的结合。一些用于预先施加防水应用的可商购得到的膜包含阻挡层和无纺织物层作为接触层,其通过胶黏剂层粘附至阻挡层。使用胶黏剂层来固定接触层与阻挡层,但也能够改进阻挡层和浇注在接触层上的新鲜混凝土之间的结合。然而,胶黏剂层的存在提高这些类型的防水膜的生产成本和通常为羊毛的无纺织物层实际上防止在膜的重叠边缘之间通过热焊接形成的接缝的密封。
专利申请WO2017/108843A1公开包含基于聚合物的阻挡层和由热塑性聚合物组合物组成的接触层的防水膜,所述热塑性聚合物组合物包含大量的无机填料例如无机粘合剂。可通过共挤出阻挡层和功能层的熔融加工的组合物和例如使用压延冷却辊彼此结合如此获得的层来生产防水膜。WO2017/108843A1中公开的防水膜当混凝土浇注在接触层的表面上并在正常大气条件下使其硬化28天时在预先施加的防水应用中提供与混凝土的高粘附强度。尽管在硬化之后与新鲜混凝土建立高结合强度,还发现了WO2017/108843A1的防水膜提供对浇注混凝土的不是最佳的早期粘附强度即获得的粘附强度,使浇注混凝土在正常大气条件下硬化一天。与浇注混凝土的低的早期粘附强度可导致预先施加的防水膜脱离,因为通常在浇注混凝土的硬化24小时之后去除混凝土结构的浇注中使用的模板例如底板。
因此需要新型的防水膜,其在预先施加的防水应用中与浇注在膜表面上的新鲜混凝土建立高的早期粘附强度。
发明概述
本发明的目的是提供密封装置,其例如在地下室防水、屋顶和隧道应用中可用于使表面免受水渗透,并在硬化之后与浇注至密封装置上的混凝土和其它水泥基组合物完全且永久地结合,以及提供在建筑工业中常使用的胶黏剂。
本发明的另一目的是提供密封装置,其在一天的硬化之后建立与浇注在密封装置表面上的混凝土和其它水泥基组合物的高的早期粘附强度。
令人惊讶地发现了包含阻挡层和基于高度填充的热塑性聚合物组合物的功能层并具有高表面粗糙度的密封装置在硬化之后提供与浇注在功能层表面上的混凝土的高的早期粘附强度。
本发明的主题是根据权利要求1的密封装置。
本发明的密封装置的优点之一在于可在24小时的硬化之后在没有密封装置从浇注的混凝土体的垂直表面脱离的风险的情况下去除模板。
本发明的密封装置的另一优点在于可通过使用现有技术泡沫挤出工艺来实现提高的表面粗糙度,其与通过共挤出在没有使用发泡气体的情况下生产的现有技术密封装置相比,容易实施并且没有明显提高密封装置的生产成本。
本发明的其它主题呈现在其它独立权利要求中。本发明的优选方面呈现在从属权利要求中。
附图简要描述
图1显示本发明的包含具有第一和第二主表面的功能层(2)和与功能层(2)的第二主表面直接连接的阻挡层(3)的密封装置(1)的横截面。
图2显示本发明的包含第一功能层(2)、第二功能层(2’)和阻挡层(3)的密封装置(1)的横截面,其中阻挡层(3)的第一主表面与第一功能层(2)的第二主表面直接连接和阻挡层(3)的第二主表面与第二功能层(2’)的第一主表面直接连接。
发明详述
本发明的主题是包含具有第一主表面和第二主表面的功能层(2)和与功能层(2)的第二主表面直接或间接连接的阻挡层(3)的密封装置(1),功能层(2)包含:
a)20–75重量%、优选25–70重量%的至少一种热塑性聚合物P1和
b)25–80重量%、优选30–75重量%的至少一种固体填料F,所有比例基于功能层(2)的总重量,其中
功能层(2)的第一主表面具有由至少0.0125 1/mm、优选至少0.0135 1/mm、更优选至少0.0145 1/mm的波度因子Wf表征的表面粗糙度,所述波度因子Wf作为波度的均方根粗糙度WSq和波度的峰密度WSpd的乘积确定,其中波度参数WSq和WSpd根据ISO 25178标准由使用截止长度λc为0.8mm的测量横截面曲线获得的波度曲线测定。
术语“聚合物”是指由聚合反应(聚合、加聚、缩聚)产生的化学上均匀的大分子集合,其中大分子在它们的聚合度、分子量和链长度方面不同。该术语还包含由聚合反应产生的所述大分子集合的衍生物,即通过预定大分子中官能团的反应例如加成或取代获得的化合物,其可以是化学上均匀或化学上不均匀的。
术语“热塑性”是指可在物理性质很少或没有改变的情况下熔融和再凝固的任何聚合物材料。
术语“分子量”是指分子或分子的一部分(也称作“结构部分”)的摩尔质量(g/mol)。术语“平均分子量”是指分子或结构部分的低聚物的或聚合物的混合物的数均分子量(Mn)。可通过常规方法,优选通过凝胶渗透色谱法(GPC)使用聚苯乙烯作为标准、具有100埃、1000埃和10000埃孔隙度的苯乙烯-二乙烯基苯凝胶作为柱和四氢呋喃作为溶剂在35℃的温度下测定分子量。
术语“玻璃化转变温度”(Tg)是指高于该温度聚合物组分变软且柔韧,并且低于该温度聚合物组分变硬且玻璃状的温度。玻璃化转变温度(Tg)优选通过动态力学分析(DMA)测定,为使用1Hz的施加频率和0.1%的应变水平所测量损耗模量(G″)曲线的峰。
术语“软化点”是指化合物软化为橡胶状状态的温度或化合物内结晶部分熔融的温度。软化点可通过根据DIN EN 1238标准进行的环球测量法测定。
术语“熔融温度”是指材料经历从固态至液态转变的温度。优选通过差示扫描量热法(DSC)根据ISO 11357标准使用2℃/min的加热速率来测定熔融温度(Tm)。测量可使用Mettler Toledo DSC 3+装置进行并且Tm值可由测量的DSC曲线借助DSC软件确定。如果测量的DSC曲线显示几个峰温度,则在热谱图中来自较低温度侧的第一峰温度取为熔融温度(Tm)。
组合物中“至少一种组分X的量或含量”,例如“至少一种热塑性聚合物P1的量”是指组合物中含有的所有热塑性聚合物P1的各个量之和。例如,如果组合物包含20重量%的至少一种热塑性聚合物P1,则组合物中含有的所有热塑性聚合物P1的量之和等于20重量%。
术语“正常室温”是指23℃的温度。
功能层和阻挡层优选是具有长度和宽度是元件的最大厚度的至少5倍、优选至少25倍、更优选至少50倍的片状元件。术语“主表面”在本公开内容中是指片状元件的顶和底表面,其限定在它们之间元件的厚度。
在防水应用中,最重要的特性之一是粘附强度,通过该粘附强度将膜结合至待密封的基材例如混凝土表面,从而密封防止水渗透。如果粘附强度过低,气体更容易在膜和基材的表面之间形成,这可导致水密性的损失。
已经发现了在预先施加的防水应用中,其中在形成待防水的混凝土结构之前施加本发明的密封,可通过提高在其上浇注新鲜混凝土的功能层的表面粗糙度,明显改进密封装置与形成的混凝土结构的粘附强度,特别是在浇注的混凝土的24小时硬化之后测定的早期粘附强度。
在预先施加的防水应用中观察到的与混凝土的粘附强度提高被认为由在功能层的外部外表面上存在的孔和洞的体积提高产生,这能够较快速形成在功能层和浇注的混凝土之间的机械结合。还发现了可通过使用泡沫挤出工艺容易获得具有期望表面粗糙度的功能层,在该工艺中包含功能层的成分和发泡气体的熔融聚合物组合物通过挤出机模头挤出。在从挤出机模头排放时发泡气体从熔融聚合物组合物释放,其中功能层首先膨胀并且它的表面最终被释放的发泡气体穿透,导致可表征为功能层的“表面粗糙度”的孔和/或洞和其它表面缺陷的形成。
本发明的密封装置包含具有第一和第二主表面的功能层和与功能层的第二主表面间接或直接连接的阻挡层,其中功能层的第一主表面具有特征为以下的表面粗糙度,波度参数Wf为至少0.0125 1/mm、优选0.0135 1/mm、更优选0.0145 1/mm、甚至更优选0.01551/mm、再更优选0.0165 1/mm,其中波度参数Wf确定为波度的均方根粗糙度WSq和波度的峰密度WSpd的乘积,并且其中波度参数WSq和WSpd根据ISO 25178标准由使用截止长度λc为0.8mm的测量横截面曲线获得的波度曲线测定。
波度的均方根粗糙度WSq和波度的峰密度WSpd是标准化的三维(3D)面积参数,其由如ISO 25178标准中定义的波度曲线计算。
术语“波度”常用于指代具有比与表面的“粗糙度”有关的不规则明显更长波长的表面不规则。可基于波度曲线或基于表面的粗糙度曲线计算根据ISO 25178标准的3D面积参数,其中可从表面的测量横截面曲线使用合适的曲线截止滤波器λc和任选λf获得波度曲线。
术语“测量横截面曲线”在本公开内容中是指在ISO 25178定义为“SF表面”的横截面曲线,其由测量的表面几何形状(提取表面)使用F-操作器和任选S-滤波器获得。可例如使用3D扫描仪smartSCAN(AICON 3D Systems GmbH的商标)来测量表面几何形状。在本发明的情况下,通过从测量的表面几何形状减去用测量的数据点拟合的二阶多项式获得功能层的第一主表面的横截面曲线,并且使用0.8mm的截止长度λc来从测量的横截面曲线获得波度曲线。优选使用合适的计算机软件例如Premium(V7)软件(DigitalSurf公司的商标)来根据ISO 25178标准测定横截面曲线、波度曲线和3D面积参数。
已经发现了包含具有如权利要求1中限定的组成和落入以上所呈现范围内的第一主表面的表面粗糙度的功能层的密封装置提供在功能层的第一主表面上浇注的新鲜混凝土的24小时硬化之后测定的高的早期粘附强度。特别地,已经发现了这样的密封装置具有早期粘附强度,其能够在预先施加的防水应用中使用密封装置,其中密封装置定位模板的垂直表面上,所述模板在浇注混凝土结构之后24小时内去除。
此外,发现了密封装置表现出至少10N/50mm、优选至少15N/50mm的早期混凝土粘附强度,其确定为在从混凝土试样的表面剥离密封装置时密封装置的每单位宽度的平均剥离阻力,所述混凝土试样浇注在功能层的第一主表面上并在标准大气(空气温度23℃,相对空气湿度50%)下硬化24小时。
根据一种或多种实施方案,功能层包含25-65重量%、优选30-60重量%、更优选30-55重量%的至少一种热塑性聚合物P1和35-75重量%、优选40-75重量%、更优选40-70重量%的至少一种固体填料F,所有比例基于功能层的总重量。
根据一种或多种实施方案,至少一种热塑性聚合物P1,至少一种固体填料F的量之和占功能层的总重量的至少85重量%、优选至少90重量%、更优选至少92.5重量%、甚至更优选至少95重量%。
至少一种固体填料F优选作为分散在包含至少一种热塑性聚合物P1的连续相中的单个固体颗粒或一个或多个固体颗粒的聚集体存在于功能层中。表述“分散在连续相中”应理解意为单个固体颗粒或一个或多个颗粒的聚集体至少部分、优选完全被包含至少一种热塑性聚合物的连续相包围。如果功能层含有在存在水的情况下经历水合反应的一种或多种无机粘合剂,即无机填料,必要的是这些在功能层内不形成水合无机粘合剂的相互交联的固体网络。因此,可以优选的是至少在密封装置用于基材的防水之前功能层基本上不含,更优选完全不含水合无机粘合剂的相互交联的固体网络。
优选地,至少一种填料F具有:
-d98粒度不大于750μm、更优选不大于500μm、甚至更优选不大于350μm、再更优选不大于250μm和/或
-中值粒度d50不大于350μm、更优选不大于250μm、甚至更优选不大于150μm、再更优选不大于100μm和/或
-d10粒度不大于100μm、更优选不大于75μm、甚至更优选不大于50μm、再更优选不大于25μm。
术语“粒度”在本公开内容中是指颗粒的面积等效球径(X面积)。
术语d90粒度在本公开内容中是指这样的粒度,低于该粒度所有颗粒的小于90体积%小于d90值。类推地,术语“中值粒度d50”是指这样的粒度,低于该粒度所有颗粒的小于50体积%小于d50值,和术语“d10粒度”是指这样的粒度,低于该粒度所有颗粒的小于10%体积小于d10值。粒度分布可通过激光衍射根据如在标准ISO 13320:2009中描述的方法测量。为了测定粒度分布,优选将颗粒悬浮在水中(湿法分散方法)。可在测量粒度分布中使用Mastersizer 2000装置(Malvern Instruments Ltd,GB的商标)。
根据一种或多种实施方案,至少一种固体填料F具有中值粒度d50在0.1–150μm、优选0.5–100μm、更优选0.5–75μm、甚至更优选1.0–50μm、再更优选1.0–25μm、最优选1.0–15μm的范围内。
优选地,至少一种固体填料F的颗粒分布遍及功能层的整个体积。术语“分布遍及”意为功能层的基本上所有部分含有至少一种固体填料F的颗粒,但是不必意味着颗粒的分布遍及功能层是完全一致的。
还可以优选的是功能层包含至少一种热塑性聚合物P1和至少一种固体填料F的均匀混合的混合物。“均匀混合的混合物”在本公开内容中是指各个成分基本上均匀分布在组合物中的组合物。至少一种热塑性聚合物P1和至少一种固体填料F的均匀混合的混合物因此是指其中至少一种固体填料F的颗粒均匀/一致地分布在包含至少一种热塑性聚合物P1的热塑性聚合物相中的组合物。对于本领域技术人员清楚的是在这样的混合组合物内可以存在形成的区域,其具有比其它区域稍高的一种或多种成分的浓度并且所有成分的100%均匀分布通常不可实现。然而,这样具有成分的“不完美”分布的混合组合物按照本发明也意图被术语“均匀混合的混合物”所包括。
至少一种固体填料F的类型在本发明中没有特别限制。根据一种或多种实施方案,至少一种固体填料F选自以下:惰性无机填料、水硬性粘合剂、非水硬性粘合剂、潜在水硬性粘合剂、火山灰粘合剂和合成有机填料。
根据一种或多种实施方案,至少一种固体填料F包含至少一种惰性无机填料F1。通常,表述“至少一种组分X包含至少一种组分XN”例如“至少一种固体填料F包含至少一种惰性无机填料F1”应理解为在本公开内容的上下文中意指功能层包含一种或多种惰性无机填料F1为至少一种固体填料F的代表。
术语“惰性无机填料”是指无机填料,其与水硬性粘合剂不同,在存在水的情况下不经历水解反应。待用作至少一种惰性无机填料F1的合适的无机填料包括例如砂、花岗岩、碳酸钙、碳酸镁、粘土、膨胀粘土、硅藻土、浮石、云母、高岭土、滑石、白云石、硬硅钙石、珍珠岩、蛭石、硅灰石、重晶石、方石英、二氧化硅、气相二氧化硅、玻璃珠、中空玻璃球、陶瓷球、铝土矿、粉碎的混凝土和沸石。
术语“砂”在本文件中是指无机碎屑沉积物(碎屑岩),其为圆形或有角的小细粒的松散聚集物(松散沉积物),其在机械和化学降解过程中与原始细粒结构分离并被运输到它们的沉积点,所述沉积物具有SiO2含量大于50重量%,特别是大于75重量%,特别优选大于85重量%。当用作惰性无机填料时术语“碳酸钙”是指由白垩、石灰石或大理石通过研磨和/或沉淀产生的固体颗粒状物质。
根据一种或多种实施方案,至少一种惰性无机填料选自以下:砂、花岗岩、碳酸钙、碳酸镁、粘土、膨胀粘土、硅藻土、浮石、云母、高岭土、滑石、钾碱、白云石、硬硅钙石、珍珠岩、蛭石、硅灰石、重晶石、方石英、二氧化硅(石英)、气相二氧化硅、熔融二氧化硅、铝土矿、粉碎的混凝土和沸石,优选选自以下:碳酸钙、碳酸镁、硅藻土、浮石、云母、滑石、白云石、硬硅钙石、珍珠岩、蛭石、硅灰石、重晶石和粉碎的混凝土。
根据一种或多种实施方案,至少一种固体填料F包含至少一种水硬性粘合剂F2。
术语“水硬性粘合剂”是指在固体无机水合物或水合物相形成下与水在水解反应中反应的物质,其不溶于水或具有低的水溶解度。因此,水硬性粘合剂例如波特兰水泥当暴露于水例如在水下或在高湿度条件下可硬化并保持它们的强度。与此相反,术语“非水硬性粘合剂”是指与通过与二氧化碳反应而硬化并因此在潮湿条件中或在水下不硬化的物质。
待用作至少一种水硬性粘合剂的合适的水硬性粘合剂的实例包括水硬性水泥和水硬性石灰。术语“水硬性水泥”这里是指硅酸盐和氧化物的混合物,包括硅酸三钙石、二钙硅酸盐、铝酸三钙和钙铁铝石。
可商购得到的水硬性水泥可根据DIN EN 197-1分为五种主要水泥类型,即波特兰水泥(CEM I)、波特兰复合水泥(CEM II)、高炉水泥(CEM III)、火山灰水泥(CEM IV)和复合水泥(CEM V)。这五种主要类型的水硬性水泥进一步细分为额外的27种水泥类型,其对本领域技术人员是已知的并列在DIN EN 197-1。自然地,根据另一标准例如根据ASTM标准或印度标准生产的所有其它水硬性水泥也适合用作至少一种水硬性粘合剂F2。
根据一种或多种实施方案,至少一种固体填料F包含至少一种非水硬性粘合剂F3。
待用作至少一种非水硬性粘合剂F3的合适的非水硬性粘合剂的实例包括风化石灰(非水硬性石灰)和石膏。术语“石膏”在本公开内容中是指任何已知形式的石膏,特别是硫酸钙脱水物、硫酸钙α-半水化合物、硫酸钙β-半水化合物或硫酸钙无水石膏或它们的混合物。
根据一种或多种实施方案,至少一种固体填料F包含至少一种潜在水硬性粘合剂F4。
术语“潜在水硬性粘合剂”在本公开内容中是指具有如在DIN EN 206-1:2000标准中限定的“潜在水硬性特性”的II型混凝土添加剂。这些类型的无机粘合剂是当与水混合时不能够直接硬化或硬化太慢的铝硅酸钙。硬化过程在存在碱性活化剂的情况下加速,所述碱性活化剂破坏粘合剂的无定形(或玻璃)相中化学键并促进离子物质的溶解和铝硅酸钙水合物相的形成。
待用作至少一种潜在水硬性粘合剂F4的合适的潜在水硬性粘合剂的实例包括研磨的颗粒状高炉渣。研磨的颗粒状高炉渣通常如下获得,来自高炉的熔融铁渣在水或蒸汽中的淬火以形成玻璃状丸粒状产物,之后干燥并研磨玻璃状为细粉末。
根据一种或多种实施方案,至少一种固体填料F包含至少一种火山灰粘合剂F5。
术语“火山灰粘合剂”在本公开内容中是指具有如在DIN EN 206-1:2000标准中限定的“火山灰特性”的II型混凝土添加剂。这些类型的无机粘合剂是硅质的或铝硅酸盐化合物,其与水和氢氧化钙反应形成硅酸钙水合物或铝硅酸钙水合物相。
待用作至少一种火山灰粘合剂F5的合适的火山灰粘合剂的实例包括天然火山灰例如火山土和人造火山灰例如飞灰和硅灰。术语“飞灰”在本公开内容中是指通过煤粉的燃烧产生的细分的灰残余物,其被从燃烧煤的炉排出的气体带走。术语“硅灰”在本公开内容中是指无定形形式的细颗粒状硅。硅灰通常作为处理硅矿石例如石英在硅熔炉中熔炼的副产物获得,其导致一氧化硅气体的形成,并且一氧化硅气体在暴露于空气时进一步氧化以产生无定形二氧化硅的小颗粒。
根据一种或多种实施方案,至少一种固体填料F包含至少一种合成有机填料F6。
待用作至少一种合成有机填料F6的合适的合成有机材料特别包括具有通过DSC根据ISO 11357标准测定的熔融温度(Tm)为等于或高于250℃、优选等于或高于275℃的塑性材料,例如聚酰胺、芳族聚酰胺、环氧化物、聚苯乙烯、发泡聚苯乙烯、聚对苯二甲酸乙二醇酯(PET)、聚(苯醚)、聚砜和聚醚砜。
根据一种或多种实施方案,至少一种固体填料F包含至少一种惰性无机填料F1和/或至少一种水硬性粘合剂F2或由至少一种惰性无机填料F1和/或至少一种水硬性粘合剂F2组成,至少一种惰性无机填料F1优选选自:碳酸钙、碳酸镁、硅藻土、浮石、白云石、硬硅钙石、珍珠岩、重晶石和粉碎的混凝土,更优选选自:碳酸钙和碳酸镁,至少一种水硬性粘合剂F2优选选自波特兰水泥(CEM I)、波特兰复合水泥(CEM II)、高炉水泥(CEM III)、火山灰水泥(CEM IV)和复合水泥(CEM V)。
至少一种热塑性聚合物P1的类型在本发明中没有特别限制。
根据一种或多种实施方案,至少一种热塑性聚合物P1具有:
-通过DSC根据ISO 11357标准测定的熔融温度(Tm)在55–250℃、优选60–200℃、更优选65–175℃、甚至更优选70–165℃、再更优选75–155℃的范围内和/或
-熔体流动速率,根据ISO 1133(190℃/2.16kg)测定的熔体流动速率不大于250g/10min、优选不大于150g/10min、更优选不大于100g/10min、甚至更优选不大于50g/10min、再更优选不大于25g/10min和/或
-玻璃化转变温度(Tg)等于或低于0℃、优选等于或低于-10℃、更优选等于或低于-20℃、甚至更优选等于或低于-25℃、再更优选等于或低于-30℃,通过动态力学分析(DMA)测定,为使用1Hz的施加频率和0.1%的应变水平所测量损耗模量(G″)曲线的峰和/或
-23℃下挠曲模量,根据ISO 178标准测定为不大于700MPa、优选不大于500MPa、更优选不大于350MPa、甚至更优选不大于250MPa、再更优选不大于150MPa、最优选不大于100MPa。
待用作至少一种热塑性聚合物P1的合适的聚合物包括例如乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-丙烯酸酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯共聚物、丙烯-α-烯烃共聚物、丙烯-乙烯共聚物、聚乙烯(PE)、聚丙烯(PP)、聚氯乙烯(PVC)、聚对苯二甲酸乙二醇酯(PET)、聚苯乙烯(PS)、聚酰胺(PA)、氯磺化聚乙烯(CSPE)、乙烯丙烯二烯单体橡胶(EPDM)和聚异丁烯(PIB)。
根据一种或多种实施方案,至少一种热塑性聚合物P1选自以下:低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-丙烯酸酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯共聚物、丙烯-α-烯烃共聚物、丙烯-乙烯共聚物和聚丙烯(PP),优选选自以下:低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-α-烯烃共聚物和乙烯-丙烯共聚物。
根据一种或多种实施方案,至少一种热塑性聚合物包含至少一种乙烯乙酸乙烯酯共聚物P11和至少一种不是乙烯乙酸乙烯酯共聚物的热塑性聚合物P12,其优选选自低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、乙烯-α-烯烃共聚物和乙烯-丙烯共聚物。
根据一种或多种实施方案,至少一种乙烯乙酸乙烯酯共聚物P11和至少一种不是乙烯乙酸乙烯酯共聚物的热塑性聚合物P12的量之比在5:1-1:5、优选3:1-1:3、更优选3:1-1:3的范围内。
根据一种或多种实施方案,功能层还包含至少一种表面活性剂SF。术语“表面活性剂”是指降低表面张力的物质,其通常是含有疏水和亲水基团两者的有机化合物。表面活性剂通常基于它们的亲水基团的电荷分为阴离子、阳离子、两性的、非离子的和聚合物表面活性剂。不受任何理论的束缚,功能层中表面活性剂的存在可以降低浇注在功能层上的新鲜混凝土中含有的水的表面张力,这可以进一步增强新鲜混凝土进入功能层的第一主表面上存在的洞和孔的能力。
待用作至少一种表面活性剂SF的合适的阴离子表面活性剂的实例包括例如含有羧酸盐、硫酸盐、磷酸盐或磺酸盐基团的表面活性剂,例如氨基酸衍生物;脂肪醇醚硫酸盐;脂肪醇硫酸盐;肥皂;烷基酚乙氧基化物;脂肪醇乙氧基化物;链烷磺酸盐;烯烃磺酸盐;和烷基磷酸盐。
待用作至少一种表面活性剂SF的合适的阳离子表面活性剂的实例包括例如季铵或磷化合物,例如四烷基铵盐、N,N-二烷基咪唑啉化合物、二甲基二硬脂基铵化合物、N-烷基吡啶化合物和氯化铵。
两性的(两性离子的)表面活性剂具有与同一分子附着的阳离子和阴离子中心。待用作至少一种表面活性剂SF的合适的两性表面活性剂的实例包括例如两性电解质例如氨基羧酸和甜菜碱。
待用作至少一种表面活性剂SF的合适的非离子表面活性剂的实例包括例如乙氧基化物例如醇的乙氧基化加合物,例如聚氧化亚烷基多元醇;胺;脂肪酸;脂肪酸酰胺;烷基酚;乙醇酰胺;脂肪胺;聚硅氧烷;脂肪酸酯;烷基或烷基苯基聚二醇醚,例如脂肪醇聚二醇醚;烷基糖苷;糖酯;脱水山梨糖醇酯;聚山梨酸酯或三烷基胺氧化物;聚(甲基)丙烯酸与聚亚烷基二醇或氨基聚亚烷基二醇的酯和酰胺,其最多可以在一端带有烷基。
聚合物表面活性剂可分为两组化合物。第一组包括梳型或耙型(rake)聚合物,其中存在有机聚合物链,沿着该链以规则间隔具有疏水基团和沿着该链以随机的或规则间隔具有亲水基团。聚合物表面活性剂的第二组包括嵌段共聚物,其中通常以A-B-A构造存在疏水基团的嵌段(B)和亲水基团的嵌段(A)。某些聚合物表面活性剂例如环氧乙烷-环氧丙烷共聚物表面活性剂还可分类为非离子表面活性剂。
根据一种或多种实施方案,至少一种表面活性剂SF选自以下:甘油单硬脂酸酯、聚羧酸酯醚、聚醚改性的聚硅氧烷、聚环氧烷硅氧烷、羟乙基胺、芥酸酰胺、硬脂基硬脂酰胺、碱金属链烷磺酸盐和烷基芳基磺酸盐。
合适的聚羧酸酯醚包括基于聚羧酸醚的超增塑剂(PCE),其由与甲基丙烯酸共聚物(主链)接枝的甲氧基-聚乙二醇共聚物(侧链)组成。合适的基于聚羧酸醚的超增塑剂可商购得到,例如以Polymer PC-2、Polymer RMC-2、125 P和R-750 MC(来自Sika AG)的商品名。
如果存在于功能层中,至少一种表面活性剂SF优选占功能层的总重量的至少0.01重量%、更优选至少0.05重量%、甚至更优选至少0.1重量%。还优选的是功能层中至少一种表面活性剂SF的量不大于10重量%、更优选不大于5重量%、甚至更优选不大于3.5重量%,基于功能层的总重量。
根据一种或多种实施方案,至少一种表面活性剂SF占功能层的总重量的0.05-7.5重量%、优选0.1-5.0重量%、更优选0.25-3.5重量%、甚至更优选0.5-3.0重量%、再更优选0.5-2.5重量%。
由于功能层的第一主表面中存在的不对称的表面结构,功能层的厚度通常沿着密封装置的长度和宽度变化。功能层的一些孔和洞甚至可以到达阻挡层的第一主表面,在该情况下在这样的特定位置处测量的功能层的厚度甚至可以是不可测量的。然而,可以优选的是功能层具有最大厚度不大于25mm、优选不大于15mm、更优选不大于10mm、甚至更优选不大于5mm、再更优选不大于2.5mm。在本发明的上下文中,可根据DIN EN 1849-2标准使用光学显微镜例如具有30倍放大倍数的Keyence VHX-600型来测定功能层的最大厚度。
作为功能层的第一主表面的表面粗糙度补充,还发现了功能层的每单位面积的质量也影响密封装置在预先施加的防水应用中获得的早期粘附强度。因此可以优选的是功能层具有每单位面积的质量为至少100g/m2、更优选至少150g/m2、甚至更优选至少200g/m2。根据一种或多种实施方案,功能层具有每单位重量的质量在100–1500g/m2、优选150–1250g/m2、更优选250–1000g/m2、甚至更优选350–1000g/m2、再更优选450–1000g/m2、最优选500–1000g/m2的范围内。
功能层还可以包含一种或多种添加剂例如UV和热稳定剂、抗氧化剂、增塑剂、阻燃剂、染料、颜料例如二氧化钛和炭黑、消光剂、抗静电剂、冲击改性剂、杀生物剂、和加工助剂例如润滑剂、增滑剂、抗粘连剂和脱模(denest)助剂。优选的是这些类型的添加剂的总量占功能层总重量的不大于10重量%、优选不大于5重量%。
密封装置还包含阻挡层,其与功能层的第二主表面直接或间接连接。
功能层和阻挡层可例如通过连接层例如胶黏剂层或通过基于纤维的层或它们的组合彼此间接连接。在多孔连接层例如稀松组织织物的情况下,功能层可以与阻挡层部分直接连接和部分间接连接。
表述“直接连接”应理解为在本发明的上下文中意为在层之间不存在另外的层或物质,和两层的相对表面与彼此直接结合或与彼此粘附。在两层之间的过渡区域,形成层的材料还可彼此混合存在。
根据一种或多种实施方案,阻挡层具有第一和第二主表面,其中阻挡层的至少一部分第一主表面与功能层的第二主表面直接连接。根据一种或多种实施方案,阻挡层的至少50%、优选至少75重量%、更优选至少95%的面积与功能层的第二主表面直接连接。
阻挡层的组成没有特别限制。然而,阻挡层应尽可能防水,并甚至在水或湿气的延长影响下不分解或机械受损。
此外优选的是阻挡层处于柔性塑料层的形式。这允许密封装置通常在生产期间卷绕成卷,并然后容易施加至待防水的基材的表面。优选地,阻挡层具有根据EN ISO 527-3测定的弹性拉伸模量为不大于500MPa、优选不大于350MPa、更优选不大于250MPa、甚至更优选不大于150MPa、再更优选不大于100MPa。
根据一种或多种实施方案,阻挡层包含至少50重量%、优选至少65重量%、更优选至少75重量%、甚至更优选至少85重量%、甚至更优选至少90重量%、再更优选至少95重量%的至少一种热塑性聚合物P2。
根据一种或多种实施方案,至少一种热塑性聚合物P2具有:
-通过DSC根据ISO 11357标准测定的熔融温度(Tm)在55–250℃、优选60–200℃、更优选65–175℃、甚至更优选70–165℃、再更优选75–155℃的范围内和/或
-熔体流动速率,根据ISO 1133(190℃/2.16kg)测定的熔体流动速率不大于250g/10min、优选不大于150g/10min、更优选不大于100g/10min、甚至更优选不大于50g/10min、再更优选不大于25g/10min和/或
-玻璃化转变温度(Tg)等于或低于0℃、优选等于或低于-10℃、更优选等于或低于-20℃、甚至更优选等于或低于-25℃、再更优选等于或低于-30℃,通过动态力学分析(DMA)测定,为使用1Hz的施加频率和0.1%的应变水平所测量损耗模量(G″)曲线的峰和/或
-23℃下挠曲模量,根据ISO 178标准测定为不大于700MPa、优选不大于500MPa、更优选不大于350MPa、甚至更优选不大于250MPa、再更优选不大于150MPa、最优选不大于100MPa。
待用作至少一种热塑性聚合物P2的合适的聚合物包括例如乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-丙烯酸酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯共聚物、丙烯-α-烯烃共聚物、丙烯-乙烯共聚物、聚乙烯(PE)、聚丙烯(PP)、聚氯乙烯(PVC)、聚对苯二甲酸乙二醇酯(PET)、聚苯乙烯(PS)、聚酰胺(PA)、氯磺化聚乙烯(CSPE)、乙烯丙烯二烯单体橡胶(EPDM)和聚异丁烯(PIB)。
根据一种或多种实施方案,至少一种热塑性聚合物P2选自以下:低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-丙烯酸酯共聚物、乙烯-α-烯烃共聚物、乙烯-丙烯共聚物、丙烯-α-烯烃共聚物、丙烯-乙烯共聚物和聚丙烯(PP),优选选自以下:低密度聚乙烯、线性低密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-α-烯烃共聚物和乙烯-丙烯共聚物。
可以优选的是阻挡层中含有的至少一种热塑性聚合物P2与功能层中含有的至少一种热塑性聚合物P1混溶。聚合物是“混溶的”在本公开内容中意指由至少一种热塑性聚合物P1和至少一种热塑性聚合物P2组成的聚合物共混物具有负的吉格斯自由能和混合热。由完全混溶聚合物组分组成的聚合物共混物倾向具有一个单一玻璃化转变温度(Tg)。
作为至少一种热塑性聚合物P2补充,阻挡层还可包含一种或多种添加剂例如UV和热稳定剂、抗氧化剂、增塑剂、填料、阻燃剂、染料、颜料例如二氧化钛和炭黑、消光剂、抗静电剂、冲击改性剂、杀生物剂、和加工助剂例如润滑剂、增滑剂、抗粘连剂和脱模助剂。然而,优选的是这些类型的添加剂的总量不大于45重量%、优选不大于35重量%、更优选不大于25重量%、甚至更优选不大于15重量%,基于阻挡层的总重量。
阻挡层的厚度没有任何特殊限制。然而,包含阻挡层具有厚度大于10mm或小于0.1mm的密封装置通常在防水应用中不实际。优选地,阻挡层具有厚度为至少0.1mm、更优选至少0.25mm。根据一种或多种实施方案,阻挡层具有厚度为0.1–10.0mm、优选0.25–5.0mm、更优选0.3–3.5mm、甚至更优选0.35–2.5mm。可通过使用如在DIN EN 1849-2标准中限定的测量方法测定阻挡层的厚度。
本发明的密封装置可以预制制品的形式提供,预制制品以卷的形式被运送到建筑工地,然后将其解开并切割以提供具有长度超过片材宽度的片材。术语“宽度”和“长度”是指在片材的顶和底表面的水平面中测量的两个垂直尺寸。通常,片的“宽度”是该片水平尺寸中较小的。因此,密封装置的“宽度”是指在垂直于阻挡层的长度的方向上在阻挡层的水平面中测量的较小尺寸。
优选地,密封装置具有宽度不大于10m、更优选不大于5m。根据一种或多种实施方案,密封装置具有宽度在0.5–5m、优选0.75–4m、更优选0.85–3.5m、甚至更优选1.0–3m的范围内。根据一种或多种另外的实施方案,密封装置具有宽度在0.05–1m、优选0.1–0.85m、更优选0.15–0.65m、甚至更优选0.15–0.5m的范围内。
尤其是如果密封装置用于屋顶基材的防水,可以优选的是阻挡层包含一个或多个增强层,其用于改进阻挡层的尺寸稳定性。然而,可以或甚至优选的是阻挡层不含有这样的增强层,特别是如果密封装置用于地下结构的防水。
如果使用,增强层可以至少部分嵌入、优选完全嵌入阻挡层。表述“至少部分嵌入”意为增强层至少部分被阻挡层的基体覆盖。增强层的类型没有特别限制。例如,可使用常使用于改进热塑性防水和屋顶膜的尺寸稳定性的增强层。优选地,增强层包含至少一层纤维材料,优选选自无纺织物、纺织织物和无纺粗布,更优选选自无纺织物和无纺粗布。
术语“无纺织物”在本公开内容是指由纤维组成的材料,其通过使用化学、机械或热结合方式结合在一起,并且其即不是纺织的也不是针织的。无纺织物可例如通过使用梳理或针刺法来生产,其中将纤维机械缠结以获得无纺织物。在化学结合中,使用化学粘合剂例如胶黏剂材料将纤维一起保持在无纺织物中。
术语“无纺粗布”在本公开内容中是指网状的无纺产物,其由纱线组成,所述纱线彼此层叠并彼此化学结合。无纺粗布的典型材料包括金属、纤维玻璃和塑料,特别是聚酯、聚丙烯、聚乙烯和聚对苯二甲酸乙二醇酯(PET)。
根据一种或多种实施方案,密封装置还包含具有第一和第二主表面的第二功能层(2’),其中阻挡层(3)的第二主表面与第二功能层(2’)的第一主表面直接或间接连接,并且其中第二功能层(2’)包含:
a)20–75重量%、优选25–70重量%的至少一种热塑性聚合物P1和
b)25–80重量%、优选30–75重量%的至少一种固体填料F,所有比例基于第二功能层(2’)的总重量。
根据一种或多种实施方案,第二功能层的第二主表面具有由至少0.0125 1/mm、优选至少0.0135 1/mm、更优选至少0.0145 1/mm的波度因子Wf表征的表面粗糙度,波度因子Wf作为波度的均方根粗糙度WSq和波度的峰密度WSpd的乘积确定,其中波度参数WSq和WSpd根据ISO 25178标准由使用截止长度λc为0.8mm的测量横截面曲线获得的波度曲线测定。
以上对于功能层、阻挡层、至少一种热塑性聚合物P1、至少一种固体填料F和至少一种表面活性剂SF的优选条件同等适用于本发明的所有其它主题,除非另外说明。
本发明的另一主题是用于生产密封装置的方法,该方法包括通过挤出机模头挤出或共挤出包含如以上限定的功能层的成分的第一熔融聚合物组合物的步骤,其中第一熔融聚合物组合物还含有发泡气体,所述发泡气体通过从挤出机摸头排出的功能层的表面从第一熔融聚合物组合物释放。
在熔融聚合物组合物从挤出机模头排出之后,由于发泡气体的体积增加所致功能层首先膨胀,这导致功能层材料中闭孔结构的形成。最终,功能层的表面被发泡气体穿透,这导致可从功能层的第一主表面侧进入的开放或半开放的泡孔、孔、洞和其它表面缺陷的形成。可从功能层的第一主表面侧进入的这些表面结构的分布和尺寸可使用如以上讨论的3D-表面粗糙度参数表征。
为了防止发泡气体从熔融聚合物组合物的过早释放,即在熔融聚合物组合物通过挤出机模头排出之前释放,挤出机应使用封闭的排气单元(一个或多个)操作。
优选通过熔融加工包含功能层的成分的第一起始组合物来获得第一熔融聚合物组合物。优选使用挤出机例如单或双螺杆挤出机或行星辊式挤出机来进行熔融加工。
通过功能层的表面从第一熔融聚合物组合物释放的发泡气体优选以物理或化学发泡剂的形式存在于第一起始组合物或第一熔融聚合物组合物中。如果是化学发泡剂,优选将发泡剂添加至第一起始组合物,并且在第一起始组合物的熔融加工期间产生发泡气体。如果是物理发泡剂,优选在第一熔融聚合物组合物通过挤出机模头挤出之前将发泡剂添加至第一起始组合物或熔融加工的起始组合物。
待用于生产密封装置的方法中的合适的物理发泡剂包括气态和液体物理发泡剂。气态物理发泡剂例如压缩的氮气或二氧化碳可在高压下直接注入熔融加工的起始组合物,其通过熔融加工设备例如挤出机机筒运送。液体物理发泡剂包括通过蒸发产生气体的挥发性液体。合适的液体物理发泡剂通常包括水、短链脂族烃,例如具有五至七个碳原子,和它们的卤化的,特别是氯化的和氟化的衍生物。特别合适的液体物理发泡剂具有在1巴的压力下测量的标准沸点不大于250℃、优选不大于200℃。可使用沸点计测量液体物理发泡剂的标准沸点。
化学发泡剂(blowing agent)(还称为发泡剂(foaming agent))通常是当暴露于较高温度时借助于化学反应例如分解释放气体(一种或多种)的固体。化学发泡剂可以要么是无机的要么是有机的。
根据一种或多种实施方案,通过熔融加工包含功能层的成分和另外至少一种化学发泡剂CBA的第一起始组合物来获得第一熔融聚合物组合物。
根据一种或多种实施方案,至少一种化学发泡剂CBA具有在85-225℃、优选95-215℃、更优选105-205℃、甚至更优选115-195℃范围内的通过差示扫描量热法(DSC)测量的最大分解峰温度。优选通过DSC测量的最大分解峰由来自Mettler-Toledo的DSC822e差示扫描量热计测定,通过保持样品在25℃下2min,然后以5℃/min的速率将样品从25℃加热至280℃,然后保持样品在280℃下2min,并最后以10℃/min的速率将样品从280℃冷却至25℃。
待用作至少一种化学发泡剂CBA的合适的物质包括例如偶氮二甲酰胺、偶氮二异丁腈、偶氮环己腈、二亚硝基五亚甲基四胺、偶氮二氨基苯、叠氮化钙、4,4′-二苯基二磺酰叠氮化物、苯磺酰肼、4,4-氧苯磺酰氨基脲、4,4-氧双(苯磺酰肼)、二苯砜-3,3-二磺酰肼、对甲苯磺酰肼、对甲苯磺酰氨基脲、三肼基三嗪、N,N′-二甲基-N,N′-二亚硝基对苯二甲酰胺、重氮氨基苯、重氮氨基甲苯、亚肼基二甲酰胺、偶氮二羧酸钡、5-羟基四唑、碳酸氢钠、碳酸铵、碳酸氢铵、碳酸氢钾和有机酸。
大多数以上列出的优选化学发泡剂例如碳酸氢钠在正常室温下是固体并通常以粉末形式提供。这样的粉末的粒度优选不太低以便防止预混合过程期间例如预混合第一起始组合物的成分期间化学发泡剂的过早分解。还可以优选窄的粒度分布以便更好控制化学发泡剂的分解温度。
根据一种或多种实施方案,至少一种化学发泡剂CBA以具有中值粒度d50在0.5–100μm、优选1.0–75μm、更优选2.5–50μm、甚至更优选5–35μm的范围内的固体颗粒的形式存在于第一起始组合物中。
用作至少一种化学发泡剂CBA的合适的有机酸包括例如一元羧酸例如乙酸和丙酸,固体多元羧酸例如固体、羟基官能化或不饱和二元羧酸、三元羧酸、四元羧酸或多元羧酸,特别是柠檬酸、酒石酸、苹果酸、富马酸和马来酸。
虽然一些本发明中使用的化合物特征在于可用于特定功能,但是应理解这些化合物的用途不限于它们的所述功能。例如,还可能的是以上作为化学发泡剂呈现的一些物质也可用作至少一种化学发泡剂CBA的活化剂。
例如,常使用的用于基于有机酸的化学发泡剂的活化剂包括碳酸氢盐(碳酸氢盐)和碳酸盐,特别是具有式XHCO3或X2CO3的那些,其中X表示一般的阳离子例如Na+、K+、NH4 +、1/2 Zn2+、1/2 Mg2+和1/2 Ca2+,特别是Na+和K+。在另一方面,这些类型的活化剂可以自身适合用作至少一种化学发泡剂CBA。
根据一种或多种实施方案,第一起始组合物除至少一种化学发泡剂CBA还包含用于至少一种化学发泡剂CBA的至少一种活化剂。
根据一种或多种实施方案,至少一种化学发泡剂CBA选自式XHCO3的碳酸氢盐和式X2CO3的碳酸盐,其中X表示一般的阳离子,特别是Na+、K+、NH4 +、1/2 Zn2+、1/2 Mg2+或1/2 Ca2 +,优选选自XHCO3的碳酸氢盐,其中X表示一般的阳离子,特别是Na+、K+、NH4 +、1/2 Zn2+、1/2Mg2+或1/2 Ca2+,更优选选自碳酸氢钠和碳酸氢钾。
至少一种化学发泡剂CBA优选以不大于10重量%、更优选不大于7.5重量%、甚至更优选不大于5重量%、再更优选不大于3.5重量%、最优选不大于2.0重量%的量存在于第一起始组合物中,基于第一起始组合物的总重量。
根据一种或多种实施方案,至少一种化学发泡剂CBA占第一起始组合物的总重量的至少0.1重量%、优选至少0.15重量%、更优选至少0.2重量%、甚至更优选至少0.25重量%。根据一种或多种另外的实施方案,至少一种化学发泡剂CBA占第一起始组合物的总重量的0.1-3.0重量%、优选0.15-2.5重量%、更优选0.2-2.0重量%、甚至更优选0.2-1.75重量%、再更优选0.2-1.5重量%、最优选0.25-1.25重量%。
发现了以落入以上列举范围内的量将至少一种化学发泡剂CBA添加至第一起始组合物能够提供功能层期望的表面粗糙度。此外,发现了以第一起始组合物的总量的大于2.0重量%的量使用至少一种化学发泡剂CBA可以在一些情况下导致在功能层的外表面之间延伸的孔和洞的形成。在一些情况下,已经发现了使用过量的至少一种化学发泡剂导致还在阻挡层中形成孔和洞,阻挡层则不能够起到它的防水功能。
尤其是如果至少一种固体填料F包含水硬性粘合剂,可以优选的是第一起始组合物仅含有少量的水。根据一种或多种实施方案,第一起始组合物包含小于10重量%、优选小于7.5重量%、更优选小于5重量%、甚至更优选小于3.5重量%的水。
优选使用包含挤出机和模头的挤出设备来挤出或共挤出第一熔融聚合物组合物。
这样的挤出设备对于本领域技术人员是公知的。合适的挤出机包含机筒和在机筒中容纳的螺杆单元或柱塞。可以使用任何常规挤出机例如柱塞式挤出机、单螺杆挤出机或双螺杆挤出机。优选地,挤出机是螺杆挤出机、更优选双螺杆挤出机。常规的螺杆挤出机的螺杆单元通常被认为包含进料段、过渡段和计量段。在进料段中热塑性组合物进入旋转螺杆的通道并被运送至过渡段,在过渡段中压缩和熔融组合物。当组合物离开过渡段时应完全熔融。计量段的功能是均化熔融的组合物并允许其以恒定速率计量或泵出。挤出设备还包含模头,优选平模头,其由歧管、通道和唇区域组成。如果是共挤出过程,挤出设备优选包含至少两个挤出机优选双螺杆挤出机和单或多歧管模头。
挤出机机筒包含将待挤出的材料加入挤出机的进料口,和材料离开机筒的输出口。输出口与模头通过浇口(gate)或接头(adapter)部件连接。混合装置可以介于机筒和模头之间。进料口通常与加入待挤出材料的料斗连接。优选的是将筛网组件和多孔板放置在机筒的末端以避免喷嘴中阻塞。挤出机还包含加热元件、冷却元件、温度传感器和温度控制元件从而沿着机筒提供温度受控区域,还称为机筒区域。挤出机可以包含例如3至8个机筒区域,优选至少5个机筒区域,通过使用机筒区域可在机筒中实现温度分布。
优选地,通过进料口将大部分、优选全部量的至少一种热塑性聚合物P1加入挤出机。可以优选的是通过位于进料口下游的另一个口将至少一部分的至少一种固体填料F加入挤出机。术语“下游”在本文件中是指至输出口的方向。例如,可以有利的是通过进料口将至少一种固体填料F的总量的不大于50重量%、优选不大于30重量%、更优选不大于10重量%的至少一种固体填料F与全部量的至少一种热塑性聚合物P1一起加入挤出机,和通过位于进料口下游的另一个口将剩余部分的至少一种固体填料F加入挤出机。
还可以优选的是通过进料口将仅一部分的至少一种化学发泡剂CBA和/或至少一种表面活性剂SF(如果使用)加入挤出机和通过位于进料口下游的另一个口将这些组分总量的至少10重量%、优选至少20重量%加入挤出机。
还可混合第一起始组合物的一些或所有的成分以获得预混物,然后通过进料口将其加入挤出机。可使用本领域技术人员已知的任何类型的常规共混设备进行预混。在预混过程中,在升高的温度下将至少一种热塑性聚合物P1的颗粒与其它成分例如与至少一种固体填料F和/或与至少一种化学发泡剂CBA混合以获得均匀混合的混合物。还可以在配混挤出机中将第一起始组合物的一些或所有成分加工为粒料或丸粒,然后通过进料口将其加入挤出机。
优选的挤出温度取决于密封装置的实施方案,特别取决于功能层的聚合物基础的类型。术语“挤出温度”是指模口出口中所挤出组合物的温度。根据一种或多种实施方案,挤出温度在80–250℃、优选100–240℃、更优选120–220℃、甚至更优选140–200℃的范围内。
优选的挤出压力取决于密封装置的实施方案,特别取决于功能层的聚合物基础的类型和取决于功能层中至少一种固体填料F的量。术语“挤出压力”是指正好在组合物进入模头入口之前组合物在计量区域末端的压力。
根据一种或多种实施方案,挤出压力在20–350巴、优选30–240巴、更优选35–200巴、甚至更优选40–130巴的范围内。
可以通过使用不同的温度分布来进行挤出过程,例如提高的温度分布(其中在机筒下游温度提高),降低的温度分布(其中在机筒下游温度降低),和驼峰状温度分布(其中温度从进料口朝向某一设定点,例如向机筒中部提高)。可以优选的是通过使用驼峰状温度分布进行挤出过程。
优选地,在将第一起始组合物运送通过机筒时并在熔融加工的起始组合物进入模头前,至少部分,例如至少5重量%、特别是至少10重量%、优选25重量%、更优选至少50重量%、最优选至少75重量%的至少一种化学发泡剂CBA分解。这通过选择合适的化学发泡剂或合适的化学发泡剂和活化剂的混合物和通过调节进料段、过渡段和计量段中的温度分布来确保。优选地,当第一起始组合物运送通过挤出机机筒时,第一起始组合物维持在大于至少一种化学发泡剂CBA的分解温度至少10℃的温度下。
此外,挤出机优选使用封闭的排气单元(一个或多个)操作。必要的是挤出机机筒内部释放的至少大部分的发泡气体保持截留在熔融加工的聚合物组合物中并在第一熔融聚合物组合物离开挤出机模头之前未释放。
根据一种或多种实施方案,生产密封装置的方法包括通过挤出机模头挤出或共挤出包含如以上限定的阻挡层的成分的第二熔融聚合物组合物的另外步骤。
优选地,通过熔融加工包含阻挡层的成分的第二起始组合物来获得第二熔融聚合物组合物。
生产密封装置的方法的另外的细节取决于密封装置的实施方案。
根据一种或多种实施方案,生产密封装置的方法包括通过常用的挤出机模头优选平模头使用共挤出设备共挤出第一熔融聚合物组合物和第二熔融聚合物组合物。优选地,共挤出设备包含熔融加工第一起始组合物的第一挤出机和熔融加工第二起始组合物的第二挤出机。将第一和第二熔融聚合物组合物通过常用的挤出机模头挤出,所述挤出机模头可配备有单或多歧管。可通过调节共挤出设备的模唇容易控制挤出的功能层和阻挡层的厚度以及层之间的粘附。优选的是第一挤出机使用封闭的排气单元(一个或多个)操作以便防止发泡气体的过早释放。
可以优选的是生产密封装置的方法包括采用间隔开的压延冷却辊的另外步骤,在共挤出步骤之后包含挤出的功能层和挤出的阻挡层的复合制品牵拉通过所述间隔开的压延冷却辊。可通过调节压延冷却辊之间的间隙大小进一步控制功能层和阻挡层的厚度。优选地,调节压延冷却辊之间的间隙,使得在功能层的表面上基本上没有施加压力以便获得具有期望表面粗糙度的功能层。
根据一种或多种另外的实施方案,生产密封装置的方法包括使用第一挤出设备通过第一挤出机模头挤出第一熔融聚合物组合物和使用第二挤出设备通过第二挤出机模头挤出第二熔融聚合物组合物并彼此结合如此获得的功能层和阻挡层。可例如彼此热层合或使用胶黏剂彼此粘附挤出的功能层和阻挡层。术语“热层合”这里是指这样的方法,包括在应用热能时部分熔融至少一层,之后进行冷却步骤,这导致在没有使用粘合剂例如胶黏剂的情况下在层之间形成结合。
根据一种或多种另外的实施方案,生产密封装置的方法包括通过挤出机模头将第二熔融聚合物组合物挤出在预先形成的功能层的第二主表面上或通过挤出机模头将第一熔融聚合物组合物挤出在预先形成的阻挡层的第一主表面上。在这些实施方案中,阻挡层与之前形成的功能层同时形成和结合,反之亦然。
本发明的另一主题是通过使用生产根据本发明的密封装置的方法获得的密封装置。
密封装置可为防水膜、屋顶膜、隧道膜或密封胶带。
本发明的又一主题是根据本发明的密封装置用于基材防水的用途。待防水的基材可为任何结构或土木工程结构,其将被密封以防湿气和水。
根据一种或多种实施方案,使用密封装置用于基材防水包括以下步骤:
i)施加根据本发明的密封装置至基材的表面,使得阻挡层的第二主表面面向基材的表面,
ii)将新鲜混凝土组合物浇注在功能层的第一主表面上,和
iii)使新鲜混凝土组合物硬化。
术语“新鲜混凝土组合物”是指在硬化之前,特别是在混凝土组合物凝固之前的混凝土组合物。在硬化之后浇注的混凝土组合物可为结构的一部分,特别是地上或地下结构,例如建筑、车库、隧道、填埋场、水库、池塘、堤坝或用于在预制建筑结构中使用的元件。
根据一种或多种另外的实施方案,使用密封装置用于基材防水包括以下步骤:
i)提供根据本发明的密封装置,
ii)在基材的至少一部分表面上施加胶黏剂层,
iii)使胶黏剂层与功能层的第一主表面接触。
胶黏剂可为新鲜水泥基组合物或基于合成树脂的胶黏剂组合物,例如反应性的基于环氧的、基于聚氨酯的或基于丙烯酸类化合物的胶黏剂组合物或非反应性的基于热塑性材料或基于橡胶的胶黏剂组合物。
术语“水泥基组合物”是指混凝土、喷混凝土、水泥浆、砂浆、泥浆或它们的组合。术语“泥浆”、“砂浆”、“混凝土”、“喷混凝土”和“水泥浆”是现有技术中公知的术语。泥浆是包含水硬性水泥粘合剂的混合物,通常是波特兰水泥、砌筑水泥、砂浆水泥的混合物。砂浆是额外包括细骨料例如砂的泥浆。混凝土是额外包括粗骨料例如破碎砂砾或石头的砂浆。喷混凝土是通过软管运送并以高速气动喷射至表面上的混凝土(或有时是砂浆)。水泥基组合物可通过混合所需量的某些组分例如水硬性水泥、水和细和/或粗骨料形成,以产生特定水泥基组合物。
根据一种或多种另外的实施方案,使用密封装置用于基材防水包括以下步骤:
i)提供根据本发明的密封装置,
ii)在基材的至少一部分表面上施加胶黏剂组合物层以形成第一胶黏剂膜并在功能层的第一主表面上施加胶黏剂组合物层以形成第二胶黏剂膜,
iii)使第一和第二胶黏剂层接触以实现基材和密封装置之间的胶黏结合。
实施例
在实施例中使用表1中显示的以下化合物:
表1
密封装置的制备
使用包含两个双螺杆挤出机(Berstorff GmbH)、平模头和一组水冷却压延辊的实验室规模的共挤出设备生产示例性密封装置Ex-1至Ex-4和参考密封装置Ref-1和Ref-2。基于乙烯乙酸乙烯酯共聚物和线性低密度聚乙烯(LLDPE)的聚合物共混物的热塑性防水膜用作全部密封装置中的阻挡层。
在第一双螺杆挤出机中熔融加工含有功能层的成分的第一起始组合物。如果第一起始组合物含有化学发泡剂,挤出机使用封闭的排气单元操作以便防止发泡气体的泄漏。在第二双螺杆挤出机中同时熔融加工含有阻挡层的成分的第二起始组合物并且将获得的第一和第二熔融聚合物组合物通过平模头共挤出在彼此顶部上从而产生双层膜复合材料,将其随后在压延辊之间冷却。调节压延冷却辊之间的间隙以稍微大于共挤出膜的厚度。功能层的每单位面积质量从582变化至651g/m2和阻挡层的厚度为大约0.7mm。
表2中呈现在密封装置的生产过程中共挤出设备的操作条件和功能层的组成。挤出温度和压力在熔融加工的物质进入平模头的入口的点处测量。冷却辊的温度在生产过程期间为大约20℃。
阻挡层的厚度
通过使用如在DIN EN 1849-2标准中限定的测量方法测定阻挡层的厚度。具有30倍放大倍数的Keyence VHX-600型光学显微镜用于测量横截面的厚度。
功能层的每单位面积的质量
为了测定密封装置的功能层每单位面积的质量,首先生产由与对应的示例性密封装置的阻挡层具有相同厚度和组成的阻挡层组成的参考膜。然后从密封装置和对应的参考膜切割具有直径为8cm的57个圆形样品。以0.01g的精度测量每个样品的质量并且通过测量的质量除以样品的计算面积来计算每单位面积的质量。然后通过从密封装置的样品的每单位面积的质量减去参考膜的样品的每单位面积的质量来确定从密封装置切割的样品的功能层涂层重量。从密封装置和参考膜在沿着大约5.5m的长度的纵向方向上切割圆形样品,其中相邻样品之间的距离为大约30cm。
波度参数和波度因子
为了表征功能层的表面粗糙度,从产生的密封装置中每个切割具有尺寸为100mm(长度)×100mm(宽度)的样品条并粘附至具有尺寸为100mm(长度)×100mm(宽度)×5mm(厚度)的硬PVC片,其中功能层朝上以确保样品的完全平放。在粘附样品与硬PVC片时使用双侧胶带。
使用来自AICON 3D Systems GmbH公司的3D-扫描仪smartSCAN测量每个样品条的功能层的表面几何形状。在以下段落中括号中的符号是指ISO 25178标准中使用的术语。
首先从表面几何形状(提取表面)减去对于测量数据点(F操作器)拟合的二阶多项式,以获得横截面曲线(SF表面)。然后使用具有值为0.8mm的截止长度λc(S滤波器)从横截面曲线获得波度曲线。从测定的波度曲线计算根据ISO 25178标准的波度参数WSq和WSpd(面积参数)和波度因子Wf计算为WSq和WSpd之积。使用Premium(V7)软件(来自DigitalSurf)进行从测量的表面几何形状获得横截面曲线、波度曲线和波度参数WSq和WSpd需要的计算。
混凝土测试试样的制备
从如以上描述生产的密封装置中每个切割尺寸为200mm(长度)×50mm(宽度)的三个样品条。将样品条置于具有尺寸为200mm(长度)×50mm(宽度)×30mm(高度)的模板中,其中功能层朝上并且阻挡层(如果存在)抵靠模板的底部。
功能层侧上每个样品条的一边覆盖有具有长度为50mm和宽度与条的宽度相一致的胶带以防止与硬化的混凝土粘附。使用胶带以使测试样品较容易安装至剥离阻力测试设备。
为了制备混凝土试样,制备一批新鲜混凝土配制物。通过在转鼓式混合器中混合8.9900kg的符合EN 1766标准的MC 0.45型混凝土干批料、0.7440kg的水和0.0110kg的Viscocrete 3082持续五分钟从而获得新鲜混凝土配制物。MC 0.45型混凝土干坯料含有1.6811kg的CEM I 42.5N水泥(Normo 4,Holcim)、7.3089kg的含有3%Nekafill-15(来自KFN)混凝土添加剂(石灰石填料)的骨料、24%具有粒度为0-1mm的砂、36%具有粒度为1-4mm的砂和37%具有粒度为4-8mm的砂砾。在与水和Viscocrete 3082共混之前,在转鼓式混合器中将混凝土干坯料匀化五分钟。
含有样品条的模板随后用新鲜混凝土配制物填充并振动两分钟以释放截留的气体。在标准大气(气温23℃、相对空气湿度50%)下硬化24小时之后,将测试混凝土试样从模板剥离并测量混凝土剥离阻力(早期粘附强度)。
混凝土剥离阻力
按照标准DIN EN 1372:2015-06中规定的工序进行剥离阻力的测量。使用配备有Zwick Roell 90°-剥离装置(型号316237)的Zwick Roell AllroundLine Z010材料测试设备进行剥离阻力测量。
在剥离阻力测量中,在包含样品条的胶带部分的混凝土试样的端部,用材料测试设备的上夹具将混凝土试样夹紧10mm的长度。之后,从混凝土试样的表面以90°的剥离角和100mm/min的恒定横梁速度剥离该条。在测试期间辊的距离为大约570mm。继续样品条的剥离直至长度为大约140mm的条从混凝土试样的表面剥掉。剥离阻力值计算为在大约70mm的长度上剥离过程中平均剥离力/样品条的宽度[N/50mm],因此从计算中排除总剥离长度的前四分之一和后四分之一。
表2中呈现的平均剥离阻力值计算为使用相同密封装置进行的三次测量的平均。
表2
Claims (16)
1.包含具有第一主表面和第二主表面的功能层(2)和与功能层(2)的第二主表面直接或间接连接的阻挡层(3)的密封装置(1),功能层(2)包含:
a)20–75重量%、优选25–70重量%的至少一种热塑性聚合物P1和
b)25–80重量%、优选30–75重量%的至少一种固体填料F,
所有比例基于功能层(2)的总重量,其中
功能层(2)的第一主表面具有由至少0.0125 1/mm、优选至少0.0135 1/mm、更优选至少0.0145 1/mm的波度因子Wf表征的表面粗糙度,所述波度因子Wf作为波度的均方根粗糙度WSq和波度的峰密度WSpd的乘积确定,其中波度参数WSq和WSpd根据ISO 25178标准由使用截止长度λc为0.8mm的测量横截面曲线获得的波度曲线测定。
2.根据权利要求1所述的密封装置,其中至少一种固体填料F的颗粒分布遍及功能层(2)的整个体积。
3.根据权利要求1或2所述的密封装置,其中至少一种固体填料F选自以下:惰性无机填料、无机粘合剂和合成有机填料。
4.根据前述权利要求中任一项所述的密封装置,其中至少一种固体填料F包含至少一种无机填料F1,选自砂、花岗岩、碳酸钙、粘土、膨胀粘土、硅藻土、浮石、云母、高岭土、滑石、白云石、硬硅钙石、珍珠岩、蛭石、硅灰石、重晶石、碳酸镁、二氧化硅、气相二氧化硅、熔凝二氧化硅、气凝胶、玻璃珠、中空玻璃球、陶瓷球、铝土矿、粉碎的混凝土和沸石。
5.根据前述权利要求中任一项所述的密封装置,其中功能层(2)还包含至少一种表面活性剂SF,优选选自甘油单硬脂酸酯、聚羧酸酯醚、聚醚改性的聚硅氧烷、聚环氧烷硅氧烷、羟乙基胺、芥酸酰胺、硬脂基硬脂酰胺、碱金属链烷磺酸盐和烷基芳基磺酸盐。
6.根据前述权利要求中任一项所述的密封装置,其中功能层(2)具有每单位重量的质量在100–1500g/m2、优选150–1250g/m2、更优选250–1000g/m2的范围内。
7.根据前述权利要求中任一项所述的密封装置,其中阻挡层(3)具有第一和第二主表面,其中阻挡层(3)的至少一部分第一主表面与功能层(2)的第二主表面直接连接。
8.根据前述权利要求中任一项所述的密封装置,其中阻挡层包含至少50重量%、优选至少65重量%的至少一种热塑性聚合物P2。
9.生产密封装置的方法,该方法包括通过挤出机模头挤出或共挤出包含如在前述权利要求中任一项限定的功能层(2)的成分的第一熔融聚合物组合物的步骤,其中第一熔融聚合物组合物还含有发泡气体,所述发泡气体通过从挤出机摸头排出的功能层(2)的表面从第一熔融聚合物组合物释放,其中通过熔融加工包含功能层(2)的成分的第一起始组合物来获得第一熔融聚合物组合物。
10.根据权利要求9所述的方法,其中第一起始组合物还包含至少化学发泡剂CBA。
11.根据权利要求10所述的方法,其中至少一种化学发泡剂CBA选自偶氮二甲酰胺、偶氮二异丁腈、偶氮环己腈、二亚硝基五亚甲基四胺、偶氮二氨基苯、叠氮化钙、4,4′-二苯基二磺酰叠氮化物、苯磺酰肼、4,4-氧苯磺酰氨基脲、4,4-氧双(苯磺酰肼)、二苯砜-3,3-二磺酰肼、对甲苯磺酰肼、对甲苯磺酰氨基脲、三肼基三嗪、N,N′-二甲基-N,N′-二亚硝基对苯二甲酰胺、重氮氨基苯、重氮氨基甲苯、亚肼基二甲酰胺、偶氮二羧酸钡、5-羟基四唑、碳酸氢钠、碳酸铵、碳酸氢铵、碳酸氢钾和有机酸。
12.根据权利要求10或11所述的方法,其中至少一种化学发泡剂CBA占第一起始组合物的总重量的0.1-3.0重量%、优选0.15-2.5重量%、更优选0.2-2.0重量%。
13.根据权利要求9-12中任一项所述的方法,包括通过挤出机模头挤出或共挤出包含如在权利要求1-8中任一项限定的阻挡层(3)的成分的第二熔融聚合物组合物的另外步骤。
14.根据权利要求13所述的方法,其中通过熔融加工包含阻挡层(3)的成分的第二起始组合物来获得第二熔融聚合物组合物。
15.通过使用根据权利要求9-14中任一项的方法获得的密封装置。
16.根据权利要求1-8或15中任一项的密封装置用于基材防水的用途。
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