CN116669941A - 至少部分覆盖有表皮材料的低密度泡沫 - Google Patents

至少部分覆盖有表皮材料的低密度泡沫 Download PDF

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CN116669941A
CN116669941A CN202280007458.2A CN202280007458A CN116669941A CN 116669941 A CN116669941 A CN 116669941A CN 202280007458 A CN202280007458 A CN 202280007458A CN 116669941 A CN116669941 A CN 116669941A
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foam
density
skin material
core
foam core
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文森特·纳韦兹
西尔万·梅尔森
格哈德·克里舍
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Nmc Corp
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Nmc Corp
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Abstract

本发明涉及一种具有低密度泡沫芯的泡沫材料，其中泡沫芯至少部分地覆盖有密度比泡沫芯高的表皮材料，其具有不超过400kg/m3的密度，而表皮材料的密度至少为800kg/m3。

Description

至少部分覆盖有表皮材料的低密度泡沫
技术领域
本发明涉及一种具有低密度泡沫芯的泡沫材料，其中泡沫芯至少部分地覆盖有密度比泡沫芯高的表皮材料，泡沫芯的密度不超过400kg/m3。
背景技术
低密度泡沫材料越来越受到人们的关注，尤其是在汽车工业中，因为它可以减轻重量，从而降低燃料消耗。低密度泡沫材料在建筑行业同样受到重视，因为它可以减少建筑的整体碳足迹。
为了保护泡沫芯并提高其机械性能，低密度泡沫材料可以覆盖有表皮材料。
US 5811039提出了一种用于制造聚合物材料主体的方法，该方法包括以下步骤：(a)将热塑性聚合物材料片预热至大于约100℃的温度，该热塑性材料片的厚度在约0.5至20mm之间；(b)将所述片材转移到第一半模中；(c)在所述第一半模具上热成型所述片材；(d)将具有热成型片材的第一半模定位为与第二半模相对，从而限定封闭在第二半模具和热成型片材之间的空腔；(e)将(1)与构成热成型片材的材料相容的可发泡热塑性聚合物材料和(2)作为发泡剂的一种或多种液态烃的混合物注入所述空腔；所述注射在大约两秒或更短的时间内进行，所述中空室具有小于或等于周围大气的压力，并且所述注射材料处于足够高的温度以在所述中空室内膨胀，并且一旦所述注射的材料与所述热成型片材的表面接触，通过热焊接基本上结合到热成型片材上；以及(f)将所述主体脱模。所获得的泡沫密度为35kg/m3。
US 4350730公开了一种适合用作图形艺术板的层压板，其包括两个固体ABS树脂片，所述ABS树脂片包括颜料和UV稳定剂，所述固体片熔融结合到泡沫树脂芯的上表面和下表面，所述泡沫树脂芯在层压板的表面上含有聚苯乙烯和ABS树脂的混合物、成核剂和抗静电剂。所采用的泡沫芯的密度为24至96kg/m3。
US 4469733涉及一种泡沫夹层结构，该泡沫夹层结构适合用作具有高刚度与重量比的承载覆层，并且是这样的类型，其中两个表皮被树脂粘合到塑料泡沫材料的芯上，每侧一个，以形成夹层，所述芯形成两个表皮之间的剪切应力传递的主要手段，所述改进包括：(a)每个表皮包括长度为至少10cm的单丝层，所述单丝层基本上彼此平行地铺设以沿着表皮延伸，方向变化保持最小，所述表皮单丝是不弯曲的并且不是编织的；(b)介于泡沫芯和每个相邻单丝表层之间的随机排列的单丝垫；和(c)所述表皮和所述垫的细丝通过热固性树脂彼此结合并结合到所述夹层结构的相邻层，其中所述树脂的存在量足以润湿所述细丝但不过量，树脂与单丝的比例在形成每个表皮的整层单丝中按重量计小于1.75:1，并且在整个夹层结构中树脂与单丝的重量比小于2∶1，从而提供了具有改进的承载强度的夹层结构。泡沫芯的密度至少为75kg/m3。
WO 2020/065564一种复合泡沫制品，包括：聚氨酯泡沫芯，所述聚氨酯泡沫芯具有第一表面和与所述第一表面相对的第二表面，设置在所述第一面上的第一表层，包括多个纤维和聚合物粘合剂；设置在所述第二表面上的第二表层，包括多个纤维和聚合物粘合剂；以及至少一个包含乙烯-丙烯酸(“EAA”)共聚物的附加层，分散在和/或设置在任何所述表层和芯之间。聚氨酯泡沫的密度范围为22至80kg/m3。
US 2011/0293914一种制造包括泡沫芯和一个或多个表皮的成形泡沫复合制品的方法，包括以下步骤：(A)通过包括以下步骤的步骤制备泡沫芯：(i)用发泡剂挤出热塑性聚合物以形成热塑性聚合物泡沫板，该板具有厚度、顶面和底面，其中所述表面位于由挤出方向和板的宽度限定的平面内，其中泡沫板具有等于或大于0.4的垂直压缩平衡，并且(ii)通过制备一个或多个挤压表面由泡沫板形成泡沫坯料，(B)将一个或更多个表皮施加到泡沫芯的一个或几个表面上，以及(C)为所述泡沫芯体提供形状，其中所述表皮与所述泡沫核心体的形状一致，从而提供成形的泡沫复合制品。合适的泡沫密度优选等于或小于160kg/m3，特别是小于100kg/m3。
然而，低密度泡沫材料重量减轻的优点通常伴随着许多缺点，例如弯曲强度和肖氏硬度的降低，这限制了这种材料的应用。
这个问题已经通过在泡沫上共同挤出覆盖层来解决。然而，低密度泡沫的共挤出仍然是一个挑战，需要仔细控制压力和温度，如EP 0 553 522中所述。根据上述文件，温度不应过高以避免泡沫破裂，也不应过低以限制泡沫膨胀。此外，在离开模具之前，压力必须足够高，以防止过早发泡。因此，必须仔细控制复合物流的粘度，并使其适用于每种材料组成。
DE 10 2019 110 423提出了一种复合型材，该复合型材包括泡沫芯，该泡沫芯在空气中发泡至高达250kg/m3的密度，并且该复合型材在其一侧上包括至少一个通过共挤出施加的功能元件。
尽管现有技术的建议为如何提高泡沫材料的硬度的问题提供了解决方案，但硬度的增加通常伴随着弯曲强度的损失，因此到目前为止还没有发现可接受的折衷方案。
因此，仍然存在对低密度泡沫材料的需求，其物理性能与较高密度材料的物理性能相当，特别是在肖氏硬度和弯曲强度方面。
发明内容
令人惊讶地发现，这种需求可以通过具有低密度泡沫芯的泡沫材料来解决，特别是密度不超过400kg/m3的泡沫芯，其中泡沫芯至少部分被密度比泡沫芯高的表皮材料覆盖。
因此，本发明的第一个目的是一种具有低密度泡沫芯的泡沫材料，其中泡沫芯至少部分地被表皮材料覆盖，表皮材料具有比泡沫芯更高的密度，并且其中泡沫芯的密度不超过400kg/m3，并且其中表皮材料的密度至少为800kg/m3。
在本发明的过程中，密度通常根据DIN 53479进行测定。
令人惊讶的是，发现本发明的泡沫材料显示出低密度泡沫重量减轻的优点，同时表皮覆盖物提供了足够的肖氏硬度，同时对弯曲强度的影响最小。
在优选实施例中，泡沫芯的至少一个表面被表皮材料覆盖。在另一个优选实施方案中，泡沫芯的至少两个相对表面被表皮材料覆盖。
本发明特别关注低密度泡沫。因此，在优选实施方案中，泡沫芯的密度不超过325kg/m3，更优选不超过300kg/m3，特别是不超过250kg/m3。
在优选实施方案中，泡沫芯的密度大于40kg/m3，优选大于50kg/m3、更优选大于60kg/m3。特别优选密度为40至400kg/m3，优选60至300kg/m3的泡沫芯。
本发明的概念可以应用于各种不同的泡沫芯。在优选实施方案中，泡沫芯由选自聚苯乙烯(PS)、高抗冲聚苯乙烯(HIPS)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)、高密度聚乙烯(HDPE)、丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丁二烯嵌段共聚物(SBS)、苯乙烯-乙烯-丁烯共聚物(SEBS)及其共混物的聚合物制成。在一个特别优选的实施方案中，泡沫芯是挤出的聚苯乙烯(XPS)。
本发明的泡沫材料还具有可使用回收聚合物制造泡沫的优点。由于使用回收材料而引起的任何光学退化都可以通过用表皮材料覆盖泡沫的表面来补偿。因此，优选一个实施方案，其中泡沫材料包含至少20wt.-％的再循环聚合物，优选至少40wt.-％，特别是至少60wt.-％，分别基于泡沫材料的总重量。在一个特别优选的实施方案中，泡沫材料，特别是泡沫芯，完全由回收聚合物制成。
本发明的泡沫材料的有利性能尤其是通过将低密度泡沫芯与高密度表皮材料相结合来实现的。在一个优选的实施方案中，表皮材料具有至少1000kg/m3，特别是至少1100kg/m3的密度。令人惊讶的是，用更高密度的表皮材料覆盖低密度泡沫芯允许低重量和硬度的有利组合。在优选实施方案中，表皮材料的密度是泡沫芯密度的至少两倍。更优选的是表皮材料的密度，其比泡沫芯的密度高至少三倍。
本发明的泡沫材料结合了低重量和高硬度的优点而不损失柔韧性。在优选实施方案中，泡沫材料的总密度，即具有表皮覆盖物的总密度小于500kg/m3，优选100至400kg/m3、更优选150至250kg/m3。
表皮材料优选地适于泡沫芯。在一个优选实施方案中，表皮材料选自聚苯乙烯(PS)、高抗冲聚苯乙烯(HIPS)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)、高密度聚乙烯(HDPE)、聚对苯氧基(PPO)；聚氯乙烯(PVC)、丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丁二烯嵌段共聚物(SBS)、苯乙烯-乙烯-丁烯共聚物(SEBS)及其共混物。表皮材料的一种特别优选的材料是挤出聚苯乙烯(XPS)。在另一个优选实施方案中，表皮材料是高抗冲聚苯乙烯(HIPS)。表皮材料可以是固体材料或稍微发泡的材料。在优选的实施方案中，表皮材料可以包括一种或多种增强剂，优选玻璃纤维。
覆盖泡沫芯的表皮材料的厚度可以根据需要进行调整。然而，为了确保表皮材料所需的硬度，同时保持低密度泡沫的柔韧性，表皮材料的厚度优选为100至2000μm，更优选为150至1000μm，特别是300至700μm。
本发明构思进一步提供了这样的优点，即表皮材料可以仅应用于泡沫芯的一侧，从而节省材料成本。由于本发明的泡沫材料可以用作地板或墙壁覆盖物，因此优选的是，在安装之后至少任何可见的侧面都覆盖有表皮材料。
本发明的泡沫材料显示出许多有利且令人惊讶的特性，这将在下文中更详细地描述。应当理解，在泡沫芯仅部分被表皮材料覆盖的情况下，所给出的值是指泡沫芯的覆盖部分。
本发明的泡沫材料还提供了这样的优点，即泡沫芯的性质以及因此泡沫材料的性质可以根据需要进行调整，而不会影响光学性质。例如，可以添加阻燃剂，以改进安全措施并满足相应的法规要求。因此，在一个优选的实施方案中，泡沫材料的特征在于分别根据EN13501-1测定的至少E s1 d0级，优选至少D s1 d0级、最优选至少C s1 d0级的耐火性。
本发明的泡沫材料可以通过挤出生产，特别是通过共挤出将表皮材料直接挤出到泡沫芯上。在不受理论约束的情况下，认为共挤出工艺在泡沫芯和表皮材料之间产生了牢固的界面，从而实现了本发明泡沫材料的有利性能。
生产泡沫芯和共挤出的条件取决于材料的性质以及用于发泡的气体，并且本领域技术人员可以根据需要进行调整。在使用无定形聚合物作为泡沫材料的情况下，发泡温度优选选择为高于聚合物的玻璃化转变温度(Tg)。在一个特别优选的实施方案中，发泡温度选择为高于聚合物的玻璃化转变温度至少25℃，优选至少30℃，特别是至少40℃。在半结晶或结晶聚合物的情况下，发泡温度优选选择为高于结晶转变温度，并且优选在聚合物的结晶温度(Tc)和熔融温度(Tm)之间。玻璃化转变温度(Tg)、结晶温度(Tc)和熔融温度(Tm)可以根据标准方法确定，并根据科学表格进行描述。
为了施加表皮材料，表皮材料的质量温度优选选择为高于发泡温度。在无定形聚合物的情况下，表皮材料的质量温度优选比发泡温度高至少5℃，特别是比发泡温度高7至20℃。在使用半结晶或结晶聚合物作为表皮材料的情况下，挤出过程中表皮材料的质量温度优选选择为比各自的发泡温度高至少5℃，特别是比发泡温度高15-35℃。
在本发明的过程中，令人惊讶地发现，通过在泡沫的至少一个表面上提供比泡沫密度更高的表皮材料，可以显著改善低密度泡沫芯的物理性能，从而在不影响泡沫芯的弹性的情况下提高本发明泡沫材料的硬度。在一个特别优选的实施方案中，泡沫材料的特征在于根据ISO 178的E模量为至少0.1GPa，优选至少0.3GPa，最优选至少0.5GPa。
进一步优选的是一个实施方案，其中根据本发明的泡沫材料具有根据ISO 178(23℃，50％RH，20mm/min)的至少1.5MPa，优选至少5MPa，最优选至少10MPa的弯曲强度。
同样优选的是本发明的一个实施方案，其中根据DIN 53799，泡沫材料在15牛顿的Wegner试验中没有显示出可见的冲击。
本发明的泡沫材料的特别特征在于其令人惊讶的硬度，尽管其密度和重量较低。在优选实施方案中，泡沫材料具有根据ASTM D 3240测定的至少40，优选至少50，最优选至少60的肖氏O硬度。
此外，泡沫材料具有根据DIN 53505测定的至少60，优选至少70，最优选至少80的肖氏D硬度。
根据本发明的泡沫材料可以用于多种应用中。因此，本发明的另一个目的是将本发明的泡沫材料应用于隔热和/或隔音、密封、以减弱或消除振荡或振动为目的的阻尼、加固、作为结构元件和/或用于密封门、窗和立面或用于装饰目的的那些结构元件，特别是在建筑业、汽车行业和航空业。在一个特定的优选实施例中，本发明的泡沫材料用于装饰性模塑和/或用作基板，特别是用作踢脚板。
具体实施方式
实施例
将参照以下实施例更详细地描述本发明，这些实施例决不应被理解为限制本发明的范围和精神。
使用GPPS泡沫芯，在155℃的温度下以200kg/m3的密度发泡，制备了厚度为12.8mm、宽度为38mm的本发明泡沫材料的几个样品。通过在170℃的温度下共同挤出泡沫芯和表皮材料，用不同厚度的高抗冲聚苯乙烯表皮覆盖样品，并分析其力学性能。为了进行比较，提供了GPPS的低密度泡沫的性能，分别具有200kg/m3(对比例1)和400kg/m3(对比例2)的密度，而没有皮肤覆盖。
方法
密度根据DIN 53479测定
肖氏D硬度根据DIN 53505测定。
E模量根据ISO 178测定。
弯曲强度根据EN 12089测定。
本发明的泡沫材料是通过挤出制备的。从表1中提供的数据可以看出，与没有表皮材料的泡沫(对比例1和对比例2)相比，根据本发明的泡沫材料(实施例1、实施例2和实施例3)提供了具有改进的肖氏D硬度的优异性能组合，同时保持了其他机械性能。
表1
此外，本发明的泡沫材料在根据DIN 53799的Wegner测试后没有显示出可见的凹痕，而在对比例1和对比例2中使用的泡沫清楚地显示出在15牛顿下的冲击位置。Wegner试验的结果如图1所示，图片A和B分别描绘了200kg/m3和400kg/m3的普通泡沫，没有覆盖物，而图片C和D显示了本发明泡沫材料的例子。可以清楚地看到，在本发明的泡沫材料的情况下，几乎看不到冲击痕迹。

Claims (16)

1.一种具有低密度泡沫芯的泡沫材料，其中泡沫芯至少部分地被表皮材料覆盖，其特征在于，所述的表皮材料的密度高于泡沫芯的密度，并且所述的泡沫芯的密度不超过400kg/m3，并且所述的表皮材料的密度至少为800kg/m3。
2.根据权利要求1所述的泡沫材料，其特征在于，所述的泡沫芯的密度高于40kg/m3，优选高于50kg/m3、更优选高于60kg/m3。
3.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的泡沫材料的总密度小于500kg/m3，优选100至400kg/m3、更优选150至250kg/m3。
4.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的泡沫芯由选自聚苯乙烯(PS)、高抗冲聚苯乙烯(HIPS)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)、高密度聚乙烯(HDPE)、丙烯腈-丁二烯-苯乙烯(ABS)、苯乙烯-丁二烯嵌段共聚物(SBS)的聚合物制成，苯乙烯-乙烯-丁烯共聚物(SEBS)及其共混物的聚合物制成，特别是挤出聚苯乙烯(XPS)。
5.根据权利要求4所述的泡沫材料，其特征在于，所述的泡沫材料，特别是所述的泡沫芯，至少部分地由至少20wt.-％的回收聚合物获得。
6.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的表皮材料的密度为至少1000kg/m3，更优选为至少1100kg/m3。
7.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的表皮材料选自聚苯乙烯(PS)、高抗冲聚苯乙烯(HIPS)、聚对苯二甲酸乙二醇酯(PET)、聚丙烯(PP)、聚乙烯(PE)、高密度聚乙烯(HDPE)、聚对苯氧基(PPO)、聚氯乙烯(PVC)、丙烯腈-丁二烯-苯乙烯(ABS)，苯乙烯-丁二烯嵌段共聚物(SBS)、苯乙烯-乙烯-丁烯共聚物(SEBS)及其共混物，特别是高抗冲聚苯乙烯(HIPS)。
8.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的表皮材料为固体材料或稍微发泡的材料。
9.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的表皮材料的厚度为100至2000μm，优选为150至1000μm，最优选为300至700μm。
10.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的泡沫材料具有根据EN 13501-1测定的至少Es1 d0级的耐火性，优选至少D s1 d0级，最优选至少Cs1 d0级。
11.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的泡沫材料根据ISO178具有至少0.1GPa，优选至少0.3GPa，最优选至少0.5GPa的E模量。
12.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的泡沫材料根据ISO178(23℃、50％RH、20mm/min)具有至少1.5MPa，优选至少5MPa，最优选至少10MPa的弯曲强度。
13.根据前述任一项权利要求所述的泡沫材料，其特征在于，在根据DIN 53799的15牛顿的Wegner试验中，由表皮材料覆盖的泡沫芯的表面没有显示出可见的冲击。
14.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的泡沫材料具有根据ASTM D 3240测定的至少40，优选至少50，最优选至少60的肖氏O硬度。
15.根据前述任一项权利要求所述的泡沫材料，其特征在于，所述的泡沫材料具有根据DIN 53505测定的至少60，优选至少70，最优选至少80的肖氏D硬度。
16.根据权利要求1至15中任一项所述的泡沫材料在隔热和/或隔音、密封、以减弱或消除振荡或振动为目的的阻尼、加固、作为结构元件和/或用于密封门、窗以及立面或用于装饰目的的用途，特别是在建筑业，汽车行业和航空业，尤其是装饰成型和/或用作底板，尤其是用作踢脚板。
CN202280007458.2A 2021-07-14 2022-07-07 至少部分覆盖有表皮材料的低密度泡沫 Pending CN116669941A (zh)

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US4350730A (en) 1981-10-16 1982-09-21 Standard Oil Company (Indiana) Plastic laminate
US5215691A (en) 1990-09-05 1993-06-01 The Dow Chemical Company Method of forming a coextruded foam composite
IT1252203B (it) 1991-12-12 1995-06-05 Sviluppo Settori Impiego Srl Procedimento ed attrezzatura per la realizzazione di corpi di materiale polimerico con nucleo espanso.
US20110293914A1 (en) 2010-05-27 2011-12-01 Maurer Myron J Shaped foam composite article
WO2020065564A1 (en) 2018-09-25 2020-04-02 Proprietect L.P. Composite foam article
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