CN117500972A - 用作仿皮革的新型层状复合材料 - Google Patents
用作仿皮革的新型层状复合材料 Download PDFInfo
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- CN117500972A CN117500972A CN202280027202.8A CN202280027202A CN117500972A CN 117500972 A CN117500972 A CN 117500972A CN 202280027202 A CN202280027202 A CN 202280027202A CN 117500972 A CN117500972 A CN 117500972A
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Abstract
本发明涉及一种用作仿皮革的层状复合材料、包含该层状复合材料的服装以及制造该层状复合材料的方法。
Description
本发明的主题
本发明涉及一种用作仿皮革的层状复合材料、包含该层状复合材料的服装以及制造该层状复合材料的方法。
发明背景
皮革工业是极有可能造成环境污染的工业之一。鞣制时使用的化学品,特别是抗生素、鞣制剂、杀生物剂和挥发性有机化学品(例如甲醛),如果使用不当,可能会对环境造成持续损害。但是,相应地正确使用化学品需要大量金钱和时间投入。此外,所用的一些物质可能会保留在材料中,并可能在后续使用期间释放。这会给最终客户带来健康风险。动物皮的使用也存在伦理问题。
一段时间以来,人们在努力用合成生产的材料取代皮革。通常,这些替代品被称为人造皮革。这通常是一种纺织品基载体和施加至该载体的塑料层(如聚氯乙烯(PVC)或聚氨酯(PU))的复合材料。
DE 1 635 546 A描述了一种通过造纸方法生产的人造皮革,所述人造皮革基本由非纤维弹性聚氨酯以及短纤维(优选合成纤维或皮革纤维)的少量掺合料组成。
DE 199 37 808A1涉及一种皮革替代材料,其具有基本布状的载体层、施加于其上的较薄的阻隔层和设置在该阻隔层上的覆盖层。
DE 10 2015 101 331 A1涉及一种具有纺织品载体结构并且具有至少一层PU或PVC层的半透明人造皮革。该层状复合材料还可以具有表面涂层。
通过这些方法获得的人造皮革具有优于动物皮革的多个优点。PVC人造皮革便宜且坚固(robust),而PU人造皮革具有有利的材料性能,例如,可重复清洗性。由于人造皮革是一种连续材料,因此将其切割成一定尺寸也比动物皮革容易得多。由于消除了耗时的鞣制过程,制造过程也大大缩短。此外,人造皮革制造商不受某些动物皮市场供应的约束。
然而,先前已知的人造皮革材料基本基于合成塑料,所述合成塑料由有限的化石资源(例如石油)生产并且不是可生物降解的。另外,这种人造皮革材料通常仍然具有溶剂或分散剂残留物和软化剂,并因此对健康并不是完全无害的。此外,用人造皮革通常不能实现与用动物皮革相同的视觉和触觉性能。
上述许多问题通过EP 3 710 631 A1中公开的层状复合材料得以解决。其包括纺织品载体层、覆盖层和装饰层,所述装饰层包括植物叶片材料并且设置在载体层和覆盖层之间。然而,该层状复合材料所需的覆盖层导致人造皮革的生物降解性降低,从而降低其可持续性。此外,通常由合成聚合物材料组成的覆盖层的应用与额外的工作步骤有关,因此与更复杂的制造过程相关。此外,EP 3 710 631 A1的层状复合材料的应用范围受到限制,这与用植物叶片材料作为装饰层所能实现的性能有关。例如,浅色调的皮革颜色只有在装饰层中添加额外的(人造)染料才能实现。
发明目的
因此,在该背景下,本发明的任务是提供一种人造皮革,该人造皮革比已知的天然和/或人造皮革更容易生产,并且可以更环保和/或可持续的方式生产,所述人造皮革至少是部分可生物降解的,并且可以应用于尽可能广泛的领域。
发明详述
根据本发明,该任务通过用作仿皮革的层状复合材料解决,所述层状复合材料具有以下层或由以下层组成:
a)具有纺织品材料或由纺织品材料组成的载体层;以及
b)装饰层,
其中,
装饰层包含以下组分或由以下组分组成:
i.粘结剂;
ii.填充材料,其包括无机盐和/或木质素和/或植物叶片材料和树胶材料(优选淀粉胶)的组合;以及
iii.润湿剂。
与已知的皮革替代品,特别是由EP 3 710 631 A1已知的层状复合材料不同,根据本发明的层状复合材料不需要保护性覆盖层。这通过具有足够稳定性和耐久性的装饰层而成为可能。在根据本发明的层状复合材料中,装饰层因此不仅具有视觉和触觉功能,而且对层状复合材料的结构稳定性和柔韧性至关重要。
为此目的,装饰层总共具有三种组分:粘结剂、填料材料和润湿剂。粘结剂充当基质材料来保持填料材料,赋予装饰层机械稳定性。通过将填料材料嵌入粘结剂中,形成了柔性层,即可弹性拉伸且可弯曲但又稳定的层。第三种组分为润湿剂,其可以防止装饰层变干。装饰层还可以具有几种相应的组分,例如几种不同的润湿剂。在优选实施方式中,层状复合材料还可以具有多层装饰层和/或载体层。通过组合多个装饰层和/或载体层,层状复合材料的光学和结构性能可以更加单独的方式适应。
具体来说,装饰层的机械性能以及由此的层状复合材料的机械性能可以通过填料材料的性能、特别是其硬度来控制。例如,使用无机盐作为填料,通常可以获得明显更牢固(strong)的材料,而植物叶片材料作为填料往往会产生软的(即高柔性)的层状复合材料。木质素作为填料也会导致相对结实(firm)的装饰层。然而,取决于填料材料,装饰层不仅使层状复合材料具有良好的抓力、吸引人的外观和足够的稳定性,而且还能产生令人愉快的气味。这种效果尤其可以通过复合材料的各个层部分或完全进行针刺而不是胶合和/或压制来增强。以此方式,层状复合材料具有增加的渗透性。
通过使用各种无机盐或植物叶片材料或上述材料的混合物(可以与木质素结合),根据本发明的层状复合材料可用于再现几乎所有可想到的皮革颜色。根据本发明的层状复合材料因此可以用于各种不同的应用。
粘结剂用作填充材料的基质材料。因此,其以其设定形式(set form)存在于装饰层中,并因此使得填充材料能够稳固地结合到装饰层中。特别优选地,粘结剂是有机粘结剂。特别优选地,其是优选的有机聚合物粘结剂,例如,交联或部分交联的聚合物。通过粘结剂和填料的组合可以获得具有足够稳定性的装饰层,该装饰层同时是(弹性地)可变形的。层状复合材料在其他性能(如摩擦阻力和磨损性能)方面也类似于皮革材料。为了在更长的时间内保持这些性能、特别是通过填料材料和粘结剂的混合物所实现的性能,装饰层必须具有润湿剂。润湿剂是通过将水结合至其和/或从空气中吸收水分来防止装饰层变干的添加剂。这保持弹性变形能力。
根据本发明,“植物叶片材料”是指完整或切碎的未经处理或经处理的叶片,特别是叶尘。“经处理的叶片”是指已经通过发酵、化学处理(特别是用醇进行处理)或通过干燥进行保存的那些植物叶子或其切碎部分。在优选实施方式中,使植物叶片材料发酵,即,其经受发酵过程,使干燥的叶片达到适合储存和使用的状态。
作为替代或者附加方式,植物叶片材料可以在装饰层中使用前进行化学处理,优选使用水和多羟基醇(polyhydric alcohol)(例如甘油)的混合物进行化学处理。当植物叶片材料包含完整叶片或叶片部分或由完整叶片或叶片部分组成时,这是特别有利的。这为植物叶片材料提供了弹性变形能力和提高的破裂强度,特别是提高的抗张强度和抗弯强度。此外,已经确定,植物叶片材料还可以继续经历熟化过程,甚至在层状复合材料中进行,这改进了材料的变形能力和断裂强度。熟化过程的持续时间为至少一周,优选两周,更优选一个月,最优选两个月。如果任选的覆盖层具有蜡材料或由蜡材料组成时,特别提供了由熟化过程导致的性能改善。
如果装饰层的填充材料包括植物叶片材料,则与使用无机盐或木质素作为填充材料的实施方式不同,橡胶材料也必须是填充材料的组分。这是获得足够稳定但又柔性的装饰层的唯一方法,所述装饰层不需要用额外覆盖层来保护。树胶材料理解为包括杂多糖和多糖,其与溶剂如水形成高粘性(viscous)和黏(sticky)的溶液,其可以弹性地硬化,从而使具有植物叶片材料的装饰层具有稳定但又柔性的结构。特别优选的,树胶材料是淀粉胶(糊精)
在装饰层的填料材料是无机盐或木质素的情况下,在优选实施方式中,装饰层可以进一步具有树胶材料。
在优选的实施方式中,填充材料包括无机盐和/或木质素和/或植物叶片材料和树胶材料的组合,所述树胶材料优选淀粉胶。植物叶片材料和树胶材料的组合优选作为混合物、特别优选作为均匀混合物,在装饰层制造期间作为填充材料引入装饰层中。在另一优选实施方式中,植物叶片材料和橡胶材料在装饰层制造期间作为单独组分引入。
在本发明的优选实施方式中,当装饰层的填料材料包括植物叶片材料时,其基本不含木纤维。在本发明的上下文中,这意味着木纤维(例如来自木屑、锯末、树干和树枝的材料)的比例小于5重量%,优选小于1重量%,甚至更优选小于0.5重量%,最优选小于0.1重量%。相应的木纤维能对材料层状复合材料的视觉和触觉性能产生负面影响。
特别优选地,植物叶片材料选自:玫瑰叶(rose leaf)、葡萄藤叶、桂樱叶和烟草。特别优选的是植物叶片材料烟草。
烟草具有超越其它植物叶片材料的许多优点。作为原材料,它具有非常好的全年可获得性。由于对烟草的需求下降,通常生产能力过剩,能以低的价格购买。此外,烟草具有高天然生物碱含量,特别是尼古丁,其可用作杀虫剂。这可以使螨虫和其他害虫远离层状复合材料,并且可以获得特别耐用的仿皮革。此外,烟叶具有特别高的柔性和抗撕裂性,特别是在用水和多羟基醇的混合物处理之后。除了视觉性能外,天然气味也支持在仿皮革中使用烟草作为装饰层。这些有利性质在经发酵烟草的情况下特别明显。
在优选实施方式中,装饰层的植物叶片材料是精细研磨的烟草和/或烟草尘和/或烟草碎料,其中,植物叶片材料优选通过多糖粘结入装饰层中,即,粘结剂是多糖。在本发明的优选实施方式中,在形成装饰层之前,使多糖溶解或悬浮在溶剂或分散剂中,所述溶剂或分散剂具有润湿剂如多羟基醇(如甘油)或由其组成。
在另一优选实施方式中,植物叶片和/或部分区段和/或穗(panicle)是装饰层的植物叶片材料。该装饰层为层状复合材料提供特别自然且优异的外观,并且因此也可以称为饰面层。与动物鳄鱼皮或蛇皮的情况类似,该装饰层创造了层状复合材料的独特的、始终以不同方式结构化和鲜明的外观。为了获得视觉和触觉性质特别良好的复合材料,在本发明的优选实施方式中,将片材以重叠方式放置。这产生具有不同厚度的区段的装饰层。层状复合材料的这些“不规则性”给使用者留下了特别天然的仿皮革的印象。
根据本发明,“无机盐”理解为包含带正电的离子(阳离子)和带负电荷的离子(阴离子)的无机晶体物质。这些离子之间存在离子键。作为固体,其一起形成了负责材料强度的离子晶格。无机盐优选为矿物化合物,即,地球上物质均匀、天然的无机组分。术语无机盐还包括配位化合物,其包含一个或多个中心颗粒和一个或更多个配体。通过使用矿物,可以进一步提高层状复合材料中天然组分比例。
“木质素”是优选三维连接的酚类大分子组的统称。木质素如同装饰层的无机盐,可以赋予装饰层特别显著的强度。
在优选的实施方式中,填料材料或粘结剂用合成着色剂、或者优选用天然着色剂进行染色。这允许模仿各种类型动物皮革的光学性质。在本发明特别优选的实施方式中,着色剂是部分或完全食品安全的,并且/或者由可以作为生物营养素反馈到工艺循环中或者作为工艺养分在工艺循环中连续保存(摇篮到摇篮认证(cradle-to-cradlecertification))的物质组成。
在优选实施方式中,装饰层的厚度为0.1至10mm,优选0.1至5mm,更优选0.1至2mm,最优选0.2至1mm。
在优选实施方式中,装饰层的基量(克重)为100至3,000g/m2,更优选400至2,500g/m2,特别优选600至1800g/m2,最优选700至1200g/m2。由于低的单位面积重量,可以生产特别轻的层状复合材料。
该层状复合材料是稳定的,比动物皮革轻,耐刮擦且斥水。它的特征还为:耐擦性(rub fastness)、耐热性和优异的耐磨性。特别是用无机盐作为填充材料的版本,其特征在于高且持久的耐光性。由于不同且可组合的填料(植物叶片材料和橡胶材料、无机盐和/或木质素),层状复合材料的性能可以适应特定的应用。例如,通过使用二氧化钛作为填料,可以获得非常耐晒(lightfast)且明亮的层状复合材料。此外,由于双层结构,层状复合材料比现有技术中已知的仿皮革更容易且更快生产。通常,层状复合材料可以在载体层上的装饰层施加并干燥后使用。层状复合材料的大部分、在一些实施方式中甚至整个层状复合材料,进一步是可回收的,因为所使用的材料是可降解的和/或天然来源的。
在优选实施方式中,装饰层中填料材料的重量百分比为至少10重量%,更优选至少15重量%,甚至更优选至少20重量%,甚至显著更优选至少25重量%,甚至明显更优选至少30重量%,最优选至少40重量%,但也优选≤60重量%。高比例的填料材料提高了装饰层的机械性能,特别是其稳定性。
层状复合材料的装饰层可以包括一种或多种润湿剂剂。润湿剂防止装饰层变干,从而确保层状复合材料的装饰层保持永久柔性。考虑到根据本发明的层状复合材料不一定需要保护装饰层不会干掉的覆盖层,这是特别必要的。
在本发明的优选实施方式中,润湿剂选自:甘油,聚葡萄糖,山梨醇,多羟基醇和多元醇(polyalcohol)如1,2-丙二醇、二醇(glycol)或醛醇,芦荟凝胶,蜂蜜,氯化锂,糖蜜,脲,木糖醇,羟基羧酸,透明质酸以及透明质酸的盐或酯、三乙酸甘油酯,纤维素粉末、皂树提取物,脲,泛内酯或前述物质的混合物。
在优选实施方式中,装饰层中润湿剂的重量百分比为至少15重量%,更优选至少20重量%,甚至更优选至少25重量%,甚至显著更优选至少30重量%,甚至明显更优选至少35重量%,仍然显著更优选至少40重量%,最优选至少45重量%,但也优选≤60重量%。高比例的润湿剂改进了装饰层的弹性,并且由此防止褶皱(buckling)/破裂。
层状复合材料的装饰层可以包含一种或多种无机盐作为填料材料。
在本发明的优选实施方式中,一种或多种无机盐选自:卤化物,特别是氯化物和溴化物,氧化物,氢氧化物,硫化物,碳酸盐,硫酸盐,磷酸盐,硝酸盐以及上述物质的混合物。氯化物、溴化物、磷酸盐和硫酸盐是特别优选的。在本发明的优选实施方式中,无机盐是pH中性的,即0.1摩尔盐在水中的溶液的pH为5-9,优选6-8。通过这种方式,可以避免对层状复合材料其他组分的损害,并且可以获得更耐用的层状复合材料。
在本发明的优选实施方式中,无机盐包括金属阳离子,优选选自主族金属元素(main metallic group element),特别优选碱金属和碱土金属。特别优选地,无机盐不含重金属,即在无机盐中密度为g/cm3的金属的比例≤1重量%,优选≤0.1重量%。这确保了根据本发明的层状复合材料是特别可持续的和环境相容的。特别优选地,无机盐是矿物,特别优选白垩,高岭土(kaolin),高岭石(kaolinite),层状硅酸盐,尤其是粘土矿物,辉沸石,大理石、尤其是大理石粉末,铁氧化物、尤其是氧化亚铁(II)和氧化铁(III),氧化钛或沸石。因为其吸附能力,例如其可以用来吸收气味,沸石是特别优选的。
如果填充材料包括植物材料,则填充材料必须还包括树胶材料以确保获得稳定又柔性的装饰层。
橡胶材料优选选自阿拉伯树胶、黄芪胶、天然橡胶和合成橡胶的硫化物、刺梧桐橡胶和淀粉橡胶。
装饰层还包含至少一种粘结剂,即能够粘附到载体层并且填料材料可以结合在其中的成膜材料,从而在载体材料上形成其中包含填料材料的装饰层。粘结剂还赋予材料一定程度的柔性,这在用作仿皮革时是有利的。粘结剂可以是合成的聚合物材料。然而,为了提高层状复合材料的生物相容性和可持续性,粘结剂优选为生物聚合物,其优选由生物原材料,即可再生原材料组成或至少包括生物原材料,并且/或者是可生物降解的。特别优选地,粘结剂是基于植物或动物蛋白的胶凝剂,或基于多糖、特别是多糖如半乳糖聚合物的粘结剂。特别优选的是胶凝剂,其选自琼脂、壳聚糖、果胶和黄原胶、天然和合成树脂、明胶、海藻酸和海藻酸盐、纤维素、角叉菜胶、叉红藻胶(furcellan)、刺槐豆胶、瓜尔胶、黄芪胶、塔拉胶(tara gum)、结冷胶(gellan)、纤维素醚、改性淀粉、胶水或上述物质的混合物。
特别优选地,粘结剂和/或装饰层和/或层状复合材料基本上不含聚氨酯或聚氯乙烯,特别强烈地优选不含聚氨酯和聚氯乙烯。这是优选的,因为这些聚合物在其分解期间会部分释放出有毒的化合物。这使得可以获得特别生态安全的材料。在本文中,基本上不含是指聚氨酯和/或聚氯乙烯在粘结剂剂和/或装饰层和/或层状复合材料的总重量中的重量比例为≤20重量%,优选≤10重量%,更优选≤5重量%,更加优选≤2重量%,甚至更优选≤1重量%,最优选≤0.5重量%。
在优选实施方式中,装饰层中粘结剂的重量百分比为至少10重量%,更优选至少15重量%,甚至更优选至少20重量%,甚至显著更优选至少25重量%,甚至明显更优选至少30重量%,最优选至少40重量%,但也优选≤60重量%。高比例的粘结剂有利于获得其中填料材料可以均匀分布的稳定装饰层。
优选地,装饰层中粘结剂与填料材料的重量比为1:10至10:1,优选地为1:2至10:1,更优选地为1:1至5:1或1:2至2:1,甚至更优选地是1:1至3:1,最优选地为1:1至2:1。
优选地,装饰层中粘结剂与润湿剂的重量比为1:10至10:1,优选地为1:2至10:1,更优选地为1:1至5:1或1:2至2:1,甚至更优选地是1:1至3:1,最优选地为1:1至2:1。
在优选实施方式中,装饰层和/或层状复合材料中的水的重量比例为至少1重量%,更优选至少2重量%,还相当优选至少5重量%,还更优选至少10重量%,最优选至少15重量%,但还优选≤30重量%。
载体层确定了复合材料的结构强度并且确保了良好的可加工性,特别是通过缝纫对层状复合材料进行加工时尤为显著。
在优选的实施方式中,纺织品载体层具有选自下组的材料或由选自下组的材料组成:非织造织物、机织织物、针织织物、编织物、或上述物质的混合物。
非织造织物、机织织物、针织织物、编织物、或上述物质的混合物是包含纤维但纤维排列彼此不同的纺织品材料。
根据本发明,非织造织物理解为是指由有限长度的纤维、任意类型和任意来源的连续纤维(纤丝)或切制纱线(chopped yarn)制成的结构,其已以一些方式接合来形成纤维层,并且已经以一些方式彼此连接。这不包括机织、针织、蕾丝制作、编织和簇绒产品制造中出现的纱线交错(interlacing)或交织(intertwining)。该定义对应于标准DIN EN ISO9092。根据本发明,术语“非织造物”还包括毡织物。然而,薄膜和纸张并不属于非制造物。
优选地,非织造物是各向异性非织造物,即,具有纤维取向的那些。以此方式,可以产生层状复合材料的各向异性机械性能,由此提高其撕裂强度。
根据本发明,机织织物理解为由两个纱线体系(经纱(经线)和纬纱(纬线))组成的纺织品织物,如织物表面上观察,其根据图案以精确90°的角度或大约90°的角度彼此交叉。这两个体系各自可以由多个类型的经纱或纬纱构成(例如,地经、绒头(pile)经纱、和填充经纱(filling warp);地纬、接结纬(binding weft)和填充纬纱(filling weft))。经线沿着与织物边缘平行的织物纵向方向延伸,而纬线沿着与织物边缘平行的横向方向延伸。线主要通过摩擦连接至织物。为了使织物充分抗剪切,经线和纬线通常必须相对紧密地织造。因此,相对于少数例外,织物还具有致密织物外观。该定义对应于标准DIN 61100,第1部分。
根据本发明,术语机织物和非织造物还包括已簇绒的那些纺织品材料。簇绒是通过压缩空气和/或电力运行的机器,使纱线在机织织物或非织造织物中锚固的过程。
根据本发明,针织织物是指由线体系通过形成线迹所生产的纺织品织物。这包括钩编和针织的织物。
为了本发明的目的,编织是指几股柔性材料的规则交错。与机织的区别在于:编织时,线不会按照与产品的主方向成直角来进料。
非织造织物、机织织物、针织织物、编织物或这些材料的混合物的纤维可以是天然纤维、化学纤维或上述材料的混合物。
优选地,纤维是植物或动物来源的,或者是由天然聚合物或基于天然原料的聚合物所制成的化学纤维。以此方式,可以改进层状复合材料的天然组分的比例,并因此可以改进其可持续性和可生物降解性
优选地,天然纤维选自下组:种子纤维、韧皮纤维、叶纤维和动物纤维。特别优选地,这些材料选自下组:棉花、动物毛(animal wool)、动物发(animal hair)、丝绸、木棉、阿孔(acon)、杨树绒毛(poplar fluff)、竹纤维、荨麻纤维、大麻(hemp)、鼬瓣花(hempnettle)、黄麻、梵天花(urena)、亚麻、苎麻、洋麻、洛神葵(roselle)、印度麻(sunns)、青麻、蓬杉(pung)、蓖麻、剑麻、蕉麻(abaca)、柑桂(curaua)、菲比(fibe)、伊斯特尔野纤维(xtlefibre)、桄榔(arenga)、阿弗里克(afrik)、灰叶剑麻(hequen)、菲奎叶纤维(fique)、新西兰麻(phormium)、非洲蒲草(alfa)、龙舌兰(maguey)、丝兰、皮塔(pita)、椰子壳纤维(coir)、金雀花(broom)、蛇麻草(hop)、芦苇和棕榈叶纤维(raffia)。
优选地,化学纤维选自天然聚合物或基于天然原料的聚合物。特别优选地,这些材料选自下组:粘胶、莫代尔、莱赛尔、醋酸铜纤维(curpo)、乙酸纤维素、蛋白质纤维(例如酪蛋白纤维)、聚交酯、藻酸盐、甲壳素、生物基聚酰胺、聚酯和聚异戊二烯。
在另一实施方式中,化学纤维由选自下组的合成聚合物制成:聚酯,例如PET或PBT,聚酰胺,聚酰亚胺,聚酰胺酰亚胺,芳族聚酰胺,聚(甲基)丙烯酸酯,变性聚丙烯腈(modyacryl),聚四氟乙烯(PTFE),聚乙烯,聚丙烯,多氯化物,PVC,氨纶,聚苯乙烯,聚碳酸酯,聚乙烯醇,乙烯醇纤维(vinylal)、聚苯硫醚、三聚氰胺、聚脲、聚氨酯、聚苯并咪唑、聚苯并噁唑。
在优选实施方式中,纺织品载体层的厚度为0.1至10mm,优选0.1至5mm,更优选0.1至2mm,最优选0.2至1mm。
在优选实施方式中,载体层的基量(克重)为50至500g/m2,更优选65至300g/m2,特别优选80至200g/m2,最优选90至150g/m2。通过低的单位面积重量可以生产特别轻质的层状复合材料。
层状复合材料还可以具有其它层。优选地,这些层选自下组:载体层、装饰层、粘合剂层和覆盖层。特别优选地,层状符合材料具有设置在载体层和任选的覆盖层之间的一层或多层附加装饰层。在优选实施方式中,附加层设置在载体层两侧上。在本文中,特别优选的是所述层相对于载体层的对称设置,例如,如下层顺序:第一覆盖层、第一装饰层、载体层、第二装饰层、第二覆盖层。
在本发明的优选实施方式中,层状复合材料仅具有粘合剂层作为其它层。在另一优选实施方式中,层状复合材料不具有除了载体层和装饰层之外的层。
在优选实施方式中,这些附加层的单独厚度为0.1至10mm,更优选0.2至8mm,特别优选0.5至5mm,最优选0.8至3mm。
在优选实施方式中,附加层的基量(克重)为50至200g/m2,更优选65至300g/m2,特别优选80至200g/m2,最优选90至150m2。低的单位面积重量特别允许生产轻质的层状复合材料。
在优选实施方式中,层状复合材料可以具有一层或多层粘合剂层。粘合剂层的粘合剂可以是化学固化和/或物理凝固(setting)的。
粘合剂层的粘合剂优选选自下组:氰基丙烯酸酯、甲基丙烯酸甲酯、不饱和聚酯、分散体粘合剂、包含溶剂或分散体的湿粘合剂、包含分散体的湿粘合剂、蛋白质基粘合剂、热熔粘合剂、增塑溶胶、环氧粘合剂、聚氨酯粘合剂、硅酮、树脂(特别是酚醛树脂)、聚酰亚胺、多硫化物、聚(甲基)丙烯酸酯、聚乙酸乙烯酯、橡胶和双马来酰亚胺。
为了以极其环保的方式生产该材料,特别优选蛋白质粘合剂。
优选地,粘合剂通过化学硬化或通过冷却凝固来固化。以此方式,可以使用少量的溶剂或分散剂,或者甚至可以完全省去溶剂或分散剂。这不仅具有特别高的可持续性,通常层状复合材料内的加工时间和粘结也更好。
在其它有利的实施方式中,特别是一个、多个或全部载体层和/或任选的覆盖层和/或任选的粘合剂层的拉伸强度和/或弯曲强度大于至少一个装饰层的拉伸强度和/或弯曲拉强度。
拉伸强度,也就是撕裂强度,其是主体经受的最大拉伸应力。其可以通过拉伸试验来确定。
抗弯拉强度(bending tensile strength)是在经受弯曲时主体可以承受的最大拉伸应力。其可以通过3点或4点弯曲拉伸试验来确定。
在有利的实施方式中,如果一个、多个或全部载体层和/或任选的覆盖层和/或任选的粘合剂层的强度(特别是拉伸强度和/或抗弯拉强度)大于至少一个装饰层时,载体层和/或任选的覆盖层和粘合剂层可以承受经受机械应力时的所产生应力,因此至少一个装饰层不会破裂,或者仅在更高应力下破裂,由此,在确定外观的层中出现了不利的裂纹。
特别优选地,装饰层、甚至优选整个层状复合材料的弹性模量(拉伸)≤3GPa,更优选≤2GPa,甚至更优选≤1.5GPa,还更优选地≤1GPa,并且最优选≤0.5GPa。
任选的覆盖层具有塑料、蜡或蛋白质材料或橡胶材料和粘合剂的组合或上述材料的混合物,或者由其组成。其主要用于保护下方装饰层免受外部影响,例如湿气、磨损和/或辐照。因此,其优选覆盖至少50%的下方层表面,优选超过70%,更优选超过80%,并且最优选超过90%。
在非常高的强度、防水性和耐磨性要求的情况下,优选塑料材料。根据本发明,这意味着所有由天然或合成来源的大分子组成的材料。
在优选实施方式中,塑料材料具有选自下组的材料或由选自下组的材料组成:聚丙烯(PP);聚乙烯(PE);聚乙烯醇缩丁醛(PVB);聚酰胺(PA);聚酯,尤其是聚对苯二甲酸丁二酯(PBT)和聚对苯二甲酸乙二酯(PET);聚氨酯(PU);聚环氧乙烷;聚苯醚;热塑性聚氨酯(TPU);聚脲;聚缩醛;聚丙烯酸酯;聚(甲基)丙烯酸酯;聚甲醛(POM);聚乙烯醇缩醛;聚苯乙烯(PS);丙烯酸-丁二烯-苯乙烯(ABS);丙烯腈-苯乙烯-丙烯酸酯(ASA);多糖,特别是果胶和琼脂;聚碳酸酯;聚醚砜;聚磺酸酯;聚四氟乙烯(PTFE);聚脲;甲醛树脂;三聚氰胺树脂;聚醚酮;聚氯乙烯;聚交酯;聚硅氧烷;酚醛树脂;环氧树脂;聚酰亚胺;双马来酰亚胺-三嗪;热塑性聚氨酯;乙烯-乙酸乙烯酯(EVA);聚交酯(PLA);聚羟基丁酸(PHB);上述聚合物的共聚物和/或混合物。特别优选PE、PET、PU和PA。
优选地,塑料以薄膜形式使用。根据本发明,这理解为是指以层厚度<5mm、优选<1mm的幅材所生产的薄片状塑料材料。
在高的触感、气味和外观要求的情况下,蛋白质材料或蜡的覆盖层是优选的。
根据本发明,蜡理解为是指天然或人工获得的物质,其在20℃下是可捏合的,呈固体至硬脆,具有粗糙至精细的晶体结构,是有色半透明至不透明的但不是玻璃状的,高于40℃时熔融而不分解,刚高于熔点时呈略液状,即,有点粘稠,具有很强的温度依赖连贯性和溶解性,并且可以在轻压力下进行抛光。这对应于根据罗姆普化学词典(ChemieLexikon),第10版,1999年,乔治·蒂姆出版社(Georg Thieme Verlag)的定义。
蜡可以区分天然蜡、化学改性蜡和合成蜡。在本发明的优选实施方式中,蜡材料选自下组:天然蜡,特别优选选自植物蜡的组,特别是小烛树蜡、巴西棕榈蜡、日本蜡、西班牙草蜡(esparto grass wax)、软木蜡(cork wax)、小冠挪子腊(guaruma wax)、米糠油蜡(rice germ oil wax)、甘蔗蜡、蜡叶油椰蜡(ouricury wax)、褐煤蜡。
在另一优选实施方式中,天然蜡选自动物蜡和矿物蜡,特别是选自蜂蜡、紫胶蜡、鲸蜡、羊毛脂(羊毛蜡)、刷脂(brushing fat)、微晶蜡(ceresin)、地蜡(ozokerite/earthwax)。
天然蜡提供了如下优点:其并不是石油基的,因此有助于层状复合材料的可持续性和可生物降解性。
在另一实施方式中,蜡选自化学改性蜡或合成蜡,特别是选自褐煤酯蜡(montanester wax)、沙索蜡(sasol wax)、石蜡、氢化霍霍巴蜡、聚亚烷基蜡、聚乙二醇蜡。
在其它优选实施方式中,层状复合材料的任选的覆盖层具有蛋白质材料或由蛋白质材料组成。优选地,这些材料是植物来源的蛋白质。这里,羽扇豆、大豆、豌豆、亚麻籽、小麦、玉米和/或油菜籽中所含的蛋白质是特别优选的。
在其它实施方式中,蛋白质是动物来源的,并且明胶、酪蛋白、乳清蛋白和/或其衍生物是特别优选。
蛋白质涂层的优点是生产蛋白质层的成本非常低,并且对健康无害。所述层还可以在没有有机溶剂(即,是水基的)的情况下进行加工过。还应强调的是,蛋白质覆盖层由可生物降解以及自粘或粘性的可再生原料组成。
在优选实施方式中,任选的覆盖层的厚度为5μm至1mm,更优选10μm至0.5mm,特别优选20μm至0.1mm,最优选50μm至0.1mm。
任选的覆盖层正如装饰层那样,还可以具有添加剂,如染料、UV填料、粘结剂或其它填料。通过添加添加剂和填料,可以改变层的性能,特别是颜色、强度和制造价格。
在优选的实施方式中,覆盖层包括粘合剂(优选琼脂)、树胶材料(优选糊精)和润湿剂剂的组合或由该组合组成。这样的覆盖层为层状复合材料提供了特别高的耐刮擦性。覆盖层可以进一步帮助改进置于下方的层的色牢度。
本发明还包括根据本发明的层状复合材料和包含根据本发明层状复合材料的制品的各种用途。
该层状复合材料是牢固的,比动物皮革轻,耐刮擦以及斥水。因此,其可以优选用作服装和时尚配件的材料。根据本发明,服装(clothing)定义为所有材料的总和,作为人造覆盖物,以或多或少的紧身方式围绕着人体。其还包括头饰(headgear),尤其是帽子,以及鞋子。根据本发明,时尚配件是指用于服装的配件。其优选是皮带、手套、扇、阳伞或雨伞、包、围巾和珠宝,尤其是表带。所有这些材料都可以包括根据本发明的层状复合材料。
该层状复合材料还可用于家具的覆盖物和装饰物,特别是用于汽车设备。因此,本发明还涉及包括根据本发明的层状复合材料的覆盖物和装饰物。特别优选地,这涉及机动车内部配件的装饰物和覆盖物,特别是座椅和仪表板的装饰物。
在优选实施方式中,装饰层的粘结剂在可见光波长范围内的透射率为≥30%,优选≥50%,更优选≥70%,并且最优选≥90%。这使得填充材料(例如烟草或无机盐)的光学性能特别突出。
在其它优选实施方式中,纺织品载体层和装饰层的粘结剂在可见光波长范围内的透射率≥30%,优选≥50%,更优选≥70%,并且最优选≥80%。这可以获得层状复合材料,该层状复合材料可以特别良好地进行背光照明,并且因此可以用于照明领域的各种应用中,例如,用作灯罩或用于机动车的内部。
本发明还涉及包括用于生产层状复合材料的方法,所述方法具有以下步骤:
A)将以下组分、优选将以下组分作为混合物施加至纺织品载体层,以获得装饰层,所述装饰层设置在载体层上、并且优选覆盖≥90%的载体层的平面侧:
i.粘结剂;
ii.填充材料,其包括无机盐和/或木质素和/或植物叶片材料和树胶材料(例如,淀粉胶)的组合;以及
iii.润湿剂;
iv.任选地:有机或无机溶剂。
任选地:层状复合材料进行干燥,即,去除层状复合材料中所含的溶剂,直到出现重量恒定(即在50℃下干燥时每小时重量损失小于0.1%),优选在≥30℃的温度下进行。
根据本发明,施加理解为是指为在层之间建立稳固结合。这可以通过粘结、使层固化、针刺或3D打印来完成。
在本发明的优选实施方式中,在生产方法中使用转移膜。
在优选实施方式中,可以将已经固化的层,例如固化的、即凝固(set)的装饰层施加到载体层。为了制备固化的装饰层,上述组分可以优选作为混合物施加到非粘附基材上以形成连续层。在粘结剂凝固后,例如通过物理干燥或化学交联凝固,将所得到的装饰层从基材上去除并施加到载体层上。该施加可以通过将粘合剂施加到载体层和/或已经固化的装饰层上,将装饰层置于载体层上,并将这些层(优选在压力下)压在一起来完成。替代地和/或附加地,层可以进行针刺。
在另一优选实施方式中,粘结剂可以以其非凝固形式施加到纺织品载体层上,使得其在施加后通过物理(例如溶剂的蒸发)和/或化学过程(例如交联、聚合或氧化)凝固,即固结(solidify),并且形成稳固但柔性的装饰层。粘结剂优选在溶剂中施加到纺织品载体层,其优选还包括其它组分,即填料和润湿剂。粘结剂的凝固优选在≥30℃、更优选≥50℃的温度下发生。
包含粘结剂、填料材料和润湿剂的组合物的固化和装饰层的形成也可以在升高的温度、压力和/或辐照的影响下进行。
如果根据本发明的层状复合材料具有任选的覆盖层,那么在该方法的特别优选的实施方式中,聚乙烯层可以在用于纸制品的层压设备中粘附到装饰层上。
在本发明的另一个实施方式中,仍待固化的组合物可以施加至装饰层以形成任选的覆盖层。例如,一种或多种蜡可以施加至装饰层,从而在装饰层上固化。
组合物的固化和任选的覆盖层的形成也可以在升高的温度、压力和/或辐照的影响下发生。
在本发明的另一实施方式中,这些层还额外进行针刺。对这些层进行针刺的优点在于,可以显著提高渗透性,例如对于气体(如水蒸气)的渗透性。
由于载体层通常作为连续幅材提供,因此层状复合材料可以以连续工艺生产,这与动物皮革生产中使用的不连续工艺相比是相当大的优点。
丝网印刷的覆盖层在纺织品行业是常见的,也已作为任选的覆盖层成功进行测试。在本文中特别优选的是由用于纺织品印刷的水基混合体系制成的覆盖层。这些水基混合体系具有水基粘结剂,特别是合成树脂分散体粘结剂,其优选具有≥80%的透明度和/或包含其他组分,例如颜料、粘合促进剂或填料。不含有机溶剂或分散剂、邻苯二甲酸酯、甲醛、烷基酚和烷基酚乙氧基化物的水基混合体系是特别优选的。水基混合体系优选是无标记、无毒且对皮肤友好的。
在施加至装饰层之后,水基混合体系优选在供应热量的情况下进行干燥,然后在150℃至160℃的温度下进行热固定。固定可以使用压铸机、烘道、热风枪、熨斗、熨烫机或在烤箱中完成。在上述温度下,熔融时间为2-3分钟。
在特别优选的实施方式中,生产方法按如下所述进行。首先,载体层通过辊运输。在后续区段中,将未凝固粘结剂、填料和润湿剂的混合物施加到载体层上,进行干燥并任选地进行压制。还可以提供额外覆盖层。如果覆盖层是薄膜形式的塑料材料,则可以通过经加热的压延机进行粘附。
在本发明的优选实施方式中,该方法具有以下附加工艺步骤中至少一个,优选所有以下附加工艺步骤:
B)在施加至载体层之前,将填料材料、粘结剂和润湿剂溶解和/或分散在一种或多种水性溶剂和/或分散剂中,
C)在施加至支撑物或覆盖层之后,去除一种或多种水性溶剂和/或分散剂,优选在升高的温度和/或降低的压力下去除,由此形成装饰层。
任选的:
D)对所述层状复合材料的至少两层进行针刺和/或粘结;
E)对装饰层进行压花,优选地用辊、压延机或压机进行压花。
在优选实施方式中,步骤A)至E)以A)、B)、C)、D)、E)的顺序进行。
通过对装饰层进行压花,表面结构受到影响,从而获得在视觉上更接近天然皮革层的层。这种结构化还可以用于隐藏装饰层中的缺陷。当木质素或无机盐用作填充材料时,这种压花是特别有利的,因为这可以破坏装饰层通常相对均匀的外观。
在优选实施方式中,润湿剂可以是一种或多种水性溶剂和/或分散剂中的一种或多种。
在使用植物叶片材料和橡胶材料的组合作为填料材料的方法的优选实施方式中,在将填料材料施加到纺织品载体层之前,先将粘合剂施加至植物叶片材料和/或载体层。通过这种方式,可以在载体层和装饰层之间实现特别牢固的结合。
在该方法的优选实施方式中,复合材料的层在升高的压力下进行压制,压制在压铸机(transfer press)中和/或使用升高的温度进行。
在该方法的优选实施方式,水性溶剂或分散剂具有粘结剂,所述粘结剂优选选自多糖,特别是琼脂、果胶、黄原胶、天然和合成树脂、明胶、海藻酸盐、壳聚糖、纤维素醚、改性淀粉、胶水或上述物质的混合物。由于粘结剂,在该制造过程中,填料、粘结剂、润湿剂和溶剂的组合物具有更高的粘度。这使其更容易施加至载体层。如果溶剂或分散剂是水和多羟基醇(特别是甘油)的混合物,则该效果特别显著。
在本发明的优选实施方式中,水性溶剂或分散剂因此包括醇,优选多羟基醇,例如甘油、乙二醇(glycol)、聚乙二醇或聚环氧乙烷。
实施例
现在参考根据本发明的层状复合材料的具体实施方式、生产实施例以及附图对本发明进行进一步解释。
在以下实施方式中,层状复合材料具有包含相应单元格中所列材料的层。这些层或填料材料具有相应单元格中所述的材料或由其组成。
1.植物叶片材料和橡胶材料的组合作为装饰层的填料材料的实施方式
以下层状复合材料中的粘结剂优选为琼脂。润湿剂优选为甘油。
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2.用木质素作为装饰层的填料材料的实施方式
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3.用无机盐作为装饰层的填料材料的实施方式
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4.具有不同装饰层的实施方式
以下层状复合材料中的粘结剂优选为琼脂。润湿剂优选为甘油。
# | 载体层 | 装饰层填料材料 |
D1 | 亚麻非织造织物 | 玫瑰叶和糊精 |
D2 | 机织织物 | 玫瑰叶和糊精 |
D3 | 针织织物 | 玫瑰叶和糊精 |
D4 | 亚麻非织造织物 | 葡萄藤叶和糊精 |
D5 | 机织织物 | 葡萄藤叶和糊精 |
D6 | 针织织物 | 葡萄藤叶和糊精 |
D7 | 亚麻非织造织物 | 玫瑰叶和糊精 |
D8 | 机织织物 | 玫瑰叶和糊精 |
D9 | 针织织物 | 玫瑰叶和糊精 |
D10 | 亚麻非织造织物 | 葡萄藤叶和糊精 |
D11 | 机织织物 | 葡萄藤叶和糊精 |
D12 | 针织织物 | 葡萄藤叶和糊精 |
D13 | 亚麻非织造织物 | 玫瑰叶和糊精 |
D14 | 机织织物 | 玫瑰叶和糊精 |
D15 | 针织织物 | 玫瑰叶和糊精 |
D16 | 亚麻非织造织物 | 葡萄藤叶和糊精 |
D17 | 机织织物 | 葡萄藤叶和糊精 |
D18 | 针织织物 | 葡萄藤叶和糊精 |
5.具有额外层的实施方式
以下层状复合材料中的粘结剂优选为琼脂。润湿剂优选为甘油。
制造实施例
将50克玫瑰叶分散在50毫升的甘油、糊精(dextrin)和琼脂在水中的混合物中,并在倾析溶剂或分散剂后,将其施加到克重100g/m2的亚麻非织造织物的表面部分。通过在50℃下进行空气干燥来去除水性溶剂或分散剂,从而在载体层上获得均匀的装饰层。
附图的简要说明
图1:根据本发明的具有载体层和装饰层的层状复合材料的示意性截面图。
图2:根据本发明的具有载体层、装饰层和覆盖层的层状复合材料的示意性截面图。
图3:根据本发明的具有载体层、装饰层、第二装饰层和覆盖层的层状复合材料的示意性截面图。
附图标记
1 载体层
2 装饰层(无机盐作为填料材料)
3 覆盖层
4 第二覆盖层(烟草和糊精作为填料材料)
附图详述
图1显示了根据本发明的层状复合材料的分层结构,其具有载体层1和装饰层2。装饰层2包含无机盐作为填充材料。
图2显示了根据本发明的层状复合材料的分层结构,其具有载体层1、装饰层2和覆盖层3。装饰层2包含无机盐作为填充材料。
图3显示了根据本发明的层状复合材料的分层结构,其具有载体层1、装饰层2、覆盖层3和额外第二装饰层4,所述额外第二装饰层4设置在装饰层2和覆盖层3之间。装饰层2包含无机盐作为填充材料。额外第二装饰层包含烟草和糊精的组合作为填料材料。覆盖层3通过粘合剂(由液滴显示)粘结至第二装饰层。
Claims (12)
1.用作仿皮革的层状复合材料,其具有以下层:
a)具有纺织品材料的载体层;以及
b)装饰层,
其特征在于,
装饰层包含以下组分:
i.粘结剂;
ii.填料材料,其包括无机盐和/或木质素和/或植物叶片材料和树胶材料的组合;以及
iii.润湿剂。
2.如权利要求1所述的层状复合材料,其中,润湿剂选自下组:甘油,聚葡萄糖,山梨醇,多羟基醇和多元醇如1,2-丙二醇、乙二醇或醛醇,芦荟凝胶,蜂蜜,氯化锂,糖蜜,脲,木糖醇,羟基羧酸,三乙酸甘油酯,皂树提取物,脲,泛内酯或前述物质的混合物。
3.如前述权利要求中任一项所述的层状复合材料,其中,无机盐选自下组:铁氧化物、二氧化钛、白垩、高岭土、大理石粉末和沸石。
4.如前述权利要求中任一项所述的层状复合材料,其中,树胶材料选自下组:阿拉伯树胶、黄芪胶、刺梧桐胶和淀粉胶。
5.如前述权利要求中任一项所述的层状复合材料,其中,粘结剂优选多糖,所述多糖选自下组:琼脂、壳聚糖、果胶和黄原胶、天然和合成树脂、明胶、海藻酸盐、纤维素醚、改性淀粉、胶水或上述物质的混合物。
6.如前述权利要求中任一项所述的层状复合材料,其中,粘结剂与填料材料的重量比范围为1:10至10:1,优选1:2至2:1。
7.如前述权利要求中任一项所述的层状复合材料,其中,粘结剂与润湿剂的重量比范围为1:10至10:1,优选1:2至2:1。
8.如前述权利要求中任一项所述的层状复合材料,其中,载体层具有非织造物,优选亚麻非织造物;和/或机织织物,优选天然纤维、化学纤维或混纺织物。
9.如前述权利要求中任一项所述的层状复合材料,其中,所述层状复合材料具有一层或多层粘合剂层。
10.一种服装,其包括如前述权利要求中任一项所述的层状复合材料。
11.一种制造如权利要求1-9中任一项所述的层状复合材料的方法,所述方法包括以下步骤:
A)将以下组分施加至纺织品载体层,以获得设置在载体层上的装饰层,优选覆盖≥90%的载体层平面侧:
i.粘结剂;
ii.填料材料,其包括无机盐和/或木质素和/或植物叶片和树胶材料如淀粉胶的组合;以及
iii.润湿剂。
12.如权利要求11所述的方法,其特征在于,所述方法包括以下额外步骤:
B)填料材料、粘结剂和润湿剂在施加至载体层之前溶解和/或分散在一种或多种水性溶剂和/或分散剂中;
C)在施加至载体层之后,去除一种或多种水性溶剂和/或分散剂,优选在升高的温度和/或降低的压力下去除,从而形成装饰层;以及
任选地:
D)对所述层状复合材料的至少两层进行针刺和/或粘结;
E)对装饰层进行压花,优选地用辊、压延机或压机进行压花。
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