CN118019637A - 多层膜、覆盖材料、其用途和制造方法 - Google Patents
多层膜、覆盖材料、其用途和制造方法 Download PDFInfo
- Publication number
- CN118019637A CN118019637A CN202280062037.XA CN202280062037A CN118019637A CN 118019637 A CN118019637 A CN 118019637A CN 202280062037 A CN202280062037 A CN 202280062037A CN 118019637 A CN118019637 A CN 118019637A
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- Prior art keywords
- layer
- multilayer film
- polyamide
- μιη
- copolymer
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical class OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2607/00—Walls, panels
- B32B2607/02—Wall papers, wall coverings
Landscapes
- Laminated Bodies (AREA)
Abstract
本发明涉及具有不对称层顺序的多层膜(100),其包括以下层:包含聚丙烯异相(嵌段)共聚物和/或聚丙烯均聚物的第一层(110);包含聚酰胺共聚物和/或聚酰胺均聚物的第二层(130);和成核剂;其中在第一层(110)和第二层(130)之间存在包含偶联剂的第三层(120)。本发明还涉及包含该多层膜的覆盖材料、制造该膜的方法、以及多层膜和覆盖材料的用途。
Description
本发明涉及多层膜、包括多层膜的覆盖材料(也称为防水材料或密封材料)以及制造和使用多层膜和覆盖材料的方法。
现有技术已知大量的多层膜,其适用于广泛的技术应用。
然而,对于这些技术应用中的一些,有利的是用于该目的的多层膜的特征在于其具有非常特殊的机械性能以及特殊的阻隔性能的组合。这特别适用于用于制造覆盖膜的多层膜,尤其是沥青覆盖膜。例如,这种沥青覆盖膜用于屋顶。ASTM 1970标准中章节1970“Standard Specification for Self-Adhering Polymer Modified Bituminous SheetMaterials Used as Steep Roofing Underlayment for Ice Dam Protection”部分中的标准适用于美国和加拿大。
这类包括多层膜的覆盖膜在现有技术中是已知的。
然而,使用多层膜生产的这些覆盖膜的缺点是,它们通常对油类、尤其是矿物油没有足够的阻隔效果。这类油是沥青化合物的主要成分。这些油从沥青化合物迁移至多层膜中不仅会导致沥青化合物变干,还会降低多层膜的黏附力,随着时间的推移,它会从沥青化合物中分离出来。
此外,现有技术中用于制造覆盖膜的多层膜的特征在于其通常具有较差的机械性能,如不足的撕裂强度、起皱、较差的撕裂传播性和不足的刺穿抗性。然而,包括多层膜的防水薄膜如屋顶防水薄膜,对多层膜机械要求很高,因为它们由于人流量、建筑材料的储存和移动以及天气的影响,多层膜暴露在高机械负荷下。
DE 102017122004 A1涉及多层膜,所述多层膜包括层(a)和层(c),每一种分别基于层(a)和层(c)的总重量,每一层基于至少一种量为至少15wt%的丙烯共聚物,至少一种用量为至少40wt%的丙烯聚合物;至少一个多层内层(b)基于至少一种具有异佛尔酮二胺单元作为聚酰胺组分的均聚和/或共聚酰胺;增黏剂层(d)和增黏剂层(e),其中多层层(b)的厚度为多层膜总厚度的至少50%。
DE 102009057862 A1涉及多层膜,其包括层(a)和层(c),每一层基于至少一种丙烯共聚物,其量为至少30重量%,和至少一种聚丙烯均聚物,其量至少20重量%,在每一种情况下分别基于层(a)和层(c)的总重量,这些聚合物组分的总和总是高达100重量%;至少一个内层(b),其基于至少一种具有异佛尔酮二胺单元作为聚酰胺组分的均聚和/或共聚酰胺;在每种情况下,一个增黏剂层(d)或增黏剂层(e)被布置在层(a)和层(b)或层(b)和层(c)之间,在每一种情况下基于至少一个改性的热塑性烯烃均聚或共聚物,还涉及包括这种多层膜的防水板及其用于覆盖屋顶的用途。
到目前为止生产的5层阻隔膜往往由于厚度需要满足机械要求,最终产品会发生严重的起皱。这些褶皱可以导致制造的防水膜和胶带渗漏,从而对产品的功能产生负面影响,直至产品失效。
EP 3 074 228 B1描述了具有相同结构并用于相同应用的三层膜。然而,类似于描述或由于缺少细节,它不能以这种方式表示,缺少生产的要点(成核剂或水浴)。这样的产品可以单独卷到一侧,可能是聚丙烯一侧。
EP 3 074 228 B1描述了另一种五层膜,但是其具有不同的聚丙烯外层。
因此,需要多层膜,特征在于其对油类具有非常好的阻隔性能和非常好的机械稳定性。
因此,本发明的目的是提供多层膜,并且与已知的多层膜相比,该多层膜的特征在于其对油类具有非常好的阻隔效果和改善的机械性能,如改善的抗撕裂性、刺穿抗性、低起皱性和良好的撕裂强度。
另一目的是提供包含这种多层膜的覆盖材料。更进一步的任务是提供制造该多层膜和覆盖材料的方法及其用途。
通过提供根据权利要求1的多层膜、根据权利要求13的用于制备多层膜的方法、根据权利要求14的覆盖材料、根据权利要求17的多层膜的用途和根据权利要求18的覆盖材料的用途来解决前述任务。
在本发明的第一方面,提供了具有不对称层顺序的多层膜,包括以下层:
-第一层,其包含聚丙烯异相(嵌段)共聚物和/或聚丙烯均聚物;
-第二层,其包含聚酰胺共聚物和/或聚酰胺均聚物和成核剂;其中包含增黏剂的第三层布置在第一层和第二层之间。优选地,多层膜包括第一层、第二层和第三层,因此多层膜是包括第一层(外层)、第二层(外层)和第三层(中间层)的三层膜。根据本发明,层可以包括单层或多个类似的层。
不依赖于任何特定的理论,假设添加成核剂作为微晶形成的成核剂有利于形成均质和细粒的微晶结构。进一步假设这种微晶结构有利于尺寸稳定的塑料产品,特别是表现出非常少或没有卷曲的塑料产品。
优选地,成核剂是无机填料,优选选自金属氧化物、金属盐、硅酸盐和氮化硼及其混合物的无机填料;填充增强剂,优选选自滑石、合成二氧化硅、高岭土及其混合物;着色剂;颜料或其混合物。特别地,成核剂优选为滑石粉。
优选地,通过根据ISO 13317-3:2001(“通过重力液体沉降法测定粒度分布-第3部分:X射线比重法”)重力液体沉降法测量的成核剂的累积度为50%的平均粒度(D50)为0.5μm至5μm、优选0.5μm至4μm、更优选1μm至3μm、特别为1.5μm至2.5μm。
优选地,成核剂在第二层(130)中的浓度为0.1重量%至5重量%、优选0.1重量%至3重量%、更优选0.1重量%至2重量%、特别是0.1重量%至1重量%。
出人意料地,与先前已知的5层阻隔膜相比,根据本发明的多层膜在最终产品中具有较低的起皱倾向。因此,根据本发明的多层膜可用于生产具有高度不渗透性的覆盖膜和胶带并长期保存。这种效果尤其基于这样的事实,即尽管符合ASTM 1970的机械要求,但是根据本发明的膜可以制造得相对较薄,因此具有抵抗膜内部卷绕的可压缩性。
此外,包括根据本发明的聚酰胺/增黏剂/聚丙烯层顺序的根据本发明的多层膜可以用黏合剂组合物直接涂覆在聚酰胺侧。与涂覆聚丙烯相比,直接涂覆聚酰胺的优点是聚酰胺更耐温,因此热诱导的材料变化如褶皱发生的程度较低。此外,聚酰胺和丁基/沥青黏合剂化合物之间的复合材料黏附力至少等于或优于聚丙烯或HDPE对这种黏合剂系统的复合材料黏附力,并有助于防止膜和相应黏合剂系统的分层。
此外,使用根据本发明的多层膜,当在聚酰胺侧涂覆黏合剂化合物时,可以在很大程度上避免增黏剂或油从基于沥青的黏合剂化合物或基于丁基的黏合剂化合物中迁移。因此,还可以避免包含异相聚丙烯(嵌段)共聚物和/或聚丙烯均聚物的第一层的膨胀效应和/或后结晶。因此,与现有技术相比,避免了双金属效应,双金属效应导致膜的所谓“卷曲效应”,并最终导致膜从黏合剂组合物上分层或膜-黏合剂层压材料从基材上分层。
最后,当在聚酰胺侧涂覆黏合剂时,尤其是当使用基于沥青的黏合剂时,根据本发明的多层膜受到良好的保护,不会由于油和光的结合引起的化学反应而导致面向黏合剂的增黏剂层失效。
根据本发明,第一层包含任何比例的异相聚丙烯(嵌段)共聚物和聚丙烯均聚物。
优选地,第一层包含至少40重量%、特别是50重量%至90重量%的均聚丙烯。这进一步提高了多层膜的机械强度和耐温性。
第二层可以包含任何比例的聚酰胺共聚物和/或聚酰胺均聚物。
与共聚酰胺不同,均聚酰胺可以用单个重复单元来描述。均聚酰胺和/或共聚酰胺可以选自热塑性脂肪族、部分芳香族和芳香族均聚酰胺或共聚酰胺。这些均聚酰胺和共聚酰胺可以选自二胺,如具有两个至十个碳原子的脂肪族二胺,特别是六亚甲基二胺和/或异佛尔酮二胺,和具有六个至十个碳原子的芳香族二胺,特别是对苯二胺,以及二羧酸、具有六个至十四个碳原子的脂肪族二羧酸和芳香族二羧酸,例如己二酸、对苯二甲酸或异对苯二甲酸,和内酰胺类,例如ε-己内酰胺。例如,聚酰胺6、聚酰胺12、聚酰胺66、聚酰胺6I、聚酰胺6T、聚酰胺6/IPDI、其共聚物或至少两种聚酰胺的共混物可以被用作聚酰胺。
均聚酰胺优选包含选自聚酰胺6、聚酰胺66及其组合的化合物。均聚酰胺可以包含这些化合物的至少80重量%或全部,特别是聚酰胺6,其可回归至ε-己内酰胺。
共聚酰胺优选为包含异佛尔酮二胺单元的共聚酰胺。这种共聚酰胺的实例为聚酰胺6/IPDI。其可以包含1重量%至10重量%、特别是1.8重量%至7重量%的异佛尔酮二胺单元(IPD),其与间苯二甲酸(I)一起存在于IPDI中。异佛尔酮二胺(3-氨基甲基-3,5,5-三甲基环己胺)和间苯二甲酸(1,3-苯二甲酸)中官能团的1,3排列产生无定形聚酰胺。这比高结晶度的聚酰胺具有更高的撕裂强度和韧性。
在一个实施方案中,第二层包括含有聚酰胺共聚物的层。
在一个实施方案中,第二层包括多个层,其中各层包括均聚酰胺,优选聚酰胺6。优选地,相对于第二层(130)的所有层中的聚酰胺总量,均聚酰胺优选聚酰胺6的量最高为65重量%、优选1重量%至49重量%、更优选1重量%至25重量%、更优选1重量%至15重量%、更优选1重量%至10重量%、更优选3重量%至9重量%。
根据本发明,根据本发明的多层包括布置在第一层和第二层之间的第三层,第三层包含偶联剂。增黏剂可以包括或组成为选自热塑性聚合物、有机酸、有机酸酐及其混合物和化合物的材料。有机酸或有机酸酐特别选自羧酸和羧酸酐。例如,增黏剂可以是改性热塑性聚合物,特别是改性聚烯烃均聚物或改性聚烯烃共聚物,例如用至少一种有机酸或有机酸酐例如马来酸酐改性的改性丙烯均聚物、改性丙烯共聚物、改性乙烯均聚物、改性乙烯乙烯醇共聚物或改性乙烯乙酸乙烯酯共聚物。
优选地,偶联剂是基于马来酸酐接枝的均聚丙烯的偶联剂。增黏剂层也可以组成为至少70重量%,特别是至少80重量%或100重量%。
此外,如果需要,第一层、第二层和第三层可以各自包含独立选择的添加剂。这些添加剂可以选自抗氧化剂、防黏连剂、防雾剂、抗静电剂、抗微生物剂、光稳定剂、UV吸收剂、紫外滤光片、染料、彩色颜料、稳定剂,特别是热稳定剂、工艺稳定剂和UV稳定剂和/或光稳定剂,优选地基于至少一种空间位阻胺(HALS)、加工助剂、阻燃剂、成核剂、结晶剂,特别是晶体成核剂、润滑剂、光学增白剂、增韧剂、密封剂、增塑剂、硅烷、间隔剂、填充剂、剥离添加剂、蜡、润湿剂、表面活性化合物、优选表面活性剂、分散剂及其组合。
第一层、第二层和第三层可以各自独立地包含0.01重量%至30重量%、特别是0.1重量%至20重量%的一种或多于一种上述添加剂。例如,第一层可以包含5重量%至20重量%、特别是5重量%至15重量%,例如5重量%的染料。如果第一外层还包含例如0.5重量%至10重量%、特别是1重量%至7重量%、例如5重量%的UV稳定剂,则对于保护多层膜也是有利的。
选地,相对于第一层、第二层和第三层的总厚度,第二层的厚度为20%至75%、优选30%至70%、更优选45%至68%。
优选地,多层膜的总厚度为40μm至140μm、优选50μm至130μm、更优选55μm至120μm。
优选地,根据ASTM 1970/ASTM D2523,多层膜的撕裂强度大于110N。ASTM 1970规定了要达到的性能,而ASTM D 2523描述了在“Standard Practice for Testing Load-Strain Properties of Roofing Membranes”章节中使用的测量方法、试验样品等。
在本发明的第二方面,提供了制造根据第一方面的本发明的多层膜的方法。
根据本发明,至少第一层、第二层和布置在其间的第三层通过共挤出在一个工艺步骤中生产。在此过程中形成多层膜。
共挤出可以特别以吹塑薄膜共挤出的形式进行。该工艺和适合该工艺的设备是本领域技术人员已知的。因此,根据本申请的多层膜优选为所谓的吹塑薄膜,特别是三层吹塑薄膜。
在多层膜包含黏合剂层和任选地还包含保护层或保护膜的情况下,这些层可以在共挤出之后在至少一个其他工艺步骤中生产。
该工艺可用于生产根据本申请的至少一个实施方案的多层膜。因此,上面给出的解释也适用于该制造工艺。
在本发明的第三方面,提供包含根据本发明的第一方面的多层膜(100)和黏合剂组合物的覆盖材料。优选地,黏性组合物是沥青或自黏性密封组合物。优选地,将黏性组合物施加至第二层。
在本发明的第四方面,提供了根据第一方面的多层膜用于涂覆、用于制造覆盖材料或胶带的用途。
在本发明的第五方面,提供了根据第三方面的防水材料作为建筑材料、用于屋顶、用于外墙包层、用于覆盖建筑物或建筑物的一部分、或者用于覆盖管道的用途。
图1示出了根据本发明的具有不对称层顺序的多层膜(100),其包括包含聚丙烯共聚物和/或聚丙烯均聚物的第一层(110);包含聚酰胺共聚物和/或聚酰胺均聚物的第二层(130);其中在第一层(110)和第二层(130)之间存在包含增黏剂的第三层(120)。
图2示出了覆盖材料(200),其包括如图1所示的多层膜(100)和设置在第二层上的黏性组合物(140)。
图1示出了根据本申请的至少一个实施方案的多层膜100的横截面示意图。多层膜100包括第一层110、第二层130和中间层120。中间层120是增黏剂层。在优选的实施方案中,多层膜是三层膜,其包括第一外层110、第二外层130和中间层120。
多层膜100的总厚度可以为40μm至140μm、优选为50μm至130μm、特别为55μm至120μm。第一层110的层厚度可以为5μm至50μm、特别为10μm至30μm。包含增黏剂的第三层110的层厚度可以为1μm至30μm、特别为2μm至20μm。第二层130的层厚度可以为5μm至100μm、优选为10μm至80μm、特别为20μm至80μm。
第一层110包括均聚丙烯,例如40重量%至60重量%的均聚丙烯,和聚丙烯异相(嵌段)共聚物(乙烯含量7重量%至9重量%),例如15重量%至30重量%的聚丙烯异相(嵌段)共聚物(乙烯含量7重量%至9重量%)。第二层130包含至少30重量%的共聚酰胺,例如80重量%至100重量%的共聚酰胺。特别地,共聚酰胺可以包含异佛尔酮二胺单元,如聚酰胺6/IPDI。增黏剂层120可以包括用马来酸酐改性或接枝的聚丙烯聚合物。
图1所示的薄膜可以例如是所谓的吹塑薄膜,例如三层吹塑薄膜。在第二层(外层)130背向第三层(中间层)120的一侧上,可以施加黏合层,并且如果需要的话,可以施加保护层或保护膜(此处未示出)。
图2示出了根据至少一个实施方案的密封材料200的横截面示意图。覆盖材料200包括例如如图1所述的多层膜100。将多层膜100层压至黏合剂组合物140上,该黏合剂组合物140包含或组成为例如沥青。图2中所示的覆盖材料200可具体实现为例如覆盖膜,特别是沥青覆盖膜,其中多层膜100作为表面涂层或表面膜,可适用于防水或覆盖屋顶或建筑物的其他部分。
在该方面,多层膜100保护不透水材料70免受有害气体例如大气中的氧气的影响,并且充当油屏障,特别是在防水材料的安装期间。
实施例
在实施例中,使用下表1中列出的缩写:
表1
在实施例中,通过吹塑薄膜共挤出由层110、层120和层130生产三层膜。这些层具有以下组成:
实施例1表2
实施例2
表3
比较例
在比较例中,通过吹塑薄膜共挤出由连续的层1至层5生产五层膜。这些层具有以下组成:
比较例1
表4
比较例2
表5
比较例3
表6
比较例4
表7
比较例5
表8
片的评价
根据ASTM 1970测试薄膜在断裂时的撕裂强度。
表9
沥青I和沥青II是来自不同制造商的沥青块
表10
附图标记列表
110 第一层,其包含异相聚丙烯(嵌段)共聚物和/或聚丙烯均聚物;
120 第三层(120),其包含增黏剂
130 第二层(130),其包含聚酰胺共聚物和/或聚酰胺均聚物
140 黏性物质。
Claims (18)
1.一种具有不对称层顺序的多层膜(100),其包括以下层:
第一层(110),其包含聚丙烯异相(嵌段)共聚物和/或聚丙烯均聚物;
第二层(130),其包含聚酰胺共聚物和/或聚酰胺均聚物和成核剂;
其中包含偶联剂的第三层(120)设置在第一层(110)和第二层(130)之间。
2.根据权利要求1所述的多层膜(100),其中所述成核剂是无机填料,优选选自金属氧化物、金属盐、硅酸盐和氮化硼及其混合物;填充增强剂,优选选自滑石粉、合成二氧化硅、高岭土及其混合物;着色剂;颜料或其混合物,特别优选为滑石粉。
3.根据权利要求1或2所述的多层膜(100),其中所述成核剂通过根据ISO 13317-3:2001(“通过重力液体沉降法测定粒度分布-第3部分:X射线比重法”)的重力液体沉降法测量的累积度为50%的平均粒度(D50)为0.5μm至5μm、优选0.5μm至4μm、更优选1μm至3μm、特别为1.5μm至2.5μm。
4.根据前述权利要求中任一项所述的多层膜(100),其中所述成核剂在第二层(130)中存在的浓度为0.1重量%至5重量%、优选0.1重量%至3重量%、更优选0.1重量%至2重量%、特别为0.1重量%至1重量%。
5.根据前述权利要求中任一项所述的多层膜(100),其中所述多层膜包括第一层(110)、第二层(130)和第三层(120)。
6.根据前述权利要求中任一项所述的多层膜(100),其中所述第二层(130)由包含聚酰胺共聚物的层组成。
7.根据权利要求1至5中任一项所述的多层膜(100),其中所述第二层(130)由多个层组成并且包含单独的聚酰胺均聚物、优选聚酰胺6的层。
8.根据权利要求7所述的多层膜(100),其中相对于所述第二层(130)的所有层中聚酰胺的总量,聚酰胺均聚物、优选聚酰胺6的量最高为65重量%。
9.根据前述权利要求中任一项所述的多层膜(100),其中相对于第一层(110)、第二层(130)和第三层(120)的总厚度,第二层(130)的厚度为20%至75%、优选为30%至70%、特别优选为45%至68%。
10.根据前述权利要求中任一项所述的多层膜(100),其中多层膜(100)的总厚度为40μm至140μm、优选为50μm至130μm、更优选为55μm至120μm。
11.根据前述权利要求中任一项所述的多层膜(100),其中根据ASTM 1970,所述多层膜(100)的撕裂强度大于110N。
12.根据前述权利要求中任一项所述的多层膜(100),其中根据ASTM 1970,断裂时纵向(md)断裂力与横向(cd)断裂力之比小于1.1。
13.一种制造根据权利要求1至12中任一项所述的多层膜(100)的方法,其中将第一层(110)、第二层(130)和第三层(120)共挤出。
14.一种覆盖材料(200),其包含根据权利要求1至12中任一项所述的多层膜(100)和黏合剂组合物(140)。
15.根据权利要求14所述的覆盖材料(200),其中所述黏合剂组合物(140)为沥青或自黏性防水组合物。
16.根据权利要求14或15所述的覆盖材料(200),其中所述黏合剂组合物(140)被施加至第二层(130)。
17.根据权利要求1至12中任一项所述的多层膜(100)用于涂覆、用于制造覆盖材料(200)或胶带的用途。
18.根据权利要求14至16中任一项所述的覆盖材料(200)作为建筑材料、用于屋顶、用于外墙包层、用于覆盖建筑物或建筑物的一部分、或者用于覆盖管道的用途。
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