CN1277641A - 改良的共聚物粘合纤维 - Google Patents

改良的共聚物粘合纤维 Download PDF

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CN1277641A
CN1277641A CN98810497A CN98810497A CN1277641A CN 1277641 A CN1277641 A CN 1277641A CN 98810497 A CN98810497 A CN 98810497A CN 98810497 A CN98810497 A CN 98810497A CN 1277641 A CN1277641 A CN 1277641A
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copolyesters
dicarboxylic acid
mole
binder fiber
fiber
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CN1146679C (zh
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L·R·迪安
W·A·海勒
M·D·兰伯特
F·H·蒂罗
M·E·廷切尔
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Eastman Chemical Co
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Eastman Chemical Co
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Abstract

本发明涉及从共聚酯中制得的粘合纤维、这些共聚酯本身以及用于生产此共聚酯的各种催化剂和方法。更具体地说,本发明涉及从1,4－环己烷二甲醇、1,2－亚乙基二醇和对苯二酸、萘二甲酸、1,4－环己烷二羧酸及其酯或酸酐中制成的各种共聚酯。可将这类共聚酯做成各种产品,特别是用于无纺织物的粘合纤维。

Description

改良的共聚物粘合纤维
优先权资料
本申请要求1997年8月28日申请的根据35 U.S.C.§119临时申请60/057,800的权益。此临时申请的整个公开内容此处通过引用并入本文。
本发明领域
本发明涉及从各种共聚酯中制得的粘合纤维、涉及这些共聚酯本身以及用于生产此共聚酯的各种催化剂和方法。更具体地说，本发明涉及从1，4-环己烷二甲醇、1，2-亚乙基二醇和对苯二酸、萘二甲酸、1，4-环己烷二羧酸及其酯或酸酐中制成的各种共聚酯。可将这种共聚酯做成各种产品，特别是用于无纺织物的粘合纤维。
本发明背景
无纺织物广泛用于各种产品中。例如，无纺织物适用于填料、屋面材料、复合材料、基材、衬料、衬里、绝缘、医学/外科应用、被褥、桌布和尿布。高蓬松度棉胎(high loft batting)无纺织物也用于各种产品中，包括羊毛围巾、长袍服装和胸罩(bra cups)。无纺织物通常基于可与各种胶乳粘合剂、粘合纤维或粉末状的聚合物粘合在一起的聚酯、丙烯酸、尼龙、玻璃和纤维素纤维。无纺织物与粘合纤维的粘合为制造无纺织物提供了一种方便的途径而无须各种对环境不利的水基粘合剂。采用粘合纤维粘合的无纺织物可经济地进行生产，并提供一种用于制造具有独特或优异性能制品的方法。
我们已发现某些共聚酯可用作粘合纤维。例如，比浓对数粘度(I.V.)值为约0.6-约0.8的含有1，4-环己烷二甲醇的聚对苯二甲酸乙二酯(PET)共聚酯在过去已用作粘合聚酯或其它纤维的粘合纤维。然而我们相信，具有低I.V.值的共聚酯没有足够的粘合强度。
众所周知，共聚酯可通过各种方法(包括聚酯化和缩聚作用)进行制备。一般而言，如美国专利2,901,466、5,017,680、5,106,944、5,668,243和5,668,243中所述，反应剂为一种二元醇组分和一种二羧酸组分。通常二羧酸组分为对苯二酸，而二元醇为1，2-亚乙基二醇。这种共聚酯是较为惰性的疏水性材料，适用于各种用途，包括模塑制品、食品托盘、纤维、压片、薄膜及容器如瓶子。但1，2-亚乙基二醇用作唯一的二元醇带来了各种不合需要的性能，如黄色褪去和弱的纤维粘合性能。实际上，这些聚合物趋向于为具有高熔融温度的不透明、晶体聚合物，使其不适宜于用作粘合纤维。为了解决聚对苯二甲酸乙二酯存在的各种问题，人们采用1，4-环己烷二甲醇来生成聚对苯二甲酸乙二酯共聚酯。
采用1，2-亚乙基二醇、1，4-环己烷二甲醇和对苯二酸制备共聚酯通常在催化剂材料的存在下进行。这些催化剂材料的选择通常集中在各种材料的组合，包括衍生自锑、镉、钙、镓、锗、锂、镁、锰、钛和锌的各种催化剂。用于制备聚对苯二甲酸乙二酯的一个示意性催化剂体系述于美国专利3,907,754中。然而遗憾的是，先前的各种催化剂体系并不是完全成功的，因它们可以产生具有不合需要的褪色的共聚酯。因此在本领域中存在着能提供高效反应时间，同时又能生产出高透明度的共聚酯、特别是高透明度的共聚酯粘合纤维的催化剂体系的需要。
此外，以前采用1，4-环己烷二甲醇生成共聚酯的各种尝试都将焦点集中在比浓对数粘度I.V.值大于0.6的共聚酯上，这是源于人们相信低的比浓对数粘度无法得到足够的强度。具体而言，人们相信低比浓对数粘度的共聚酯无法提供足够的粘合强度以便生成市场上可为人接受的粘合纤维。实际上以前人们将具有1，4-环己烷二甲醇的聚对苯二甲酸乙二酯共聚酯制成其比浓对数粘度为0.6-0.8，以便生成粘合纤维以粘合各种聚酯或其它纤维。但是这些尝试在提供具有所需高透明度和色调或当以粘合纤维的形式时在低的活化温度下具有粘合能力的共聚酯方面没有取得完全成功。因此，在本领域中存在着人们对比浓对数粘度低于0.6，而同时具有改进的透明度、颜色和在低的活化温度下粘合纤维粘合强度的共聚酯的需求。
本发明概要
本发明通过提供具有优异颜色、热塑流和提高的粘合多功能性的粘合纤维共聚酯以及用于生产这种共聚酯的催化剂从而解决了与先前粘合纤维及共聚酯有关的各种问题。本发明的共聚酯适用于各种各样的用途，如用于制造纺织品和工业纱的无纺织物的粘合纤维。
更具体地说，本发明提供采用一种二元醇组分及一种二羧酸组分进行制备的共聚酯。此二元醇组分通常含有10-60％(摩尔)的1，4-环己烷二甲醇和约40-约90％(摩尔)的1，2-亚乙基二醇。至少约90％(摩尔)的二羧酸组分选自以下物质的酸、酯或酸酐：对苯二酸、萘二甲酸、1，4-环己烷二羧酸及其各种混合物。本发明的共聚酯形成后所得的共聚酯的比浓对数粘度低于0.6并且具有优异的热塑流及粘合能力。实际上本发明的共聚酯特别适用作为粘合纤维，因该共聚酯拥有低的I.V.，使在较低温度下用于无纺织物的粘合纤维具有改进的粘合性能。本发明在下文做更详细的讨论。详述
本发明涉及从共聚酯制得的粘合纤维、共聚酯本身和用于生产共聚酯的各种催化剂及方法。本发明的共聚酯具有优异的颜色，因为它们更加纯净，表现出中性色调或外观比先前的共聚酯更加明亮并且比较高I.V.的共聚酯更加容易接收染料。实际上，通过使用较低的I.V.获得了纯净和非不透明且容易加工成具有优良粘合性能的粘合纤维的共聚酯聚合物。此外，通过本发明较低I.V.的共聚酯的较低纺熔温度有助于将共聚酯加工成粘合纤维。
本发明的共聚酯形成自二元醇组分与二羧酸组分的反应。通常二元醇组分包括10-60％(摩尔)的1，4-环己烷二甲醇和约40-约90％(摩尔)的1，2-亚乙基二醇。二羧酸组分含有至少约90％(摩尔)的以下物质的酸、酯或酸酐：对苯二酸、萘二甲酸、1，4-环己烷二羧酸及其各种混合物。本发明的共聚酯具有约0.36-0.58的I.V.。这些及其它特征在以下将做更详细的讨论。二元醇组分
如上所述，二元醇组分通常包括10-60％(摩尔)的1，4-环己烷二甲醇和约40-约90％(摩尔)的1，2-亚乙基二醇。优选1，4-环己烷二甲醇的量为约20％-约40％(摩尔)、更优选为约25％-约35％(摩尔)。1，4-环己烷二甲醇可以是顺式-异构体、反式-异构体或顺式/反式异构体混合物。1，2-亚乙基二醇的量优选为约60％-约80％(摩尔)、更优选为约65％-75％(摩尔)。
除了1，4-环己烷二甲醇和1，2-亚乙基二醇之外，二元醇组分还可包括高达约20％(摩尔)、优选高达约4％(摩尔)的二甘醇和高达约10％(摩尔)的常规二元醇，包括(但不限于此)各种含有约3-约12个碳原子的二元醇，如丙二醇、1，3-丙二醇、1，4-丁二醇、1，5-戊二醇、新戊二醇、2，2-二甲基-1，3-丙二醇、1，6-己二醇、2，2，4-三甲基-1，3-丙二醇、2-乙基-2-丁基-1，3-丙二醇、2，2，4，4-四甲基-1，3-环丁烷二醇、2，4-二甲基-2-乙基己烷-1，3-二醇、2-乙基-2-异丁基-1，3-丙二醇、1，3-丁二醇、新戊二醇、1，8-辛二醇、2，2，4-三甲基-1，6-己二醇、硫代二乙醇(thiodiethanol)、1，2-环己烷二甲醇和1，3-环己烷二甲醇。二羧酸组分
二羧酸组分含有不少于约90％(摩尔)的对苯二酸、萘二甲酸和1，4-环己烷二羧酸的酸、酯或酸酐。我们应注意到，可以使用任何萘二甲酸异构体或各种异构体的混合物，优选1，4-、1，5-、2，6-和2，7-异构体。此外，1，4-环己烷二羧酸部分可以是顺式-异构体、反式-异构体或顺式/反式异构体混合物。优选的二羧酸组分为对邻苯二甲酸二甲酯。
可加入高达10％(摩尔)的其它二羧酸组分(对苯二酸、萘二甲酸和1，4-环己烷二羧酸的酸、酯或酸酐除外)。适宜的其它二羧酸组分含有约4-约40个碳原子并述于美国专利5,608,031和5,668,243中，此处通过引用其整篇文献并入本文。优选此其它二羧酸组分为芳族二羧酸的酸、酯或酸酐(优选具有8-14个碳原子)、脂族二羧酸的酸、酯或酸酐(优选具有4-12个碳原子)或环脂族二羧酸的酸、酯或酸酐(优选具有8-12个碳原子)。
所使用的除了对苯二酸、萘二甲酸和1，4-环己烷二羧酸之外的其它二羧酸组分的特别优选实例包括(但不限于此)间苯二酸、磺基间苯二酸、1，3-环己烷二羧酸、1，4-环己烷二乙酸、二苯基-4，4’-二羧酸、琥珀酸、戊二酸、己二酸、壬二酸、癸二酸、1，12-二癸烷二酸和二聚体酸。从上述一种或一种以上二羧酸中可制备出共聚酯。支化剂
少量(通常低于约2％(摩尔))的常规支化剂可与二元醇组分及二羧酸组分一起反应生成本发明的共聚酯。常规支化剂包括多官能酸、酸酐、醇及其各种混合物。适宜支化剂的实例包括(但不限于此)1，2，4-苯三酸酐、苯均四酸二酐、甘油、三羟甲基丙烷和季戊四醇。生成共聚酯的反应过程
在生成本发明的共聚酯中，采用各种常规聚酯聚合条件可以进行二元醇组分与二羧酸组分的反应。例如，当通过酯交换反应即从二羧酸组分的酯形式中制备共聚酯时，反应过程可以包括两个步骤。在第一个步骤中，使二元醇组分和二羧酸组分如对苯二甲酸二甲酯在通常为约180℃-约280℃的高温及约0.0-约60psig的压力下进行反应。优选用于酯交换反应的温度范围为约190℃-约240℃，而优选的压力范围为约15-约40psig。然后，在更高的温度和减压下加热反应产物，随着二元醇的消除(在这些条件下很容易挥发并离开体系)生成了聚酯。第二个步骤或缩聚步骤，在较高真空下，通常为约240℃-约300℃、优选为约250℃-约290℃、最优选为约270℃-约285℃的温度下继续进行直到获得具有所需聚合度(通过I.V.确定)的聚合物为止。缩聚步骤可在约400mmHg(托)-约0.1mmHg(托)的减压下进行。如果没有适宜催化剂的协助，则上述反应无法以显著的速率继续进行。
为了确保使二元醇组分与二羧酸组分之间按酯交换反应机理进行的反应充分完成，1摩尔的二羧酸组分优选采用3摩尔、更优选约2.3-约2.6摩尔的二元醇组分。然而应理解的是，二元醇组分与二羧酸组分之间的比率通常应通过反应在其中进行的反应器的设计来决定。
在通过直接酯化即从二羧酸组分的酸形式中制备聚酯中，通过使二羧酸如对苯二酸、萘二甲酸、1，4-环己烷二羧酸或其各种混合物与二元醇组分进行反应制备共聚酯。反应在约1-约1000磅/英寸2表压、优选低于100psig的压力下进行，得到平均聚合度为约1.4-约10的低分子量直链或支链聚酯产物。直接酯化反应期间所采用的温度通常为约180℃-约280℃、更优选为220℃-约270℃。然后可通过缩聚反应对此低分子量的聚合物进行聚合。
为了确保使二元醇组分与二羧酸组分之间按直接酯化反应机理进行的反应充分完成，1摩尔的二羧酸组分优选采用约3.0-1.05摩尔的二元醇组分。然而应理解的是，二元醇组分与二羧酸组分之间的比率通常应通过反应在其中进行的反应器的设计来决定。
与生成较高I.V.的共聚酯的过程相比，通过采用较短的停留时间或慢的反应速率通常可获得较低I.V.的共聚酯。例如，通过降低反应温度、减少催化剂浓度、提高反应器内的绝对压力或这些因素的组合可使反应速率减慢。
生成本发明共聚酯的过程可以以间歇、半间歇或连续的过程进行。优选该过程以连续过程进行。实际上，当采取连续过程时可以得到具有优良颜色的共聚酯，因如果在高温下让共聚酯停留在反应器内太长时间时可能对该共聚酯外观产生不利影响。催化剂体系
各种催化剂体系可用于促进二元醇组分与二羧酸组分之间的反应。通常催化剂体系包含催化材料及催化抑制剂。
催化材料
适用于催化剂体系的各种催化材料包括(但不限于此)含有钛、锰、锌、钴、锑、镓、锂、钙、硅和锗的材料。实际上，这些催化剂体系见述于美国专利3,907,754、3,962,189、4,010,145、4,356,299、5,668,243和5,681,918中，此处通过引用其整篇文献并入本文。通常本发明的催化剂体系包括含有钛、锰和/或锌及其各种混合物的材料。虽然催化剂体系中各种催化材料的量可以有所变化，但催化剂体系中各种催化材料的总量必须低于约125ppm、优选低于约100ppm、最优选低于约80ppm。用于催化剂体系以及下述催化抑制剂的“ppm”指所提及元素的重量并基于最终共聚酯产物的理论重量。
钛催化材料通常以醇盐的形式加入，其用量范围为约10-约35ppm、更优选为约10-约25ppm、最优选为约12-约20ppm。实际上，当保持在熔体中时，采用较低水平的钛催化材料制成的共聚酯具有更好的稳定性。适宜的钛醇盐包括(但不限于此)钛酸乙酰基三异丙基酯、钛酸四异丙基酯和钛酸四异丁基酯。钛催化材料可在直接酯化或酯交换反应之前或在缩聚反应之前加入到反应过程中。
锰通常以盐如有机酸盐的形式加入，其量为约0-约70ppm、优选为约30-约70ppm、更优选为约40-约50ppm。适宜锰盐的实例包括(但不限于此)锰的苯甲酸盐四水合物、氯化锰、氧化锰、乙酸锰、乙酰丙酮锰和琥自酸锰。在直接酯化或酯交换反应之前将锰加入到反应过程中。
锌可与锰一起或代替锰催化剂加入到催化剂体系中。锌通常以盐的形式加入，其量为0-100ppm、优选为约25-约100ppm、更优选为约50-约80ppm。适宜锌化合物的实例包括(但不限于此)乙酸锌、磷酸锌一水合物、琥珀酸锌和锌烷氧化物。通常在直接酯化或酯交换反应之前将锌加入到反应过程中。
如需要，也可以将钴催化材料作为催化剂体系的一部分使用。使用时钴通常以盐如有机酸盐的形式加入。适宜钴盐的实例包括(但不限于此)乙酸钴三水合物、硝酸钴、氯化钴、乙酰丙酮钴、环烷酸钴和水杨酸钴。钴的加入量可为约0.0-90ppm。如下所述，钴可起催化材料及色料两种作用。在直接酯化或酯交换反应之后将钴加入到反应过程中。
在一些实施方案中可使用锑。使用时，适宜锑的化合物的实例包括(但不限于此)无机酸的锑酸酯、氧化锑、各种锑烷氧化物如异丙醇锑、卤化锑如氯化锑、溴化锑和氟化锑、锑酸钠或锑酸钾、各种羧酸锑如乙酸锑和甘醇酸锑或其各种混合物。优选锑组分为甘醇酸锑或氧化锑。通常在酯交换或直接酯化反应之后将锑加入。当共聚酯用来制成粘合纤维时，由于存在含锑催化剂而导致泛黄现象，可将锑从催化剂体系中除去。
虽然不那么优选，但镓和硅催化材料仍可用于催化剂体系中。适宜的钙化合物的实例包括(但不限于此)乙酸钙、calcium glycoxide和磷酸钙一水合物。适宜的镓化合物的实例包括(但不限于此)氯化镓、硝酸镓水合物、氧化镓、乳酸镓和磷化镓。适宜的硅化合物的实例包括(但不限于此)乙酸硅和原硅酸四乙酯。锗催化材料包括(但不限于此)各种氧化物、有机酸盐，特别是锗的甘醇酸盐。
用于使对苯二酸、萘二甲酸和1，4-环己烷二羧酸的酯反应的优选酯交换催化剂体系含有钛、锰和任选钴材料。在酯交换催化剂体系中，钛的存在量为约10-约35ppm、优选为约10-约25ppm，锰的存在量为约30-约70ppm。此外，在酯催化剂体系的另一个实施方案中，催化剂体系中的各种催化材料总量不超过约125ppm、优选少于约100ppm、更优选少于约80ppm、最优选少于70ppm。优选的酯催化剂体系通常与包括约40-约90ppm的P、有效量如约2-约10ppm的兰色和/或红色取代蒽醌染料的色料的催化抑制剂结合使用。通常优选的酯催化剂体系基本上不含Zn催化材料、更优选含有低于5ppm的Zn催化材料、最优选不含Zn催化材料。此外，当需要的是粘合纤维时，优选的酯催化剂体系基本上不含Sb催化材料、更优选含有低于5ppm的Sb催化材料、最优选不含Sb催化材料。催化抑制剂
为了稳定催化剂体系的效果以及为了提高锌、锰和钴催化材料的效率，需在酯交换或直接酯化反应之后但在进行缩聚反应步骤之前将磷催化抑制剂加入到反应过程中。通常磷以磷酸盐如磷酸或有机磷酸酯的形式加入，其量为约40-90ppm、更优选为约60-75ppm。用于本发明中的适宜磷酸酯包括(但不限于此)酸式磷酸乙酯、酸式磷酸二乙酯、磷酸三乙酯、磷酸芳烷基酯和磷酸三-2-乙基己基酯。一种可用的磷酸酯催化抑制剂为可购自Du Pont的以MerpolA售卖的磷酸酯催化抑制剂。色料
在制备本发明的共聚酯时，可加入色料(有时称为有机调色剂)以将所需中性色调和/或亮度赋予所得的共聚酯。当需要着色的共聚酯时，在二元醇组分与二羧酸组分进行反应期间各种颜料或色料可包括在反应混合物中，或者可将其与预制的共聚酯熔体混合在一起。包括色料的一种优选方法是采用具有热稳定的有机着色化合物(具有反应基)的色料，使色料被共聚合并结合到共聚酯中以改进共聚酯的色调。例如，可将各种色料如具有反应性羟基和/或羧基基团的染料包括(但不限于此)兰色和红色取代蒽醌共聚合进聚合物链中。各种色料和染料详细见述于美国专利4,521,556、4,740,581、4,749,772、4,749,773、4,749,774、4,950,732、5,384,377、5,372,864、5,340,910和5,681,918中，此处通过引用其整篇文献并入本文。当染料用作色料时，它们可在酯交换或直接酯化反应之后加入到共聚酯反应过程中。此外，当染料或染料混合物用作共聚酯的有机调色剂色料时，优选染料的总量少于10ppm。
或者可将各种无机颜料如二氧化钛和含钴材料加入到反应中。优选当催化剂材料含有钴时，此钴也可起色料的作用。为了避免在本发明共聚酯中出现不透明性和黯淡，必须注意控制钴的含量。为了控制不透明性和黯淡的水平，钴的用量应在约0.0-90ppm。本发明的共聚酯
本发明的共聚酯的比浓对数粘度I.V.为约0.36-0.58。优选本发明的共聚酯的I.V.为约0.38-约0.58、更优选为约0.4-约0.53、更优选为约0.4-约0.50、最优选为约0.41-约0.49。通过在25℃下采用每100毫升溶剂(由60％(重量)苯酚和40％(重量)四氯乙烷组成)含0.5克聚合物测量I.V.来确定本发明共聚酯的I.V.。确定共聚酯的I.V.的基本方法见述于ASTMD-2857-70中。采用较低I.V.值制成的共聚酯具有优异的颜色，因它们比先前的共聚酯更加透明，并且比较高I.V.的共聚酯更容易接收染料。此外，低I.V.的共聚酯与类似较高I.V.的共聚酯相比在低温下更易于染色和更易于打印。再者，由于本发明的共聚酯具有低的I.V.值，因此共聚酯的生产率相当地快速。
可控制1，4-环己烷二甲醇与1，2-亚乙基二醇和对苯二酸的聚合，得到玻璃化转变温度类似于聚对苯二甲酸乙二酯的无定形聚对苯二甲酸乙二酯聚合物。如在本领域中所公知的那样，无定形聚合物通常具有较高的透明度并且不像许多结晶共聚物那样不透明。因此，虽然一些所用的1，4-环己烷二甲醇水平可能会得到具有一定结晶度的共聚酯，但无定形聚酯的优良透明度提供了一些独特的优点。
通常较低I.V.的共聚酯具有较低的挤出温度。因此，本发明的共聚酯在较低温度下可有利地熔纺成纤维。例如，I.V.为0.47的本发明共聚酯可在大约233℃的温度下进行熔纺，而I.V.为0.6-0.7的类似共聚酯通常要求在275-285℃的温度下进行纤维纺丝。通常本发明的共聚酯在低于约250℃、在一些情况下低至235℃的温度下进行熔纺，这已接近聚丙烯纺丝所用的条件。这些共聚酯可通过一具有约332个孔、孔的大小约为0.55毫米的喷丝板进行熔纺。通常熔纺压力为约1000psig-2000psig。
通常共聚酯的透明度及颜色(色调)可采用标准光谱色度计进行评价。例如，一种适宜的用于评价共聚酯透明度及颜色的光谱色度计为可购自HunterLab of Reston，Virginia的HunterLab UltraScan。通过使用HunterLab UltraScan光谱色度计可定量测量透明度及颜色即泛黄度和/或泛兰度。使用HunterLab UltraScan光谱色度计用于评价及定量测量共聚酯的颜色及透明度见述于美国专利5,681,918中，此处通过引用整篇文献并入本文。当使用HunterLab UltraScan时，L*值指的是透明度水平，较高L*值代表较高水平的透明度。泛黄度和/或泛兰度的水平通过b*值进行定量，0.0代表中等，超过0.0则指示共聚酯中泛黄度水平，低于0.0则代表共聚酯中泛兰度水平。本发明的共聚酯通常的L*值超过约65、通常为约69-约72，b*值为约-2.5至约+2.5、优选为约-1.0至约+1.0、更优选为约-0.5至约+0.5、最优选为约0.0。从本发明共聚酯制得的产物
本发明的共聚酯可用于各种制品的生产，或可用作添加剂，如作为配合添加剂提浓物或另一个聚合物体系的母炼胶。此外，采用共聚酯可制成各种粘合纤维及其它制品，包括(但不限于此)塑料和薄膜，包括容器、模塑部件、压片和挤压薄膜及纤维。本发明的共聚酯可作为制品的一部分，也可以构成整个制品。
根据共聚酯所需的最终用途可将各种常规添加剂加入到本发明的共聚酯中。适用于共聚酯的添加剂详细见述于美国专利5,608,031和5,773,554中，此处通过引用其整篇文献并入本文。通常用于共聚酯的各种添加剂包括颜料、抗氧化剂、稳定剂、阻燃剂、增韧剂、环氧化合物、脱模剂、成核剂、自由基稳定剂、润滑剂和其它加工助剂。
本发明的一种优选制品为纤维。此纤维可以制成本领域中公知的任何所需长度的形式，通常是做成长丝或短纤维的形式。通过任何常规的方式，包括(但不限于此)将共聚酯熔纺、熔体喷射或挤压成纤维形式可从本发明的共聚酯中制得纤维。根据其最终用途，采用本发明的共聚酯可做成任何所需纤度的纤维，包括纤度值为微旦至约50旦、优选高达约20旦的纤维。
共聚酯可用来制成本领域中公知的任何所需结构的粘合纤维。本发明的共聚酯优选为具有纤维状结构的粘合纤维。粘合纤维的主要优点是，仅通过采用加热、射频或超声频对未粘合的长丝棉胎进行施用处理，其形状不发生变化或仅发生少量变化即可获得粘合产物。实际上，本发明的共聚酯特别适用作为粘合纤维，因该共聚酯具有较低的I.V.，在低温下能得到更好的流动及软化性能。因此，当使用含有本发明共聚酯的粘合纤维时，在较低温度下可获得比先前已知粘合纤维粘合性能被改进的用于无纺织物的粘合纤维。实际上，从本发明共聚酯中制得的粘合纤维特别适用于粘合聚酯、丙烯酸、尼龙、玻璃、棉和洗净羊毛。通常采用本发明的共聚酯做成的粘合纤维为约1.5-约20旦。然而，其它纤维状形式如熔体喷射织物或纺纱粘合也可以具有微旦的尺寸。
本发明的粘合纤维可以是单组分粘合纤维的形式，而双组分外鞘或其它表面部分可采用本发明I.V.为约0.36-约0.58的共聚酯做成。挤压期间采用粘合剂材料封闭的截面拉丝(cross-sectional legs)的顶部可做成成形粘合纤维。
双组分粘合纤维可具有并排的皮/芯，或本领域中已知的结构。低熔融温度的双组分粘合纤维的制备及粘合的方法详细见述于美国专利3,589,956中，此处通过引用其整篇文献并入本文。在本发明双组分纤维中，本发明的共聚酯的量为双组分纤维的约10-约75％(重量)。其它组分可来自各种其它聚合材料，包括(但不限于此)各种聚酯如聚对苯二甲酸乙二酯或聚对苯二甲酸丁二酯。双组分粘合纤维可与其它纤维掺合，或单独使用以制备具有各种性能的无纺织物和高蓬松棉胎。双组分粘合纤维通常含有具有高熔点的聚合物以确保粘合过程中的结构完整性以及较低熔点或无定形聚合物以将基质粘合于无纺织物中。或者通过经济分析可确定使用极为廉价的心层材料。
来自本发明的粘合纤维很容易地与各种其它纤维进行掺合，随后加热或能量激活以提供具有良好整体性和强度的无纺织物。例如，掺合物中的其它纤维可以包括(但不限于此)聚酯、丙烯酸、尼龙、玻璃、纤维素(棉、纸浆基的纤维、纤维素酯纤维等)和其它类似的纤维。无纺织物中的掺合也有助于层压至其它纤维、薄膜和一些金属表面上。无纺掺合物中的粘合纤维的量通常为约5-约30％(重量)；然而也有100％粘合纤维用作织物形式的情况。
另一种可用本发明共聚酯制成的纤维结构是复合纤维，其可通过使聚烯烃或官能化的聚烯烃与本发明的共聚酯进行熔融掺合形成。可将熔融掺合的共聚酯/聚烯烃按纤维进行纺丝成纤维状结构。
本发明纤维状结构特别可用于加工成各种不同用途的无纺、针织和簇绒纺织品，但特别适用于生产粘合的无纺织物和纺织品(缝制或非缝制，可通过各种方法进行操作)。它们也适用于制造各种产品，包括(但不限于此)高蓬松棉胎、针刺织物、平无纺织物、hydroentangeled织物、缝编织物(以最大限度减少起球现象)、湿法成网(wet-laid)无纺织物和纸、过滤介质、面具、散射地毯、棉地毯、纤维绝缘材料、吸收材料、纤维玻璃复合材料、枕头填充材料、用于睡袋的填充材料、垫层、衬套、羊毛围巾、床罩、褥垫、褥垫填料、褥垫顶盖、家具和自动装饰、床单、用于工业及服装用途的绒头织物、覆盖材料、妇女长袍、运动衫、汽车盖布、内衬、外衣、地板覆盖材料、弹性砖片、地毯、足踏浴室垫、丝带和各种模塑制品。
本发明共聚酯的另一种适宜用途是作为共聚酯载体材料。例如，本发明的共聚酯可与色料或添加剂混合制得共聚酯载体材料，然后再与另一种聚合物进行配料。通过本领域中已知的任何适宜技术可将共聚酯进行掺合或混合。
                    实施例实施例1  用于粘合纤维的低催化剂、低I.V.共聚酯
对分别采用I.V.为0.59与低I.V.为0.47制成的共聚酯进行比较。采用较高I.V.为0.59制成的共聚酯使用具有高浓度的催化材料的催化剂体系进行制备。相反，采用低I.V.为0.47制成的共聚酯使用具有低浓度的催化材料的催化剂体系进行制备。
从1，4-环己烷二甲醇、1，2-亚乙基二醇和对邻苯二甲酸二甲酯制备含有约31％(摩尔)1，4-环己烷二甲醇和约69％(摩尔)的1，2-亚乙基二醇的低I.V.共聚酯。反应在二元醇组分过量的情况下进行。反应首先进行酯交换反应步骤，然后再进行缩聚反应步骤。酯交换反应在190℃-240℃的温度和15-40psig的压力下，在含有16ppm Ti(以钛酸四异丙基酯的形式)和46ppm Mn(以乙酸锰的形式)的催化剂体系的存在下进行。酯交换反应的产物再经历缩聚反应步骤，其中开始时温度为250℃-260℃，结束时温度为269℃-282℃。类似地，缩聚反应开始时的压力为75-200托，结束时为0.3-2.5托。在缩聚步骤开始前将少于约10ppm的兰色和红色蒽醌染料加入到催化剂体系中，还加入其量约为70ppm的P的包括来自Du Pont的Merpol A的催化抑制剂。
将较高I.V.的共聚酯(I.V.0.59)制备成其组成与低I.V.共聚酯相同。对于低I.V.共聚酯，反应首先进行酯交换反应步骤，接着进行缩聚反应步骤。酯交换反应在190℃-240℃的温度和15-40psig的压力下，在含有56ppm Ti(以钛酸四异丙基酯的形式)和46ppm Mn(以乙酸锰的形式)的催化剂体系的存在下进行。酯交换反应的产物再经历缩聚反应步骤，其中开始时温度为250℃-260℃，结束时温度为275℃-285℃。缩聚反应开始时的压力为75-200托，结束时为0.3-2.0托。需要使用较长的反应时间来获得较高I.V.的共聚酯。在开始缩聚步骤之前将56ppm的乙酸钴加入到催化剂体系中，还加入其量为79ppm的P的包括来自Du Pont的Merpol A的催化抑制剂。
使用HunterLab UltraScan光谱色度计用于评价及定量三种共聚酯的颜色及透明度。
                    表1
    IV     L*颜色     b*颜色
    0.47     69-72     -0.5-+0.5
    0.59     64.2     2.7
从表1中可看出，采用低的催化剂浓度体系制得的较低I.V.共聚酯具有优良的透明度及颜色。实施例2  分别采用低和高I.V.共聚酯制成的粘合纤维的粘合强度
在类似于实施例1的反应条件下，从1，4-环己烷二甲醇、1，2-亚乙基二醇和对苯二甲酸二甲酯中制备含有约31％(摩尔)1，4-环己烷二甲醇和约69％(摩尔)的1，2-亚乙基二醇的I.V.为0.47的共聚酯颗粒。用来形成低I.V.颗粒的催化剂体系含有35ppm Ti(以钛酸四异丙基酯的形式)和46ppm Mn(以乙酸锰的形式)及50ppm乙酸钴，而催化抑制剂则包括70ppm P的来自Du Pont的Merpol A。
I.V.为0.47的共聚酯颗粒在65℃下的旋转式干燥器中干燥4小时。通过将该颗粒熔融挤压成9旦/单丝的复丝纤维从低和高I.V.共聚酯颗粒中制成单组分粘合纤维。采用具有332孔(0.55毫米小孔)的喷丝板、熔融温度为233℃和卷绕速度为100m/m做成长丝。将来自实施例1的I.V.为0.59的共聚酯颗粒类似地做成单组分粘合纤维，不同之处在于颗粒在275℃的熔融温度下进行纺丝。
随后将初纺纤维在一2-阶段过程(70℃水，然后是加热室)中牵伸，3∶1的总牵伸比，填塞箱以7卷曲/英寸和88°的卷曲角进行卷曲。然后所得3旦的长丝纤维用水基整理剂进行润滑并在烘箱中干燥。
使低I.V.为0.49与高I.V.为0.59的共聚酯单组分粘合纤维与75％聚对苯二甲酸乙二酯纤维混合制成3oz/yd2紧密掺合的粗梳无纺织物。活化无纺织物并进行粘合强度测试，将紧密掺合的无纺织物粘合到一压机上，上下两块加热板在压力下接触无纺织物。在200-275°F的温度下活化30秒。采用1英寸宽的窄条来获得在5英寸计量长度的英斯特朗电子强力。粘合强度测试结果详细示于下表2中。
                              表2
                        PET/单组分无纺织物样品
            无纺织物w/从0.47I.V.共聚酯中制成的粘合纤维
活化温度，°F  平均断裂力，克  平均伸长率，％  平均模量，克
    200     333     12.0     12,637
    225     820     4.1     61,637
    250     2899     15.3     116,625
    275     4837     22.6     97,984
             无纺织物w/从0.59I.V.共聚酯中制成的粘合纤维
活化温度，°F  平均断裂力，克  平均伸长率，％  平均模量，克
    200     35     18.5     481
    225     196     5.0     9,273
    250     617     6.9     29,340
    275     2366     15.4     71,949
采用具有35％0.41I.V.的共聚酯粘合剂外鞘和65％聚对苯二甲酸乙二酯芯层(约为4旦)的共挤塑皮/芯双组分粘合纤维进行类似的测试。获得类似的结果。实施例3  粘合纤维的粘合强度测试
从含有31％(摩尔)1，4-环己烷二甲醇和69％1，2-亚乙基二醇的对苯二甲酸酯共聚酯和含有100％(摩尔)对苯二甲酸二甲酯的二羧酸组分中制成单组分粘合纤维。
从在具有低水平催化材料的催化剂体系的存在下制成的第一种共聚酯中制成第一种单组分粘合纤维。对于第一种共聚酯而言，在含有35ppm Ti(以钛酸四异丙基酯的形式)和46ppm Mn(以乙酸锰的形式)的催化剂体系的存在下进行酯交换反应步骤。在开始缩聚步骤之前，将50ppm Co(以乙酸钴的形式)加入到催化剂体系中并加入其量为70ppm P的包括来自Du Pont的Merpol A的催化抑制剂。所制成的第一种共聚酯的I.V.为0.47，纤度约为3。
从实施例1的I.V.为0.47的共聚酯颗粒中制成第二种单组分粘合纤维。在较低浓度催化剂体系的存在下制成实施例1的I.V.为0.47的共聚酯颗粒。第二种单组分粘合纤维的纤度约为3。
将第一种和第二种单组分粘合纤维与纤度为6的聚对苯二甲酸乙二酯纤维混合成无纺织物。该粘合纤维包括25％无纺织物，聚对苯二甲酸乙二酯纤维纤维包括剩余的75％。活化含有粘合纤维的无纺织物并通过上述实施例2中的程序进行粘合强度测试，不同之处在于上下板留有空隙以便进行轻微接触，在压力表上没有压力显示。粘合强度测试的结果示于下表3中。
                          表3
           无纺织物w/从第一种共聚酯中制成的粘合纤维
活化温度，°F  平均断裂力，克  平均伸长率，％  平均模量，克
    300     2,591     18     31,636
    325     2,476     26     17,340
           无纺织物w/从第二种共聚酯中制成的粘合纤维
活化温度，°F  平均断裂力，克  平均伸长率，％  平均模量，克
    300     2,434     17     45,586
    325     2,661     21     27,966
如上表3中所示，使用本发明范畴内的不同水平的催化剂材料对采用类似的特性粘度制备的粘合纤维的粘合强度并未显示显著的影响。实施例4
从含有3 1％(摩尔)的1，4-环己烷二甲醇和69％的1，2-亚乙基二醇的共聚酯和含有100％(摩尔)对邻苯二甲酸二甲酯的二羧酸组分中制成单组分粘合纤维。从实施例3的低I.V.、较低催化剂的第二种共聚酯中制得第一种单组分粘合纤维。从实施例1的I.V.为0.59的共聚酯中制得第二种单组分粘合纤维。通过实施例2中所述的过程制得第一种和第二种单组分粘合纤维。从第一种和第二种单组分粘合纤维中通过实施例2中所述过程制成紧密掺合的粗梳无纺织物。类似于实施例3中所述进行粘合强度测试。粘合强度测试结果示于下表4中。
                          表4
            无纺织物w/从0.47I.V.共聚酯中制成的粘合纤维
活化温度，°F  平均断裂力，克  平均伸长率，％  平均模量，克
    225     133     7     5,841
    250     393     6     15,827
    275     883     12     29,362
    300     2434     17     45,586
    325     2,661     21     27,966
         无纺织物w/从0.59I.V.共聚酯中制成的粘合纤维
活化温度，°F  平均断裂力，克  平均伸长率，％  平均模量，克
    225     45     20     652
    250     219     5     7,947
    275     590     12     15,372
    300     1,748     22     20,433
    325     2,640     29     17,902
如表4中所示，在较低的活化温度下采用较低I.V.0.47制成的粘合纤维具有较高的粘合强度。实施例5  含有1，4-环己烷二甲醇30/70的顺式/反式混合物的低粘度
     PET共聚酯
从二元醇组分和二羧酸组分中制成聚对苯二甲酸乙二酯共聚酯。二元醇组分含有31％(摩尔)的1，4-环己烷二甲醇30/70顺式/反式混合物和69％(摩尔)的1，2-亚乙基二醇。二羧酸组分含有100％(摩尔)对苯二甲酸二甲酯。通过熔融相缩聚过程，采用含有32ppm Ti、46ppmMn、50ppm Co和70ppm P的催化剂体系制备聚对苯二甲酸乙二酯共聚酯。所得的聚对苯二甲酸乙二酯共聚酯的I.V.为0.50。
该共聚酯的颗粒在60℃下干燥2小时，然后采用具有332孔(0.55毫米小孔)的喷丝板、卷绕速度为1000m/m、熔纺温度为240℃、挤压速率为43磅/小时将其熔融挤压成9旦/单丝的复丝纤维。挤压期间采用145英尺3/分的速度来使长丝急冷。随后初纺纤维在一1-阶段拉丝过程(采用68℃的水浴)中进行牵伸。用填塞箱对纤维进行卷曲以提供7.5卷曲/英寸并采用9.5psi的自动活门(clapper setting)(没有直接蒸汽)提供90°的卷曲角。纤维在松弛的状态下在60℃下干燥2分钟。所得的短纤维经测定具有3旦/单丝。
当共聚酯在纺丝操作之前不进行干燥时可获得类似良好的结果。
从含有22％(摩尔)CHDM(I.V.为0.40)或45％(摩尔)CHDM(I.V.为0.49)的PET共聚酯中也很容易地制得纤维。实施例6  无纺织物的制备
将得自实施例5的3旦/单丝的单组分粘合纤维与聚对苯二甲酸乙二酯短纤维(21/4旦/单丝)掺合以提供含有20％(重量)粘合纤维的掺合物。通过粗梳得到1-1/4 oz/yd2紧密掺合的无纺织物。通过将该织物输送通过红外线烘箱然后进行热压轧(80℃)使无纺织物粘合。得到良好的纵向拉伸强度和横向拉伸强度以及悬垂性。
通过将织物从粗梳机经150℃的气流烘箱停留2分钟也可获得良好的粘合效果。
得自本发明组合物的粘合纤维经确定证明可被超声和射频所活化。实施例7  鲜艳着色无纺织物的制备
类似于实施例6制备1-1/2 oz/yd2无纺织物纤维，但基质聚酯被染成红色。由得自实施例5的单组分粘合纤维所提供的明亮、非不透明粘合对色泽的亮度影响程度极小。与间苯二酸改性的聚对苯二甲酸乙二酯共聚酯粘合纤维(通常是更为不透明并且在干的物品上经常导致低光泽和模糊的外观)相比这是一个优点。实施例8  皮/芯双组分纤维
采用聚对苯二甲酸乙二酯均聚物(I.V.为0.54)作为芯层和类似于实施例5中的聚对苯二甲酸乙二酯共聚酯(I.V.为0.41)作为外鞘制备50/50皮/芯双组分纤维。双组分纤维如下制成：将已结晶的PET干燥颗粒熔融于压出机中并在295℃的熔融温度下作为芯层送料。将PET共聚酯的干燥颗粒转移到进料外鞘熔融物流的压出机的进料斗中。外鞘物流在225℃的熔融温度下进行挤压。熔融的物流经过一具有皮/芯孔结构的喷丝板进行共挤压，调节其进料速率以得到具有50％共聚酯外鞘/50％PET芯层的纤维。以长丝和短纤维的形式也制备类似的35/65皮/芯双组分纤维。将纤维用牵引辊速度拉伸成4旦/单丝的纤维，然后再进行卷曲并切成短纤维(51毫米长)。
这些双组分粘合纤维可用于制备与聚对苯二甲酸乙二酯和/或其它基质短纤维结合的无纺织物和高蓬松棉胎。这些粘合纤维也可以以100％的形式使用。

Claims (25)

1.一种包括从二元醇组分与二羧酸组分的反应产物制成的共聚酯的粘合纤维，其中所述二元醇组分包括10-60％(摩尔)的1，4-环己烷二甲醇和约40-约90％(摩尔)的1，2-亚乙基二醇，其中至少约90％(摩尔)的二羧酸组分选自对苯二酸、萘二甲酸、1，4-环己烷二羧酸的酸、酯或酸酐及其各种混合物，其中所述共聚酯的I.V.为约0.36-0.58。
2.权利要求1的粘合纤维，其中在低于约275°F的活化温度下，此粘合纤维具有比从I.V.不低于0.6的共聚酯中制成的粘合纤维更为优良的粘合强度。
3.权利要求1的粘合纤维，其中此粘合纤维可被超声和射频所活化。
4.权利要求1的粘合纤维，其中此粘合纤维的纤度(denier)为约1-约20。
5.权利要求1的粘合纤维，其中此粘合纤维为单组分粘合纤维。
6.权利要求1的粘合纤维，其中此粘合纤维为双组分粘合纤维。
7.一种包括二元醇组分与二羧酸组分的反应产物的共聚酯，其中所述二元醇组分包括10-60％(摩尔)的1，4-环己烷二甲醇和约40-约90％(摩尔)的1，2-亚乙基二醇，其中至少约90％(摩尔)的二羧酸组分选自对苯二酸、萘二甲酸、1，4-环己烷二羧酸的酸、酯或酸酐及其各种混合物，其中所述共聚酯的I.V.为约0.36-0.58。
8.根据权利要求7的共聚酯，其中L*值大于约65，b*值为约-2.5-约+2.5。
9.根据权利要求7的共聚酯，其中所述二羧酸组分为对苯二酸、萘二甲酸或1，4-环己烷二羧酸的酯或酯的混合物。
10.根据权利要求7的共聚酯，其中在包括约10-约35ppm Ti、约30-约70ppm Mn、约0-约90ppm Co的催化剂体系的存在下以及在包括约40-约90ppm P(基于共聚酯的重量计)的催化抑制剂的存在下生成共聚酯。
11.根据权利要求7的共聚酯，还包括高达所述二羧酸组分10％(摩尔)的其它二羧酸组分，其中此其它二羧酸组分选自具有约8-14个碳原子的芳族二羧酸、具有约4-12个碳原子的脂族二羧酸、具有约8-12个碳原子的环脂族二羧酸及其各种酯或酸酐。
12.根据权利要求7的共聚酯，其中所述二元醇组分包括20-40％(摩尔)的1，4-环己烷二甲醇和约60-约80％(摩尔)的1，2-亚乙基二醇。
13.根据权利要求7的共聚酯，其中所述二元醇组分包括25-35％(摩尔)的1，4-环己烷二甲醇和约65-约75％(摩尔)的1，2-亚乙基二醇。
14.根据权利要求7的共聚酯，其中所述二元醇组分含有高达20％(摩尔)的二甘醇。
15.根据权利要求7的共聚酯，其中I.V.值为约0.41-0.49。
16.根据权利要求7的共聚酯，其中在支化剂的存在下制成所述共聚酯。
17.根据权利要求7的共聚酯，其中在低于约270℃的温度下所述共聚酯能够被熔纺成纤维。
18.一种共聚酯组合物，它包括根据权利要求7的共聚酯和选自以下的添加剂：颜料、色料、稳定剂、抗氧化剂、挤压助剂、滑爽剂、碳黑、成核剂、阻燃剂、填料、导电材料及其各种混合物。
19.根据权利要求7的共聚酯，其中此共聚酯是纤维状的形式。
20.根据权利要求19的共聚酯，其中此共聚酯的纤维状形式具有从20-微旦大小的纤度。
21.一种纤维状结构，它包括由聚烯烃或官能化的聚烯烃与权利要求7的共聚酯进行熔融掺合所制成的纤维。
22.一种包括二元醇组分与二羧酸组分的反应产物的共聚酯，其中所述二元醇组分包括10-60％(摩尔)的1，4-环己烷二甲醇和约40-约90％(摩尔)的1，2-亚乙基二醇，其中至少约90％(摩尔)的二羧酸组分选自对苯二酸、萘二甲酸、1，4-环己烷二羧酸的酸、酯或酸酐及其各种混合物，其中在包括约10-约35ppm Ti的催化剂体系的存在下制成共聚酯，其中所述共聚酯的I.V.为约0.36-0.58。
23.一种用于生产共聚酯的催化剂体系，它包括：
包括约10-约35ppm Ti和约30-约70ppm Mn的催化材料；包括约40-约90ppm P的催化抑制剂；和有效量的色料以得到所需的颜色；其中催化材料在催化剂体系中的总量不超过约125ppm，其中各种催化剂体系组分的量基于采用此催化剂体系制成的共聚酯产物的重量计。
24.权利要求23的催化剂体系，其中催化材料在催化剂体系中的总量不超过100ppm。
25.权利要求23的催化剂体系，其中催化剂基本上不含Sb和Zn催化剂。
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US6139954A (en) 2000-10-31
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CN1146679C (zh) 2004-04-21
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