CN102704036B - 获自磺基聚酯的水可分散的多组分纤维 - Google Patents
获自磺基聚酯的水可分散的多组分纤维 Download PDFInfo
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- CN102704036B CN102704036B CN201210181276.5A CN201210181276A CN102704036B CN 102704036 B CN102704036 B CN 102704036B CN 201210181276 A CN201210181276 A CN 201210181276A CN 102704036 B CN102704036 B CN 102704036B
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- water
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- sulfonic polyester
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- fiber
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
- D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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Abstract
公开了多组分纤维,其源自磺基聚酯与水不可分散的聚合物的共混物,其中初纺旦数小于约6并且其中水可分散的磺基聚酯显示出熔体粘度小于12,000泊,在240℃在1弧度/秒的应变速率下测量的,并且其中磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数。多组分纤维能够在较高的纤维速度,特别是至少约2000m/min,进行拉伸,并且可以用于生产微旦数(microdenier)纤维。纤维制品可以由多组分纤维和微旦数(microdenier)纤维生产。还公开了一种用于多组分纤维、非织造织物和微旦数(microdenier)网的方法。
Description
本申请是国际申请日为2007年1月16日(国际申请号为PCT/US2007/001082)、进入国家阶段申请号为200780001225.7、发明名称为“获自磺基聚酯的水可分散的纤维和多组分纤维”的申请的分案申请。
技术领域
本发明涉及包括磺基聚酯的水可分散的纤维和纤维制品。本发明进一步涉及多组分纤维,其包括磺基聚酯,和微旦数(microdenier)纤维,以及由其制备的纤维制品。本发明还涉及用于水可分散的、多组分和微旦数(microdenier)纤维以及由其制备的非织造织物的方法。所述纤维和纤维制品应用于可冲洗的(flushable)个人护理产品和医用产品。
背景技术
纤维、熔吹网及其他熔纺纤维制品已经由热塑性聚合物制成,如聚(丙烯),聚酰胺和聚酯。这些纤维和纤维制品的一种常见应用是非织造织物,特别是在个人护理产品中,如抹布、女性卫生产品、婴儿尿布、成人失禁内裤、医院/外科和其它的医疗一次性用品、保护织物和层、土工织物、工业用拭纸和过滤介质。不幸地,由常规的热塑性聚合物制成的个人护理产品难以处理并且通常置于垃圾中。一种有前途的备选的处理方法是使得这些产品或者其组分“可冲洗(flushable)”,即,与公共排水系统相容。水可分散的或水溶性的材料的使用还改进了个人护理产品的再回收性和再生。现在用于个人护理产品中的各种热塑性聚合物不是固有地水可分散或可溶,因此,没有生产出容易分解并且可以在排水系统中处理或者容易循环的制品。
对可冲洗的(flushable)个人护理产品的期望已经导致一种对具有不同水响应性的纤维、非织造物和其它纤维制品的需要。解决这些需要的各种方法已经描述于例如以下文献中:美国专利6,548,592;6,552,162;5,281,306;5,292,581;5,935,880;和5,509,913;美国专利申请09/775,312;和09/752,017;和PCT国际公开WO01/66666A2。然而,这些方法具有许多缺点并且没有提供一种纤维制品,如纤维或非织造织物,其具有各种表现性能的令人满意的平衡,如拉伸强度,吸收性,柔性和织物完整性,在湿或干条件下。
例如,典型的非织造技术基于多方向纤维沉积,其用树脂结合粘合剂处理以形成一种具有牢固完整性和其它令人期望的性能的网。所得的纤维束(assembly),然而,通常具有差的水响应性并且不适用于可冲洗的(flushable)应用。结合剂的存在还可能导致最终产品中的不希望的性能,如降低的薄板湿润性、提高的刚度、粘性和较高的生产成本。此外还难以生产一种结合剂,其将在使用期间显示出足够的湿强度,当处理时又迅速地分散。因此,使用这些结合剂的非织造纤维束(assembly)可能在环境条件下慢慢地分解或者在体液存在下具有不足的湿强度。为解决这种问题,pH和离子-敏感的水可分散的结合剂,例如,含丙烯酸或甲基丙烯酸的晶格物(lattices),添加或不添加盐的情况下,是已知的并且描述于,例如,美国专利6,548,592B1中。在公共污水和住宅污水处理系统中离子浓度和pH水平,然而,可以在各个地理位置中变化很大,并且对于结合剂来说未必足够以变得可溶和分散。在这种情况下,纤维制品在处理后将不会分解,并且可能阻塞排水或下水道的支线。
含水可分散的组分和热塑性水不可分散的组分的多组分纤维已经在例如以下美国专利中进行了描述:5,916,678;5,405,698;4,966,808;5,525282;5,366,804;5,486,418。例如,这些多组分纤维可以是双组分纤维,具有成形或加工横断的断面,例如海岛型,皮芯型,并列型,或者扇饼型(segmentedpie)构型。多组分纤维可以经历水或者稀碱性溶液,其中水可分散的组分被溶解掉而随后以具有极小细度的独立的、单独的纤维的形式留下水不可分散的组分。具有良好的水分散性的聚合物,然而,常常将胶粘性赋予给所得的多组分纤维,这导致纤维在缠绕或数天后的存储期间粘在一起粘连或者融合,特别是在热、潮湿条件下。为防止融合,常常将脂肪酸或油型面层(finish)施加到纤维的表面。另外,有时将大比例的颜料或填料添加到水可分散的聚合物以防止纤维的融合,如美国专利6,171,685中所述的。这种油面层(finish),颜料和填料要求另外的加工步骤并且可能向最终的纤维赋予不希望的性能。许多水可分散的聚合物还要求碱性溶液,用于它们的除去,这可能引起纤维的其它聚合物组分的分解,例如比浓对数粘度、韧度和熔体强度降低。进一步,一些水可分散的聚合物在水缠结期间不能经受暴露于水的考验,因此,不适用于制造非织造网和织物。
或者,水可分散的组分可以用作非织造网中的热塑性纤维的结合剂。当暴露于水时,纤维与纤维的结合瓦解,使得非织造网失去了其完整性并且分解为单独的纤维。这些非织造网的热塑性纤维组分,然而,不是水可分散的,并且保持存在于水介质中,因此,必须最后被从城市废水处理厂中除去。水缠结可以用于生产可分离的非织造织物,有或者没有极低水平(小于5wt%)的另加的结合剂,以便将纤维保持在一起。虽然这些织物在处理时可以分解,但是它们常常利用不是水溶性的或者水可分散的纤维,并且可能在污水管道系统中造成缠结和堵塞。任何另加的水可分散的结合剂还必须是受水缠结影响最小的,并且不形成凝胶状的堆积或交联,由此有助于织物处理或者解决与下水道有关的问题。
一些水溶性的或水可分散的聚合物是可以获得的,但是通常不适用于熔吹成纤操作或者熔纺。聚合物,如聚乙烯醇,聚乙烯基吡咯烷酮和聚丙烯酸不是可熔融加工的,因为热分解在低于其中获得合适的熔体粘度的点的温度下发生。高分子量聚氧化乙烯可以具有合适的热稳定性,但是将在聚合物界面处提供高粘度溶液,这产生了慢的分解速率。例如在以下美国专利中已经描述了水可分散的磺基聚酯:6,171,685;5,543,488;5,853,701;4,304,901;6,211,309;5,570,605;6,428,900;和3,779,993。典型的磺基聚酯,然而,是低分子量热塑性塑料,其是脆性的并且缺少柔性,而这种性能使得经受缠绕操作以获得没有断裂或弄碎的一卷材料。在加工成薄膜或纤维期间,磺基聚酯还可以显示出粘连或融合,这可能要求使用油面层(finish)或大量颜料或填料来避免。低分子量聚氧化乙烯(更一般被称为聚乙二醇)是一种弱/脆性聚合物,其还不具有纤维应用所需的物理性能。经由溶液技术从已知的水溶性聚合物形成纤维是一种备选方案,但是除去溶剂(特别是水)的附加的复杂性增加了生产成本。
因此,需要一种水可分散的纤维和由其制备的纤维制品,其显示出足够的拉伸强度、吸收性、柔性和织物完整性,在水分存在下,特别是当暴露于人类体液时。另外,需要一种纤维制品,其不要求结合剂并且完全分散或溶于住宅或市政排水系统中。潜在的应用包括但不局限于,熔吹网,纺粘织物,水缠结织物,干铺非织造物,双组分纤维组分,粘合促进层,纤维素塑料结合剂,可冲洗的(flushable)非织造物和薄膜,可溶解的粘合纤维,保护层和用于待释放或溶于水中的活性成分的载体。还需要一种具有水可分散的组分的多组分纤维,其在纺丝操作期间没有显示过度的长丝的粘连或融合,易于在中性或略酸性pH条件下被热水除去,并且适于水缠结方法以制造非织造织物。其它可挤出的和熔纺纤维材料也是可能的。
发明内容
我们已经出人意料地发现柔性的、水可分散的纤维可以由磺基聚酯制备。因此本发明提供了一种水可分散的纤维,其包括:
(A)玻璃化转变温度(Tg)为至少25℃的磺基聚酯,该磺基聚酯包括:
(i)一种或多种二羧酸的残基;
(ii)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中该官能团是羟基,羧基或其组合;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;
(B)任选地,与磺基聚酯共混的水可分散的聚合物;和
(C)任选地,与磺基聚酯共混的水不可分散的聚合物,前提是该共混物是不溶混的共混物;
其中该纤维包含小于10wt%的颜料或填料,基于纤维的总重量。
本发明的纤维可以是单组分(unicomponent)纤维,其迅速地分散或溶于水中并且可以通过熔吹或熔纺来生产。纤维可以由单一磺基聚酯或者磺基聚酯与水可分散的或水不可分散的聚合物的共混物来制备。因此,本发明的纤维,任选地,可以包括与磺基聚酯共混的水可分散的聚合物。另外,纤维可以任选地包括与磺基聚酯共混的水不可分散的聚合物,条件是该共混物是不溶混的共混物。我们的发明此外包括纤维制品,其包括我们的水可分散的纤维。因此,我们的发明的纤维可以用于制备各种的纤维制品,如纱线、熔吹网、纺粘网和非织造织物,其进而是水可分散的或可冲洗的(flushable)。我们的发明的切断纤维还可以与天然或合成纤维在纸、非织造网和纺织纱线中共混。
本发明的另一方面是水可分散的纤维,其包括:
(A)玻璃化转变温度(Tg)为至少25℃的磺基聚酯,该磺基聚酯包括:
(i)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(ii)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;
(iv)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;
(B)任选地,与磺基聚酯共混的第一水可分散的聚合物;和
(C)任选地,与磺基聚酯共混形成共混物的水不可分散的聚合物,前提是该共混物是不溶混的共混物;
其中该纤维包含小于10wt%的颜料或填料,基于纤维的总重量。
本发明的水可分散的纤维制品包括个人护理制品,例如抹布、纱布、薄纸(tissue)、尿布、训练裤、卫生巾、绷带、伤口护理品和外科敷料。除是水可分散的之外,我们的发明的纤维制品是可冲洗的(flushable),即,其与住宅和市政排水系统相容并且适于在其中进行处置(disposal)。
本发明还提供了多组分纤维,其包括水可分散的磺基聚酯和一种或多种水不可分散的聚合物。纤维具有这样的加工几何形状,使得水不可分散的聚合物以通过介于其间的磺基聚酯基本上彼此隔离的区段(segment)的形式存在,后者用作水不可分散的区段(segment)的结合剂或封装基质。因此,我们的发明的另一方面是具有成形断面的多组分纤维,其包括:
(A)玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯,该磺基聚酯包括:
(i)一种或多种二羧酸的残基;
(ii)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中该官能团是羟基,羧基或其组合;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;和
(B)多个区段(segment),其包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离;
其中该纤维包含小于10wt%的颜料或填料,基于纤维的总重量。
磺基聚酯具有至少57℃的玻璃化转变温度,这大大地降低了在缠绕和长期储存期间纤维的粘连(blocking)和融合(fusion)。可以通过使多组分纤维与水接触而除去磺基聚酯,留下微旦数(microdenier)纤维形式的水不可分散的区段(segment)。我们的发明,因此,还提供了一种用于微旦数(microdenier)纤维的方法,包括:
(A)将玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,该磺基聚酯包括:
(i)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(ii)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;
其中该纤维具有多个包括水不可分散的聚合物的区段(segment),其中该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离,该纤维包含小于10wt%的颜料或填料,基于纤维的总重量;和
(B)使多组分纤维与水接触而除去磺基聚酯,由此形成微旦数(microdenier)纤维。
水不可分散的聚合物可以是生物可分解的(biodistintegratable),如根据德国工业标准(DINStandard)54900测定的和/或生物可降解的,如根据ASTM标准方法,D6340-98测定的。多组分纤维还可以用于制备纤维制品如纱线、织物、熔吹网、纺粘网或非织造织物,并且其可以包含一层或多层的纤维层。具有多组分纤维的纤维制品,进而可以和水接触以生产包含微旦数(microdenier)纤维的纤维制品。
因此,本发明的另一个方面是一种用于微旦数(microdenier)纤维网的方法,包括:
(A)将玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,该磺基聚酯包括:
(i)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(ii)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。
其中该多组分纤维具有多个包括水不可分散的聚合物的区段(segment),该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离,该纤维包含小于10wt%的颜料或填料,基于所述纤维的总重量;
(B)对步骤A的多组分纤维进行交叠(overlapping)和收集,以形成非织造网;和
(C)使非织造网与水接触而除去磺基聚酯,由此形成微旦数(microdenier)纤维网。
我们的发明还提供一种用于制造水可分散的非织造织物的方法,包括:
(A)加热水可分散的聚合物组合物到高于其流点(flowpoint)的温度,其中聚合物组合物包括
(i)玻璃化转变温度(Tg)为至少25℃的磺基聚酯,该磺基聚酯包括:
(a)一种或多种二羧酸的残基;
(b)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个金属磺酸根基团,其中该官能团是羟基,羧基或其组合;
(c)一种或多种二醇残基,其中至少20mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;
(d)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;
(ii)任选地,与磺基聚酯共混的水可分散的聚合物;和
(iii)任选地,与磺基聚酯共混形成共混物的水不可分散的聚合物,前提是该共混物是不溶混的共混物;
其中该聚合物组合物包含小于10wt%的颜料或填料,基于聚合物组合物的总重量;
(B)熔纺长丝;和
(C)对步骤B的长丝进行交叠(overlapping)和收集,以形成非织造网。
在本发明的另一方面中,提供了一种多组分纤维,其具有成形断面,包括:
(A)至少一种水可分散的磺基聚酯;和
(B)多个域(domains),所述域包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离,
其中该纤维的初纺旦数(as-spundenier)小于约6单丝旦数(denierperfilament);
其中该水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,和其中该磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数。
在本发明的另一方面中,提供了多组分挤出物,其具有成形断面,包括:
(A)至少一种水可分散的磺基聚酯;和
(B)多个域,所述域包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离,其中该挤出物能够以至少约2000m/min的速度熔融拉伸。
在本发明的另一方面中,提供了一种用于制造具有成形断面的多组分纤维的方法,包括纺丝至少一种水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中多组分纤维具有多个域,所述域包括水不可分散的聚合物并且该域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;其中多组分纤维的初纺旦数小于约6单丝旦数;其中水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,和其中该磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数。
在本发明的另一个方面中,提供了一种用于制造具有成形断面的多组分纤维的方法,包括挤出至少一种水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物以生产多组分挤出物,其中多组分挤出物具有多个域,所述域包括所述水不可分散的聚合物并且所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;和以至少约2000m/min的速度熔融拉伸多组分挤出物以生产该多组分纤维。
在另一方面中,本发明提供了一种用于生产微旦数(microdenier)纤维的方法,包括:
(A)将至少一种水可分散的磺基聚酯和与水可分散的磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,其中该多组分纤维具有多个域,所述域包括水不可分散的聚合物,其中所述域通过介于所述域之间的磺基聚酯基本上彼此隔离;其中多组分纤维的初纺旦数小于约6单丝旦数;其中所述水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,和其中该磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数;和
(B)使多组分纤维与水接触而除去所述水可分散的磺基聚酯,由此形成水不可分散的聚合物的微旦数(microdenier)纤维。
在另一方面中,本发明提供了一种用于生产微旦数(microdenier)纤维的方法,包括:
(A)挤出至少一种水可分散的磺基聚酯和与水可分散的磺基聚酯不溶混的一种或多种水不可分散的聚合物以生产多组分挤出物,其中多组分挤出物具有多个域,所述域包括水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;
(B)以至少约2000m/min的速度熔融拉伸多组分挤出物以形成多组分纤维;和
(C)使多组分纤维与水接触而除去所述水可分散的磺基聚酯,由此形成水不可分散的聚合物的微旦数(microdenier)纤维。
在本发明的又一个方面中,提供了一种用于制造微旦数(microdenier)纤维网的方法,包括:
(A)将至少一种水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,该多组分纤维具有多个域,所述域包括水不可分散的聚合物,其中所述域通过介于所述域之间的水可分散的磺基聚酯基本上彼此隔离;其中多组分纤维的初纺旦数小于约6单丝旦数;其中水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,和其中磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数;
(B)收集步骤(A)的多组分纤维以形成非织造网;和
(C)使非织造网与水接触而除去磺基聚酯,由此形成微旦数(microdenier)纤维网。
在本发明的又一个方面中,提供了一种用于制造微旦数(microdenier)纤维网的方法,包括:
(A)挤出至少一种水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物以生产多组分挤出物,多组分挤出物具有多个域,所述域包括水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;
(B)以至少约2000m/min的速度熔融拉伸多组分挤出物以形成多组分纤维;
(C)收集步骤(B)的多组分纤维以形成非织造网;和
(D)使非织造网与水接触以除去所述磺基聚酯,由此形成微旦数(microdenier)纤维网。
我们的发明因此提供了一种新型且廉价的用于水可分散的非织造织物的方法,包括熔纺水可分散的磺基聚酯和形成非织造网。所述非织造织物可以是平幅针织物(flatfabric)或三维形状的形式,其可以被引入到各种纤维制品中,例如,上文提及的个人护理制品,或者用于制造水可分散的和/或可冲洗的(flushable)保护性外层物品,例如,外科手术服和用于化学和生物危险物清除和实验室工作的防护服。
具体实施方式
本发明提供了水可分散的纤维和纤维制品,其在水分存在下,特别是当暴露于人体液时,显示出拉伸强度、吸收性、柔性和织物完整性。我们的发明的纤维和纤维制品没有要求油、蜡或脂肪酸面层(finish)的存在或者使用大量(通常为10wt%或更多)的颜料或填料以阻止在加工期间纤维的粘连或融合。另外,由我们的新型纤维制备的纤维制品没有要求结合剂并且容易地分散或溶于家庭或公共排水系统中。
在一般性的实施方案中,我们的发明提供了水可分散的纤维,其包括玻璃化转变温度(Tg)为至少25℃的磺基聚酯,其中该磺基聚酯包括:
(A)一种或多种二羧酸的残基;
(B)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中该官能团是羟基,羧基或其组合;
(C)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和(iv)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。我们的纤维可以任选地包括与磺基聚酯共混的水可分散的聚合物和,任选地,与磺基聚酯共混的水不可分散的聚合物,前提是该共混物是不溶混的共混物。我们的纤维包含小于10wt%的颜料或填料,基于纤维的总重量。本发明还包括纤维制品,其包括这些纤维并且可包括个人护理产品如抹布、纱布、薄纸、尿布、成人失禁内裤、训练裤、卫生巾、绷带和外科敷料。纤维制品可以具有一层或多层的纤维吸收层。
我们的发明的纤维可以是单组分(unicomponent)纤维、双组分或多组分纤维。例如,本发明的纤维可以通过熔纺单一磺基聚酯或磺基聚酯共混物来制备并且包括切段纤维、单丝纤维和多丝纤维,具有成形断面。另外,我们的发明提供多组分纤维,如例如在美国专利5,916,678中所描述的,其可以通过挤出磺基聚酯和一种或多种水不可分散的聚合物来制备,后者是与磺基聚酯不溶混的,单独地通过具有成形或加工横断几何形状(例如,海岛型、皮芯型、并列型或扇饼型(segmentedpie)构型)的喷丝板。可以通过溶解界面层或饼状区段(segment)并且留下水不可分散的聚合物的较小的长丝或微旦数(microdenier)纤维而随后除去磺基聚酯。水不可分散的聚合物的这些纤维具有的纤维尺寸远远小于在除去磺基聚酯前的多组分纤维的尺寸。例如,磺基聚酯和水不可分散的聚合物可以进料到聚合物分配系统,其中聚合物被引入扇形(segmented)喷丝板。聚合物按照单独的路径到达纤维喷丝板,并且在喷丝板孔处结合,所述喷丝板孔包括两个同心的圆孔,因而提供了皮芯型纤维,或者其包括圆形的喷丝板孔,该喷丝板孔沿着直径分为多个部分,从而提供并列型纤维。或者,不溶混的水可分散的磺基聚酯和水不可分散的聚合物可以被单独地引入具有多个径向通道的喷丝板以生产具有扇饼型(segmentedpie)断面的多组分纤维。一般地,磺基聚酯将形成皮芯型构型的“皮”组分。在具有多个区段(segment)的纤维横断面中,水不可分散的区段(segment),一般地,被磺基聚酯基本上彼此隔离。或者,多组分纤维可以这样形成,在单独的挤出机中熔融磺基聚酯和水不可分散的聚合物,并且将聚合物流动导入一个具有多个分布流动路径的喷丝板,形式为小的细管或区段(segment),以提供具有海岛型成形断面的纤维。这种喷丝板的实例描述在美国专利5,366,804中。在本发明中,一般地,磺基聚酯将形成“海”组分,水不可分散的聚合物将形成“岛”组分。
除非另有陈述,说明书和权利要求中所用的表示成分的数量、性能如分子量、反应条件等的所有数字应被理解为在一切情况下被术语“约”所修饰。因此,除非相反地指出,在以下说明书和所附权利要求中所述的数值参数是近似的,其可以变化,这取决于设法通过本发明获得的期望的性能。至少,各个数值参数应当至少根据所报道的有效数字的数目并且通过应用常规的取整技术来理解。进一步,在本说明书和权利要求中所述的范围意图特别包括整个范围,而非仅仅端点。例如,描述为0~10的范围意图公开0~10之间的所有整数,比如1、2、3、4等,0~10之间的所有分数,例如1.5、2.3、4.57、6.1113等,以及端点0和10。并且,与化学取代基团相关的范围,例如“C1-C5烃类”,意图特别地包括和公开了C1和C5烃类以及C2、C3和C4烃类。
尽管在本发明宽泛范围内所列的数值范围和参数都是近似值,但是列于具体实施例中的数值都尽可能精确地进行报告。然而,任何数值都固有地包含某些必然源于其各自测试测量中存在的标准偏差的误差。
本发明的单组分(unicomponent)纤维和纤维制品是水可分散的,一般地,在室温下完全分散。可使用较高的水温以促进其分散性或者从非织造或多组分纤维中除去的速率。如本文中使用的,术语“水可分散的”,就单组分(unicomponent)纤维和由单组分(unicomponent)纤维制备的纤维制品而论,意图与术语“水-可驱散的”、“水-可分离的”、“水-可溶解的”、“水可消除的”、“水溶性的”、“水-可除去的”、“水溶的”和“水分散性的”同义,并且意图是指所述纤维或纤维制品是在水的作用下分散或溶解于其中或者通过其分散或溶解。术语“分散”、“可分散的”、“驱散”或“可驱散的”是指,使用足够量的去离子水(例如,100∶1的水∶纤维,按重量计)以形成纤维或纤维制品的疏松的悬浮液或浆料,在约60℃的温度下,和在至多5天的时间内,纤维或纤维制品溶解、分解或分离成多个不连贯的部分或颗粒,它们或多或少分布遍及介质中,使得当例如通过过滤或蒸发除去水时,没有可识别的长丝可以从介质中回收。因此,如本文中使用的,“水可分散的”不意图包括缠结或结合的、然而却是水不溶性的或不可分散性的纤维的纤维束(assembly)的简单分解,其中该纤维束(fiberassembly)简单地在水中分裂而产生在水中的纤维的浆料,其可以通过除去水而进行回收。在本发明的范围内,全部这些术语是指水或者水和水-可混溶的助溶剂的混合物对本文中所述的磺基聚酯的活性。这种水-可混溶的助溶剂的实例包括醇、酮、二醇醚(glycolethers)、酯等等。对于这种术语来说,意图包括这样的状况,其中磺基聚酯被溶解以形成真溶液,以及其中磺基聚酯被分散在含水介质中。经常地,由于磺基聚酯组合物的统计学性质,当将单一磺基聚酯样品置于含水介质中时,有可能具有可溶性级分和被分散的级分。
同样,如本文中使用的,关于作为多组分纤维或纤维制品的一种组分的磺基聚酯,术语“水可分散的”还意图与术语“水-可驱散的”、“水-可分离的”、“水-可溶解的”、“水可消除的”、“水溶性的”、“水-可除去的”、“水溶的”和“水分散性的”同义,并且意图是指磺基聚酯组分被充分地从多组分纤维中除去并且在水的作用下被分散或溶解,从而能够释放和分离其中所含的水不可分散的纤维。术语“分散”、“可分散的”、“驱散”或“可驱散的”是指,使用足够量的去离子水(例如,100∶1的水∶纤维,按重量计)以形成纤维或纤维制品的疏松的悬浮液或浆料,在约60℃的温度下,和在至多5天的时间内,磺基聚酯组分将多组分纤维溶解、分解或与其分离,从水不可分散的区段(segment)中留下多个微旦数(microdenier)纤维。
术语“区段(segment)”或“域”或“区”,当用于描述多组分纤维的成形断面时,是指包括水不可分散的聚合物的断面中的区域,其中这些域或区段(segment)通过介于区段(segment)或域之间的水可分散的磺基聚酯而基本上彼此隔离。如本文中使用的,术语“基本上隔离”,意图是指区段(segment)或域彼此分开,从而当除去磺基聚酯时,允许区段(segment)、域形成单独的纤维。区段(segment)或域或区可以具有相似的大小与形状或者不同的大小与形状。此外,区段(segment)或域或区能够以任何构型排列。这些区段(segment)或域或区沿多组分挤出物或纤维的长度方向,是“基本上连续的”。术语“基本上连续的”是指沿多组分纤维的至少10厘米的长度是连续的。
如本发明中所说明的,多组分纤维的成形断面可以例如是以下形式的:皮芯型、海岛型、扇饼型(segmentedpie)、空心的扇饼型(segmentedpie)、偏心的扇饼型(segmentedpie)等等。
本发明的水可分散的纤维是由聚酯,或者更具体地说,磺基聚酯,制备的,其包括二羧酸单体残基、磺基单体残基、二醇单体残基和重复单元。磺基单体可以是二羧酸、二醇或羟基羧酸。因此,术语“单体残基”,如本文中使用的,是指二羧酸、二醇或羟基羧酸的残基。“重复单元”,如本文中使用的,是指具有2个通过羰氧基连接的单体残基的有机结构。本发明的磺基聚酯包含基本上等摩尔比的酸残基(100mol%)和二醇残基(100mol%),其以基本上相等的比例反应,使得重复单元的总摩尔数等于100mol%。因此,本公开内容中提供的摩尔百分比可以基于酸残基的总摩尔数、二醇残基的总摩尔数或重复单元的总摩尔数。例如,基于总重复单元包含30mol%的可以是二羧酸、二醇或羟基羧酸的磺基单体的磺基聚酯是指这样的磺基聚酯,在总共100mol%的重复单元中,包含30mol%磺基单体。因此,在每100mol重复单元中,存在30mol的磺基单体残基。同样,基于总酸残基包含30mol%的二羧酸磺基单体的磺基聚酯,是指在总共100mol%酸残基中,磺基聚酯包含30mol%磺基单体。因此,在后一情况中,在每100摩尔的酸残基中存在30mol的磺基单体残基。
本文中所述的磺基聚酯具有至少约0.1dL/g的比浓对数粘度,在下文缩写为“Ih.V.”,优选约0.2-0.3dl/g,和最优选大于约0.3dl/g,在25℃在60/40重量份的苯酚/四氯乙烷溶剂的溶液中以及以100mL的溶剂中约0.5g的磺基聚酯的浓度测量的。如本文中使用的,术语“聚酯”包含“均聚酯”和“共聚酯”并且是指通过双官能羧酸与双官能羟基化合物的缩聚而制备的合成聚合物。如本文中使用的,术语“磺基聚酯”意思是任何包含磺基单体的聚酯。通常双官能羧酸是二羧酸,双官能羟基化合物是二元醇,例如二醇(glycol)和二醇(diol)。或者,双官能羧酸可以是羟基羧酸,例如对羟基苯甲酸,而双官能羟基化合物可能是带有2个羟基取代基的芳基核,例如氢醌。如本文中使用的,术语“残基”意思是任何通过涉及相应的单体的缩聚反应而引入聚合物的有机结构。因此,二羧酸残基可以衍生自二羧酸单体或其相关的酰卤、酯、盐、酸酐或其混合物。因此,如本文中使用的,术语二羧酸意图包括二羧酸和二羧酸的任何衍生物,包括其相关的酰卤、酯、半酯、盐、半盐、酸酐、混合酸酐或其混合物,它们可用于与二醇的缩聚过程以制备高分子量聚酯。
本发明的磺基聚酯包括一种或多种二羧酸残基。取决于磺基单体的类型和浓度,二羧酸残基可以包含约60-约100摩尔%的酸残基。二羧酸残基的浓度范围的其他例子是约60摩尔%-约95摩尔%,和约70摩尔%-约95摩尔%。可以使用的二羧酸的例子包括脂族二羧酸、脂环族二羧酸、芳族二羧酸,或两种或更多种这些酸的混合物。因此,合适的二羧酸包括但不局限于,琥珀酸;戊二酸;己二酸;壬二酸;癸二酸;富马酸;马来酸;衣康酸;1,3-环己烷二羧酸;1,4-环己烷二羧酸;二羟乙酸;2,5-降莰烷二羧酸;邻苯二甲酸;对苯二甲酸;1,4-萘二羧酸;2,5-萘二羧酸;联苯甲酸;4,4′-氧联二苯甲酸(oxydibenzoic);4,4′-磺酰二苯甲酸;和间苯二甲酸。优选的二羧酸残基是间苯二甲酸、对苯二甲酸和1,4-环己烷二羧酸,或者如果使用二酯的话,对苯二甲酸二甲酯、间苯二甲酸二甲酯、和1,4-环己烷二羧酸二甲酯,其中间苯二甲酸和对苯二甲酸的残基是特别优选的。尽管二羧酸甲酯是最优选的实施方案,但是也可接受的是包括高阶(higherorder)烷基的酯,例如乙基、丙基、异丙基、丁基等等。此外,芳族酯,特别是苯基酯,也可以使用。
磺基聚酯包括约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中该官能团是羟基,羧基或其组合。对于磺基单体残基的浓度范围的其它例子是约4-约35摩尔%,约8-约30摩尔%,和约8-约25摩尔%,基于总的重复单元。磺基单体可以是包含磺酸根基团的二羧酸或其酯、包含磺酸根基团的二醇、或包含磺酸根基团的羟酸。术语“磺酸盐”指的是具有结构“-SO3M”的磺酸盐,其中M是磺酸盐的阳离子。磺酸盐的阳离子可以是金属离子,如Li+、Na+、K+、Mg++、Ca++、Ni++、Fe++等等。或者,磺酸盐的阳离子可以是非金属的,如在,例如,美国专利4,304,901中描述的含氮碱。氮基的阳离子来源于含氮碱,其可以是脂族的、环脂族的、或芳族的化合物。这样的含氮碱的例子包括氨、二甲基乙醇胺、二乙醇胺、三乙醇胺、吡啶、吗啉和哌啶。因为包含氮基的磺酸盐的单体通常在需要制备熔融状态的聚合物的条件下是热不稳定的,因此本发明的用于制备含氮基磺酸根基团的磺基聚酯的方法是以其碱金属盐的形式将包含所需量的磺酸根基团的聚合物分散、驱散、或溶解在水中,然后用氮基阳离子交换碱金属阳离子。
当一价碱金属离子用作磺酸盐的阳离子时,所得到的磺基聚酯完全地可分散在水中,其分散的速率(rate)取决于聚合物中的磺基单体的含量、水的温度、磺基聚酯的表面积/厚度等等。当使用二价金属离子时,所得到的磺基聚酯不容易被冷水分散,但是更容易地通过热水分散。在单一的聚合物组合物中利用大于一种的平衡离子是可行的并且可以提供定制或微调所得制品的水响应性(water-responsivity)的方法。磺基单体残基的例子包括这样的单体残基,其中磺酸根基团连接到芳族酸环(nucleus),例如,苯;萘;联二苯(diphenyl);氧联二苯(oxydiphenyl);磺酰联二苯(sulfonyldiphenyl);和亚甲基联二苯(methylenediphenyl),或环脂族环,例如,环已基;环戊基;环丁基;环庚基和环辛基。可用于本发明的磺基单体残基的其它实例是磺基邻苯二甲酸、磺基对苯二甲酸、磺基间苯二甲酸或其组合的金属磺酸盐。可以使用的磺基单体的其它例子是5-钠代磺基间苯二甲酸和其酯。如果磺基单体残基来自5-钠代磺基间苯二甲酸,通常磺基单体浓度范围是约4-约35摩尔%,约8-约30摩尔%,和约8-25摩尔%,基于酸残基的总摩尔数。
用在制备磺基聚酯中的磺基单体是已知的化合物,和可以使用本领域众所周知的方法制备。例如,其中磺酸根基团连接到芳族环的磺基单体可以这样制备,包括用发烟硫酸磺化芳族化合物以获得相应的磺酸,然后和金属氧化物或碱,例如,乙酸钠,反应来制备磺酸盐。制备不同的磺基单体的方法描述在,例如,美国专利3,779,993;3,018,272和3,528,947中。
也可能的是当聚合物是分散的形式时,使用,例如,钠磺酸盐,和离子交换方法来用如锌等的不同的离子替换钠来制备聚酯。在钠盐通常更易溶解在聚合物反应物熔融相的范围内,这种类型的离子交换方法通常优于用二价盐制备聚合物。
磺基聚酯包括一种或多种二醇残基,其可以包括脂族、环脂族和芳烷基二醇。环脂族二醇,例如,1,3-和1,4-环己烷二甲醇,可能以它们的纯顺式或反式异构体的形式或以顺式和反式异构体混合物的形式存在。如本文中使用的,术语“二醇(diol)”是和术语“二醇(glycol)”同义的,并且是指任何的二元醇。二醇的例子包括但是不限于,乙二醇;二甘醇;三甘醇;聚乙二醇;1,3-丙二醇;2,4-二甲基-2-乙基己烷-1,3-二醇;2,2-二甲基-1,3-丙二醇;2-乙基-2-丁基-1,3-丙二醇;2-乙基-2-异丁基-1,3-丙二醇;1,3-丁二醇;1,4-丁二醇;1,5-戊二醇;1,6-己二醇;2,2,4-三甲基-1,6-己二醇;硫代二乙醇;1,2-环己烷二甲醇;1,3-环己烷二甲醇;1,4-环己烷二甲醇;2,2,4,4-四甲基-1,3-环丁二醇;对苯二甲醇(xylylenediol),或这些二醇中的一种或多种的组合。
二醇残基可以包括约25摩尔%-约100摩尔%,基于总二醇残基,的具有以下结构的聚(乙二醇)的残基
H-(OCH2-CH2)n-OH
其中n是2-约500的整数。较低分子量的聚乙二醇的非限制性实例,例如,其中n是2-6,是二甘醇、三甘醇和四甘醇。在这些较低分子量的二醇中,二甘醇和三甘醇是最优选的。较高分子量的聚乙二醇(在此缩写为“PEG”),其中n是7-约500,包括市售可得的已知的名称为CARBOWAX的产品,其是DowChemicalCompany(以前的UnionCarbide)的产品。通常,PEG和其它的二醇组合使用,所述二醇例如为,二甘醇或乙二醇。基于n的值,其在大于6至500范围内变化,分子量可以在大于300-约22,000g/mol之间变化。分子量和摩尔%是彼此成反比的;具体地说,随着分子量的增大,摩尔%将会降低以达到指定程度的亲水性。例如,这个概念说明性的是设想具有1000分子量的PEG可构成总二醇的高达10摩尔%,而具有10,000分子量的PEG将通常以低于总二醇的1摩尔%的水平引入。
由于副反应,可能在原位形成某些二聚物、三聚物和四聚物二醇,所述副反应可以通过改变工艺条件来控制。例如,变化量的二甘醇、三甘醇和四甘醇可以由乙二醇形成,这来自于在酸性条件下进行缩聚反应时容易发生的酸催化脱水反应。本领域技术人员众所周知,存在的缓冲溶液可以添加到反应混合物来延迟这些副反应。但是,其它的组成范围是可能的,如果省略缓冲溶液和容许二聚反应、三聚反应和四聚反应进行的话。
本发明的磺基聚酯可以包括0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。支化单体的非限制性实例是1,1,1-三羟甲基丙烷、1,1,1-三羟甲基乙烷、甘油、季戊四醇、赤藓醇、苏糖醇、二季戊四醇、山梨糖醇、偏苯三酸酐、均苯四酸二酐、二羟甲基丙酸或其组合。支化单体浓度范围的进一步的实例是0-约20mol%和0-约10mol%。支化单体的存在可能导致对本发明的磺基聚酯的许多可能的益处,包括但不限于,对定制流变性、溶解性和拉伸性能的能力。例如,在恒定的分子量下,支化的磺基聚酯,与线性的类似物相比,将会具有更大的端基浓度,其可以促进聚合后交联反应。但是,在高的支化剂浓度下,磺基聚酯可能倾于凝胶化。
用于本发明的纤维的磺基聚酯具有的玻璃化转变温度,在此缩写为“Tg”,为至少25℃,其是使用如本领域技术人员众所周知的差示扫描量热法(“DSC”)的标准技术对干燥的聚合物测量的。本发明的磺基聚酯的Tg测量是使用“干燥的聚合物”进行的,即,一种聚合物样品,其中通过把聚合物加热到约200℃的温度并且使样品回到室温来驱散外来的或吸收的水。通常,磺基聚酯在DSC仪器中通过进行最初的热扫描而干燥,其中,样品加热到大于水汽化温度的温度,样品保持在这个温度下直到聚合物中吸收的水完全汽化为止(如由大的、宽的吸热所指示的),把样品冷却到室温,然后进行第二次热扫描以获得Tg测量。磺基聚酯显示出的玻璃化转变温度的进一步的实例是至少30℃,至少35℃,至少40℃,至少50℃,至少60℃,至少65℃,至少80℃,和至少90℃。尽管其它的Tg是可能的,我们的发明的干燥的磺基聚酯的通常的玻璃化转变温度是约30℃,约48℃,约55℃,约65℃,约70℃,约75℃,约85℃和约90℃。
我们的新型的纤维可以基本上由上文所述的磺基聚酯组成,或者,由上文所述的磺基聚酯组成。在另一实施方案中,然而,本发明的磺基聚酯可以是单一聚酯,或者,可以与一种或多种辅助的聚合物共混而改变所得的纤维的性能。辅助的聚合物可以是或者可以不是水可分散的,这取决于应用,并且可以是与磺基聚酯可混溶的或者不溶混的。如果辅助的聚合物是水不可分散的,优选的是与磺基聚酯的共混物是不溶混的。术语“可混溶的”,如本文中使用的,意图是指共混物具有单一、均质的无定形相,如由单一组成-依赖的Tg所指明的。例如,与第二聚合物可混溶的第一聚合物可以用于“增塑”第二聚合物,例如,如在美国专利6,211,309中所举例说明的。相比之下,术语“不溶混的”,如本文中使用的,表示这样的共混物,其显示出至少2个、随机混合的相并且显示出多于一个Tg。一些聚合物可以是与磺基聚酯不溶混的,但与磺基聚酯相容。可混溶的和不溶混的聚合物共混物的进一步的概述和用于其表征的各种分析技术可见于以下文献中:PolymerBlends(聚合物共混物)卷1和2,编者D.R.Paul和C.B.Bucknall,2000,JohnWiley&Sons,Inc。
可以与磺基聚酯共混的水可分散的聚合物的非限制性实例是聚甲基丙烯酸、聚乙烯基吡咯烷酮、聚乙烯-丙烯酸共聚物、聚乙烯甲醚、聚乙烯醇、聚氧化乙烯、羟基丙基纤维素、羟丙基甲基纤维素、甲基纤维素、乙基羟乙基纤维素、异丙基纤维素、甲基醚淀粉、聚丙烯酰胺、聚(N-乙烯基己内酰胺)、聚乙基噁唑啉、聚(2-异丙基-2-噁唑啉)、聚乙烯基甲基噁唑烷酮、水可分散的磺基聚酯、聚乙烯基甲基噁唑烷酮(oxazolidimone)、聚(2,4-二甲基-6-三嗪基乙烯)和氧化乙烯-氧化丙烯共聚物。可以与磺基聚酯共混的水不可分散的聚合物的实例包括但不局限于聚烯径,如聚乙烯和聚丙烯的均聚物和共聚物;聚(对苯二甲酸乙二酯);聚(对苯二甲酸丁二酯);和聚酰胺,如尼龙-6;聚交酯;己内酯;EastarBio(聚(四亚甲基己二酸酯-co-对苯二甲酸酯),EastmanChemicalCompany的产品);聚碳酸酯;聚氨酯;和聚氯乙烯。
根据我们的发明,多于一种的磺基聚酯的共混物可以用于定制所得纤维或纤维制品,例如非织造织物或纤维网,的终端使用性能。一种或多种磺基聚酯的共混物将具有下述Tg,对于水可分散的、单组分(unicomponent)纤维为至少25℃,对于多组分纤维为至少57℃。因此,共混还可被利用而改变磺基聚酯的加工特性从而促进非织造物的制造。在另一实例中,聚丙烯和磺基聚酯的不溶混的共混物可提供一种常规的非织造网,当不需要真溶解度(truesolubility)时,其将分裂并且完全分散在水中。在该后一实例中,预期的性能相关于保持聚丙烯的物理性能,而在产品的实际使用期间,磺基聚酯仅仅是一旁观者,或者,磺基聚酯是短效的(fugitive)并且在使用最终形式的产品之前被除去。
磺基聚酯和辅助的聚合物可以以间歇、半连续或连续过程进行共混。小规模的批料可易于在本领域技术人员众所周知的任何高强度的混合设备中进行制备,如班伯里密炼机,然后熔纺纤维。所述组分还可在合适的溶剂中在溶液中进行共混。熔融共混方法包括在足以熔融聚合物的温度下共混磺基聚酯和辅助的聚合物。共混物可以被冷却并且粒化以便进一步的使用,或者熔融共混物可以被直接地由这种熔融共混物熔纺成纤维形式。术语“熔融”,如本文中使用的,包括但不局限于仅仅软化聚酯。对于聚合物技术领域中通常已知的熔融混合方法来说,参见MixingandCompoundingofPolymers(I.Manas-Zloczower&Z.Tadmoreditors,CarlHanserVerlagPublisher,1994,NewYork,N.Y.).
我们的发明还提供了一种水可分散的纤维,其包括玻璃化转变温度(Tg)为至少25℃的磺基聚酯,其中该磺基聚酯包括:
(A)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(B)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(C)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;(iv)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。如上文中所述,纤维可以任选地包括与磺基聚酯共混的第一水可分散的聚合物;和,任选地,与磺基聚酯共混的水不可分散的聚合物,使得该共混物是不溶混的共混物。我们的纤维包含小于10wt%的颜料或填料,基于纤维的总重量。第一水可分散的聚合物是如上文所描述的。磺基聚酯应当具有至少25℃的玻璃化转变温度(Tg),但是可以具有例如下述的Tg:约35℃、约48℃、约55℃、约65℃、约70℃、约75℃、约85℃和约90℃。磺基聚酯可以包含其它浓度的间苯二甲酸残基,例如,约60摩尔%-约95摩尔%,和约70摩尔%-约95摩尔%。间苯二甲酸残基的浓度范围的进一步的实例是约70摩尔%-约85摩尔%,约85摩尔%-约95摩尔%,和约90摩尔%-约95摩尔%。磺基聚酯还可以包含约25-约95mol%的二甘醇的残基。二甘醇残基的浓度范围的进一步的实例包括约50-约95mol%、约70-约95mol%和约75-约95mol%。磺基聚酯还可以包括乙二醇和/或1,4-环己烷二甲醇(在本文中缩写为“CHDM”)的残基。CHDM残基的典型的浓度范围为约10-约75mol%、约25-约65mol%和约40-约60mol%。乙二醇残基的典型的浓度范围为约10-约75mol%、约25-约65mol%和约40-约60mol%。在另一实施方案中,磺基聚酯包括约75-约96mol%的间苯二甲酸的残基和约25-约95mol%的二甘醇的残基。
本发明的磺基聚酯,使用典型的缩聚反应条件,易于由合适的二羧酸、酯、酸酐或盐,磺基单体和合适的二醇或二醇混合物来制备。它们可以通过连续、半连续和间歇的操作方式来制备并且可以利用各种反应器类型。合适的反应器类型的实例包括但不局限于搅拌罐、连续搅拌罐、浆液反应器、管式反应器、揩薄膜反应器(wiped-filmreactor)、降膜反应器或挤出反应器。术语“连续”,如本文中使用的,是指一种方法,其中反应物的引入和产品的回收以非间断方式同时进行。“连续”是指在操作中该方法是基本上或者完全连续的,与“间歇”方法形成对比。“连续”不以任何方式意味着禁止在连续性的方法中由于例如启动、反应器维修或预定停车周期所造成的正常的中断。术语“间歇”方法,如本文中使用的,是指一种方法,其中全部反应物被添加到反应器中,随后根据预定的反应过程进行处理,在此期间,没有物料进料到反应器中或者从反应器中取出物料。术语“半连续”是指一种方法,其中一些反应物在方法开始时加入,而剩余的反应物随着反应发展而连续地进料。或者,半连续过程还可包括一种类似于间歇过程的方法,其中在方法开始时,添加全部的反应物,不同的是,随着反应发展,连续地取出一种或多种产物。所述方法以连续过程的方式操作是有利的,这是出于经济的原因,并且以便产生聚合物的优良颜色,因为如果使磺基聚酯在高温下在反应器中停留太长的时间的话,其在外观上可能变差。
本发明的磺基聚酯通过本领域技术人员已知的方法制备。磺基单体最通常是被直接添加到反应混合物中,由所述反应混合物制备聚合物,但是其他方法是已知的并且可以被使用,例如,如美国专利3,018,272、3,075,952和3,033,822中所描述的。使用常规的聚酯聚合条件,可以进行磺基单体、二醇组分和二羧酸组分的反应。例如,当通过酯交换反应制备磺基聚酯时,即由二羧酸组分的酯形式来制备,反应过程可以包括两个步骤。在第一步骤中,二醇组分和二羧酸组分,例如间苯二甲酸二甲酯,在升温下进行反应,一般为约150℃-约250℃,进行约0.5-约8小时,压力为约0.0kPa(表压)-约414kPa(表压)(60磅/平方英寸,“psig”)。优选地,酯交换反应的温度为约180℃-约230℃,进行约1-约4小时,而优选的压力为约103kPa(表压)(15psig)-约276kPa(表压)(40psig)。其后,反应产物在较高的温度和在降低的压力进行加热而形成具有消除二醇的磺基聚酯,其在这些条件下是容易挥发的并且从系统中被除去。该第二步骤,或者缩聚步骤,在较高的真空和一定温度下继续,通常为约230℃.-约350℃,优选地约250℃-约310℃和最优选约260℃-约290℃达约0.1-约6时,或者优选地,约0.2-约2小时,直到获得具有期望的如根据比浓对数粘度测定的聚合度的聚合物。缩聚步骤可以在降低的压力进行,所述压力为约53kPa(400托)-约0.013kPa(0.1托)。搅拌或者合适的条件被用于两阶段中以确保足够的热传递和反应混合物的表面更新。两阶段的反应可以受到合适的催化剂的促进,例如,烷氧基钛化合物,碱金属氢氧化物和醇化物,有机羧酸的盐,烷基锡化合物,金属氧化物等。还可使用三阶段的制造方法,类似于美国专利5,290,631中所述的那些的,特别是当使用酸和酯的混合单体进料时。
为了保证驱动二醇组分和二羧酸组分的反应通过酯交换反应机理而完成,优选使用约1.05-约2.5摩尔的二醇组分∶1摩尔二羧酸组分。然而,本领域技术人员将理解,二醇组分和二羧酸组分的比值通常是通过其中发生反应过程的反应器的设计所确定的。
在通过直接酯化制备磺基聚酯中,即,从酸式的二羧酸组分出发,通过二羧酸或二羧酸的混合物与二醇组分或二醇组分的混合物的反应生产磺基聚酯。反应在以下条件下进行:压力约7kPa(表压)(1psig)-约1379kPa(表压)(200psig),优选地小于689kPa(100psig),以生产低分子量线性或分枝的磺基聚酯产物,其具有约1.4-约10的平均聚合度。在直接酯化反应期间使用的温度一般为约180℃-约280℃,更优选地约220℃-约270℃。这种低分子量聚合物然后可以通过缩聚反应来聚合。
本发明的水可分散的和多组分的纤维和纤维制品还可能包含其它常规添加剂和成分,其没有有害地影响它们的最终用途。例如可以使用添加剂如填料,表面摩擦改性剂,光和热稳定剂,挤出助剂,抗静电剂,着色剂,染料,颜料,荧光增白剂,抗微生物,防伪标记,疏水和亲水增强剂,粘度调节剂,滑爽剂,增韧剂,粘合增进剂等。
我们的发明的纤维和纤维制品没有要求存在添加剂,例如颜料,填料,油、蜡或脂肪酸面层(finish),以阻止在加工期间纤维的粘连或融合。术语“粘连或融合”,如本文中使用的,应理解为是指纤维或纤维制品粘在一起或者融合成一团,使得纤维不能被加工或者用于其预定的目的。粘连和融合可以在纤维或纤维制品的加工期间或者在数天或数周的存储期间发生,并且在热、潮湿的条件下加重。
在本发明的一种实施方案中,纤维和纤维制品将包含小于10wt%的这种防粘连添加剂,基于纤维或纤维制品的总重量。例如,纤维和纤维制品可以包含小于10wt%的颜料或填料。在其它实例中,纤维和纤维制品可以包含小于9wt%,小于5wt%,小于3wt%,小于1wt%和0wt%的颜料或填料,基于纤维的总重量。着色剂,有时称为调色剂,可以被添加以便赋予磺基聚酯所期望的中性的色调(hue)和/或亮度(brightness)。当有色纤维是期望的时候,颜料或着色剂可以在二醇单体和二羧酸单体的反应期间被添加在磺基聚酯反应混合物中,或者它们可以与预形成的磺基聚酯熔融共混。添加着色剂的优选的方法是使用具有热稳定性的有机有色化合物(其具有活性基团)的着色剂,使得着色剂被共聚合并且引入到磺基聚酯中,从而改进其色调。例如,着色剂,如染料,其具有反应性羟基和/或羧基,包括但不限于,蓝和红取代的蒽醌,可以被共聚合到聚合物链中。
当染料用作着色剂时,它们可以在酯交换或者直接酯化反应后,被添加到共聚酯反应过程中。
就本发明的目的而言,术语“纤维”是指高纵横比(aspectratio)的聚合物物体,其能够成形为二维或三维制品,如织造或非织造织物。在本发明的范围内,术语“纤维(fiber)”与“纤维(fibers)”同义,并且意图是指一种或多种纤维。我们的发明的纤维可以是单组分(unicomponent)纤维、双组分,或者多组分纤维。术语“单组分(unicomponent)纤维”,如本文中使用的,是指通过熔纺单一磺基聚酯或一种或多种磺基聚酯的共混物,或者一种或多种磺基聚酯与一种或多种另外的聚合物的共混物来制备的纤维并且包括切段纤维、单丝纤维和复丝纤维。“单组分(unicomponent)”意欲与术语“单组分(monocomponent)”同义,并且包括“双成分”或“多成分”纤维,是指已经由至少两种从同一挤出机以混合物的形式挤出的聚合物形成的纤维。单组分(unicomponent)或双成分纤维,沿纤维的断面不具有在相对恒定设置的不同区中排列的各种聚合物组分,并且各种聚合物沿纤维的全部长度通常是不连续的,相反,通常形成随意开始和结束的纤丝或原纤丝。因此,术语“单组分(unicomponent)”不意图排除由这样的聚合物或一种或多种聚合物的共混物形成的纤维,其中为着色、抗静电性能、润滑、亲水性等可以向其中添加少量的添加剂。
相形之下,术语“多组分纤维”,如本文中使用的,意图是指这样制备的纤维,包括将两种或更多种成纤聚合物在单独的挤出机中熔融,将所得的多个聚合物流导到一个具有多个分布流动路径的喷丝板中,但是纺丝在一起而形成一种纤维。多组分纤维有时还称为共轭或双组分纤维。聚合物沿共轭纤维的断面在基本上固定设置的不同区段(segment)或区中排列并且沿着共轭纤维的长度连续地延伸。这种多组分纤维的构型可以是,例如,皮/芯结构,其中一种聚合物由另一种围绕,或者可以是并列结构,饼状结构或者“海岛型”结构。例如,多组分纤维可以这样制备,包括将磺基聚酯和一种或多种水不可分散的聚合物单独地挤出通过喷丝板,所述喷丝板具有成形或者加工横断几何形状,例如“海岛型”或者扇饼型(segmentedpie)构型。单组分(unicomponent)纤维,一般地,是切段纤维、单丝纤维或复丝纤维,其具有成形或圆形断面。大多数纤维形式是热定形的。纤维可以包括各种的抗氧化剂,颜料和添加剂,如本文中所述的。
单丝纤维通常的尺寸为约15-约8000单丝旦数(在本文中缩写为“d/f”)。我们的新型的纤维一般地将具有约40-约5000的d/f值。单丝的形式可以是单组分(unicomponent)或多组分纤维。我们的发明的复丝纤维将优选地具有以下尺寸,对于熔吹网,从约1.5微米起,对于切段纤维,约0.5-约50d/f,对于单丝纤维,最高约5000d/f。复丝纤维还可用作卷曲或未卷曲的纱线和丝束。用于熔吹网和熔纺织物中的纤维可以以微旦数(microdenier)尺寸来生产。术语“微旦数(microdenier)”,如本文中使用的,意图是指d/f值为1d/f或以下。例如,本发明的微旦数(microdenier)纤维一般d/f值为1或以下,0.5或以下,或者0.1或以下。纳米纤维还可以通过静电纺纱来生产。
如上所述,磺基聚酯还有利于制备具有成形断面的双组分和多组分纤维。我们已经发现,玻璃化转变温度(Tg)为至少57℃的磺基聚酯或磺基聚酯的共混物可特别用于多组分纤维,以防止在纺丝和卷取(takeup)期间纤维的粘连和融合。因此,我们的发明提供了一种多组分纤维,其具有成形断面,包括:
(A)玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯,该磺基聚酯包括:
(i)一种或多种二羧酸的残基;
(ii)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中该官能团是羟基,羧基或其组合;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;和
(B)多个区段(segment),其包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离;
其中纤维具有海岛型或扇饼型(segmentedpie)断面并且包含小于10wt%的颜料或填料,基于纤维的总重量。
二羧酸、二醇、磺基聚酯、磺基单体和支化单体残基,如前所述的,用于本发明的其它实施方案中。对于多组分纤维来说,有利的是磺基聚酯的Tg为至少57℃。可由我们的多组分纤维的磺基聚酯或磺基聚酯共混物显示出的玻璃化转变温度的进一步的实例是至少60℃,至少65℃,至少70℃,至少75℃,至少80℃,至少85℃,和至少90℃。进一步,为获得具有至少57℃的Tg的磺基聚酯,可以以变化的比例使用一种或多种磺基聚酯的共混物以获得具有期望的Tg的磺基聚酯共混物。可以通过使用磺基聚酯组分的Tg的加权平均值来计算磺基聚酯共混物的Tg。例如,Tg为48℃的磺基聚酯可以与Tg为65℃的另一磺基聚酯以25∶75(wt∶wt)的比例共混而得到Tg为大约61℃的磺基聚酯共混物
在本发明的另一实施方案中,多组分纤维的水可分散的磺基聚酯组分呈现了各种性能,其容许下列中的至少一种:
(A)多组分纤维被纺丝成期望的低旦数,
(B)在这些多组分纤维中磺基聚酯在由纤维形成的纤维网的水缠结期间对除去具有耐受性,但是在水缠结后在升温下被有效地除去,知
(C)多组分纤维是热可定形的,从而得到一种稳定的、坚固的织物。使用具有某种熔体粘度和磺基单体残基水平的磺基聚酯,在促进这些目的中获得了令人惊奇且出人意料的结果。
因此,在本发明的这种实施方案中,提供了一种多组分纤维,其具有成形断面,包括:
(A)至少一种水可分散的磺基聚酯;和
(B)多个域(domains),所述域包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离,
其中该纤维的初纺旦数小于约6单丝旦数;
其中水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,和
其中磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数。
在这些多组分纤维中使用的磺基聚酯的熔体粘度通常小于约12,000泊。优选地,磺基聚酯的熔体粘度小于10,000泊,更优选地,小于6,000,和最优选,小于4,000泊,测量于240℃和1弧度/秒剪切速率。在另一方面中,磺基聚酯显示出这样的熔体粘度:约1000-12000泊,更优选地2000-6000泊,最优选2500-4000泊,测量于240℃和1弧度/秒剪切速率。在测定粘度前,样品在60℃在真空烘箱中干燥2天。熔体粘度是在流变仪上测量的,以1mm间隙调定,使用25mm直径的平行盘几何结构。动态扫频(dynamicfrequencysweep)是在应变速率为1-400弧度/秒和10%应变幅度的条件下进行的。然后在240℃和1弧度/秒的应变速率的条件下测量粘度。
根据本发明的这个方面,所用的磺基聚酯聚合物中的磺基单体残基的水平通常是小于约25mol%,优选地,小于20mol%,以磺基聚酯中的总二酸或二醇残基的百分数来报道。更优选地,该水平为约4-约20mol%,更优选地,约5-约12mol%,最优选地,约7-约10mol%。用于本发明的磺基单体优选地具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中该官能团是羟基,羧基或其组合。钠代磺基间苯二甲酸单体是特别优选的。
除如前所述的磺基单体之外,磺基聚酯优选包括一种或多种二羧酸的残基,一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数,和0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。
在特别优选的实施方案中,磺基聚酯包括约80-96mol%二羧酸残基,约4-约20mol%磺基单体残基,和100mol%一醇残基(总mol%为200%,即100mol%二酸和100mol%二醇)。更具体地说,磺基聚酯的二羧酸部分包括约60-80mol%对苯二甲酸,约0-30mol%间苯二甲酸,和约4-20mol%的5-钠代磺基间苯二甲酸(5-SSIPA)。二醇部分包括约0-50mol%二甘醇和约50-100mol%乙二醇。下文阐述根据本发明的这种实施方案的示范性的配方。
多组分纤维的水不可分散的组分可以包括本文中所述的那些水不可分散的聚合物中的任一种。纤维的纺丝还可根据本文中所述的任何方法来进行。然而,根据本发明的这个方面的多组分纤维的改进的流变性质提供了提高的拉伸速度。当磺基聚酯和水不可分散的聚合物被挤出以生产多组分挤出物时,使用本文中所公开的任何方法,以至少约2000m/min的速度,更优选地至少约3000m/min,更优选地至少约4000m/min,和最优选至少约4500m/min,多组分挤出物能够被熔融拉伸以生产该多组分纤维。虽然不意欲受理论学说的约束,在这些速度熔融拉伸多组分挤出物导致在多组分纤维的水不可分散的组分中的至少一些取向结晶度。这种取向结晶度可以提高在下一工序期间由多组分纤维制成的非织造材料的尺寸稳定性。
多组分挤出物的另一个优点在于它可以被熔融拉伸成初纺旦数小于6单丝旦数的多组分纤维。多组分纤维尺寸的其它范围包括初纺旦数小于4单丝旦数和小于2.5单丝旦数。
因此,在本发明的另一实施方案中,多组分挤出物,其具有成形断面,包括:
(A)至少一种水可分散的磺基聚酯;和
(B)多个域(domains),所述域包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离,
其中挤出物能够以至少约2000m/min的速度熔融拉伸。
多组分纤维包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物的多个区段(segment)或域,其中所述区段(segment)或域通过介于所述区段(segment)或域之间的磺基聚酯基本上彼此隔离。如本文中使用的,术语“基本上隔离”,意图是指区段(segment)或域彼此分开,从而当除去磺基聚酯时,允许区段(segment)、域形成单独的纤维。例如,区段(segment)或域可以彼此接触,例如,以扇饼型(segmentedpie)构型,但是通过冲击或者当除去磺基聚酯时,可以分裂开。
在本发明的多组分纤维中,磺基聚酯与水不可分散的聚合物组分的重量比通常为约60∶40-约2∶98,或者,在另一实例中,约50∶50-约5∶95。一般地,磺基聚酯占多组分纤维总重量的50wt%或以下。
多组分纤维的区段(segment)或域可以包括一种或多种(oneofmore)水不可分散的聚合物。可用于多组分纤维的区段(segment)中的水不可分散的聚合物的实例包括但不局限于聚烯径、聚酯、聚酰胺、聚交酯、聚己内酯、聚碳酸酯、聚氨酯和聚氯乙烯。例如,水不可分散的聚合物可以是聚酯如聚对苯二甲酸乙二酯,聚对苯二甲酸丁二酯,聚环己烷二甲酸环己二酯,聚对苯二甲酸环己二酯,聚对苯二甲酸丙二酯等。在另一实例中,水不可分散的聚合物可以是生物可分解的(biodistintegratable),如根据德国工业标准54900测定的和/或生物可降解的,如根据ASTM标准方法,D6340-98测定的。生物可降解的聚酯和聚酯共混物的实例公开在美国专利5,599,858;5,580,911;5,446,079;和5,559,171中。术语“生物可降解的(biodegradable)”,如本文中使用的,关系到本发明的水不可分散的聚合物,应理解为是指聚合物在合适的并且明显的时间跨度中在环境影响下例如在堆肥(composting)环境中降解(degrade),例如,由题为″StandardTestMethodsforDeterminingAerobicBiodegradationofRadiolabeledPlasticMaterialsinanAqueousorCompostEnvironment(在含水或者堆肥环境中用于测定放射性标记的塑料材料的曝气生物降解的标准测试方法)″的ASTM标准方法,D6340-98所定义的。本发明的水不可分散的聚合物也可以是“生物可分解的(biodisintegratable)”,这是指聚合物容易在堆肥环境中支离破碎(fragment),例如由德国工业标准54900所定义的。例如,可生物降解的聚合物,在热、水、空气、微生物及其他因素的作用下,最初在环境中在分子量方面降低。分子量的这种降低导致物理性能(韧度)的损失并且常常导致纤维断裂。一旦聚合物的分子量足够低,单体和低聚物于是被微生物所同化。在含氧环境中,这些单体或者低聚物最终氧化为CO2、H2O和新的细胞生物质。在缺氧环境中,单体或者低聚物最终转化为CO2、H2、乙酸盐(酯)、甲烷和细胞生物质。
例如,水不可分散的聚合物可以是脂族-芳族聚酯,其在本文中缩写为“AAPE”。术语“脂族-芳族聚酯”,如本文中使用的,是指包括来自脂族或者环脂族二羧酸或者二醇和芳族二羧酸或者二醇的残基的混合物的聚酯。术语“非芳族”,如本文中使用的,相对于本发明的二羧酸和二醇单体而言,是指单体的羧基或者羟基没有通过芳族环进行连接。例如,己二酸在其主链(即连接羧酸基团的碳原子链)中不包含芳族环,因此是“非芳族”的。相形之下,术语“芳族”是指在主链中二羧酸或者二醇包含芳族环,例如,对苯二甲酸或2,6-萘二甲酸。“非芳族”,因此,意图包括脂族和环脂族结构,例如,二醇和二羧酸,其包含组成碳原子的直链或支链或环状结构作为主链,所述组成碳原子在性质上可以是饱和或链烷的,不饱和的,即包含非芳族碳-碳双键,或者炔属,即,包含碳-碳三键。因此,在本发明的说明书和权利要求的范围内,非芳族意图包括直链和支链的链结构(在本文中称为“脂族”)和环状结构(在本文中称为“脂环族(的)”或“环脂族(的)”)。术语“非芳族”,然而,不意图排除任何芳族取代基,其可以连接到脂族或环脂族二醇或二羧酸的主链。在本发明中,双官能羧酸一般地是脂族二羧酸,例如己二酸,或芳族二羧酸,例如对苯二甲酸。双官能羟基化合物可以是环脂族二醇,例如1,4-环己烷二甲醇,线性或分枝的脂族二醇,例如1,4-丁二醇,或者芳族二醇,例如氢醌。
AAPE可以是线性或分枝的无规的共聚酯和/或链延伸的共聚酯,其包括二醇残基,所述二醇残基包括一种或多种取代的或未被取代的、线性或分枝的二醇的残基,所述二醇选自包含2-约8个碳原子的脂族二醇、包含2-8个碳原子的多亚烷基醚二醇和包含约4-约12个碳原子的环脂族二醇。取代的二醇,一般地,将包括1-约4个取代基,其独立地选自卤素、C6-C10芳基和C1-C4烷氧基。可以使用的二醇的实例包括但不局限于乙二醇,二甘醇,丙二醇,1,3-丙二醇,2,2-二甲基-1,3-丙二醇,1,3-丁二醇,1,4-丁二醇,1,5-戊二醇,1,6-己二醇,聚乙二醇,二甘醇,2,2,4-三甲基-1,6-己二醇,硫代二乙醇,1,3-环己烷二甲醇,1,4-环己烷二甲醇,2,2,4,4-四甲基-1,3-环丁二醇,三甘醇和四甘醇,优选的二醇包括一种或多种选自1,4-丁二醇;1,3-丙二醇;乙二醇;1,6-己二醇;二甘醇;或1,4-环己烷二甲醇的二醇。AAPE还包括二酸残基,其包含约35-约99mol%,基于二酸残基的总摩尔数,的一种或多种取代的或未被取代的、线性或分枝的非芳族二羧酸的残基,所述二羧酸选自包含2-约12个碳原子的脂族二羧酸和包含约5-约10个碳原子的环脂族酸。取代的非芳族二羧酸,一般地,将包含1-约4个取代基,其选自卤素、C6-C10芳基和C1-C4烷氧基。非芳族二酸的非限制性实例包括丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、壬二酸、癸二酸、富马酸、2,2-二甲基戊二酸、辛二酸、1,3-环戊烷二羧酸、1,4-环己烷二羧酸、1,3-环己烷二羧酸、二羟乙酸、衣康酸、马来酸和2,5-降莰烷二羧酸。除非芳族二羧酸之外,AAPE包括约1-约65mol%,基于二酸残基的总摩尔数,的一种或多种取代的或未被取代的包含6-约10个碳原子的芳族二羧酸的残基。在其中使用取代的芳族二羧酸的情况下,它们将一般地包含1-约4个取代基,其选自卤素、C6-C10芳基和C1-C4烷氧基。可用于我们的发明的AAPE中的芳族二羧酸的非限制性实例是对苯二甲酸、间苯二甲酸、5-磺基间苯二甲酸的盐和2,6-萘二羧酸。更优选地,非芳族二羧酸将包括己二酸,芳族二羧酸将包括对苯二甲酸,而二醇将包括1,4-丁二醇。
其它对于我们的发明的AAPE可行的组成是由下列二醇和二羧酸(或其成聚酯的等价物,如二酯)制备的那些,按如下的摩尔百分数,基于100mol%的二酸组分和100mol%的二醇组分:
(1)戊二酸(约30-约75%);对苯二甲酸(约25-约70%);1,4-丁二醇(约90-100%);和改性二醇(0-约10%);
(2)琥珀酸(约30-约95%);对苯二甲酸(约5-约70%);1,4-丁二醇(约90-100%);和改性二醇(0-约10%);和
(3)己二酸(约30-约75%);对苯二甲酸(约25-约70%);1,4-丁二醇(约90-100%);和改性二醇(0-约10%)。
改性二醇优选地选自1,4-环己烷二甲醇,三甘醇,聚乙二醇和新戊二醇。最优选的AAPE是线性、分枝或链延伸的共聚酯,其包括约50-约60mol%己二酸残基,约40-约50mol%对苯二甲酸残基,和至少95mol%的1,4-丁二醇残基。更优选地,己二酸残基占约55-约60mol%,对苯二甲酸残基占约40-约45mol%,和二醇残基包括约95mol%的1,4-丁二醇残基。这种组合物是市售可得的,以商标EASTARBIO共聚酯获自EastmanChemicalCompany,Kingsport,TN,和以商标ECOFLEX获自BASFCorporation。
另外,优选的AAPE的特定的实例包括聚(四亚甲基戊二酸酯-co-对苯二甲酸酯),其包含(a)50mol%戊二酸残基,50mol%对苯二甲酸残基,和100mol%1,4-丁二醇残基,(b)60mol%戊二酸残基,40mol%对苯二甲酸残基,和100mol%1,4-丁二醇残基或(c)40mol%戊二酸残基,60mol%对苯二甲酸残基,和100mol%1,4-丁二醇残基;聚(四亚甲基琥珀酸酯-co-对苯二甲酸酯),其包含(a)85mol%琥珀酸残基,15mol%对苯二甲酸残基,和100mol%1,4-丁二醇残基或(b)70mol%琥珀酸残基,30mol%对苯二甲酸残基,和100mol%1,4-丁二醇残基;聚(亚乙基琥珀酸酯-co-对苯二甲酸酯),其包含70mol%琥珀酸残基,30mol%对苯二甲酸残基,和100mol%乙二醇残基;和聚(四亚甲基己二酸酯-co-对苯二甲酸酯),其包含(a)85mol%己二酸残基,15mol%对苯二甲酸残基,和100mol%1,4-丁二醇残基;或(b)55mol%己二酸残基,45mol%对苯二甲酸残基,和100mol%1,4-丁二醇残基。
AAPE优选包括约10-约1,000个重复单元,优选地,约15-约600个重复单元。AAPE比浓对数粘度可以为约0.4-约2.0dL/g,或者更优选地约0.7-约1.6dL/g,如在25℃的温度使用如下浓度的共聚酯测量的:0.5克共聚酯/100ml的苯酚/四氯乙烷(60/40,按重量计算)的溶液。
AAPE,任选地,可以包含支化剂的残基。支化剂的摩尔百分数范围为约0-约2mol%,优选地约0.1-约1mol%,和最优选约0.1-约0.5mol%,基于二酸或二醇残基的总摩尔数(取决于是否支化剂包含羧基或羟基)。支化剂优选地具有以下重均分子量:约50-约5000,更优选地约92-约3000,和官能度为约3-约6。支化剂,例如,可以是具有3-6个羟基的多元醇、具有3或4个羧基的多元羧酸(或成酯等价基团)或具有总共3-6个羟基和羧基的羟基酸的酯化残基。另外,在反应挤出期间通过添加过氧化物可以使AAPE支化。
水不可分散的聚合物的各个区段(segment)可以在细度方面与其它的不同并且可以被排列成本领域技术人员已知的任何成形或加工断面的几何形态。例如,磺基聚酯和水不可分散的聚合物可以用于制备具有如下加工几何结构的双组分纤维,例如,并列型,“海岛型”,扇饼型(segmentedpie),其它可分裂型(splitables),皮/芯型,或者本领域技术人员已知的其它构型。其它多组分构型也是可能的。随后除去并列型的一侧,海岛型的“海”或者“饼”的一部分可以获得非常细的纤维。制备双组分纤维的方法也是本领域技术人员众所周知的。在双组分纤维中,本发明的磺基聚酯纤维的含量可以是约10-约90wt%并且将通常用于皮/芯纤维的皮部分。其它组分可以来自各种各样的其他的聚合物材料,例如,聚对苯二甲酸乙二酯,聚对苯二甲酸丁二酯,聚对苯二甲酸丙二酯,聚交酯等等以及聚烯径,纤维素酯,和聚酰胺。一般地,当使用不溶于水的或水不可分散的聚合物时,所得的双组分或多组分纤维不是完全水可分散的。在热收缩方面具有重大差别的并列型组合可用于形成螺旋卷曲。如果卷曲是期望的话,锯齿或填塞箱卷曲通常适用于许多应用。如果第二聚合物组分位于皮/芯构型的芯中,这种芯任选地可以被稳定。
磺基聚酯特别可用于具有“海岛型”或“扇饼型(segmentedpie)”断面的纤维,因为它们仅仅要求中性或者略酸性(即,“软”水)进行分散,相比含苛性碱(caustic)的溶液而言,后者有时被要求以从多组分纤维中除去其它水可分散的聚合物。因此,我们的发明的另一方面是多组分纤维,其包括:
(a)玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯,该磺基聚酯包括:
(i)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(ii)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;
(iv)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;和
(B)多个区段(segment),其包括与磺基聚酯不溶混的一种或多种水不可分散的聚合物,其中该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离;
其中纤维具有海岛型或扇饼型(segmentedpie)断面并且包含小于10wt%的颜料或填料,基于纤维的总重量。
二羧酸、二醇、磺基聚酯、磺基单体、支化单体残基和水不可分散的聚合物是如前所述的。对于多组分纤维来说,有利的是磺基聚酯的Tg为至少57℃。磺基聚酯可以是单一磺基聚酯或者一种或多种磺基聚酯聚合物的共混物。可由磺基聚酯或磺基聚酯共混物显示出的玻璃化转变温度的进一步的实例是至少65℃,至少70℃,至少75℃,至少85℃,和至少90℃。例如,磺基聚酯可以包括约75-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基和约25-约95mol%的二甘醇的残基。如上文所述,水不可分散的聚合物的实例是聚烯径、聚酯、聚酰胺、聚交酯、聚己内酯、聚碳酸酯、聚氨酯和聚氯乙烯。另外,水不可分散的聚合物可以是生物可降解的或生物可分解的(biodisintegratable)。例如,水不可分散的聚合物可以是脂族-芳族聚酯,如前所述的。
我们的新型多组分纤维可以由本领域技术人员已知的许多方法来制备。因此本发明提供了一种用于具有成形断面的多组分纤维的方法,包括:将玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成纤维,所述磺基聚酯包括:
(i)一种或多种二羧酸的残基;
(ii)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中该官能团是羟基,羧基或其组合;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;
其中该纤维具有多个包括水不可分散的聚合物的区段(segment)并且该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离并且该纤维包含小于10wt%的颜料或填料,基于纤维的总重量。例如,多组分纤维可以这样制备,包括在单独的挤出机中熔融磺基聚酯和一种或多种水不可分散的聚合物,并且将单独的聚合物流动导入一个具有多个分布流动路径的喷丝板或挤出模头,使得水不可分散的聚合物组分形成小的区段(segment)或细的股线,后者通过介于其间的磺基聚酯基本上彼此隔离。这种纤维的断面可以是,例如,扇饼型(segmentedpie)结构或者海岛型结构。在另一实例中,磺基聚酯和一种或多种水不可分散的聚合物被单独地供应给喷丝板孔口,随后以皮芯型形式挤出,其中,水不可分散的聚合物形成“芯”,后者基本上被磺基聚酯“皮”聚合物围绕。在这种同心纤维的情况下,供给“芯”聚合物的孔口位于纺丝孔口出口的中心,芯聚合物流体的流动条件被严格地控制以便当纺丝时保持两组分的同心度。喷丝板孔口的改变使得能够在纤维断面内获得不同的芯和/或皮的形状。在又一个实例中,具有并列型断面或构型的多组分纤维可以这样被生产,包括分别地通过孔口共挤出水可分散的磺基聚酯和水不可分散的聚合物,并且以基本上相同的速度汇集各独立的聚合物物流而以结合物流的形式在喷丝板面以下合并成并列型;或(2)通过在喷丝板表面处汇集的孔口以基本上相同的速度分别地进料两种聚合物物流,从而以结合物流的形式在喷丝板表面处合并成并列型。在两种情况中,在合并点处,各个聚合物物流的速度,是通过其计量泵速度、孔口数目和孔口尺寸来确定的。
二羧酸、二醇、磺基聚酯、磺基单体、支化单体残基和水不可分散的聚合物是如前所述的。磺基聚酯的玻璃化转变温度为至少57℃。可由磺基聚酯或磺基聚酯共混物显示出的玻璃化转变温度的进一步的实例是至少65℃,至少70℃,至少75℃,至少85℃,和至少90℃。在一个实例中,磺基聚酯可以包括约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;和约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;和0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。在另一实例中,磺基聚酯可以包括约75-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基和约25-约95mol%的二甘醇的残基。如上文所述,水不可分散的聚合物的实例是聚烯径、聚酯、聚酰胺、聚交酯、聚己内酯、聚碳酸酯、聚氨酯和聚氯乙烯。另外,水不可分散的聚合物可以是生物可降解的或生物可分解的(biodisintegratable)。例如,水不可分散的聚合物可以是脂族-芳族聚酯,如前所述的。成形断面的实例包括但不局限于海岛型,并列型,皮芯型,或者扇饼型(segmentedpie)构型。
在本发明的另一实施方案中,提供了一种用于制造具有成形断面的多组分纤维的方法,包括:纺丝至少一种水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物以生产多组分纤维,其中多组分纤维具有多个域,所述域包括水不可分散的聚合物,所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;其中水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,其中磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数;和其中多组分纤维的初纺旦数小于约6单丝旦数。
在本发明中在前文已经讨论了用于这些多组分纤维的磺基聚酯和水不可分散的聚合物。
在本发明的另一实施方案中,提供了一种用于制造具有成形断面的多组分纤维的方法,包括:
(A)挤出至少一种水可分散的磺基聚酯和与所述磺基聚酯不溶混的一种或多种水不可分散的聚合物以生产多组分挤出物,其中多组分挤出物具有多个域,所述域包括水不可分散的聚合物,和所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;和
(B)以至少约2000m/min的速度熔融拉伸多组分挤出物以生产该多组分纤维。
本发明的这种实施方案的特征还在于所述方法包括以至少约2000m/min的速度熔融拉伸多组分挤出物的步骤,更优选地,至少约3000m/min,和最优选至少4500m/min。
一般地,当离开喷丝板时,借助空气错流,纤维被骤冷,因此纤维固化。在这一步骤,各种整理剂(finish)和上浆剂(size)可以施加到纤维。冷却的纤维,一般地,随后被拉伸并且在卷取轴上卷起。其他的添加剂可以以有效量添加到整理剂(finish)中,例如乳化剂、防静电剂、抗微生物剂、消泡剂、润滑剂、热稳定剂、紫外稳定剂等。
任选地,拉伸纤维可以纹理化并且缠绕以形成蓬松连续长丝。这种一步技术在本领域中是已知的,称为纺丝-拉伸-纹理化。其它实施方案包括扁平长丝(非纹理化的)纱线,或者切段纤维,卷曲的或者未卷曲的。
随后通过溶解界面层或饼状区段(segment)并留下水不可分散的聚合物的较小的长丝或微旦数(microdenier)纤维,磺基聚酯可以被除去。因此,我们的发明提供了一种用于微旦数(microdenier)纤维的方法,包括:
(A)将玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,所述磺基聚酯包括:
(i)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(ii)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;
其中,纤维具有多个包括水不可分散的聚合物的区段(segment),其中该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离并且该纤维包含小于10wt%的颜料或填料,基于纤维的总重量;和
(B)使多组分纤维与水接触而除去磺基聚酯,由此形成微旦数(microdenier)纤维。
一般地,多组分纤维与水在以下温度接触:约25℃-约100℃,优选地约50℃-约80℃,接触时间为约10-约600秒,由此磺基聚酯被驱散或溶解。在除去磺基聚酯后,剩余的微纤维一般地将具有这样的平均细度:1d/f或以下,一般地,0.5d/f或以下,或者更一般地,0.1d/f或以下。这些剩余微纤维的典型的应用包括人造革、仿麂皮织物、抹布和过滤介质。磺基聚酯的离子性能还在盐水介质如体液中产生了有利地差的“溶解性”。这种性能在个人护理产品和清洁抹布中是令人期望的,其是可冲洗的(flushable)或者处置在生活污水系统中。所选的磺基聚酯还被用作染色浴中的分散剂和在洗涤周期期间的污垢再沉积预防剂。
在本发明的另一实施方案中,提供了一种用于制造微旦数(microdenier)纤维的方法,其包括:将至少一种水可分散的磺基聚酯和与水可分散的磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,其中所述多组分纤维具有多个域,所述域包括所述水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;其中该纤维的初纺旦数小于约6单丝旦数;其中水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,和其中磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数;和使多组分纤维与水接触而除去水可分散的磺基聚酯,由此形成微旦数(microdenier)纤维。
在本发明的另一实施方案中,提供了一种用于制造微旦数(microdenier)纤维的方法,包括:
(A)挤出至少一种水可分散的磺基聚酯和与所述水可分散的磺基聚酯不溶混的一种或多种水不可分散的聚合物以生产多组分挤出物,其中所述多组分挤出物具有多个域,所述域包括所述水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;
(B)以至少约2000m/min的速度熔融拉伸所述多组分挤出物以形成多组分纤维;和
(C)使所述多组分纤维与水接触以除去所述水可分散的磺基聚酯由此形成微旦数(microdenier)纤维。
优选的是以至少约2000m/min的速度熔融拉伸多组分挤出物,更优选地至少约3000m/min,和最优选至少4500m/min。
根据本发明适用的这种磺基单体和磺基聚酯在上文进行了描述。
由于根据本发明的这个方面所用的优选的磺基聚酯通常在随后的水缠结过程期间对除去有耐受性,优选的是为从多组分纤维中除去磺基聚酯所用的水高于室温,更优选地,所述的水是至少约45℃,更优选地,至少约60℃,和最优选至少约80℃。
本发明还包括纤维制品,其包括上文所述的水可分散的纤维、多组分纤维或者微旦数(microdenier)纤维。术语“纤维制品”应理解为是指具有或类似于所述纤维的任何制品。纤维制品的非限制性实例包括复丝纤维、纱线、绳索、带子、织物、熔吹网、纺粘网、热粘网、水缠结网、非织造网和织物和其组合;具有一层或多层纤维的物品,例如源自这种纤维的多层非织造布、层合物和复合材料,纱布,绷带,尿布,训练裤,棉塞,外科手术服和口罩,妇女卫生巾;和类似物。进一步地,纤维制品可以包括用于各种个人卫生和清洁产品的替换插入物。本发明的纤维制品可以与其它可能是水可分散的或者未必是水可分散的材料粘结、层合、附着或者共同使用。纤维制品,例如,非织造织物层,可以粘结到柔性塑料薄膜或水不可分散的材料如聚乙烯的衬背。这种纤维束(assembly),例如,可被用作一次性尿布的一个组件。另外,纤维制品可以源于将纤维过吹到另一基板上以形成加工熔吹、纺粘薄膜或膜结构的高度相配的组合。
本发明的纤维制品包括非织造织物和纤维网。非织造织物被定义为这样的织物,其直接由纤维网制造而没有进行编织或针织操作。例如,通过任何已知的织物成形过程如针织、编织、针刺和水缠结,本发明的多组分纤维可以成形为织物。通过施加足够的力来使得多组分纤维分裂或者通过使纤维网与水接触而除去磺基聚酯,使得剩余的微旦数(microdenier)纤维留下,可以将所得的织物或纤维网转化成微旦数(microdenier)纤维网。我们的发明因此提供了一种用于微旦数(microdenier)纤维网的方法,包括:
(A)将玻璃化转变温度(Tg)为至少57℃的水可分散的磺基聚酯和与磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,所述磺基聚酯包括:
(i)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(ii)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(iii)一种或多种二醇残基,其中至少25mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;和
(iv)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。
其中,多组分纤维具有多个包括水不可分散的聚合物的区段(segment),其中该区段(segment)通过介于所述区段(segment)之间的磺基聚酯基本上彼此隔离;和该纤维包含小于10wt%的颜料或填料,基于纤维的总重量;
(B)对步骤A的多组分纤维进行交叠(overlapping)和收集,以形成非织造网;和
(C)使非织造网与水接触而除去磺基聚酯,由此形成微旦数(microdenier)纤维网。
在本发明的另一实施方案中,提供了一种用于微旦数(microdenier)纤维网的方法,其包括:
(A)将至少一种水可分散的磺基聚酯和与所述磺基聚酯不溶混的一种或多种水不可分散的聚合物纺丝成多组分纤维,所述多组分纤维具有多个域,所述域包括所述水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离;其中所述纤维的初纺旦数小于约6单丝旦数;其中所述水可分散的磺基聚酯显示出小于约12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,和其中所述磺基聚酯包括小于约25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数;
(B)收集步骤(A)的所述多组分纤维以形成非织造网;和
(C)使所述非织造网与水接触以除去所述磺基聚酯,由此形成微旦数(microdenier)纤维网。
在本发明的另一实施方案中,提供了一种用于微旦数(microdenier)纤维网的方法,其包括:
(A)将至少一种水可分散的磺基聚酯和与所述水可分散的磺基聚酯不溶混的一种或多种水不可分散的聚合物挤出成多组分挤出物,所述多组分挤出物具有多个域,所述域包括所述水不可分散的聚合物,其中所述域通过介于所述域之间的所述水可分散的磺基聚酯基本上彼此隔离;
(B)以至少约2000m/min的速度熔融拉伸所述多组分挤出物以生产多组分纤维;
(C)收集步骤(B)的所述多组分纤维以形成非织造网;和
(D)使所述非织造网与水接触以除去所述磺基聚酯,由此形成微旦数(microdenier)纤维网。
该方法还优选包括,在步骤(C)前,水缠结非织造网的多组分纤维的步骤。还优选的是,水缠结步骤导致多组分纤维中所含的磺基聚酯的小于约20wt%的损失,更优选地,这种损失小于15wt%,和最优选地,小于10wt%。为促进在水缠结期间降低磺基聚酯的损失的目标,在这个方法期间所使用的水优选地温度小于约45℃,更优选地小于约35℃,最优选地,小于约30℃。优选的是在水缠结期间所用的水尽可能地接近于室温以最小化多组分纤维中的磺基聚酯的损失。相反地,在步骤(C)期间除去磺基聚酯聚合物优选这样进行:使用温度为至少约45℃的水,更优选地至少约60℃,最优选至少约80℃。
在水缠结之后和在步骤(C)之前,非织造网可以经历热定形步骤(heatsetting),所述热定形步骤包括将非织造网加热到至少约100℃的温度,更优选地至少约120℃。热定形步骤缓解了内部纤维应力并且有助于生产尺寸上稳定的织物产品。优选的是当热定形材料被再次加热到其在所述热定形步骤期间所加热到的温度时,其显示出小于其原始表面面积的约5%的表面面积收缩。更优选地,收缩小于原始表面面积约2%,最优选收缩小于约1%。
多组分纤维中所用的磺基聚酯可以是本文中所述的那些中的任一种,然而,优选的是磺基聚酯具有小于约6000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的,并且包括小于约12mol%,基于总重复单元,的至少一种磺基单体的残基。在本文中前面已经说明了这些类型的磺基聚酯。
此外,本发明方法优选包括以至少2000m/min的纤维速度拉伸多组分纤维的步骤,更优选地至少约3000m/min,更优选地至少约4000m/min,和最优选至少约5000m/min。
非织造纤维束(assembly)通过以下方式结合在一起:1)在纤维网或闷光织物中的机械纤维内聚和联锁;2)纤维融合的各种技术,包括使用粘合纤维,利用某些聚合物和聚合物共混物的热塑性性能;3)使用粘合树脂如淀粉、酪蛋白、纤维素衍生物,或合成树脂,如丙烯酸胶乳或尿烷;4)粉末粘合结合剂;或5)其组合。纤维通常以无规方式进行沉积,但是在一个方向中的取向是可能的,随后使用上述方法之一进行结合/粘合。
我们的发明的纤维制品进一步还可能包括一层或多层的水可分散的纤维、多组分纤维或微旦数(microdenier)纤维。纤维层可以是一或多非织造织物层,松弛结合的交叠(overlapping)纤维的层,或其组合。另外,纤维制品可包括个人和卫生护理产品,例如但不限于,儿童护理产品,如婴儿尿布;儿童训练裤;成人护理产品,如成人尿布和成人失禁衬垫;妇女护理产品,如妇女卫生巾、内裤衬里和棉塞;抹布;含纤维的清洁产品;医用和外科护理产品,如医用抹布、薄纸、纱布、检查床覆盖物、外科口罩、手术服、绷带和伤口涂剂;织物;弹性纱线、抹布、胶带、其它保护性阻隔物和包装材料。纤维制品可用于吸收液体或可以用各种液体组合物来预润湿并且被用于将这些组合物输送至表面。液体组合物的非限制性实例包括洗涤剂;润湿剂;清洁剂;皮肤护理产品,如化妆品、软膏、药物、润滑剂和香料。纤维制品还可以包括各种粉末和颗粒物以便改进吸收性或者用作输送载体。粉末和颗粒的实例包括但不局限于滑石,淀粉,各种吸水性、水可分散的或水可膨胀的聚合物,如超吸收聚合物、磺基聚酯和聚(乙烯醇),二氧化硅,颜料和微胶囊。还可能存在添加剂,但不是必须的,按特定应用的需要而定。添加剂的实例包括但不局限于氧化稳定剂,UV吸收剂,着色剂,颜料,遮光剂(消光剂),荧光增白剂,填料,成核剂,增塑剂,粘度调节剂,表面改性剂,抗微生物剂,消毒剂,冷态流变抑制剂,支化剂和催化剂。
除了是水可分散的之外,上述纤维制品可以是可冲洗的(flushable)。术语“可冲洗的(flushable)”,如本文中使用的,是指能够在常规盥洗室中被冲洗,并且能够被引入城市污水或住宅污水处理系统,而没有在盥洗室或污水系统中引起阻塞或堵塞。
纤维制品可以进一步包括水可分散的薄膜,其包括第二水可分散的聚合物。第二水可分散的聚合物可以与用于本发明的纤维和纤维制品中的前述的水可分散的聚合物相同或不同。在一个实施方案中,例如,第二水可分散的聚合物可以是另外的磺基聚酯,其因而包括:
(A)约50-约96mol%的间苯二甲酸或对苯二甲酸的一种或多种残基,基于总酸残基;
(B)约4-约30mol%,基于总酸残基,的钠代磺基间苯二甲酸的残基;
(C)一种或多种二醇残基,其中至少15mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;
(D)0-约20mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合。另外的磺基聚酯可以与一种或多种辅助的聚合物,如上文所述,进行共混以改变所得的纤维制品的性能。辅助的聚合物可以是或者未必是水可分散的,取决于应用而定。辅助的聚合物可以是与另外的磺基聚酯可混溶的或不溶混的。
另外的磺基聚酯可以包含其它浓度的间苯二甲酸残基,例如,约60-约95mol%和约75-约95mol%。间苯二甲酸残基浓度范围的进一步的实例为约70-约85mol%,约85-约95mol%和约90-约95mol%。另外的磺基聚酯还可能包括约25-约95mol%的二甘醇的残基。二甘醇残基浓度范围的进-步的实例包括约50-约95mol%、约70-约95mol%和约75-约95mol%。另外的磺基聚酯还可能包括乙二醇和/或1,4-环己烷二甲醇的残基。CHDM残基的典型的浓度范围为约10-约75mol%、约25-约65mol%和约40-约60mol%。乙二醇残基的典型的浓度范围为约10-约75mol%、约25-约65mol%和约40-约60mol%。在另一实施方案中,另外的磺基聚酯包括为约75-约96mol%的间苯二甲酸的残基和约25-约95mol%的二甘醇的残基。
根据本发明,纤维制品的磺基聚酯薄膜组件可以以单层或多层薄膜的形式生产。单层薄膜可以通过常规的流延技术来生产。多层化的薄膜可以通过常规的层压方法等来生产。薄膜可以具有任何适宜的厚度,但是总厚度将通常为约2-约50mil。
含薄膜的纤维制品可以包括一层或多层如上所述的水可分散的纤维层。纤维层可以是一或多个非织造织物层,松弛结合的交叠(overlapping)纤维的层,或其组合。另外,含薄膜的纤维制品可以包括个人和卫生护理产品,如上文所述。
如前所述的,纤维制品还可能包括各种粉末和颗粒以改进吸收性或者作为输送载体。因此,在一个实施方案中,我们的纤维制品包括粉末,其包括第三水可分散的聚合物,所述第三水可分散的聚合物可以与前文中所述的水可分散的聚合物组分相同或不同。其它粉末和颗粒的实例包括但不局限于滑石,淀粉,各种的吸水性、水可分散的或水可膨胀的聚合物,如聚(丙烯腈)、磺基聚酯和聚(乙烯醇),二氧化硅,颜料和微胶囊。
除上述应用之外,我们的新型的纤维和纤维制品具有许多可能的用途。一种新的应用包括将薄膜或非织造织物熔吹到扁平、曲线或成形表面以提供保护层。一种这样的层可以在运输期间为耐用设备提供表面保护。在目的地,在将所述设备投入应用前,可以洗刷掉磺基聚酯的外层。这种一般应用观念的进一步的实施方案可能涉及个人防护制品以便为一些可再用的或者使用受限的衣服或覆盖物提供临时性阻挡层。对于军队来说,活性碳和化学吸收剂可以刚好在收集器之前被喷涂到变细长丝图案上,使得熔吹的基质能够将这些实体固定在暴露表面上。通过熔吹到另一层上,当出现威胁时,甚至可以在先锋行动区域(forwardoperationarea)中改变化学吸收剂。
磺基聚酯所固有的主要优点是通过添加离子部分(即,盐)经由絮凝或沉淀能够从水分散体中除去或回收聚合物的容易性。还可使用其它方法,如pH调节、添加非溶剂、冷冻等等。因此,纤维制品,如外套防护服,在成功使用防护阻隔物以后以及即使聚合物变成有害废物时,能够潜在地以低得多的量进行安全处理,对于使用被接受的规程的处理如焚化来说。
不溶解的或干燥的磺基聚酯已知对许多基板形成了强的粘合结合作用,所述基板包括但不限于短纤浆,棉,丙烯酸树酯,人造丝(rayon),lyocell,PLA(聚交酯),醋酸纤维素,醋酸丙酸纤维素,聚对苯二甲酸乙二酯,聚对苯二甲酸丁二酯,聚对苯二甲酸丙二酯,聚对苯二甲酸环己二酯,共聚酯,聚酰胺(尼龙),不锈钢,铝,经处理的聚烯径,PAN(聚丙烯腈)和聚碳酸酯。因此,我们的非织造织物可以用作层合粘合剂或结合剂,其可以通过已知的技术被结合,如热、射频(RF)、微波和超声法。改性磺基聚酯以便能够RF活化公开在许多新近的专利中。因此,我们的新型非织造织物可以具有除粘合剂性能之外的双重或甚至多重功能。例如,可以获得一次性婴儿尿布,其中本发明的非织造物用作最终纤维束(assembly)的水-响应性粘合剂以及流体管理组分。
我们的发明还提供了一种用于水可分散的纤维的方法,包括:
(A)加热水可分散的聚合物组合物到其流点(flowpoint)以上的温度,其中聚合物组合物包括:
(i)一种或多种二羧酸的残基;
(ii)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个金属磺酸根基团,其中该官能团是羟基,羧基或其组合;和
(iii)一种或多种二醇残基,其中至少20mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;(iv)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;其中聚合物组合物包含小于10wt%的颜料或填料,基于聚合物组合物的总重量;和(II)熔纺长丝。如上文所述,水可分散的聚合物,任选地,可以与磺基聚酯共混。另外,水不可分散的聚合物,任选地,可以与磺基聚酯共混而形成这样的共混物,使得该共混物是一种不溶混的共混物。术语“流点(flowpoint)”,如本文中使用的,是指这样的温度,在该温度,聚合物组合物的粘度允许通过喷丝板或挤出模头的挤出或其他形式的加工。二羧酸残基可以占酸残基的约60-约100mol%,取决于磺基单体的类型和浓度。二羧酸残基的浓度范围的其它实例为约60mol%-约95mol%和约70mol%-约95mol%。优选的二羧酸残基是间苯二甲酸,对苯二甲酸和1,4-环己烷二羧酸,或者如果使用二酯的话,对苯二甲酸二甲酯,间苯二甲酸二甲酯和二甲基-1,4-环己烷二羧酸酯,特别优选的是间苯二甲酸和对苯二甲酸的残基。
磺基单体可以是包含磺酸根基团(sulfonategroup)的二羧酸或其酯,包含磺酸根基团(sulfonategroup)的二醇,或者包含磺酸根基团(sulfonategroup)的羟基酸。磺基单体残基的浓度范围的另外的实例为约4-约25mol%,约4-约20mol%,约4-约15mol%和约4-约10mol%,基于总重复单元。磺酸盐的阳离子可以是金属离子如Li+、Na+、K+、Mg++、Ca++、Ni++、Fe++等。或者,磺酸盐的阳离子可以是非金属物质如含氮碱,如前所述的。可用于本发明方法的磺基单体残基的实例是磺基邻苯二甲酸、磺基对苯二甲酸、磺基间苯二甲酸或其组合的金属磺酸盐。可用的磺基单体的另一实例是5-钠代磺基间苯二甲酸或其酯。如果磺基单体残基为5-钠代磺基间苯二甲酸,典型的磺基单体浓度范围为约4-约35mol%,约8-约30mol%和约10-25mol%,基于总酸残基。
本发明的磺基聚酯包括一种或多种二醇残基,其可以包括脂族,环脂族和芳烷基二醇。环脂族二醇,例如,1,3-和1,4-环己烷二甲醇,可以以它们的纯的顺式或反式异构体的形式或者以顺反异构体的混合物的形式存在。低分子量聚乙二醇的非限制性实例,例如,其中n为2-6,是二甘醇,三甘醇,和四甘醇。在这些低分子量二醇中,二甘醇和三甘醇是最优选的。磺基聚酯可以任选地包括支化单体。支化单体的实例是如上文所描述的。支化单体浓度范围的进一步的实例为0-约20mol%和0-约10mol%。我们的新的方法的磺基聚酯的Tg为至少25℃。磺基聚酯所显示的玻璃化转变温度的进一步的实例为至少30℃,至少35℃,至少40℃,至少50℃,至少60℃,至少65℃,至少80℃,和至少90℃。虽然其它的Tg是可能的,但是我们的发明的干燥磺基聚酯的典型的玻璃化转变温度为约30℃,约48℃,约55℃,约65℃,约70℃,约75℃,约85℃,和约90℃。
水可分散的纤维是通过熔吹方法制备的。聚合物在挤出机中熔融并且被强迫通过模头。离开模头的挤出物借助热的高速空气迅速变细至超细直径。纤维的取向、冷却速率、玻璃化转变温度(Tg)和结晶速率是重要的,因为它们在变细过程中影响聚合物的粘度和加工性能。长丝被收集在可更换的表面上,例如,运送带、圆柱形鼓轮、旋转心轴等。粒料的预干燥(如果需要的话),挤出区温度,熔融温度,螺杆设计,通过速率,空气温度,空气流量(速度),模头空气隙和退位部件,鼻尖孔径尺寸,模头温度,模头-收集器(DCP)距离,骤冷环境,收集器速度和后处理全部是影响产品特性,如长丝直径,基重,纤维网厚度,孔径,柔软性和收缩量,的因素。还可以使用高速空气,从而以略微随机方式移动长丝,这导致了大规模的交织。如果运送带在模头下通过,通过长丝的交叠铺列、机械内聚和热结合的组合,可以生产非织造织物。过吹到另一基板上,如纺粘层或垫层,也是可能的。如果在旋转心轴上卷取长丝,形成了圆柱形产品。水可分散的纤维的铺列还可以通过纺粘方法来进行。
因此本发明进一步提供了一种用于水可分散的非织造织物的方法,包括:
(A)加热水可分散的聚合物组合物到其流点(flowpoint)以上的温度,其中聚合物组合物包括:
(i)一种或多种二羧酸的残基;
(ii)约4-约40mol%,基于总重复单元,的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个金属磺酸根基团,其中该官能团是羟基,羧基或其组合;
(iii)一种或多种二醇残基,其中至少20mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-约500的整数;
(iv)0-约25mol%,基于总重复单元,的具有3或以上官能团的支化单体的残基,其中该官能团是羟基,羧基或其组合;其中磺基聚酯的玻璃化转变温度(Tg)为至少25°;其中聚合物组合物包含小于10wt%的颜料或填料,基于聚合物组合物的总重量;
(B)熔纺长丝;和
(C)对步骤B的长丝进行交叠(overlapping)和收集,以形成非织造网。如上文所述,水可分散的聚合物,任选地,可以与磺基聚酯共混。另外,水不可分散的聚合物,任选地,可以与磺基聚酯共混而形成这样的共混物,使得该共混物是一种不溶混的共混物。二羧酸,磺基单体和支化单体残基是如前所述的。磺基聚酯的Tg为至少25℃。磺基聚酯所显示的玻璃化转变温度的进一步的实例为至少30℃,至少35℃,至少40℃,至少50℃,至少60℃,至少65℃,至少80℃,和至少90℃。虽然其它的Tg是可能的,但是我们的发明的干燥磺基聚酯的典型的玻璃化转变温度为约30℃,约48℃,约55℃,约65℃,约70℃,约75℃,约85℃,和约90℃。本发明通过以下实施例来举例说明。
实施例
全部粒料样品在真空条件下在室温下预干燥至少12小时。表3中所示的分散时间对应于非织造织物样品的完全分散或者溶解。表2和3中所用的缩写“CE”是指“对比例”。
实施例1
使用表1中所示的条件,将磺基聚酯通过标称6-英寸模头(30孔/英寸,在喷嘴(nosepiece)中)熔喷到圆柱体收集器上,所述磺基聚酯包含76mol%,间苯二甲酸,24mol%的钠代磺基间苯二甲酸,76mol%二甘醇,和24mol%1,4-环己烷二甲醇,Ih.V.为0.29,Tg为48℃。不需要夹层纸。获得了柔软可处理的柔性纤维网,其在辊筒缠绕操作期间没有粘连。物理性能列于表2中。借助轻微的搅拌,如表3中的数据显示,小片(1″x3″)非织造织物易于分散在室温(RT)和50℃水中。
表1-熔吹条件
表2-非织造物的物理性能
表3-非织造物的分散性(Dispersability)
实施例2
使用类似于表1中的条件,将磺基聚酯通过6-英寸模头进行熔喷,所述磺基聚酯包含89mol%,间苯二甲酸,11mol%的钠代磺基间苯二甲酸,72mol%二甘醇,和28mol%乙二醇,Ih.V.为0.4,Tg为35℃。获得了柔软可处理的柔性纤维网,其在辊筒缠绕操作期间没有粘连。物理性能列于表2中。在50℃和80℃;小片(1″x2″)非织造织物容易地且完全地被分散,在RT(23℃),所述织物需要较长的时间完全分散,如表3中的数据所示。
发现,实施例1和2中的组合物可以过吹到其它非织造基板上。还可以冷凝并且缠绕成型或者波状形式,其被使用代替常规的纤维网收集器。因此,有可能获得圆形“粗纱”或者柱形的纤维网。
对比例1-3
磺基聚酯的粒料与聚丙烯(BasellPF008)粒料结合,按以下双组分比值(按wt%计),所述磺基聚酯包含89mol%,间苯二甲酸,11mol%的钠代磺基间苯二甲酸,72mol%二甘醇,和28mol%乙二醇,Ih.V.为0.4,Tg为35℃:
75PP:25磺基聚酯(实施例3)
50PP:50磺基聚酯(实施例4)
25PP:75磺基聚酯(实施例5)
PP的MFR(熔体流动速率)为800。熔吹操作在装备有24-英寸宽模头的作业线上进行,获得了可处理的柔软、柔性的、但无粘连的纤维网,物理性能列于表2中。小片(1″x4″)的非织造织物易于分解,如表3所述。然而,所有纤维均不是完全水可分散的,由于不溶的聚丙烯组分。
实施例3
实施例2中生产的圆形片(4″直径)非织造物在两片棉织物之间用作粘合层。使用Hannifin熔体压机将两棉片融合在一起,包括施加压力35psig,在200℃达30秒。所得的纤维束(assembly)显示出特别强的结合强度。在粘合或结合失效前,棉基板破碎。使用其它纤维素塑料和PET聚酯基板,同样获得了相似的结果。通过超声结合技术产生强结合。
对比例4
使用24″模头熔吹1200MFR的PP(Exxon3356G),而得到柔性的非织造织物,其没有粘连并且易于从辊筒退绕。当在RT或50℃浸于水中15分钟时,小片(1″x4″)没有显示出任何对水的响应(即,没有分解或者基重损失)。
实施例4
磺基聚酯的单组分(unicomponent)纤维,在熔融温度245℃(473℉)在实验室切段纤维纺丝作业线上熔纺,所述磺基聚酯包含82mol%间苯二甲酸,18mol%的钠代磺基间苯二甲酸,54mol%二甘醇,和46mol%1,4-环己烷二甲醇,Tg为55℃。初纺旦数为大约8d/f。在卷绕管上遇到了一定的粘连,但是在82℃和pH为5-6的条件下,10-长丝股容易地在10-19秒内溶解在未搅动的软化水中。
实施例5
将获自分别包含82mol%间苯二甲酸,18mol%的钠代磺基间苯二甲酸,54mol%二甘醇,和46mol%1,4-环己烷二甲醇的磺基聚酯(Tg为55℃)和包含91mol%间苯二甲酸,9mol%的钠代磺基间苯二甲酸,25mol%二甘醇,和75mol%1,4-环己烷二甲醇的磺基聚酯(Tg为65℃)的共混物(75∶25)的单组分(unicomponent)纤维在实验室切段纤维纺丝作业线上熔纺。共混物的Tg为57℃,如通过对各组分的磺基聚酯的Tg的加权平均而计算的。在卷绕管上,10-长丝股没有显示任何粘连,但是在未搅动的软化水中在82℃和pH为5-6的条件下容易地在20-43秒内溶解。
实施例6
实施例5中所述的共混物与PET进行共纺以获得双组分海岛型纤维。获得了一种构型,其中磺基聚酯“海”是纤维的20wt%,所述纤维包含80wt%的PET“岛”。在纺丝后,即刻,纺丝纱线的伸长率是190%。没有遇到粘连,纱线令人满意地从线轴上退绕并且在纺丝后1周进行加工。在随后的操作中,通过使纱线经过88℃软水浴而将“海”溶解,留下仅仅细PET长丝。
实施例7
这个预言的实施例举例说明了用于制备特种纸的本发明的多组分和微旦数(microdenier)纤维的可能的应用。实施例5中所述的共混物与PET进行共纺以获得双组分海岛型纤维。所述纤维包含大约35wt%磺基聚酯“海”组分和大约65wt%的PET“岛”。未卷曲纤维被切成1/8英寸长。在模拟造纸中,这些切短双组分纤维被添加到精制操作中。在搅动的含水浆液中除去磺基聚酯“海”,由此将微旦数(microdenier)PET纤维释放到混合物中。在可比重量下,微旦数(microdenier)PET纤维(“岛”),在增加纸的拉伸强度上是更有效的,相比于添加粗的PET纤维来说。
对比例8
在纺粘作业线上,使用24″宽双组分喷丝板模头(获自HillsInc.,Melbourne,FL,在模头盘中总共具有2222模头孔),制造具有108岛/海结构的双组分纤维。两个挤出机连接到熔体泵,后者又连接到纤维纺丝模头中的两组分的入口。主要挤出机(A)连接到入口,其测量了EastmanF61HCPET聚酯的流速,所述聚酯用于在岛/海纤维断面结构中形成岛域。挤出区设定为在285℃温度熔融进入模头的PET。第二挤出机(B)加工EastmanAQ55S磺基聚酯聚合物,其获自EastmanChemicalCompany,Kingsport,TN,比浓对数粘度为约0.35,熔体粘度为约15,000泊(测量于240℃和1弧度/秒剪切速率)和9,700泊(测量于240℃和100弧度/秒剪切速率),在RheometricDynamicAnalyzerRDAII(RheometricsInc.Piscataway,NewJersey)流变仪中进行的。在进行熔体粘度测量前,在60℃在真空烘箱中干燥样品两天。使用25mm直径的平行盘几何结构,在1mm辊隙调定下,进行粘度测试。动态扫频(dynamicfrequencysweep)是在应变速率为1-400弧度/秒和10%应变幅度的条件下进行的。然后在240℃和1弧度/秒的应变速率的条件下测量粘度。在测定用于以后的实施例中的磺基聚酯材料的粘度中遵循这一程序。第二挤出机设定为在255℃的熔融温度将AQ55S聚合物熔融并且进料到喷丝板模头。通过在0.6g/孔/min处理量速率下挤出,将两种聚合物成形为双组分挤出物。在双组分挤出物中PET和AQ55S的量比被调节而得到60/40和70/30的比值。
使用吸气装置来熔融拉伸双组分挤出物以生产双组分纤维。经过吸气室的空气的流动将所产生的纤维下拉。向下流过吸气组件的空气的量通过进入吸气装置的空气的压力来控制。在本实施例中,为熔融拉伸双组分挤出物的用于吸气装置中的空气的最大压力是25psi。高于该值,流过吸气装置的空气流将引起挤出物在该熔融拉伸纺丝过程期间断裂,因为施加于双组分挤出物上的熔融拉伸速率大于双组分挤出物的固有延展性。双组分纤维被铺列为非织造网,织物重量为95克每平方米(gsm)。通过光学显微术评估在这种非织造网中的双组分纤维显示PET以岛的形式存在于纤维结构的中心,但是围绕双组分纤维的外周边的PET岛几乎接合一起而形成几乎连续的围绕纤维周缘的PET聚合物的环,这是不期望的。显微技术发现非织造网中的双组分纤维的直径通常为15-19微米,相当于约2.5单丝旦数(dpt)的平均纤维初纺旦数。这表示了熔融拉伸纤维速度为约2160米/分钟。初纺旦数定义为通过熔体挤出和熔融拉伸步骤所获得的纤维旦数(9000米长的纤维的克重量)。双组分纤维直径的变化表明在纤维的纺丝-拉伸中的不均匀性。
在120℃,在强迫的空气烘箱中将非织造网样品调理5分钟。热处理的纤维网显示出显著的收缩,其中非织造网的面积减少到加热前纤维网的初始面积的仅仅约12%。虽然不意欲受到理论的约束,由于纤维中所用的AQ55S磺基聚酯的高分子量和熔体粘度,双组分挤出物不能被熔融拉伸到引起纤维中的PET区段(segment)的应变诱导结晶所要求的程度。总之,具有这种特定的比浓对数粘度和熔体粘度的AQ55S磺基聚酯不是可接受的,因为双组分挤出物不能均匀地熔融拉伸到期望的细旦数。
实施例8
生产了与商品化的EastmanAQ55S聚合物化学成分相同的磺基聚酯聚合物,然而将分子量控制到较低值,其特别为比浓对数粘度为约0.25。这种聚合物的熔体粘度是3300泊,测量于240℃和1弧度/秒剪切速率。
实施例9
在纺粘设备上,使用双组分喷丝板模头(获自HillsInc.,Melbourne,FL,在24″宽模头盘中总共具有2222模头孔),制造具有16-区段(segment)扇饼型(segmentedpie)结构的双组分挤出物。使用两个挤出机将两种聚合物熔融并且进料到该喷丝板模头。主要挤出机(A)连接到入口,其将EastmanF61HCPET聚酯熔体进料以形成扇饼型(segmentedpie)断面结构中的域或区段(segment)部分(slices)。挤出区设定为在285℃熔融进入喷丝板模头的PET。第二挤出机(B)将实施例8的磺基聚酯聚合物熔融并且进料。第二挤出机设定为在255℃的熔融温度将磺基聚酯聚合物挤出到喷丝板模头中。除了所用的喷丝板模头和磺基聚酯聚合物的熔体粘度以外,本实施例中所用的程序与对比例8中的相同。熔体处理量/孔是0.6gm/min。在双组分挤出物中PET和磺基聚酯的量比被设定为70/30,这代表约70/30的重量比。
使用与对比例8中所用的相同的吸气装置来熔融拉伸双组分挤出物以生产双组分纤维。最初,至吸气装置的输入空气被设定为25psi,纤维的初纺旦数为约2.0,而双组分纤维显示出均匀的直径轮廓,约14-15微米。至吸气装置的空气被增加到最大可用压力45psi,而在熔融拉伸期间没有使熔融挤出物断裂。使用45psi空气,双组分挤出物被熔融拉伸成纤维初纺旦数为约1.2,其中当在显微镜下观察时,双组分纤维显示出11-12微米的直径。在熔融拉伸过程期间的速度经计算为约4500m/min。虽然不意欲受到理论的约束,在接近于这种速度的熔融拉伸速率下,据信在熔融拉伸过程期间PET的应变诱导结晶开始出现。如上所述令人期望的是:在纤维熔融拉伸过程期间,在PET纤维区段(segment)中形成一些取向的结晶,使得非织造网在下一工序期间将是更加尺寸上稳定的。
使用45psi吸气装置空气压力,双组分纤维被铺列为非织造网,重量为140克每平方米(gsm)。通过在120℃,在强迫的空气烘箱中将材料调理5分钟,测量非织造网的收缩。本实施例表现出收缩明显减少,相比于对比例8的纤维和织物来说。
在各种温度下在静态去离子水浴中浸透这种具有140gsm织物重量的非织造网达5分钟。干燥所浸透的非织造网,并且测量由于在各种温度在去离子水中浸透所造成的重量损失%,示于表4中。
表4
浸透温度 | 25℃ | 33℃ | 40℃ | 72℃ |
非织造网重量损失(%) | 3.3 | 21.7 | 31.4 | 31.7 |
在约25℃,磺基聚酯非常容易地驱散入去离子水中。在非织造网中磺基聚酯从双组分纤维的除去由重量损失%表示。在33℃或以上,观察到了从双组分纤维中磺基聚酯的大规模的或完全的除去。如果使用水缠结来生产这些双组分纤维(包括实施例8的本发明磺基聚酯聚合物)的非织造网,预计如果水温在周围环境以上,将通过水缠结水喷射器大范围地或者完全地除去磺基聚酯聚合物。如果期望在水缠结步骤期间极少的磺基聚酯聚合物从这些双组分纤维中除去,那么应当使用低水温,小于约25℃。
实施例10
使用下列二酸和二醇组成来制备磺基聚酯聚合物:二酸组成(71mol%对苯二甲酸,20mol%间苯二甲酸,和9mol%的5-(钠代磺基)间苯二甲酸)和二醇组成(60mol%乙二醇和40mol%二甘醇)。在真空条件下通过高温聚酯化作用来制备磺基聚酯。控制酯化条件以生产比浓对数粘度为约0.31的磺基聚酯。这种磺基聚酯的熔体粘度的测量结果为约3000-4000泊,在240℃和1弧度/秒剪切速率的条件下。
实施例11
根据实施例9中所述的相同程序,将实施例10的磺基聚酯聚合物纺丝成双组分扇饼型(segmentedpie)纤维和非织造网。主要挤出机(A)将EastmanF61HCPET聚酯熔体进料以在扇饼型(segmentedpie)结构中形成较大的区段(segment)部分(slices)。挤出区设定为在285℃熔融进入喷丝板模头的PET。第二挤出机(B)加工实施例10的磺基聚酯聚合物,其在255℃的熔融温度被进料到喷丝板模头中。熔体处理速率/孔是0.6gm/min。在双组分挤出物中PET和磺基聚酯的量比被设定为70/30,这代表约70/30的重量比。双组分挤出物的断面具有PET的楔形域,磺基聚酯聚合物将这些域分开。
使用与对比例8中所用的相同的吸气组件来熔融拉伸双组分挤出物以生产双组分纤维。在拉伸期间使双组分纤维不断裂的条件下,空气至吸气装置的最大可用压力是45psi。使用45psi空气,双组分挤出物被熔融拉伸成初纺旦数约1.2的双组分纤维,其中当在显微镜下观察时,双组分纤维显示出约11-12微米的直径。在熔融拉伸过程期间的速度经计算为约4500m/min。
双组分纤维被铺列为非织造网,其重量为140gsm和110gsm。通过在120℃,在强迫的空气烘箱中将材料调理5分钟,测量纤维网的收缩。收缩后非织造网的面积为纤维网开始面积的约29%。
熔融拉伸的纤维和取自非织造网的纤维的断面的显微镜检查显示出很好的扇饼型(segmentedpie)结构,其中各个区段清楚地限定并且显示了相似的大小与形状。PET区段(segment)彼此是完全分开的,使得在从双组分纤维中除去磺基聚酯后,它们将形成8个独立的PET单组分纤维,后者具有饼状部分形状。
在各种温度下在静态去离子水浴中浸透所述具有110gsm织物重量的非织造网达8分钟。干燥所浸透的非织造网,并且测量由于在各种温度在去离子水中浸透所造成的重量损失%,示于表5中。
表5
在高于约46℃的温度下,磺基聚酯聚合物非常容易地驱散入去离子水中,在高于51℃的温度下磺基聚酯聚合物从纤维中的除去是非常大规模的或者完全的,如重量损失所示的。约30%的重量损失表示在非织造网中磺基聚酯从双组分纤维中的完全脱除。如果使用水缠结来加工双组分纤维(包括这种磺基聚酯)的这种非织造网,预计在低于40℃的水温条件下,将不会通过水缠结水喷射大范围地除去聚合物。
实施例12
使用Fleissner,GmbH,Egelsbach,Germany制造的水缠结装置,水缠结实施例11的基重140gsm和110gsm的非织造网。所述机器具有总共5个水缠结工作台,其中三组喷射器接触非织造网的顶侧,两组喷射器接触非织造网的相对侧。水喷射器包括一系列细孔口,直径约100微米,加工成2英尺宽的喷射器带。至喷射器的水压被设置为60巴(喷射器带#1),190巴(喷射器带#2和3),和230巴(喷射器带#4和5)。在水缠结过程期间,至喷射器的水温为约40-45℃。离开水缠结装置的非织造织物被牢固连接一起。连续纤维被打结在一起以生产水缠结的非织造织物,当在双向拉伸时,其具有高耐撕裂性。
接下来,水缠结的非织造织物被固定到拉幅机上,所述拉幅机包括刚性矩形机架,一系列针围绕其周边。织物被固定在针上,以便当其受热时防止织物收缩。在130℃将机架与织物样品置于强迫的空气烘箱达3分钟,引起所述织物的热定形,同时受到约束。在热定形后,调理过的织物被切成测量尺寸的样品试样,所述试样不受限制地通过拉幅机在130℃下调理。在这种调理后,测量水缠结的非织造织物的尺寸,并且观察到仅仅极小的收缩(尺寸减小低于0.5%)。很明显水缠结的非织造织物的热定形足以生产尺寸上稳定的非织造织物。
水缠结的非织造织物,在如上所述的热定形后,在90℃去离子水中洗涤以便除去磺基聚酯聚合物并且留下水缠结织物中保留的PET单组分纤维区段(segment)。在反复洗涤后,干燥织物显示出重量损失为大约26%。在水缠结前洗涤非织造网显示出重量损失为31.3%。因此,水缠结过程从非织造网中除去一些磺基聚酯,但是这种量是较小的。为了减小在水缠结期间除去的磺基聚酯的量,水缠结喷射器的水温应该降低到低于40℃。
发现实施例10的磺基聚酯产生了具有良好的区段(segment)分布的扇饼型(segmentedpie)纤维,其中在除去磺基聚酯聚合物后,水不可分散的聚合物区段(segment)形成了相似的大小与形状的单独的纤维。磺基聚酯的流变学适于使双组分挤出物以高速熔融拉伸而获得细旦数的双组分纤维,其中初纺旦数低到约1.0。这些双组分纤维能够被铺列为非织造网,其还可以进行水缠结以生产非织造织物,而没有经历显著的磺基聚酯聚合物的损失。通过水缠结非织造网生产的非织造织物显示出高强度并且可以在约120℃或更高的温度下热定形以生产具有极好的尺寸稳定性的非织造织物。在洗涤步骤中,从水缠结的非织造织物中除去磺基聚酯聚合物。这产生了牢固的非织造织物产物,其具有更轻的织物重量和大很多的柔性和更柔软的手感。在这种非织造织物产物中的单组分(monocomponent)PET纤维是楔形的并且显示了约0.1的平均旦数。
实施例13
使用下列二酸和二醇组成来制备磺基聚酯聚合物:二酸组成(69mol%对苯二甲酸,22.5mol%间苯二甲酸,和8.5mol%5-(钠代磺基)间苯二甲酸)和二醇组成(65mol%乙二醇和35mol%二甘醇)。在真空条件下通过高温聚酯化作用来制备磺基聚酯。控制酯化条件以生产比浓对数粘度为约0.33的磺基聚酯。这种磺基聚酯的熔体粘度的测量结果为约3000-4000泊,在240℃和1弧度/秒剪切速率的条件下。
实施例14
在纺粘作业线上,将实施例13的磺基聚酯聚合物纺丝成双组分海岛型断面构型,具有16个岛。主要挤出机(A)将EastmanF61HCPET聚酯熔体进料以在海岛型结构中形成岛。挤出区设定为在约290℃熔融进入喷丝板模头的PET。第二挤出机(B)加工实施例13的磺基聚酯聚合物,其在260℃的熔融温度被进料到喷丝板模头中。在双组分挤出物中PET和磺基聚酯的量比被设定为70/30,这代表约70/30的重量比。通过喷丝板的熔体处理速率是0.6g/孔/分钟。双组分挤出物的断面具有PET的圆形岛域,磺基聚酯聚合物将这些域分开。
使用吸气组件来熔融拉伸双组分挤出物。在熔融拉伸期间使双组分纤维不断裂的条件下,空气至吸气装置的最大可用压力是50psi。使用50psi空气,双组分挤出物被熔融拉伸成初纺旦数约1.4的双组分纤维,其中当在显微镜下观察时,双组分纤维显示出约12微米的直径。在拉伸过程期间的速度经计算为约3900m/min。
Claims (10)
1.一种具有成形断面的多组分挤出物,其包括:
(A)至少一种水可分散的磺基聚酯;和
(B)多个域,所述域包括与所述磺基聚酯不溶混的至少一种水不可分散的聚合物,其中所述域通过介于所述域之间的所述磺基聚酯基本上彼此隔离,
其中所述挤出物能够以至少2000m/min的速度熔融拉伸;且
其中所述磺基聚酯包括间苯二甲酸的残基和60-80mol%的对苯二甲酸的一种或多种残基,且所述间苯二甲酸的残基的含量为30mol%或以下,基于总酸残基;并且所述水可分散的磺基聚酯具有至少57℃的玻璃化转变温度Tg,以及显示出小于12,000泊的熔体粘度,在240℃在1弧度/秒的应变速率下测量的。
2.根据权利要求1的多组分挤出物,其中所述磺基聚酯包括小于25mol%的至少一种磺基单体的残基,基于二酸或二醇残基的总摩尔数。
3.根据权利要求1的多组分挤出物,其中所述磺基聚酯包括:
(A)一种或多种二羧酸的残基,其中所述一种或多种二羧酸的残基是间苯二甲酸的残基和60-80mol%的对苯二甲酸的一种或多种残基,且所述间苯二甲酸的残基的含量为30mol%或以下,基于总酸残基;
(B)5-20mol%的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中所述官能团是羟基、羧基或其组合;和
(C)一种或多种二醇的残基。
4.根据权利要求3的多组分挤出物,其中所述磺基聚酯包括:
(A)一种或多种二羧酸的残基,其中所述一种或多种二羧酸的残基是间苯二甲酸的残基和60-80mol%的对苯二甲酸的一种或多种残基,且所述间苯二甲酸的残基的含量为30mol%或以下,基于总酸残基;
(B)5-20mol%的至少一种磺基单体的残基,其具有2个官能团和附着到芳族或环脂族环的一个或多个磺酸根基团,其中所述官能团是羟基、羧基或其组合;
(C)一种或多种二醇残基,其中至少5mol%,基于总二醇残基,是具有以下结构的聚(乙二醇)
H-(OCH2-CH2)n-OH
其中n是2-500的整数;和
(D)0-25mol%,基于总重复单元,的一种或多种具有3或以上官能团的支化单体的残基,其中所述官能团是羟基、羧基或其组合。
5.根据权利要求3的多组分挤出物,其中所述磺基聚酯还包括其它二羧酸,所述其它二羧酸选自脂族二酸、环脂族二羧酸、芳族二羧酸和其组合。
6.根据权利要求5的多组分挤出物,其中所述其它二羧酸选自琥珀酸、戊二酸、己二酸、壬二酸、癸二酸、富马酸、马来酸、衣康酸、1,3-环己烷二羧酸、1,4-环己烷二羧酸、二羟乙酸、2,5-降莰烷二羧酸、邻苯二甲酸、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、2,7-萘二羧酸、联苯甲酸、4,4'-氧联二苯甲酸、4,4'-磺酰二苯甲酸和其组合。
7.根据权利要求3的多组分挤出物,其中所述磺基单体是磺基邻苯二甲酸、磺基对苯二甲酸、磺基间苯二甲酸或其组合的金属磺酸盐。
8.根据权利要求3的多组分挤出物,其中所述二醇残基选自乙二醇、二甘醇、三甘醇、聚乙二醇、1,3-丙二醇、2,4-二甲基-2-乙基己烷-1,3-二醇、2,2-二甲基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、2-乙基-2-异丁基-1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2,4-三甲基-1,6-己二醇、硫代二乙醇、1,2-环己烷二甲醇、1,3-环己烷二甲醇、1,4-环己烷二甲醇、2,2,4,4-四甲基-1,3-环丁二醇、对苯二甲醇和其组合。
9.根据权利要求4的多组分挤出物,其中所述支化单体选自1,1,1-三羟甲基丙烷、1,1,1-三羟甲基乙烷、甘油、季戊四醇、赤藓醇、苏糖醇、二季戊四醇、山梨糖醇、偏苯三酸酐、均苯四酸二酐、二羟甲基丙酸或其组合。
10.根据权利要求1的多组分挤出物,其中所述水不可分散的聚合物选自聚烯烃、聚酯、聚酰胺、聚交酯、聚己内酯、聚碳酸酯、聚氨酯、聚氯乙烯、纤维素酯和其组合。
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