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CN101903589B - 基础内衬、其生产方法和应用 - Google Patents

基础内衬、其生产方法和应用 Download PDF

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Publication number
CN101903589B
CN101903589B CN2008801209708A CN200880120970A CN101903589B CN 101903589 B CN101903589 B CN 101903589B CN 2008801209708 A CN2008801209708 A CN 2008801209708A CN 200880120970 A CN200880120970 A CN 200880120970A CN 101903589 B CN101903589 B CN 101903589B
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China
Prior art keywords
fabric
starch
weight
base interlining
unsaturated carboxylic
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CN101903589A (zh
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斯文·戈默特
克里斯特·德拉克索
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Johns Manville
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Johns Manville
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Abstract

本发明涉及新型粘结剂系统及其用于粘结织物的用途，以及涉及包含这种经粘结的织物的产品。本发明的材料可用于生产基础内衬，其可用于生产用于衬板、屋顶膜和密封膜的基础内衬，特别是用于生产被涂覆的衬板、屋顶膜和密封膜。

Description

基础内衬、其生产方法和应用
本发明涉及新的粘结剂系统及其在织物中的应用，以及涉及包含所述粘结剂系统的产品或用其配备的织物。
织物，特别是用于生产屋顶膜的基础内衬，必须满足许多要求。特别地，基础内衬要具有足够的机械稳定性，诸如，例如在加工(诸如用沥青处理或铺设)中存在良好的顶破强度以及良好的抗拉强度。另外，要求具有在例如用沥青处理期间的高热稳定性或抗辐射热的稳定性以及抗火蔓延。因此，已经进行了许多试验来改善目前的与这些要求有关的基础内衬。
一种改善方法是将基于合成的无纺织物的非织造织物与增强纤维诸如玻璃纤维组合，以便改善它们的机械稳定性。关于这种密封膜的实施例可参见文献GB-A-1,517,595，DE-Gbm-77-39，489，JP-A-81-5879，EP-A-160，609，EP-A-176-847，EP-A-403，403和EP-A-530，769。所述非织造织物和所述增强纤维根据目前的工艺水平进行粘结，即使用粘结剂粘合或采用由不同材料制成的层的针刺进行粘结。
另一个改善方法是通过针织或缝编粘结生产复合材料(DE-A-3,347,280，US-A-4,472,086，EP-A-333，602和EP-A-395，548)，或通过实现双组分纤维形式的增强纤维与基于合成纤维的非织造织物的组合(US-A-4,504,539和EP-A-0,281,643)。
目前工艺水平已知的产业用织物显示良好的应用特异性性质，但是，永久性的任务仍是改善这些产品，并且如果可能的话，不增加生产成本。
因此，本发明的任务是提供改善的织物，其特别适合用作用于被涂覆的衬板、屋顶膜和密封膜的基础内衬，并且其可以合理的价格以商业量生产。本发明的另一个任务是确保所述织物可通过已知的和已确立的方法配备涂层。令人惊讶地，目前已发现用特定的粘结剂系统硬化的织物具有改善的热尺寸稳定性，并且与吸水性无关地，老化特性、挠性或稳定性不显著降低。
因此，本发明的目的是用粘结剂系统硬化的织物，所述粘结剂系统包含：
a)10到90重量％的基于脂肪族共轭二烯和乙烯基芳香族化合物的聚合产物的水性分散体，
b)90到10重量％的淀粉，
c)0到10重量％的添加剂，
其中重量百分数的数值与粘结剂系统的干质量(即无水)相关。
本发明的另一个目的是根据本发明使用的粘结剂系统。
令人惊讶地，用本发明的粘结剂系统生产的织物与只用组分a)粘结的织物相比具有更高的热尺寸稳定性。还令人惊讶地，尽管本领域技术人员会预期发生恶化，但是稳定性和老化特性保持是稳定的。
根据本发明硬化的织物与只具有组分b)作为粘结剂的织物相比具有改善的稳定性、老化特征和挠性。
通过部分地使用淀粉作为替代物，可实现显著的成本节约。另外，获得了完全无甲醛的粘结剂系统，而不必接受产品性质的削减。令人惊讶地，产品性质甚至有所改善。
根据本发明使用的基于脂肪族共轭二烯和乙烯基芳香族化合物的聚合产物的水性分散体本身是已知的。适合的分散体和生产方法描述于，例如，DE-A-2602445，DE-A-2602444和US-B-3575913中。
一般地，可将已知的乳化剂或保护性胶体加入，以稳定所述水性聚合物分散体。这些是本领域技术人员已知的(参见，Houben-Weyl，Methoden der org.Chemie，vol.XIV/1，1961，Stuttgart)。乳化剂的实例是聚烷撑二醇，磺化的石蜡烃，高级烷基硫酸酯盐(例如月桂基硫酸酯盐)，脂肪酸的碱金属盐诸如硬脂酸钠或油酸钠，乙氧基化的脂肪酸醇的硫酸半酯，烷基聚氧乙烯磺基丁二酸的酯和半酯的盐，磺化的烷基芳香化物的盐诸如十二烷基苯磺酸钠，乙氧基化的C4-C12-烷基酚类和它们的磺化产物，以及磺基琥珀酸的酯。保护性胶体的实例是烷基羟基烷基纤维素，部分水解或完全水解的聚乙烯醇和它们的共聚物，丙烯酸，它们的均聚物和共聚物以及部分中和的盐，丙烯酰胺共聚物，聚丙烯酸酯共聚物和它们的盐，羧基烷基纤维素诸如羧甲纤维素及其盐。
另外，所述聚合物分散体可具有被插入所述聚合物中用于稳定目的的羧基。
根据本发明使用的所述水性分散体一般通过以下物质在水、乳化剂和水溶性引发剂的存在下进行的乳液聚合生产：
a)20到80重量份的脂肪族共轭二烯，
b)20到80重量份的乙烯基芳香族化合物，
c)0到10重量份的烯属不饱和羧酸类和/或二羧酸类，
d)0到20重量份的烯属不饱和羧酸腈类。
乳化剂的含量通常为1到5重量份(相对于组分a)到d)的100重量份计算)。
优选的分散体可以通过25到65重量份的组分a)、25到65重量份的组分b)、0.1到6重量份的组分c)和/或0.1到15重量份的组分d)进行乳液聚合获得。
特别优选的分散体包含最多5重量份的烯属不饱和羧酸类和/或二羧酸类，特别包含最多3重量份的烯属不饱和羧酸类和/或二羧酸类，非常特别优选不含烯属不饱和羧酸类和/或二羧酸类，所述烯属不饱和羧酸类和/或二羧酸类包括上述的酸及其衍生物。
特别优选的分散体包含最多5重量份的烯属不饱和羧酸腈类，特别包含最多3重量份的烯属不饱和羧酸腈类，非常特别优选不含烯属不饱和羧酸腈类。
优选丁二烯，异戊二烯，1，3-戊二烯，二甲基丁二烯和/或环戊二烯作为脂肪族共轭二烯(组分a))。
特别提及苯乙烯，a-甲基苯乙烯和/或乙烯基甲苯作为乙烯基芳香族化合物(组分b))。
优选具有3-6个碳原子的α，β-单烯属不饱和一羧酸类或二羧酸类诸如丙烯酸，甲基丙烯酸，马来酸，富马酸和衣康酸作为烯属不饱和羧酸类和/或二羧酸类(组分c))。
特别提及丙烯腈和/或甲基丙烯腈作为烯属不饱和羧酸腈类。
在乳液聚合中常用的系统作为引发剂被加入。这些水溶性系统，诸如过氧化物和偶氮化合物，是本领域技术人员已知的。通常，所述水溶性引发剂以相对于待聚合单体的总质量为0.1到2.0重量％的量被加入。
另外，已知的分子量调节剂和其它助剂，例如用于干扰金属离子的络合剂，或抑制剂如对苯二酚单甲醚，可被加入用于乳液聚合(参见，Houben-Weyl，Methoden der organischen Chemie，vol.XIV/l，pp.297ff.，1961，Stuttgart；Hans-Georg Elias；Makromoleküle；1990；Hüttig&WepfVerlag，Basel，Heidelberg，New York)。
在不饱和羧酸类和/或二羧酸类(组分c))用于聚合的情况中，会要求使用碱进行中和。
根据本发明使用的所述分散体的固体含量为30到70重量％、优选35到68重量％、特别优选40到67重量％(根据DIN EN ISO 3251测定)。
根据本发明使用的所述分散体的粘度为10到2200mPa*s，特别是10到500mPa*s，特别优选是15到300mPa*s(根据DIN EN 3219在23℃下测定)。
根据本发明使用的所述聚合物分散体优选是阴离子分散体。另外，优选自动交联的(bathotonic)和/或可热交联的分散体。优选那些在120℃到200℃之间的温度范围内交联的可热交联的分散体。所述自动交联的分散体可能已经部分地发生交联，特别是如果已从所述水性分散体中除去一部分水时。
根据本发明使用的所述分散体以诸如以下的名称市售：Synthomer(Synthomer Ltd.)，
Figure GPA00001159738000051
或
Figure GPA00001159738000052
(BASF AG)，SRG型(DowChemicals)和Plextol SBV型(PolymerLatex)。
根据本发明使用的淀粉不受任何限制，然而，它们必须与所述水性聚合物分散体相容以及与所述粘结剂液相容。适合的淀粉是天然淀粉和改性淀粉，诸如阳离子淀粉或阴离子淀粉或淀粉衍生物(所谓的化学改性淀粉)。通常有利的是在冷和/或热的介质中具有足够溶解度的淀粉。
可用于本发明的一组淀粉包括从植物原材料提取的淀粉。这些尤其包括来自块茎的淀粉，所述块茎诸如是马铃薯、木薯、竹芋、红薯，来自种子的淀粉，所述种子诸如是小麦、玉米、黑麦、稻、大麦、粟、燕麦、高粱，来自果实的淀粉，所述果实诸如是栗子、槲果、大豆、豌豆和其它豆类，香蕉，以及来自植物茎髓(plant marrow)的淀粉，例如来自苏铁(sago palm)的淀粉。
可用于本发明的淀粉实质上由不同量比的直链淀粉和支链淀粉组成。
可用于本发明的淀粉的分子量可在宽的范围内变化。所述淀粉实质上由直链淀粉和支链淀粉的混合物组成，优选具有5×102到1×108的分子量Mw、特别优选具有5×104到1×107的分子量Mw。
除了天然植物来源的淀粉以外，还同样优选经化学改性的淀粉、经酶促提取的淀粉、重组由来的淀粉或通过生物转化(生物催化)生产的淀粉。
术语“生物催化”还用作术语“生物转化”的同义词。
“化学改性淀粉”被定义为是其性质与天然性质相比经化学改性的淀粉。这实质上通过聚合物类似物转化被获得，其中淀粉用单-、双-或多-官能的试剂或氧化剂进行处理。在该处理中，优选所述淀粉的羟基通过醚化、酯化或选择性氧化进行修饰；或者所述改性基于在所述淀粉骨架上的可共聚的不饱和单体进行的由自由基引发的接枝共聚。
具体的化学改性淀粉，尤其提及淀粉酯类诸如黄原酸酯、乙酸酯、磷酸酯、硫酸酯、硝酸酯，淀粉醚类诸如非离子、阴离子或阳离子淀粉醚类，氧化淀粉类诸如双醛淀粉，羧基淀粉，通过过硫酸盐和类似物质降解的淀粉。
在本发明的语言用法中，“发酵淀粉”是指在使用天然有机物诸如真菌、藻类或细菌的发酵方法中被提取的淀粉，或可在发酵方法的活化和帮助下被提取的淀粉。通过发酵方法获得的淀粉的实例尤其包括阿拉伯树胶和相关的多糖(洁冷胶，印度胶，刺梧桐树胶，黄蓍胶)，黄原胶，艾姆森胶(emulsan)，鼠李糖胶，蔚蓝胶(wellan)，裂裥菌素，多聚半乳糖醛酸，昆布多糖，直链淀粉，支链淀粉和果胶。
本发明的“重组由来的淀粉”或“重组淀粉”是指在发酵方法中使用非天然有机物、但是在通过使用基因方法经过修饰的天然有机物诸如真菌、藻类或细菌的帮助下被提取的淀粉，或者可在发酵方法的活化和帮助下被提取的淀粉。从发酵的、基因修饰方法获得的淀粉的实例尤其包括直链淀粉、支链淀粉和多聚葡萄糖(polyglucanes)。
在本发明中的“通过生物转化生产的淀粉”是指通过在特定条件下用生物催化剂(也称：酶)使单体基本组件(即通常是低聚物糖类、特别是单糖或二糖)进行催化反应生产的淀粉、直链淀粉、支链淀粉或多聚葡萄糖。通过生物催化方法获得的淀粉的实例尤其是多聚葡萄糖和改性多聚葡萄糖，多聚果糖和改性多聚果糖。
另外，本发明还包括提及的单独淀粉的衍生物。在该处理中，术语“淀粉的衍生物”或“淀粉衍生物”泛指经过改性的淀粉，即，这种淀粉中的天然的直链淀粉/支链淀粉的比率被改变，进行了预胶化，经历了水解降解或化学衍生化处理。
特定的淀粉衍生物尤其是氧化淀粉例如双醛淀粉或带有羧基官能团的其它氧化产物，或天然离子淀粉(例如具有磷酸基)或进行另外的离子改性的淀粉，即阴离子改性和阳离子改性。
可用于本发明的变构淀粉是例如通过甘油进行均质化的那些，从而使得在X-射线衍射中不再发生结晶反射，并且在偏光显微镜下的千倍放大率下淀粉粒或双折射区域不再可见。在这方面，参见文件DE-A1-3931363，其关于变构淀粉的公开也作为本说明书的一部分。
根据本发明使用的淀粉也由Avebe，Cargill，National Starch，Penford Products Co Purac or
Figure GPA00001159738000081
销售。
尤其有利的是在冷和/或热的介质中具有足够溶解度的淀粉。如果本发明的粘结剂系统的粘度允许相应的可操作性，则认为具有足够的溶解度。
根据本发明使用的粘结剂系统还可包含最多10重量％的添加剂。其包括市售的添加剂诸如防腐剂，稳定剂，抗氧化剂，消泡剂，防水剂，紫外线稳定剂，填充剂和/或颜料。它们部分地被包含在市售产品中并用于稳定储存和转运，或者可后来被添加以便满足顾客的具体要求。
根据本发明施用于所述织物的粘结剂系统的量优选基于原始织物总重量为5到35重量％的干燥后的干粘结剂，特别是10到30重量％，特别优选是10到25重量％的干粘结剂。
本说明书中的术语“织物”在其最广泛的含义内被理解。其可指根据织物形成技术生产的任何纤维织物。纤维形成材料包括天然纤维和/或由合成聚合物制成的纤维。这种织物的实例是织造织物，稀松平纹织物，针织织物，以及优选是非织造织物。
纺粘无纺织物，所谓的通过新熔纺的细丝进行无规沉积生产的纺粘织物是优选的由合成聚合物纤维制成的无纺织物。它们由可熔纺聚合物材料制成的无终点合成纤维组成。适合的聚合物材料为例如聚酰胺，诸如聚六亚甲基二己二酰胺，聚己内酰胺，芳香的或部分芳香的聚酰胺(“芳族聚酰胺”)，脂肪族聚酰胺诸如尼龙，部分芳香的或完全芳香的聚酯，聚苯硫醚(PPS)，具有醚基和酮基的聚合物诸如聚醚酮(PEK)和聚醚醚酮(PEEK)，聚烯烃诸如聚乙烯或聚丙烯，或聚苯并咪唑类。
优选所述纺粘无纺织物由可熔纺聚酯组成。原则上，可以考虑适合纤维生产的所有类型的聚酯材料。这种聚酯大部分由得自芳香族二羧酸类和脂肪族二醇类的组分组成。常见的芳香族二羧酸组分是苯二羧酸类的二价残基，特别是对苯二甲酸和间苯二甲酸的二价残基；常见的二醇类具有2-4个碳原子，乙二醇是特别适合的。包含至少85摩尔％的聚对苯二甲酸乙二醇酯的纺粘无纺织物是特别有利的。剩余的15摩尔％则由二羧酸单元和二醇单元组成，其充当所谓的改性剂并且其将使得本领域技术人员能够特意地影响所生产的细丝的物理和化学特征。这种二羧酸单元的实例是间苯二甲酸或脂肪族二羧酸的残基，所述脂肪族二羧酸诸如是戊二酸、己二酸和癸二酸；改性用二醇残基的实例是包含更长链二醇诸如丙二醇或丁二醇或二甘醇或三甘醇的那些，或者如果存在则以少量存在的摩尔量为约500到2000的聚二醇。
包含至少95摩尔％的聚对苯二甲酸乙二醇酯(PET)的聚酯是特别优选的，特别是含有未改性的PET的那些。
如果所述基础内衬另外要求阻燃效果的话，则如果其由经阻燃改性的聚酯纺成是有利的。这种经阻燃改性的聚酯是已知的。它们包含卤素化合物、特别是溴化合物的添加剂，它们包含被缩合进所述聚酯链内的膦化合物是特别有利的。
特别优选地是，所述纺粘无纺织物包含经阻燃改性的聚酯，该聚酯在链中缩合有式(I)的组件：
其中R是碱或含2-6个碳原子的聚乙烯或苯基，R1是含1-6个碳原子的烷基，芳基或烷基。优选地，在式(I)中，R是指亚乙基和R1是指甲基，乙基，苯基或邻-、间-或对-甲基苯基，特别是甲基。这种纺粘无纺织物例如描述于DE-A-39 40 713中。
被包含在所述纺粘无纺织物中的所述聚酯优选具有与0.6到1.4的特性粘度(IV)相当的分子量，所述特性粘度由1g聚合物在25℃的100ml二氯乙酸中的溶液中测得。
在所述纺粘无纺织物中的所述聚酯细丝的单独纤度总计为1-16分特克斯，优选2-8分特克斯。
在本发明的另外的实施方案中，所述纺粘无纺织物的织物还可是由可熔粘结剂粘结的非织造织物，其包含基础纤维和热熔粘结纤维。所述基础纤维和热熔粘结纤维可来自任何的热塑性细丝形成聚合物。基础纤维还可来自非熔性细丝形成聚合物。这种热熔粘结剂纺粘的无纺织物描述于例如EP-A 0,446,822和EP-A 0,590,629中。
可以衍生基础纤维的聚合物的实例是聚丙烯腈，聚烯烃诸如聚乙烯或聚丙烯，实质上脂肪族的聚酰胺诸如尼龙6.6，实质上芳香族的聚酰胺(芳族聚酰胺)诸如聚(对苯二甲酸对苯二酚酯)或包含一定比例的芳香族间二胺单元以改善溶解度的共聚物或聚(间苯二甲酸间苯二酚酯)，实质上芳香族的聚酯诸如聚(对羟基苯甲酸酯)或优选实质上脂肪族的聚酯，诸如聚对苯二甲酸乙二醇酯。
两种纤维类型的相对比例可以在宽度的限度内进行选择，只要确保所述热熔粘结纤维的比例足以将所述基础纤维粘结到所述热熔粘结纤维上，从而赋予所述非织造织物以用于预定应用的强度即可。在源于所述热熔粘结纤维的所述非织造织物中的所述热熔粘结剂的比例通常小于50重量％(相对应所述非织造织物的重量计算)。
熔点比所述非织造织物的原料的熔点低10到50℃、优选低30到50℃的改性聚酯被特别地考虑作为热熔粘结剂。这种热熔粘结剂的实例是聚丙烯、聚对苯二甲酸丁二醇酯、或通过更长链二醇和/或间苯二甲酸或脂肪族二羧酸的缩合进行改性的聚对苯二甲酸乙二醇酯。
优选热熔粘结剂以纤维形式并入到非织造织物中。
基础纤维和热熔粘结纤维优选由一类聚合物构成。这意味着所使用的所有纤维都选自一类物质，使得这些纤维可以在非织造织物已经使用之后容易地再循环。如果基础纤维由聚酯组成，则例如所选择的热熔粘结纤维也是聚酯类的或是聚酯的混合物，例如为具有PET芯和低熔点聚对苯二甲酸乙二醇酯共聚物作为外覆层的双组分纤维形式。然而，另外，由不同聚合物构成的双组分纤维也是可能的。这种实例是聚酯和聚酰胺(芯/外覆层)的双组分纤维
基础纤维和热熔粘结纤维的单丝纤度可以在宽的范围内进行选择。常见的纤度范围的实例是1到16分特克斯，优选2到6分特克斯。
在本发明的基础内衬的情况中，在另外结合阻燃性质时，优选它们包含阻燃性热熔粘结剂。通过插入上述式(I)的链成员加以改性的聚对苯二甲酸乙二醇酯可以作为本发明的层织物中的阻燃热熔粘结剂存在。
在本发明的优选实施方案中，织物经历与本发明的粘结剂系统进行的机械粘结和化学粘结。这种粘结进一步改善基础内衬的应用性质。
所述粘结可以在单独的步骤中进行，或者一起进行，只要确保特别是在加强物存在时，任选存在的加强物没有受到破坏，或者仅受到极少的破坏即可。所述粘结可以借助已知的方法进行。不对可能的方法造成限制，机械方法，诸如针刺，特别是水动力学粘结以及化学和/或热塑方法是适合的。
在通过针刺进行粘结的情况中，其以20到100针/cm2、优选40针/cm2的针脚密度进行。也可以进行水动力学粘结来代替机械针刺或者除了进行机械针刺之外额外进行水动力学粘结。优选地，这个方法是喷水针刺(waterjet needling)。喷水针刺过程中的压力优选为5到600巴，特别是50到450巴，特别优选为100到300巴。
喷嘴直径为0.05到0.25mm，优选为0.07到0.2mm。喷嘴布置为所谓的束的形式。喷嘴数目为每英寸10到60个喷嘴，优选每英寸20到40个喷嘴。
同样地，可以使用其它流体介质代替水，以及可以在几个单独的步骤中进行所述喷水针刺。喷水针刺可以以连续喷射的形式进行，或者也可以以脉冲水注来进行，对于脉冲频率没有限制。特别地优选喷水针刺在加强物的存在下进行。
构成非织造织物的细丝或人造短纤维可以具有实质上圆形的截面，或者也可以具有其它形状，诸如哑铃形、肾脏形的、三角形的、三叶形或多叶形的截面。还可以使用中空纤维和双组分或多组分纤维。另外，热熔粘结纤维又可以以双组分或多组分纤维的形式使用。
所述织物可以是单层或多层的织物。
形成织物的纤维还可以借助通常的添加剂进行改性，例如借助抗静电剂诸如炭黑、或阻燃添加剂诸如防火保护剂。优选地，为本发明的粘结剂系统加入这些添加剂。
织物(特别是纺粘无纺织物)的每单位面积重量为20到500g/m2，优选为40到400g/m2，特别是90到250g/m2。
完全出乎本领域技术人员意外的是，使用本发明的粘结剂系统改善织物的热尺寸稳定性。因此，发现纵向尺寸稳定性有至少15％、优选至少20％的改善(相对于使用基于苯乙烯/丁二烯“SBR”分散体粘结剂为基础的粘结剂的织物)，并发现横向尺寸稳定性有至少15％、优选至少20％的改善(相对于使用基于苯乙烯/丁二烯″SBR″分散体粘结剂为基础的粘结剂的织物)。
在本发明的优选实施方案中，使用本发明的粘结剂系统粘结的织物的热尺寸稳定性在纵向上为最大1.6％，在横向上为最大1.7％，特别是在纵向上为最大1.5％和在横向上为最大1.5％。
如下测量热尺寸稳定性：冲出350mm×100mm(l/c)的样品并进行测量。之后，在样品纵向的整个宽度上加载4kg的重量，并竖直地悬挂在干燥烘箱中，在200℃的温度下保持10分钟。在去掉4kg的重量的情况下进行5分钟冷却之后测量尺寸变化。得到的百分比结果表示与原始数值相比的变化。
本发明的织物可用作被涂覆的衬板、屋顶膜和密封膜，这也是本发明的目的。
在本发明的另一个实施方案中，这种基础内衬具有至少一个加强物。优选加强物设计为使得加强物吸收力，以便具有加强物的基础内衬与没有加强物的基础内衬相比，在应力-伸长图(在20℃)上至少一个位置处在0到1％的伸长范围内，基准力(reference force)相差至少10％。
在另一个实施方案中，加强物可以被插入，使得可以仅在较高的伸长时吸收力。
特别是在使用杨氏模量至少为5GPa、优选至少为10GPa、特别优选为20GPa的加固丝和/或纱的情况中，获得基础内衬的良好的机械性质。上述的加固丝(即，单丝以及纱)具有0.1到1mm或10-400特克斯、优选0.1到0.5mm、特别是0.1到0.3mm的直径，并具有0.5到100％、优选1到60％的断裂伸长。特别有利的是，本发明的基础内衬具有低于1％的伸长保留(elongation reserve)。
伸长保留表示在作用力转移到加固丝上之前作用于基础内衬的伸长，即0％的伸长保留意思是作用于基础内衬的拉伸力将立即被转移到加固丝上。这意味着作用于织物上的力没有导致加固丝的对准或取向而是直接地转移到加固丝上，这样可以避免对织物的破坏。这特别地通过较小伸长所需力的急剧增大来证明(应力-伸长图，在室温下)。另外，在具有高断裂伸长的适合的加固丝的帮助下，可以改善可能的最高拉伸力。例如由聚酯制成的单丝或复丝是适合的加固丝。
作为加固丝，优选复丝和/或单丝基于芳族聚酰胺(优选所谓的高模量芳族聚酰胺)、碳、玻璃、玻璃粗纱、矿物纤维(玄武岩)、高强度聚酯单丝或复丝、高强度聚酰胺单丝或复丝、以及混合复丝纱(包含加固丝和低熔点粘结纤维的纱)或由金属或金属合金制成的线(单丝)。
由于经济上的原因，优选的加强物由实质上平行的经纱或稀松平纹织物(scrims)形式的玻璃复丝组成。在大多数情况下，无纺织物在纵向上由实质上平行的经纱来加强。
加固丝可以用作织造织物、稀松平纹织物、针织织物或单独作为非织造织物或为单独的织物的形式。优选使用平行的加固丝(即，经纱)、以及稀松平纹织物或织造织物的加强物。
取决于需要的性质特征，密度可以在宽的限度内变化。优选密度为每米20到200个细丝。所述密度是垂直于运行方向测量的。优选地，加固丝在形成纺粘无纺织物过程中被加入，并由此嵌入到纺粘无纺织物中。还优选的是在加强物上铺设无纺织物，或者随后通过组装形成加强物和非织造织物的层。
优选的本发明的基础内衬具有至少一个加强物，并且表现出与没有加强物的基础内衬相比，具有加强物的基础内衬的基准力在应力-伸长图(20℃)上在至少一个位置处在0到1％的伸长范围内相差至少10％，优选相差至少20％，特别优选相差至少30％。
对于应用的整个范围，还需要在室温下具有在低伸长下的高模量。这种高模量改善处置容易性，特别是改善轻质的非织造织物的处置容易性。
取决于所需特征以及取决于成本方面，经加强的基础内衬在低伸长下的基准力在织物或加强物上以不同的比例分布。
所述基准力根据标准EN 29073，第3部分(part 3)来测量，使用5cm宽度的样品，200mm的自由夹持长度。以厘牛(Centinewton)给出的预拉伸的数值对应于样品的克数数值，其单位是克/平方米。
所述基础内衬可以通过在织物中、在织物的至少一个面或在基础内衬的任何位置处插入加强物来加强，特别是插入在与第一织物不同的其它织物中，或者作为单独的织物。
本发明的基础内衬可以除已经描述的织物之外具有另外的织物。优选地，这些另外的织物与最初提及的织物不同，即，它们由不同的材料制成。
在由合成聚合物形成的织物的情况中，可能需要在本发明的基础内衬中插入另外的织物，以便优化应用特异性性质。
这些另外的织物优选是基于矿物纤维和/或玻璃纤维的无纺织物。
在本发明的基础内衬中使用的矿物纤维无纺织物可以用粘结剂或通过机械方法(诸如针刺或水动力学针刺)硬化。特别优选的是由细丝(即环状长纤维)、或人造短纤维形成的经过梳理的料片。矿物纤维的平均直径为8到15μm，优选为10到12μm。
适合的矿物纤维包括铝硅酸盐、陶瓷、白云岩纤维或得自火山岩(诸如玄武岩、辉绿岩、暗玢岩)的纤维。那些合起来表示为古生玄武岩(paleobasalts)，而辉绿岩通常称为绿岩。
本发明所使用的矿物纤维无纺织物的每单位面积重量为25到200g/m2，优选为30到70g/m2。上面信息对于将在下文中描述的玻璃纤维垫也适用。
在本发明的基础内衬中使用的玻璃纤维垫可以用粘结剂或通过机械方法(诸如针刺或水动力学针刺)粘结。玻璃纤维可以是细丝或短切玻璃纤维，后一种纤维的长度为1到40mm，优选4到20mm。
玻璃纤维的平均直径为6到20μm，优选8到15μm。
适合的玻璃纤维包括诸如E型玻璃、S型玻璃、R型玻璃或C型玻璃的玻璃类型，其中由于经济上的原因，优选E型玻璃或C型玻璃。
本发明的基础内衬除上述的另外的玻璃织物纤维和/或矿物纤维之外还可以配备有另外的功能层。下述内容应该理解为提高基础内衬的基础强度的方法或功能层。这些也是本发明的目的。
本发明的基础内衬可用于生产被涂覆的衬板、屋顶膜和密封膜，优选用于生产经沥青处理的衬板、屋顶膜和密封膜。除此之外，本发明的基础内衬可以用于地面应用和用于过滤领域。
除了沥青之外，还可以使用其它材料诸如聚乙烯或聚氯乙烯、聚氨酯、EPDM或TPO(聚烯烃)作为被涂覆的衬板、屋顶膜和密封膜的涂覆物质。
经过沥青处理的膜包含被嵌入在沥青基质中的至少一个如上所述的基础膜，经过沥青处理的屋顶膜的每单位面积重量的沥青重量份优选为60到97重量％，而纺粘无纺织物的重量份是3到40重量％。
任选地，所述被涂覆的衬板、屋顶膜和密封膜可以然后用粒状材料诸如沙子洒粉。如此生产的被涂覆的衬板、屋顶膜和密封膜的特征在于具有良好的可加工性，特别是经过沥青处理的衬板、屋顶膜和密封膜。
生产本发明的织物包括以下方法：
a)形成织物并将其机械粘结，
b)施用粘结剂系统，所述粘结剂系统包含：
I)10到90重量％的基于脂肪族共轭二烯和乙烯基芳香族化合物的聚合产物的水性分散体，
II)90到10重量％的淀粉，
III)0到10重量％的添加剂，
c)使粘结剂干燥和凝固，
其中重量百分数的数值与粘结剂系统的干质量(即无水)相关。
通过已知的方法形成织物。优选地，a)中所述的形成织物是通过借助已知的纺丝装置形成纺粘无纺织物来进行的。
为此，通过多个彼此前后排列的多排喷丝头或喷丝头排组为熔融聚合物加载聚合物。如果要生产粘结有熔融粘结剂的纺粘无纺织物，则为其交替加载形成基础纤维的聚合物和热熔粘结纤维的聚合物。将经过纺丝的聚合物物流以已知的方式拉伸，并铺放在传送带上，例如，通过采用在分散结构中使用旋转挡板或通过形成幕。
机械粘结也可以借助已知的方法进行。
任选存在的加强物的插入在形成织物过程中或之后，或者在应用本发明的粘结剂系统之前或应用过程中进行的。加强物和制造工艺中任选的任何另外的热处理优选在应力下被附加，特别是在纵向应力的存在下被附加。
任选被插入的另外的织物在本发明粘结剂系统硬化之前或过程中被添加。
得自步骤b)的粘结剂系统也是借助已知方法施加的。粘结剂施加优选各自相对于织物的总重量为5到50重量％(干质量)，特别是10到30重量％，特别优选10到25重量％。
还通过本领域技术人员已知的方法使粘结剂干燥或硬化。
单独的方法本身是已知的，但是本发明的组合或顺序是可以取得专利的。
实施例
以下表1示出了用本发明的粘结剂系统粘结的织物在粘结剂的相应的单个组分方面的对比。
考查了基于聚对苯二甲酸乙二醇酯的纺粘无纺织物(PET-纺粘的)，每单位面积的重量为180g/m2(JM33/180型)。
实施例1示出了基于SBR和脲粘结剂的标准粘结剂系统，实施例2示出了基于脲和丙烯酸酯的粘结剂系统，实施例3示出了本发明的粘结剂系统，实施例4示出了基于淀粉和丙烯酸酯的粘结剂系统，实施例5示出了基于淀粉的粘结剂系统。典型地，液体浓度是15-40％(即，液体中的固体物质)。
  试验编号   1   2   3   4   5
  SBR分散体   90   40
  脲树脂   10   10
  丙烯酸酯分散体   90   40
  淀粉   60   60   100
  设定施用(原料无纺织物的重量％)％   20   20   20   20   20
  最大纵向拉伸力[daN/5cm]   56   59   57   51   46
  最大纵向拉伸力，热[daN/5cm]   25   19   27   n.t.   31
  最大横向拉伸力[daN/5cm]   47   48   45   36   36
  纵向的TDS    [％]   1.8   1.9   1.3   1.6   0.8
  横向的TDS    [％]   -1.6   -1.8   -1.4   -1.7   -1.3
  VW-试验[mg/kg FA]   ～400   ～400   ～30   ～30   ＜10
  水抽吸[mm]   80   72   72   59   66

Claims (34)

1.用粘结剂系统进行粘结的织物，该粘结剂系统包含：
a)基于干质量，10到90重量%的基于脂肪族共轭二烯和乙烯基芳香族化合物的聚合产物的水性分散体，
b)基于干质量，90到10重量%的淀粉，和
c)基于干质量，0到10重量%的添加剂，
其中重量百分数的数值与粘结剂系统的干质量即无水相关，以及所述织物是由合成聚合物纤维制成的无纺织物，其中所述织物的热尺寸稳定性在纵向上为最大1.6%，在横向上为最大1.7%。
2.权利要求1的织物，特征在于，所述水性分散体是在水、乳化剂和水溶性引发剂的存在下生产的、基于以下物质的乳液聚合产物：
a)20到80重量份的脂肪族共轭二烯，
b)20到80重量份的乙烯基芳香族化合物，
c)0到10重量份的烯属不饱和羧酸类和/或二羧酸类，
d)0到20重量份的烯属不饱和羧酸腈类。
3.权利要求1的织物，特征在于，所述分散体包含最多5重量份的烯属不饱和羧酸类和/或二羧酸类或聚合形式的上述酸的衍生物。
4.权利要求1的织物，特征在于，所述分散体不含烯属不饱和羧酸类和/或二羧酸类或聚合形式的上述酸的衍生物。
5.权利要求1的织物，特征在于，所述分散体包含最多5重量份的聚合形式的烯属不饱和羧酸腈类。
6.权利要求1的织物，特征在于，所述分散体不含聚合形式的烯属不饱和羧酸腈类。
7.权利要求1的织物，特征在于，所述脂肪族共轭二烯是丁二烯、异戊二烯、1,3-戊二烯、二甲基丁二烯和/或环戊二烯。
8.权利要求1的织物，特征在于，所述乙烯基芳香族化合物是苯乙烯、α-甲基苯乙烯乙酸乙烯酯和/或乙烯基甲苯。
9.权利要求1的织物，特征在于，所述分散体是阴离子分散体。
10.权利要求1的织物，特征在于，所述淀粉是天然的或经改性的淀粉或淀粉衍生物。
11.权利要求10的织物，特征在于所述淀粉提取自植物原材料。
12.权利要求10的织物，特征在于所述淀粉提取自块茎、种子、果实和/或植物茎髓。
13.权利要求1的织物，特征在于，所述淀粉实质上由直链淀粉和支链淀粉的混合物组成，并具有5×102到1×108的分子量Mw。
14.权利要求1的织物，特征在于，所述淀粉实质上由直链淀粉和支链淀粉的混合物组成，并具有5×104到1×107的分子量Mw。
15.权利要求1的织物，特征在于，所述淀粉是天然植物来源的淀粉，或者是经化学改性的淀粉、经酶促提取的淀粉、重组由来的淀粉或通过生物转化生产的淀粉。
16.权利要求15的织物，其中生物转化是生物催化。
17.权利要求1的织物，特征在于，所述粘结剂系统的施用量相对于原始织物的总重量为5到35重量%的干粘结剂。
18.权利要求1的织物，特征在于，所述织物是纺粘无纺织物。
19.权利要求18的织物，特征在于，所述织物是基于以下的纺粘无纺织物：聚酰胺、部分芳香的或完全芳香的聚酯、聚苯硫醚或聚烯烃。
20.权利要求19的织物，特征在于，所述聚酰胺是芳族聚酰胺或脂肪族聚酰胺。
21.权利要求18的织物，特征在于，所述织物是基于具有醚基和酮基的聚合物的纺粘无纺织物。
22.权利要求18的织物，特征在于，所述织物是基于聚己内酰胺的纺粘无纺织物。
23.权利要求18的织物，特征在于，所述织物是基于以下的纺粘无纺织物：具有至少85摩尔%聚对苯二甲酸乙二醇酯的聚酯纤维。
24.权利要求18的织物，特征在于，所述织物是基于以下的纺粘无纺织物：具有至少95摩尔%聚对苯二甲酸乙二醇酯的聚酯纤维。
25.权利要求1的织物，特征在于，所述织物被制为具有多个层。
26.权利要求1的织物，特征在于，所述织物具有20到500g/m2的每单位面积重量。
27.权利要求1的织物，特征在于，所述织物的热尺寸稳定性在纵向上为最大1.5%和在横向上为最大1.5%。
28.权利要求1到27中任一项的织物作为用于衬板、屋顶膜和密封膜的基础内衬的用途或用于生产用于衬板、屋顶膜和密封膜的基础内衬的用途。
29.用于衬板、屋顶膜和密封膜的基础内衬，其包括权利要求1到27中的至少一种织物。
30.权利要求29的基础内衬，特征在于，其具有至少一种另外的加强物。
31.权利要求29的基础内衬，特征在于，其除了具有权利要求1到27中的织物以外，还具有至少一种不同于前述织物的另外的织物。
32.权利要求29到31中任一项的基础内衬用于生产用于衬板、屋顶膜和密封膜的基础内衬的用途。
33.权利要求29到31中任一项的基础内衬用于生产被涂覆的衬板、屋顶膜和密封膜的用途。
34.被涂覆的衬板、屋顶膜和密封膜，其包括权利要求29到31中的至少一种基础内衬和至少一种涂覆物质。
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