CN1091806C - 抗切割纤维,抗切割皮芯纤维及其用途 - Google Patents

抗切割纤维,抗切割皮芯纤维及其用途 Download PDF

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Publication number
CN1091806C
CN1091806C CN97122712A CN97122712A CN1091806C CN 1091806 C CN1091806 C CN 1091806C CN 97122712 A CN97122712 A CN 97122712A CN 97122712 A CN97122712 A CN 97122712A CN 1091806 C CN1091806 C CN 1091806C
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Prior art keywords
filler
fibre
fiber
cutting
polymer
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Expired - Fee Related
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CN97122712A
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CN1182811A (zh
Inventor
R·B·萨多尔
M·C·卡特
G·E·吉伯格－拉福斯
W·F·科里尔
J·A·富怀特
H·L·拉尼伟
S·W·汤普森
E·O·奥克利
E·R·卡切斯基
M·I·海德尔
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CNA Holdings LLC
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Hoechst Celanese Corp
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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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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    • A41D19/01511—Protective gloves resistant to mechanical aggressions, e.g. cutting. piercing made of wire-mesh, e.g. butchers' gloves
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    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
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Abstract

一种具有提高了抗切割性的纤维由成纤聚合物和莫氏硬度值大于约3的硬质填料制成。该填料的含量约为0.05%至约20%(重量)。在优选的实施方案中，该成纤聚合物是聚(对苯二甲酸乙二醇酯)或包括由6-羟基-2-萘甲酸和4-羟基苯甲酸衍生的单体单元的液晶聚酯。优选的填料包括钨和氧化铝。

Description

抗切割纤维，抗切割皮芯纤维及其用途
本申请是1994年5月16日提交的共同未决的美国专利申请08/243,344的部分继续申请，该申请是1992年11月24日提交的现已放弃的美国专利申请07/980,813的部分继续申请；本申请也是1995年6月7日提交的共同未决的美国专利申请08/482,207的部分继续申请。1995年6月7日提交的美国专利申请08/484,544和08/481,020都是美国专利申请08/243,344的一部分，该申请也包含有关本主题的内容。
本发明涉及由含有硬微粒的聚合物制成的纤维，这种纤维具有改进了的抗切割性。
关于抗利刃切割性的改进已探索了很长时间。抗切割的手套有利于在肉类加工工业和车辆制造业中使用。如美国专利4,004,295、4,384,449和4,470,251以及EP 458,343所指出，具备抗切割性的手套已由包含柔韧金属丝或包含高取向纤维的纱线制成，所述纤维具有高模量和高抗张强度，它们是例如芳族聚酰胺、热致变的液晶聚合物和伸长链的聚乙烯。
由包含柔韧金属丝的纱线制成的手套的缺点是手部疲劳而导致生产率降低和可能增加受伤。此外，由于持续的磨损和褶曲，可能使金属丝疲劳和断裂，从而造成手部割伤或擦伤。另外，当洗涤过的手套在高温下干燥时，金属丝会起热壑的作用，这会使纱线或纤维的抗张强度降低，从而降低手套的防护作用和手套的使用寿命。
就抗切割的防护用品而言，改进了的柔韧性和舒适性以及洗涤简便是所希望的。因此，需要有一种在日常洗涤后仍能保持其特性的柔韧抗切割纤维。这种纤维有利于用以生产防护用品特别是高度柔韧的抗切割手套。
已经有人将聚合物与微粒物质混合而制成纤维，但是并没有显著地改进纤维的抗切割性。例如，已将少量二氧化钛微粒用于聚酯纤维中作为褪光剂。也有人在聚酯纤维中使用少量胶体二氧化硅采提高光泽。已将磁性材料掺入纤维中以产生磁性纤维。一些实例包括：如公开的日本专利申请55/098909(1980)中的热塑性纤维中的钴/稀土元素金属互化物；公开的日本专利申请3-130413(1991)中所述的皮芯纤维中的钴/稀土元素金属互化物或铁酸锶；以及波兰专利251,452和K.Turek et al.，J.Magn.Magn.Mater.(1990)，83(1-3)，pp.279-280中所述的热塑性聚合物中的磁性材料。
已制成各种手套，在制作手套时已将金属包含在其中使手套具有防护性能。例如，美国专利2,328,105和3,185,751讲述了柔韧的遮挡X-射线的手套可以通过用磨细的重金属例如可以是铅、钡、铋或钨处理适宜的多孔片材制得，或可以由含有重金属微粒的胶乳或分散体制得。又如美国专利5,020,161所述，能防腐蚀性液体的手套可以用金属薄膜层制得。这些手套的抗切割性也未表现出显著的改进。
抗切割纤维和基于该纤维的纱线用成纤聚合物为原料并通过将均匀分布的硬质填料包含在该纤维中制成。该硬质填料具有的莫氏硬度值约大于3，且其用量约为0.05％至约20％(重量)。当采用下述Ashland防切割性能测试法(Ashland Cut Protection Performance Test)时，与没有硬质填料的相同纤维相比该纤维的抗切割性至少提高10％。还讲述了制作抗切割织物的方法。在该方法中，先配制一种成纤聚合物和约为0.05％至约20％(重量)、莫氏硬度值约大于3的硬质填料的均匀混合物。将该均匀混合物纺成纤维或纱线，然后将其织成织物，与由没有硬质填料的相同成纤聚合物织成的织物相比，该织物具有改进了的抗切割性。该抗切割织物也可以任选包括其他聚合纤维和/或例如可以是陶瓷、金属或玻璃的无机增强纤维。
还公开了一种生产更能抗利刃切割的合成纤维或纱线的新方法。该改进了的方法包括将具有莫氏硬度值大于3的足够量的硬质填料包含在该合成纤维或纱线中的步骤，以便使该纤维或纱线用Ashland防切割性能测试法测定时其抗切割性至少提高20％，优选至少提高35％。该方法一般是通过先配制熔融的聚合物或聚合物溶液(纺丝原液)的均匀混合物，然后将该熔融的聚合物或聚合物溶液(纺丝原液)纺成具有改进了抗切割性的纤维或纱线实现的。优选的方法是熔融纺丝法。
采用当今用于将纤维和纱线织成织物的任一种方法包括机织法和针织法，可将上述纤维和纱线织成具有改进了抗切割性的织物。也可以将该纤维和纱线制成具有改进了抗切割性的无纺织物。这种织物和织成抗切割织物的方法以及所得的织物都是新颖的。此外，可将该抗切割织物制成具有改进了抗切割性的防护用品例如抗刀切割的手套。
如上所述，当将硬质填料包含在纤维中时，可制得对生产防护用品有用的柔韧性抗切割纤维。该纤维可以用任一种成纤聚合物制成，并可采用任一种常用于制造纤维的方法进行生产。优选的聚合物是可熔融加工的，在这种情况下，通常采用熔融纺丝法生产抗切割纤维。对于不能呈熔体纺成纤维的聚合物而言，也可以采用湿法纺丝或干法纺丝以生产具有改进了抗切割性的纤维。无定形聚合物、半晶质的聚合物以及液晶聚合物均可用于本发明。其中，优选的是半晶质的聚合物和液晶聚合物。
本发明的说明书是针对纤维而编写的。该术语“纤维”不仅包括常规的单纤维和长丝，而且也包括由多重纤维制成的纱线。在生产防护用品、织物等时通常采用纱线。
在本发明的一个优选实施方案中，成纤聚合物是各向同性的半晶质聚合物。“各向同性的”所指的聚合物不是各向异性的液晶聚合物。优选的各向同性半晶质聚合物是可熔融加工的；即它可以在一定的温度范围内熔融，从而可使该聚合物呈熔相且在没有显著分解的情况下纺成纤维。非常有用的半晶质聚合物包括聚(对苯二甲酸烷二醇酯)、聚(萘二甲酸烷二醇酯)、聚(亚芳基硫醚)、脂族和脂族-芳族的聚酰胺以及包括由环己烷二甲醇和对苯二甲酸衍生的单体单元的聚酯。具体的半晶质聚合物的实例包括聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸丁二醇酯)、聚(萘二甲酸乙二醇酯)、聚(亚苯基硫醚)、聚(1，4-环己烷二甲醇对苯二甲酸酯)，其中1，4-环己烷二甲醇是顺式和反式异构体的混合物，尼龙-6和尼龙-66。聚烯烃，特别是聚乙烯和聚丙烯是可以用于本发明的另一类半晶质聚合物。具有高拉伸模量的伸长链的聚乙烯是通过将很高或超高分子量聚乙烯进行凝胶纺丝或熔融纺丝制得的。伸长链的聚乙烯已具有高的抗切割性，但是，根据本发明通过将微粒添加到该纤维中可制得抗切割性更高的纤维。众所周知，上述所有的聚合物均可用于制造纤维，且均可在市场上买到。优选的半晶质各向同性的聚合物是聚(对苯二甲酸乙二醇酯)。也可以采用不能呈熔体加工的各向同性的聚合物，例如通常用丙酮作为溶剂干法纺成的人造丝和乙酸纤维素，和通常采用N，N’-二甲基乙酰胺作为溶剂湿纺的通常称为聚苯并咪唑的聚[2，2’-(间亚苯基)-5，5’-双苯并咪唑]。除了对苯二甲酸和对苯二胺的聚合物以外的芳族聚酰胺(例如对苯二甲酸和一种或多种芳族二胺的聚合物)可以溶于极性的非质子传递溶剂，例如N-甲基吡咯烷酮(N-methylpyrrolidinone)，且可与添加的微粒一起湿纺，以得到抗切割的纤维。无定形、非晶性的各向同性的聚合物，例如间苯二甲酸、对苯二甲酸和双酚A(多芳基化合物)的共聚物也可加以充填，并可用于本发明。
在另一个优选的实施方案中，纤维由液晶聚合物(LCP)制成。LCP使纤维具有很高的抗张强度和/或模量。该液晶聚合物是可以呈熔体加工的(即热致变的)，在此情况下，熔融纺丝法是生产该纤维的优选方法。然而，也可以采用不能呈熔体加工的聚合物。因此，根据本发明可将显示液晶性能的聚合物在溶液状态下与硬质填料混合，然后可以进行湿纺或干纺以得到抗切割纤维。例如，如果硬质填料不与溶剂反应或不溶于溶剂中，那么，可在由对苯二胺和对苯二甲酸制得的芳族聚酰胺(例如以商标KEVLAR出售的聚合物)中添加填料并进行湿纺(即采用从浓硫酸中干喷湿纺法)以得到抗切割纤维。其它能溶于极生的非质子传递溶剂例如N-甲基吡咯烷酮中的芳族聚酰胺也可以根据本发明纺成抗切割纤维。参见实施例10。这些芳族聚酰胺在某些或所有情况下可能不是液晶的，但是仍然可以将它们制成高模量的纤维。在某些浓度下或某些溶剂中，它们有一些可以显示出感胶液晶相，但是在其它浓度下或其它溶剂中却是各向同性的溶液。
优选用于本发明的液晶聚合物(LCP)是热致变的LCP。这些热致变的LCP包括芳族聚酯、脂族-芳族聚酯、芳族聚(酯酰胺)、脂族-芳族聚(酯酰胺)、芳族聚(酯亚胺)、芳族聚(酯碳酸酯)、芳族聚酰胺、脂族-芳族聚酰胺以及聚(偶氮甲碱)。优选的热致变LCP是在低于约360℃的温度下形成液晶熔相的芳族聚酯和聚(酯酰胺)，且包括由对苯二甲酸、间苯二甲酸、1，4-氢醌、间苯二酚、4，4’-二羟基联苯、4，4’-联苯二羧酸、4-羟基苯甲酸、6-羟基-2-萘甲酸、2，6-萘二甲酸、2，6-二羟基萘、4-氨基苯酚和4-氨基苯甲酸衍生的一种或多种单体单元。有些芳基可以包括在聚合条件下不会反应的取代基例如具有1-4个碳的低级烷基、芳基、F、Cl、Br和I。在美国专利4,473,682、4,522,974、4,375,530、4,318,841、4,256,624、4,161,470、4,219,461、4,083,829、4,184,996、4,279,803、4,337,190、4,355,134、4,429,105、4,393,191以及4,421,908中讲述了一些典型的芳族聚酯的合成和结构。在美国专利4,339,375、4,355,132、4,351,917、4,330,457,、4,351,918以及5,204,443中讲述了一些典型的芳族聚(酯酰胺)的合成和结构。芳族液晶聚酯和聚(酯酰胺)可按商标VECTRA从Hoechst Celanese Corporation以及从其它制造商买到。
如美国专利4,161,470所述，最优选的液晶聚酯包括由4-羟基苯甲酸和6-羟基-2-萘甲酸衍生的单体重复单元。优选的由4-羟基苯甲酸衍生的单体单元占该聚合物的约15％至约85％(以摩尔计)，而由6-羟基2-萘甲酸衍生的单体单元占该聚合物的约85％至约15％(以摩尔计)。最优选的聚合物包括约73％由4-羟基苯甲酸衍生的单体单元和约27％由6-羟基-2-萘甲酸衍生的单体单元(均以摩尔计)。这种呈纤维形式的聚合物可按商标VECTRAN从Hoechst Celanese Corporation，Charlotte，North Carolina买到。
其它优选的液晶聚酯或聚(酯酰胺)包括上述由6-羟基-2-萘甲酸和由4-羟基苯甲酸衍生的单体单元以及由一种或多种下列单体衍生的单体单元：4，4’-二羟基联苯、对苯二甲酸和4-氨基苯酚。如美国专利4,473,682所述，优选的包括这些单体单元的聚酯是由4-羟基苯甲酸、6-羟基-2-萘甲酸、4，4’-联苯酚和对苯二甲酸衍生的，特别优选的是包括摩尔比约为60∶4∶18∶18的这些单体单元的聚合物。
如美国专利5,204,443所述，优选的聚(酯酰胺)包括由4-羟基苯甲酸、6-羟基-2-萘甲酸、对苯二甲酸、4，4’-联苯酚和4-氨基苯酚衍生的单体单元；特别优选的组合物包括摩尔比约为60∶3.5∶18.25∶13.25∶5的这些单体单元。
本发明的一个重要的方面是发现了柔韧、耐挠曲疲劳和抗切割的纤维可以由能赋予抗切割性的硬质材料充填的适宜聚合物制成。这种材料可以是金属例如元素金属或金属合金或可以是非金属。通常，具有莫氏硬度值约为3或更高的任一种填料均可采用。特别适宜的填料具有莫氏硬度值大于约4，优选大于约5。铁、钢、钨和镍是金属和金属合金的说明性实例，莫氏硬度值约为6.5至约7.5的钨是优选的。也可以采用非金属材料。它们包括但不限于金属氧化物例如氧化铝、金属碳化物例如碳化钨、金属氮化物、金属硫化物、金属硅酸盐、金属硅化物、金属硫酸盐、金属磷酸盐以及金属硼化物。其它实例包括二氧化硅和碳化硅。其它陶瓷材料也可以采用。在半晶质聚合物中不太优选的是二氧化钛和二氧化硅。
为了在保持纤维的机械性能的同时又能获得满意的抗切割性，粒度、粒度分布和微粒的数量都是重要的参数。可以采用微粒状的填料，而粉状填料通常是适宜的。也可以采用扁平的微粒(即小片状体)和细长的微粒(即针状体)。对扁平或细长的微粒而言，粒度是指沿该微粒长轴的长度(即细长微粒的长尺寸或小片状体表面的平均直径)。根据加工方法和纤维的直径选择适宜的粒度。填料微粒必须小到足以使其易于通过喷丝嘴的孔。该微粒还应足够地小到不致使纤维的抗张性能显著地降低。对纺织纤维(即具有约1.5至约15dpf旦尼尔的纤维)而言，应将该微粒过滤或筛分以除去大于约6微米的微粒。通常，该微粒的平均直径应小于约20微米，优选约为0.05至约5微米，而在特定情况下约为0.2至约2微米。对细长的微粒而言，其长尺寸应适合于通过喷丝嘴的孔。因此，细长微粒的平均颗粒长度应小于约20微米，优选约为0.05至约5微米，而在特定情况下约为0.2至约2微米。以上是通常情况下对充填了的聚合物的普遍规则。对热塑性半晶质各向同性的聚合物中的硬质微粒进一步试验表明，至少对各向同性的半晶质聚合物特别是对最优选的实施方案(PET中的煅烧氧化铝)而言，产生最佳抗切割性的粒度范围约为0.25至约10微米，优选约为1至约6微米，最优选约为3微米。该粒度应具有对数正态分布。
采用较小百分数的硬质填料。其用量根据在不造成抗张性能显著降低而能使抗切割性增强的情况下选择。采用Ashland防切割性能测试法或其它在工业上普遍认可的测试法测定时，该纤维或由该纤维织成的织物的抗切割性得到了提高，优选提高至少10％。采用上述方法，特别是Ashland防切割性能测试法测定时，优选其抗切割性至少提高20％，更优选至少提高35％，最优选至少提高50％。在实施例3中叙述了用于液晶聚合物纤维的这类测试，而实施例4中叙述了用于各向同性聚合物和LCP的纤维的这类测试。纤维的抗张性能(强度和模量)不应降低到超过约50％，优选降低不超过约25％。最优选在抗张性能上没有显著的变化(即在性能上的降低小于约10％)。以重量计，填料的含量约为0.05％至约20％，优选约为0.1％至约20％。以填料量在上述重量范围内为条件，按体积计，填料量典型地约为0.01％至约3％，通常约为0.03％至约1.5％，而在特定情况下可以约为0.05％至约1％。因此，对高密度填料例如聚(对苯二甲酸乙二醇酯)中的钨粉而言，相当于上述体积百分数而以重量表示的填料量通常约为0.14％至约20％，优选约为0.42％至约20％，更优选约为0.7％至约14％。对PET而言，采用约为0.7％(体积)，相当于约10％(重量)的钨填料可以得到满意的抗切割性。对热致变的液晶聚合物而言，当填料为钨时，采用约为0.07％至约0.14％(体积)相当于约1％至约2％(重量)的填料可以得到改进了的抗切割性。
用各向同性的半晶质聚合物的进一步试验表明，为达到高的抗切割性所需的微粒量的较好估计值如下：以体积计，微粒含量优选为约0.1％至约5％(体积)，更优选为约0.5％至约3％(体积)，最优选为约2.1％(体积)。对最优选的实施方案(PET中的煅烧氧化铝)而言，上述含量范围以重量计优选约为0.3％至约14％，更优选约为1.4％至约8.5％，最优选约为6％。
根据本发明，充填了的纤维由填充树脂制成。该填充树脂是通过将填料添加到树脂中的任一种标准方法制得的。例如，对热塑性聚合物而言，填充树脂可方便地在挤出机例如双螺杆挤出机中通过将硬质填料与熔融的聚合物在足以使填料均匀地分布于树脂中的条件下混合而制得。该填料也可以在生产这种聚合物时就已存在于其中，或可在将聚合物供入纤维纺丝装置的挤出机时将填料加入，在这种情况下，混合和纺丝步骤几乎同时进行。
除了因纤维纺丝时的定向力使细长和扁平的微粒在某种程度上定向分布外，由于填料在聚合物熔体中是均匀分布的，因此，该填料微粒通常在整个纤维中也是均匀分布的。也可能出现一些微粒向着纤维表面迁移的现象。因此，尽管把纤维中的微粒分布说成是“均匀的”，然而，“均匀的”这个词应理解为包括在均匀的聚合物混合物的加工(例如熔融纺丝)过程中出现的不均匀性。这样的纤维仍属于本发明的范围。
根据本发明可以制成任一种细度的纤维。在生产织物和纱线时，纤维的旦尼尔通常约为1至约50dpf，优选约为2至约20dpf，更优选约为3至约15dpf。对各向同性聚合物特别是对充填了的PET而言，纤维的细度优选约为1.5至约15dpf，最优选约为4dpf。抗切割的单丝也可以通过加入硬质填料制得。单丝通常具有约0.05至约2mm的直径。这种纤维可通过常规的纤维纺丝方法制得。优选的方法是熔融纺丝法，但是也可以采用湿纺法和干纺法。
抗切割的织物可以采用针织、机织或其它方法利用本发明的充填了的纤维通过常规的方法和机器织成。也可以制成无纺织物。与采用没有填料的同一种聚合物生产的纤维制得的同样织物相比，这类织物的抗切割性有了改进。通常，当采用工业上普遍认可的用于测定抗切割性的测试方法(Ashland防切割性能测试法)测定时，抗切割性提高至少约10％，优选提高至少20％、35％或甚至50％。
然后可由上述抗切割织物制成抗切割的用品。例如可以由这种织物生产设计成可用于食品加工工业的抗切割安全手套。这种手套非常柔韧而且易于清洗。该充填了的纤维耐挠曲疲劳。医用防护手套也可以采用本发明的抗切割纤维制得。这些防护手套可以由本文所述的纤维和纱线制成的织物(机织、针织或无纺的)缝合而成。或者，由包括该纤维的连续纱线直接针织成手套，或可将一些织物片附加在手套上，以保护最容易受伤的手的部位(如手掌或手指)。这类织物和单丝的其它用途包括用于卡车的侧帘和防雨帆布、软面提箱、商用室内装璜、可充气的用品、燃料箱、可折叠的包装、空运货物帘布、灭火水龙带护皮、用于金属包装的围裙、皮护腿套裤等。
也可以用本文所述的抗切割纤维材料代替常规方法制成的抗切割织物、手套等中未充填的聚合纤维，以得到更高的抗切割性。因此，与采用常规纤维的相同织物相比，利用本文所述的充填了的纤维并按现有技术加入无机增强纤维例如金属、玻璃或陶瓷纤维进一步增强了的抗切割织物应具有更高的抗切割性。这类织物可由本文公开的几股充填了的纤维与几股金属、玻璃或陶瓷增强纤维混合而成的复合纱线制成，或由充填了的纤维的纱线与金属、玻璃或陶瓷纤维的纱线以加捻或不加捻的方式组合而成。或者，将增强纤维作为绕有本文公开的抗切割纤维的芯子，或将增强纤维缠绕在包括本文所述的充填了的抗切割纤维的芯子周围。常规纤维和增强纤维的复合抗切割纱线在本领域的从业人员中是众所周知的，因而可以容易地适应于利用本文所述的充填了的纤维代替常规纤维。“复合纱线”是常用来说明由两种不同纱线以加捻或不加捻方式组合而成的纱线的措词。如上所定义的复合纱线在商业上也称为“组合纱线”。
                实施例1.制备充填了的LCP
按现在所述的方法制备充填了钨粉、可熔融加工的LCP。将LCP(粒状，95％(重量)，Hoechst Celanese Corporation生产，注册商标为VECTRAA910)和钨粉(平均粒度0.5微米，5％(重量))在大于100℃的温度下干燥，然后混合。将所得的混合物添加到Werner and Pfleiderer 28mmZSK挤出机(双螺杆型)的振动给料器的加料斗中，经过振动槽供入挤出机。该挤出机的给料器、振动槽和注入口均处于正压氮气流中。在温度为305-310℃下含有微粒状钨的熔融聚合物呈两股从挤出机中挤出然后通过水浴。此后，将冷却后的这两股供入制粒机，并将这些颗粒通过#4筛以除去带“尾”的颗粒。为了确保微粒状填料的均匀分布，将这些充填了的颗粒供入挤出机再重复加工。
          实施例2.制备和评价充填了的LCP纤维
按现在所述的方法由与1％(重量)钨金属粉混合的VECTRA聚合物熔融纺丝成充填了的纤维。将颗粒供入常规挤出机的加料斗中，在约320℃的温度下熔融的含有微粒状钨的聚合物从该挤出机中挤出。将该混合物经过计量泵(泵速38rpm；0.584毫升/转)，然后通过包括喷丝嘴筛网(15-25微米)的常规过滤组合件，并通过喷丝嘴(孔数，40；孔径，0.005”；孔长，0.007”)。所得的长丝会聚于润滑剂导槽，并到达卷取辊(2000英尺/分钟)上，该卷取辊将长丝向前送到络纱机装置上。得到约为400旦尼尔的充填了钨粉的LCP纱线(40根长丝)。该填料通常均匀分布在整个纤维中。
在不同的条件下：钨，0.1-2.0％(重量)；挤出温度，310-325℃；泵速，12-38rpm；卷取速，500-2000英尺/分钟；喷丝嘴孔径，0.005-0.013”，重复熔融纺丝过程，以得到不同旦尼尔的充填了钨粉的LCP纱线(40根长丝)，如表1中所示。在Instron电子强力测试仪上评价该充填了金属的纤维的抗张性能。该性能测定的结果列于表1。采用下述测试约定进行评价：关于强度，具有每英寸2.5捻的纤维的计量长度为10英寸、应变率为10％；关于模量，按ASTM D885评价。
                              表1
钨％             旦尼尔         强度(gpd)           模量(gpd)
1.0               444            7.9                 523
”                                  333            7.4                 521
”                                  642            7.8                 507
”                                  778            8.7                 453
0.1               678            8.9                 492
0.1               1020           --                  --
0.5               639            8.4                 516
2.0               439            7.4                 474
”                                  724            7.7                 482
”                                  770            8.1                 455
”                                  847            7.4                 444
”                                 1020           --                  --
注：”gpd”意指克/旦尼尔
                              表2
                                    至断裂的循环次数
        0.1％钨                     259
        0.5％钨                     249
        1.0％钨                     251
        2.0％钨                     141
       不锈钢丝                     2
此外，如表2所示，对由VECTRA聚合物制得的充填了钨粉的纤维的耐折性作了评价(ASTM D-2176)。所用的张力为1磅重。还对直径为0.003”的不锈钢丝作了测试。各样品均为可比的重量。表2中所列的每个结果都代表10个试验的平均值。可以看出，与不锈钢丝相比，充填了钨的纤维具有卓越的耐挠曲/耐折性。
此外，还对由充填了钨粉的VECTRA聚合物制成的纱线(0.5、1.0、2.0％(重量)的钨，dpf分别为16.0、19.5和11.0)测定了由于洗涤而降低的强度。防护用品可以反复洗涤而不降低强度是重要的。采用下述洗涤步骤：于60℃下在含有0.1％浓度的洗涤剂(以注册商标ARM &HAMMER出售)的蒸馏水中洗涤10分钟。用蒸馏水在40℃下漂洗10分钟。采用新配制的洗涤剂/水进行洗涤，再用新的蒸馏水漂洗。将样品洗涤1、3、5、10和15个循环，在最后一个循环后风干。经过15个洗涤循环后未观察到强度降低。
还对由充填了钨粉的VECTRA聚合物制成的纱线(0.5、1.0、2.0％(重量)的钨，旦尼尔分别为624、406和773)测试了由于经受漂白(2.62％Chlorox，5.24％Chlorox)而降低的强度。将足够的纱线缠绕在多孔的不锈钢管周围，并将其在适当的溶液中浸泡一定的时间(2、12和24小时)。此后，用自来水漂洗该纱线，并将其风干。将干燥后的纱线卷绕在小线轴上，并采用具有每英寸2.5捻的10英寸的纤维计量长度且应变率为10％的条件进行测定。观察到强度保留率超过85％。
           实施例3.LCP纱线抗切割性的评价
制备了如表3所示构成的由复合纱线制成的手套。高抗张强度聚乙烯纤维可从Allied Corporation of New Jersey按商标SPECTRA在市场上买到。高抗张强度芳族聚酰胺纤维可从DuPont of Wilmington，Delaware按商标KEVLAR在市场上买到。
将手套的一侧切开，取出一层织物供测试之用。将该织物在直径为4英寸的圆形试样夹上展开，并通过向该圆形试样夹的中心施加2磅的力将其预拉伸。该测试在Instron电子强力测试仪上进行。将该圆形试样夹在该测试仪中与地面呈45°角夹紧。将该试样夹以每分钟5”的速度，按与地面呈垂直的方向提升，使该织物按一定的角度与固定的(不旋转)碳化物刀片相会，从而模拟切割动作。将该织物固定以使其编织的组织垂直于模拟切割动作的方向。通过该测试仪测定割穿该织物(以磅计)所需的力。其结果示于表3。对比样号为C-1至C-6。
与未充填的相比，充填了的LCP纤维的优点清楚地示于表3。当将439和444旦尼尔的充填了的VECTRANM纤维(样品号3-3和3-4)与400旦尼尔的未充填的VECTRAN M纤维(样品号C-4)比较时，抗切割性的增强特别显著。通过将样品号3-1和3-2与样品号C-1比较可得到类似的结论。因此显而易见，当LCP纤维中含有少至约1％至约2％(重量)硬质填料时，该纤维的抗切割性可以提高。这相当于约0.07％至约0.14％(体积)的钨填料。还可看出，充填了的LCP纤维优于未充填的高抗张强度的聚乙烯纤维。VECTRAN M纤维也比聚乙烯纤维更耐热。芳族聚酰胺不能经受漂白处理，因此，当使用或洗涤期间纤维受到漂白时，充填了的VECTRAN M纤维比芳族聚酰胺更优越。
                              表3
    芯子              第一圈             第二圈             切开力(磅)3-1     650旦尼尔         847旦尼尔          847旦尼尔
    HS PE             V/2％钨            V/2％钨             5.23-2     650旦尼尔         778旦尼尔          778旦尼尔
    HS PE             V/1％钨            V/1％钨             5.8C-1     650旦尼尔         750旦尼尔          750旦尼尔
    HS PE             VECTRAN M          VECTRAN M           4.8C-2     650旦尼尔         1000旦尼尔         1000旦尼尔
    HS PE             HS芳族聚酰胺       HS芳族聚酰胺        4.4C-3     650旦尼尔         650旦尼尔          650旦尼尔
    HS PE             HS PE              HS PE               2.93-3     650旦尼尔         439旦尼尔          439旦尼尔
    HS PE             V/2％钨            V/2％钨             4.23-4     650旦尼尔         444旦尼尔          444旦尼尔
    HS PE             V/1％钨            V/1％钨             4.1C-4     650旦尼尔         400旦尼尔          400旦尼尔
    HS PE             VECTRAN M          VECTRAN M           2.6C-5     650旦尼尔         400旦尼尔          400旦尼尔
    HS PE             HS芳族聚酰胺       HS芳族聚酰胺        2.5C-6     650旦尼尔         375旦尼尔          375旦尼尔
    HS PE             HS PE              HS PE               2.9
“HS”意指高抗张强度；”PE”意指聚乙烯；”V”意指VECTRAN M
                         实施例4
对加了钨粉填料的聚(对苯二甲酸乙二醇酯)纤维叙述于下。钨的莫氏硬度值约为6.5至约7.5。在邻氯苯酚中测定的特性粘度约为0.95的轮胎纱线级粒状聚(对苯二甲酸乙二醇酯)(PET)可从Hoechst CelaneseCorporation，Somerville，New Jersey买到。通过将该聚合物与10％(重量)的钨粉在双螺杆挤出机中混合可制得母料。钨的平均粒度约为1微米。在混合前，先将该聚合物颗粒和钨干燥。将该母料与补加的PET在双螺杆挤出机中混合以得到具有1％和4％(重量)钨的混合物。通过加压使熔融混合物首先通过过滤组合件，然后经过喷丝嘴，将这些样品熔融纺丝。随后，在90℃下将该纱线从热的给料辊拉出，然后拉过热的鞋状物，最后在225℃下经受2％的松驰。将该纱线合股供作测试性能之用。所得数据归纳在表4中。为了确保没有填料过滤出，还对一种充填了10％钨的纤维进行钨的分析。该纤维的分析结果表明在纤维中含有约8.9％(重量)的钨。
抗张性能  采用ASTM D-3822测试方法测定强度、延伸率和模量。
抗切割性  首先将该纤维针织成织物以供作测试抗切割性之用。织物中纱线的表面密度按盎司/平方码(表4和表5中的OSY)量度。然后采用Ashland防切割性能(“CPP”)测试法测定织物的抗切割性。该测试是在TRI/Environmental，Inc.，9063 Bee Cave Road，Austin，Texas 78733-6201进行的。在测试中，将该织物样品放在芯轴的平整表面上。进行了一系列测试，测试时采用不同荷重的刀片拖过织物直到将该织物完全割穿为止。测量刀片移过织物直到该刀片完全割穿该织物时的距离。刀片割穿该织物的尖端就是芯轴与刀片之间形成电接触的交点。将完成切割所需的距离作为刀片上载荷的函数作图。对从约0.3英寸到约1.8英寸之间的不同切割距离的数据进行测量和作图。所得的图形近似直线。通过图上各点画出或计算出一条理想的直线，在移过该织物1英寸后割穿该织物所需的重量可从该图中量出或采用回归分析法计算出。刀片移过该织物1英寸后完成切割所需重量的内推值以”CPP”(Cut Protection Performance的缩写)示于表4和表5。最后，为比较不同织物样品厚度的数据，将CPP值除以织物的厚度(OSY)以补偿织物厚度的变化。该值以CPP/OSY示于表4和表5。充填了钨的PET纤维的抗切割性数据列于表4。
                       实施例5
在这些试验中，采用作为抛光磨料在市场上以商标MICROPOLISHII出售的氧化铝粉充填PET纤维样品。采用两种不同的具有平均粒度约为0.05微米和约为1.0微米的氧化铝粉。这两种氧化铝粉都是从Buehler，Ltd.，Waukegan Road，Lake Blugg，Illinois 60044得到的解附聚的粉末。0.05微米的氧化铝是具有立方晶体结构和莫氏硬度值为8的γ氧化铝。1.0微米的物料是具有六方晶体结构和莫氏硬度值为9的α氧化铝。采用与实施例4相同的方法将这两种氧化铝粉与PET混合，以得到氧化铝含量约为0.21％、0.86％、1.9％和2.1％(重量)的充填了的PET样品。采用与实施例4相同的方法测定了纤维的特性和抗切割性。所得数据列于表5。
表4和表5中的数据表明，在采用的所有填料的含量下抗切割性均至少提高约10％至约20％。这两组数据表明掺入纤维中的填料量约为0.07％至约0.7％(体积)。在上述用量和粒度的情况下该纤维的特性未出现明显的降低。
                          实施例6
采用一些不同粒度(0.6-1.6微米)的钨微粒按0.4-1.2％(体积)的含量作为PET中的填料进行了一系列的试验。将充填了钨的PET纺成纱线，随后将其针织成织物供测试之用。采用下述改进的方法通过Ashland防切割性能测试法再次测定抗切割性。将CPP值除以织物的表面密度，以便对不同织物密度下进行测试所得的结果作校正。所得数据列于表6。
                       抗切割性(CPP)
Ashland CPP测试按实施例4结尾所述的方法进行，但是利用对已知CPP值的标准样所作的校准来修正逐批刀片锐度的变化所得的结果。表6和表7以及实施例7-15中的数据使用了这种方法。校准用的标准样是从FAIRPRENE，85 Mill Plain Road，Fairfield，CT 06430得到的0.062英寸NS-5550型的氯丁橡胶，其CPP值为400克。在一组测试开始和结束时均以上述标准样测得CPP值，并计算出使该标准样测得的CPP值能达到400克的平均归一化因数。然后将该归一化因数用来校正该组测试所得的数据。此外，在计算CPP值时，采用切割该织物所需的长度对刀片上载荷的对数坐标图，因为它更接近直线。
                        实施例7
采用煅烧氧化铝作为该纤维的填料进行了一组试验。采用与前述实施例中所用的相同方法进行了试验，但是采用的粒度范围(0.5-3微米)和含量范围(0.8-3.2％(体积))比实施例5的更宽。
用于试验中的煅烧氧化铝从Agsco Corporation，621 Route 46，Hasbrouck，N.J.07604得到，且为小片状体，称之为Alumina#1。
采用实施例6结尾所述的方法测定CPP值。然后采用如上所述的方法计算CPP/OSY值。所得的这些数据列于表7。
从表中的数据可以看出，CPP/OSY值受到所列的所有变数(即，粒度、微粒含量、表面密度以及纤维的单丝旦数)的影响。在高表面密度(OSY)下，CPP/OSY值显著地下降。因此优选对具有类似表面密度的织物所测试的结果进行比较。
然而，从表4中的数据可以看出，在含量为2.4％(体积)(6.8％(重量))、粒度为2微米时，由纺织纤维(2.8单丝旦数)织成、且具有表面密度小于约每平方码10盎司的织物的CPP/OSY值大于约100。(样品号22-24和30)。这与可比纤维细度和表面密度的未充填PET纤维(表1中的3个对照样)测得的约53的平均CPP/OSY值相比，增加了约50％以上。表6(70)中所有用钨充填的PET样品和表7(75)中所有用氧化铝充填的PET样品，其平均CPP/OSY值也显著地高于对照样的平均值。
                        实施例8
将从Buehler得到的0.05微米氧化铝的样品与聚(对苯二甲酸乙二醇酯)(PET)在Haake锥形双螺杆挤出机上混合，以制成PET中含2％(重量)氧化铝的混合物。然后将其熔融纺丝成纱线。在测定抗张性能和抗切割性之前，先将该纱线拉伸。将未充填的PET对照样也制成纱线并拉伸。未充填的纱线具有8.6dpf(每单丝的旦数)的旦尼尔，而充填了的纱线具有的旦尼尔为6.3dpf。采用ASTM测试方法D-3822测定的抗张性能为：对未充填的纤维，强度为5.3gpd、延伸率为10％、模量为104gpd，而对充填了的纤维，强度为7.8gpd、延伸率为10％、模量为129gpd。然后将这些纱线样品在7针号的Shima Seiki针织机上直接针织成手套。最后采用实施例6中所述的Ashland防切割性能测试法测定抗切割性。未充填的手套的CPP值和表面密度(OSY)为1291克和每平方码26盎司，而充填了的手套的值为1083克和每平方码20盎司。对照样的归一化抗切割性的值(CPP/OSY)为49，而充填了的样品为54，该值增加了约10％。上述结果表明，大量很细的微粒不会使CPP/OSY值(对相同重量的织物的CPP值也如此)的增加超过约10％。
采用扫描电子显微镜测定了粒度分布以确定实际的粒度分布。厂家将平均粒度列为0.05微米。测得的粒度分布散布在0.05微米至1.32微米的范围，峰值在0.11微米处。平均粒度为0.31微米，中间值为0.23微米。
应当指出，本实施例中的数据与表5(样品号5-3、5-4、5-7和5-8)中的数据不完全一致，表5的数据采用CPP测试而没有按实施例6中所述的方法校准。在比表4和表5的数据稍迟一定时间之后开发了改进的测试方法，所得结果看来比早期的表4和表5中的数据更可靠(即，数据较少有分散)。
                       实施例9
在制造和使用本文中所述的抗切割纤维和纱线时的困难是充填纤维的磨蚀性，它会使用来加工该纤维的设备较快地磨损。已发现，可以制得包括芯中是充填的纤维而护皮是未充填的纤维的异质皮芯。这种皮芯纤维和纱线可以采用常规的双组分纤维的纺丝设备生产。芯和护皮不必由相同的聚合物制成，但是使用相同的聚合物是为了消除层与层间潜在的粘附问题和简化生产过程。充填了的纤维其组成与上述的相同。甚至在采用未充填聚合物的护皮时，采用CPP测试的抗切割性也增加了至少10％(以及如上所述的更高值)。采用的护皮越少抗切割性越高，采用10％(体积)护皮的聚合物可得到满意的CPP值和光滑的纤维。可以预期如果该护皮可低到约5％(体积)高到至多50％(体积)，那么抗切割性的总增加值就与皮芯纤维中充填的纤维的量成正比。
例如，可将PET与6％(重量)的氧化铝(从Agsco Corp.得到的具有2微米平均粒度的Grade#1煅烧氧化铝)混合。这就可以与作为护皮聚合物的未充填的PET一起熔融纺成双组分皮芯纤维。该平滑的护皮占该纤维体积的10％。该纱线被拉制和编成6股线。拉制后，旦尼尔为460/114或约为4dpf。将合股编成的纱线针织成具有不同织物重量的手套。测定各种手套的CPP值和CPP/OSY值。结果如下：(1)OSY，8.6、CPP值，1063g；CPP/OSY值为124；(2)OSY，15、CPP值，1568g；CPP/OSY值为104。这些结果可与没有护皮的充填了的PET的预计值媲美。
在显微镜下观察该纤维的横断面。可以看出，微粒都在纤维的芯中而未凸出在表面之上，从而得到外观光滑的表面且具有较平滑的感觉。
                       实施例10
将平均粒度约为2微米的煅烧氧化铝(Grade No.1，从Agsco得到)按聚合物重量6％(重量)的含量在纺丝原液中混合，该纺丝原液含有溶于N-甲基吡咯烷酮(NMP)中的6％(重量)芳族聚酰胺(可按商品名TREVARTM购得)。该芳族聚酰胺是对苯二甲酸与下列3种二胺按2∶1∶1之比的共聚物：3，3’-二甲基联苯胺、对苯二胺和1，4-双-(4-氨基苯氧基)-苯。将该芳族聚酰胺湿纺，然后按11∶1的拉伸比在380°下拉伸，以得到具有旦尼尔为4dpf、强度为22gpd和模量为675gpd的纱线。将未充填的芳族聚酰胺对照样也湿纺成具有旦尼尔为5.3dpf、强度为26gpd和模量为711gpd的纱线。还作了含有6％(重量)氧化铝(与上述的氧化铝相同)的PET的对比样。将这些纱线针织成手套，并测试了这些手套的织物的抗切割性。抗切割性的结果列于表8。充填了的芳族聚酰胺的抗切割性显然是最高的。
                       实施例11
将平均粒度为2微米的煅烧氧化铝(Grade No.1，从Agsco得到)按6％(重量)的含量与聚萘二甲酸乙二醇酯(PEN)在锥形双螺杆挤出机上混合。将充填了的PEN熔融纺丝并拉伸以得到具有5.7gpd强度和165gpd模量的纱线。将纱线机织和针织成手套。具有不同OSY值的手套的两种织物样品的抗切割性值如下：(1)OSY，12.7；CPP，1250g；CPP/OSY，99；(2)OSY，16；CPP，1695g；CPP/OSY，106。
充填了的PEN样品具有比充填了的PET或未充填的PEN更高的CPP/OSY值。在7针号手套中呈包缠纱形式的未充填的PEN具有以下抗切割性：OSY，21.2；CPP，867g；CPP/OSY，41。
                       实施例12
将平均粒度为2微米的煅烧氧化铝(Grade No.1，从Agsco得到)按7％(重量)的含量与重均分子量约为150,000的高分子量聚乙烯混合。该聚乙烯呈纤维状伸长链的聚乙烯形式，可按商标CERTRAN在市场上买到。将该充填了的聚合物熔融纺丝，按20∶1之比拉伸后，得到充填了的高模量纤维。该纱线具有提高了约45％的CPP值。该纺丝法在美国专利4,287,149；4,415,522和4,254,072中作了叙述，兹将这些专利引入本文作为参考。类似地，含有填料微粒的伸长链的聚乙烯纤维也可以采用美国专利4,356,138、4,413,110和4,663,101中所述的方法将充填了微粒的超高分子量的聚乙烯凝胶纺丝制得，兹将这些专利引入本文作为参考。
                       实施例13
将已充填了6％煅烧氧化铝(粒度2微米)的PET纱线按每英寸约8圈缠绕在3密耳不锈钢丝的周围，以制得复合纱线(也称为包缠纱)。还包括一些未充填的PET。为比较起见，将PET样品缠绕在同一类的金属丝周围以测定该填料对包缠纱的影响。这两种复合(缠绕的)纱线具有以下组成和抗切割值：(1)3密耳不锈钢丝(19％(重量))、充填了的PET纱线(70％)、未充填的PET纱线(11％)。将这种纱线针织成手套。取自该手套的织物样品具有重量为16OSY，CPP值为3648g和CPP/OSY为230。(2)3密耳不锈钢丝(18％(重量))、充填的PET纱线(82％)。将这种纱线也针织成手套。取自该手套的织物样品具有重量为18OSY，CPP值为3310g和CPP/OSY为188。
                       实施例14
将充填了6％氧化铝(粒度2微米)的PET纱线按每英寸约8圈缠绕在玻璃纤维(G75，从PPG得到)芯的周围。该玻璃纤维是具有长丝直径为9微米的600旦尼尔的纱线。该包缠纱(也称为复合纱线或组合纱线)由21％玻璃纤维和79％充填了的PET组成。为比较起见，制备了类似这种纱线但采用未充填的PET的对照样。将这两种纱线针织成手套供测试之用。取自含有充填了的PET的手套的织物样品重量为21OSY，CPP为2423g和CPP/OSY为177。对照织物的样品具有重量为23OSY，CPP值2238g和CPP/OSY为96。
                       实施例15
根据本发明，也可以制成抗切割性更强的无纺织物(也称为无纺织品和垫)。这种样品显示出无纺的纺粘织物。纺粘的无纺织物由含有6％(重量)粒度为2微米的氧化铝的PET制成。将该聚合物按8磅/小时和约在300℃下通过90孔(直径为0.5mm)的喷丝嘴纺丝。将该纤维通过高速喷嘴(即空气喷嘴)拉细到约为250∶1的拉伸比。将该纤维在4英尺×4英尺的多孔金属板上汇集为织品。针刺该垫以促进织物之间的粘合。为比较起见，还采用未充填的PET制成织品。由未充填的PET制成的织品具有重量为9.4OSY，CPP值为684g和CPP/OSY为73。充填了的PET织品具有重量为9.3OSY，CPP值为951g和CPP/OSY为102。
还制成了异质纺粘的垫，在制作时，将易熔聚合物和上述充填了的PET通过双组分喷丝嘴，这样该易熔聚合物就成为皮芯纤维的护皮。当单长丝从喷丝嘴出来时就被拉细，然后送到多孔板、皮带等处。通过在高到足以使该护皮聚合物熔融而又不致高到使芯熔融的温度下压缩该纤维垫，使纤维之间的粘合增强。易熔护皮聚合物的实例包括聚(对苯二甲酸丁二醇酯)、聚乙烯和聚丙烯。
采用任一种常用于生产无纺织物的方法，用抗切割的纤维可以制成无纺织物。例如它们可以按上述进行纺粘，而且可以通过许多方法例如针刺法、使用胶粘剂以及通过在特定的一些点上局部熔融的点粘结制得更具有粘合性的垫。这类无纺织物的用途包括剪裁并缝制的手套、剪裁并粘结的手套、将该织物剪裁然后缝制或粘结以形成各种防护用品、室内装璜、皮箱、保护层以及帆布等其它用品，所有这些均具有增强了的抗切割性。
应该理解的是，本发明的上述实施方案仅仅是说明性的，而且本领域的技术人员完全可能会想到修改。因此，不能认为本发明会受到本文所公开的实施方案的限制。
            表4.用钨充填的PET的抗切割性
样品号 钨％ 粒度 dpf T/E/M1 CPP2 OSY3 CPP/OSY
重量     体积 (微米)
对照1  -       -  -- 3.1 6.8/6.7/124 421 7.1  59
对照2  -       -  -- 5.0 -- 384 6.8  56
对照3  -       -  -- 5.0 -- 589 13.0  45
4-1 1％      0.07％ 1微米 6.0 6.3/9.0/128 540 9.1  59
4-2 1％      0.07％ 1微米 5.6 565 7.3  77
4-3 4％      0.29％ 1微米 6.0 7.2/11.6/109 643 7.0  92
4-4 4％      0.29％ 1微米 5.9 7.0/12.5/100 620 7.3  85
4-5 10％     0.72％ 1微米 11.6 6.3/10.0/123 697 7.5  93
4-6 10％     0.72％ 1微米 7.4 4.1/22.9/75 759 8.5  90
4-7 10％     0.72％ 1微米 6.0 -- 670 7.6  89
1采用ASTM D-3822测试方法测定的强度(gpd)，延伸率(％)，模量(gpd)。
2采用Ashland CPP测试法测定的抗切割性。
3盎司/平方码。
                           表5.用氧化铝充填的PET的抗切割性
样品 氧化铝％ 粒度 dpf T/E/M1 CPP2 OSY3 CPP/OSY
号 重量      体积 (微米)
5-1 0.21％    0.07％ 1微米 11.4 6.7/10.3/112  547   7.2   76
5-2 0.21％    0.07％ 1微米 5.6 7.4/12.4/104  463   7.5   62
5-3 0.86％    0.30％ 0.05微米 5.6 7.4/14.0/110  501   7.3   69
5-4 0.86％    0.30％ 0.05微米 5.7 6.9/12.8/110  497   6.7   73
5-5 1.9％     0.67％ 1微米 11.8 5.8/12.0/108  683   8.2   83
5-6 1.9％     0.67％ 1微米 5.6 7.4/10.9/108  478   6.7   71
5-7 2.1％     0.74％ 0.05微米 5.4 6.6/11.6/117  496   6.7   74
5-8 2.1％     0.74％ 0.05微米 5.9 5.4/12.8/100  431   6.2   69
1采用ASTM D-3822测试方法测定的强度(gpd)，延伸率(％)，模量(gpd)。
2采用Ashland CPP测试法测定的抗切割性。
3盎司/平方码。
                         表6.用钨充填的PET的抗切割性
  样品号    PARTSIZE     CONC     DPF     TENACITY     ELONG     MODULUS    OSY     CPP     CPP/OSY
   (微米)     (vol％)     (gpd)     (％)     (gpd) (盎司/码2)
  1    0.6     0.4     10     7.3     9     112   8     562     70
  2    0.8     1.2     10     5.5     13     102   9.5     557     59
  3    1.4     0.4     10     6     14     96   8.2     714     87
  4    1.6     1.2     10     5.9     11     100   8.2     821     100
  5    1     0.8     10   8     708     69
  6    0.8     0.8     10     5.7     8     109   7     824     103
  7    0.6     0.8     10     5.9     13     118   5.6     621     91
  8    0.8     0.8     10     5.7     8     109   7     596     85
  9    0.6     0.8     10     6.3     13     103   7.9     703     89
  10    1.5     0.8     12     6.7     9     l02   7.6     644     85
  11    0.6     0.8     2.4   13.6     656     48
  12    1     0.8     7.2     8     108   7.5     503     67
  13    0.6     0.8     2.4    28     1226     44
  14    0.6     0.8     2.4    19     964     51
  15    0.6     0.8     2.4    26     1225     47
  16    0.6     0.8     10    20     900     45
  17    0.6     0.8     2.4    12     628     52
  18    0.6     0.8     1.4    16     685     43
  19    0.6     0.8     1.4    7     580     80
PART SIZE是粒度，测定时以微米计。
CONC是硬质微粒的含量，测定时以PET中的体积％计。
DPF是纤维的旦尼尔，以dpf计。
TENACITY、ELONG和MODULUS是纤维的抗张性能、采用ASTMD-3822的测试方法测定。
OSY是针织物的表面密度，测定时以每平方码的盎司计。
CPP是CPP值，采用Ashland CPP测试法测定。
CPP/OSY是CPP值与表面密度(OSY)之比。
*采用实施例4中所述的方法测定。
                          表7.用氧化铝充填的PET的抗切割性
  样品号   PARTSIZE   CONC   DPF   TENACITY   ELONG   M0DULUS OSY     CPP     CPP/OSY
  (微米)   (vol％)   (gpd)   (％)   (gpd) (盎司/码2)
  1   0.6   2.4   3 22     1285     58
  2   0.6   0.8   10   6.6   15   109 10     990*     99
  3   0.6   1.8   10   5.2   17   100 12     912     76
  4   0.6   2.4   10   5.8   9   107 10     823     82
  5   0.6   3.2   10   4.8   14   93 10     852     85
  6   0.6   2.4   3 19     1074     57
  7   0.6   2.4   3 9     487     54
  8   3   2.4   3.6   5   23 16     1234     77
  9   3   2.4   3.6   5   23 11     981     89
  10   0.5   2.4   1.4   4.9   22 15     810     54
  11   0.5   2.4   1.4   4.9   22 13     623     48
  12   3   2.4   3.1   3.4   19 18     1555     86
  13   0.5   2.4   5.5 23     1197     52
  14   0.5   2.4   5.5 21     1082     52
  15   0.6   2.4   6.4 23     1242     54
  16   0.6   2.4   5.5 19     1505     79
  17   0.5   2.4   6.7 8     597     75
  18   0.6   2.4   4 13     818     83
  19   3   2.4   3.1 15     1370     91
  20   3   2.4   3.1 15     1283     86
  21   2   2.4   2.8   5   15   80 18     1562     87
  22   2   2.4   2.8   5   15   80 9     905     101
  23   2   2.4   2.8   5   15   80 5     611     122
  24   2   2.4   2.8   5   15   80 5     615     123
  25   2   2.4   2.8   5   15   80 11     785     71
  26   2   2.4   2.8   5   15   80 17     1593     94
  27   2   2.4   2.8   5   15   80 17     1506     89
  28   2   2.4   2.8   5   15   80 36     1022     28
  29   2   2.4   2.8   5   15   80 18     1573     87
  30   2   2.4   2.8   5   15   80 9     956     106
  31   3   1.2   10 23     1414     62
  32   0.6   2.4   6.4 18     1084     60
  33   0.6   2.4   6.4 21     996     47
  34   3   2.4   4.2 14     1079     77
  35   3   2.4   4.2 11     883     80
  36   1   2.4   12.9 7.3     943     129
表7注：
PART SIZE是粒度，测定时以微米计。
CONC是硬质微粒的含量，测定时以PET中的体积％计。
DPF是纤维的旦尼尔，以dpf计。
TENACITY、ELONG和MODULUS是纤维的抗张性能、采用ASTMD-3822的测试方法测定。
OSY是针织物的表面密度，测定时以每平方码的盎司计。
CPP是CPP值，采用Ashland CPP测试法测定。
CPP/OSY是CPP值与表面密度(OSY)之比。
*采用实施例4中所述的方法测定。
1.OSY值较高而CPP/OSY值较低，这是因为该手套涂覆了塑料以改进握持性能。
                            表8
                               OSY              CPP            CPP/OSYTREVAR芳族聚酰胺(未充填的)         3.7              379            102TREVAR芳族聚酰胺+氧化铝            4.6              951            205PET+氧化铝                         4.3              516            120

Claims (32)

1.一种抗切割的纤维，该纤维包括成纤聚合物和均匀分布在该纤维中的硬质填料，该纤维具有的旦尼尔为1至50dpf；所述填料具有的莫氏硬度值大于3，该填料的含量为0.05％至20％重量，所述填料选自平均直径至多为20微米的粉末、平均长度至多为20微米的细长微粒及其混合物；当采用Ashland防切割性能测试法测定时，与包括所述聚合物而没有该填料的纤维相比，该填料的含量足以使纤维的抗切割性至少提高20％，其中所述成纤聚合物是包括由对苯二甲酸和两种或多种芳族二胺衍生的单体单元的芳族聚酰胺。
2.权利要求1中所述的抗切割纤维，其中所述两种或多种芳族二胺选自对苯二胺、3，3′-二甲基联苯胺和1，4-双(4-氨基苯氧基)-苯。
3.权利要求2中所述的抗切割纤维，其中所述填料的平均粒度为0.25微米至10微米，其含量为0.1％至5％体积。
4.权利要求3中所述的抗切割纤维，其中所述填料是煅烧氧化铝。
5.权利要求3中所述的抗切割纤维，其中所述填料选自铁、钢、镍、钨及其混合物。
6.一种抗切割的纤维，该纤维包括成纤聚合物和均匀分布在该纤维中的硬质填料，该纤维具有的旦尼尔为1至50dpf；所述填料具有的莫氏硬度值大于3，该填料的含量为0.05％至20％重量，所述填料选自平均直径至多为20微米的粉末、平均长度至多为20微米的细长微粒及其混合物；当采用Ashland防切割性能测试法测定时，与包括所述聚合物而没有该填料的纤维相比，该填料的含量足以使纤维的抗切割性至少提高20％，其中所述成纤聚合物是具有分子量适于制成伸长链聚乙烯的聚乙烯。
7.权利要求6中所述的抗切割纤维，其中所述填料的平均粒度为0.25微米至10微米，其含量为0.1％至5％体积。
8.权利要求7中所述的抗切割纤维，其中所述填料是煅烧氧化铝。
9.权利要求7中所述的抗切割纤维，其中所述填料选自铁、钢、镍、钨及其混合物。
10.权利要求6中所述的抗切割纤维，其中所述纤维采用选自凝胶纺丝和熔融纺丝的方法制成。
11.一种抗切割的皮芯纤维，该皮芯纤维包括：
(a)一种芯，该芯包括成纤聚合物和均匀分布在该芯中的硬质填料，所述填料的莫氏硬度值大于3，该填料的含量为芯重的0.05％至20％重量，所述填料选自平均直径至多为20微米的粉末、平均长度至多为20微米的细长微粒及其混合物；和
(b)一种主要由未充填的第二种聚合物组成的护皮，所述护皮占所述纤维体积的5％至25％体积；其中所述皮芯纤维具有的旦尼尔为1至50dpf；其中当采用Ashland防切割性能测试法测定时，与没有该填料的皮芯纤维相比，所述填料的含量足以使该皮芯纤维的抗切割性至少提高20％。
12.权利要求11中所述的抗切割的皮芯纤维，其中所述护皮占所述皮芯纤维体积的10％至20％体积。
13.权利要求11或12中所述的抗切割的皮芯纤维，其中所述芯中的成纤聚合物和所述护皮中的第二种聚合物是相同的聚合物。
14.权利要求11或12中所述的抗切割的皮芯纤维，其中所述芯中的成纤聚合物和所述护皮中的第二种聚合物是不同的聚合物。
15.权利要求13中所述的抗切割的皮芯纤维，其中芯中成纤聚合物是聚对苯二甲酸乙二醇酯。
16.权利要求14中所述的抗切割的皮芯纤维，其中芯中成纤聚合物是聚对苯二甲酸乙二醇酯。
17.权利要求14中所述的抗切割的皮芯纤维，其中所述第二种聚合物的熔点比所述芯中的成纤聚合物的熔点至少低10℃。
18.一种包括抗切割纤维的手套，所述纤维包括成纤聚合物和均匀分散在所述纤维中的硬填料，所述纤维具有的旦尼尔为1-50dpf，所述填料的莫氏硬度大于3，填料含量为0.05-20％重量，所述填料选自平均直径至多20微米的粉末，平均长度至多20微米的伸长颗粒，及其混合物；与包括含所述聚合物但不含所述填料的纤维相比，按照Ashland防切割性能测试法测定，所述填料的含量足以使所述无纺织物的抗切割性至少提高20％，所说的成纤聚合物选自由分子量适用于制造长链聚乙烯的聚乙烯或芳族聚酰胺，上述的聚酰胺包括由对苯二甲酸衍生的单体单元和两种或多种芳族二胺。
19.一种包括由生产抗切割织物的方法制成的抗切割织物的手套，其中该方法包括以下步骤：
(a)制备包括成纤聚合物和0.05％至20％重量、具有莫氏硬度值大于3的硬质填料的均匀混合物，所说的成纤聚合物选自由分子量适用于制造长链聚乙烯的聚乙烯或芳族聚酰胺，上述的聚酰胺包括由对苯二甲酸衍生的单体单元和两种或多种芳族二胺；
(b)采用选自熔融纺丝、湿纺和干纺的方法，将该均匀混合物纺成纤维或纱线；和
(c)将该纤维或纱线织成织物，当采用Ashland防切割性能测试法测定时，与由成纤聚合物而没有所述硬质填料织成的同样织物相比，该织物的抗切割性至少提高10％，该织物任选包括其它热塑性纤维或选自陶瓷、金属和玻璃纤维的无机增强纤维。
20.权利要求18或19的手套，其中成纤聚合物选自聚对苯二甲酸乙二醇酯，聚对苯二甲酸丁二醇酯，聚萘二酸乙二醇酯，聚亚苯基硫醚，聚对苯二甲酸1，4-环己烷二甲醇酯，尼龙-6和尼龙-66。
21.权利要求18或19的手套，其中成纤聚合物是聚对苯二甲酸乙二醇酯。
22.一种无纺织物，该无纺织物包括由可熔融加工的聚合物和均匀分布在所述纤维中的硬质填料制成的纤维，该纤维具有的旦尼尔为1至50dpf，所述填料具有的莫氏硬度大于3，该填料的含量为0.1％至20％重量，所述填料的平均粒度为0.25微米至10微米，其中当采用Ashland防切割性能测试法测定时，与包括相同纤维而没有该填料的织物相比，该填料的含量足以使所述无纺织物的抗切割性至少提高20％，所说的成纤聚合物选自由分子量适用于制造长链聚乙烯的聚乙烯或芳族聚酰胺，上述的聚酰胺包括由对苯二甲酸衍生的单体单元和两种或多种芳族二胺。
23.权利要求22中所述的无纺织物，其中所述硬质填料的含量为0.1至5％体积。
24.权利要求22中所述的无纺织物，其中所述硬质填料的平均粒度为1至6微米，该硬质填料的含量为0.5％至3％体积。
25.权利要求24中所述的无纺织物，其中所述可熔融加工的聚合物是聚对苯二甲酸乙二醇酯。
26.权利要求25中所述的无纺织物，其中所述硬质填料是氧化铝。
27.权利要求25中所述的无纺织物，其中所述硬质填料选自铁、钢、镍、钨及其混合物。
28.权利要求22中所述的无纺织物，其中所述纤维是皮芯纤维，其中该芯包括第一种可熔融加工的聚合物和硬质填料，所述护皮包括可在比所述芯中的聚合物更低的温度下熔融的第二种聚合物。
29.一种抗切割的纤维，该纤维包括成纤聚合物和均匀分布在该纤维中的硬质填料，该纤维具有的旦尼尔为1至50dpf；所述填料具有的莫氏硬度值大于3，该填料的含量为0.05％至20％重量，所述填料选自平均直径至多为20微米的粉末、平均长度至多为20微米的细长微粒及其混合物；当采用Ashland防切割性能测试法测定时，与包括所述聚合物而没有该填料的纤维相比，该填料的含量足以使纤维的抗切割性至少提高20％，其中所述成纤聚合物是包括由对苯二甲酸和一种或多种芳族二胺衍生的单体单元的芳族聚酰胺，条件是：包括对苯二胺的单体单元还包括至少一种其它的芳族二胺。
30.一种包括抗切割纤维的手套，所述纤维包括成纤聚合物和均匀分散在所述纤维中的硬填料，所述纤维具有的旦尼尔为1-50dpf，莫氏硬度大于3，填料含量为0.05-20％重量，所述填料选自平均直径至多20微米的粉末，平均长度至多20微米的伸长颗粒，及其混合物；与包括含所述聚合物但不含所述填料的纤维相比，按照Ashland防切割性能测试法测定，所述填料的含量足以使所述无纺织物的抗切割性至少提高20％，所说的成纤聚合物选自由分子量适用于制造长链聚乙烯的聚乙烯或芳族聚酰胺，上述的聚酰胺包括由对苯二甲酸衍生的单体单元和两种或多种芳族二胺，所说的成纤聚合物选自芳族聚酰胺和长链聚乙烯，条件是：芳族聚酰胺不是由对苯二甲酸和对苯二胺组成的聚合物。
31.一种采用生产抗切割织物的方法制成的包括抗切割织物的手套，其中该方法包括以下步骤：
(a)制备包括成纤聚合物和0.05％至20％重量、具有莫氏硬度值大于3的硬质填料的均匀混合物，所说的成纤聚合物选自芳族聚酰胺和长链聚乙烯，条件是：芳族聚酰胺不是由对苯二甲酸和对苯二胺组成的聚合物；
(b)采用选自熔融纺丝、湿纺和干纺的方法，将该均匀混合物纺成纤维或纱线；和
(c)将该纤维或纱线织成织物，当采用Ashland防切割性能测试法测定时，与由成纤聚合物而没有所述硬质填料织成的同样织物相比，该织物的抗切割性至少提高10％，该织物任选包括其它热塑性纤维或选自陶瓷、金属和玻璃纤维的无机增强纤维。
32.一种无纺织物，该无纺织物包括由可熔融加工的聚合物和均匀分布在所述纤维中的硬质填料制成的纤维，该纤维具有的旦尼尔为1至50dpf，所述填料具有的莫氏硬度大于3，该填料的含量为0.1％至20％重量，所述填料的平均粒度为0.25微米至10微米，其中当采用Ashland防切割性能测试法测定时，与包括相同纤维而没有该填料的织物相比，该填料的含量足以使所述无纺织物的抗切割性至少提高20％，所说的成纤聚合物选自芳族聚酰胺和长链聚乙烯，条件是：芳族聚酰胺不是由对苯二甲酸和对苯二胺组成的聚合物。
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