CN101321618B - 具有应变响应粘性液体聚合物的多轴向织物 - Google Patents
具有应变响应粘性液体聚合物的多轴向织物 Download PDFInfo
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- CN101321618B CN101321618B CN2006800455284A CN200680045528A CN101321618B CN 101321618 B CN101321618 B CN 101321618B CN 2006800455284 A CN2006800455284 A CN 2006800455284A CN 200680045528 A CN200680045528 A CN 200680045528A CN 101321618 B CN101321618 B CN 101321618B
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Abstract
本发明涉及多轴向织物,包含:第一层,该层包含多个在第一方向上基本平行的第一纱线;第二层,该层包含多个在第二方向上基本平行并相对于第一纱线呈斜向或偏移的第二纱线;横向纱线,该纱线在所述层内横向交织;其中,每一层以高粘度聚合物涂覆,所述聚合物具有为约-40至0℃范围的Tg,及在20℃的零剪切粘度为约2×106至约1013泊。
Description
相关申请的交叉参考
本申请要求享有于2005年12月8日提交的美国申请US 60/749,147的优先权,其内容引入本文作为参考。
技术领域
本申请涉及用于防弹应用的多轴向织物。
背景技术
个人防弹身体防护服,尤其背心、头盔及其它制品,通常由用于防止子弹或其它抛射体以及任何其它被猛力地施加于所述防护服如刀子的物品刺穿的材料制成。这些制品主要用于军队,也有警务及民间应用。提高在交战环境下士兵和警察所使用的防护服系统的穿着性能和整体有效性是日益增长的需求。防护服系统的整体厚度和重量可以影响穿着性能,但是降低目前已知系统的这些参数会损失防护服抵抗刺穿的有效性。
已知用于防弹应用的织物包括具有至少两个具有单向纤维的层的那些,这样第二层的纤维相对于第一层的纤维呈斜向。见,例如美国专利申请2002/0164911,2003/0228815及2005/0081571。
相似的构造用粘合材料浸渍。见美国专利申请2004/0045428和美国专利6,238,768。美国专利5,160,776公开了一种复合材料,其具有至少一层在基质材料中的特定高强度单丝网。美国专利4,183,993公开了层压板在单向增强织物中的应用,所述织物包含有由多个纬编线圈和被固定在纬向编织物中的多个平行纵向伸长的经向引纱(warp insert)引形成的纬编纱线织物。
美国专利5,935,678公开了一种片状防弹层压板结构,其包括第一和第二组单向-取向纤维束。所述第二组纤维束相对于第一组纤维束的成角度交叉叠放。在此构造中,聚合物膜位于在第一和第二交叉叠放的纤维束组之间从而将第一和第二纤维束组粘附在一起而并没有所述膜大幅渗透入所述纤维束。美国专利5,677,029公开了具有至少一个纤维层和至少一个聚合物层的防弹制品,所述聚合物层与全部或部分所述纤维层接触并粘合。
已知某些织物既包含织造层又包含非织造层。见,美国专利申请2004/0132368。
具有改善的性能的防弹织物及制品成为需要。
发明内容
本发明提供了多轴向织物,包含:
第一层,该层包含多个在第一方向上基本平行的第一纱线,
第二层,该层包含多个在第二方向上基本平行并相对于第一纱线呈斜向或偏移的第二纱线,
横向纱线,该纱线在所述层内横向交织以将所述层固定在一起;
其中,每一层以高粘度聚合物涂覆,所述聚合物具有为约-40至约0℃范围的Tg,及20℃下的零剪切粘度为约2×106至约1013泊。
本发明还提供了包含所述织物的服装和制品以及制备所述织物的方法。
上述概括描述及下面的详细描述仅为例证及解释之用,并不限制如在所附权利要求中限定的本发明。
附图说明
在附图中举例说明下述实施方案以提高对本申请提出的概念的理解。
图1包含在所述多轴向织物的构造中使用多个单向层及横向纤维。
本领域技术人员应理解的是,附图中的物品是为简明及清楚的目的而予以说明,并不必须按比例描绘。例如,附图中的某些物品的尺寸相对于其它物品可以被夸大,以帮助提高对实施方案的理解。
具体实施方式
在一些实施方案中,本发明涉及多轴向织物,该织物包含:
第一层,该层包含多个在第一方向上基本平行的第一纱线,
第二层,该层包含多个在第二方向上基本平行并相对于第一纱线呈斜向或偏移的第二纱线,
横向纱线,该纱线在所述层内横向交织以将所述层固定在一起;
其中,每一层以高粘度聚合物涂覆,所述聚合物具有约-40至约0℃的范围的Tg,及20℃下的零剪切粘度为约2×106至约1013泊。
在一些实施方案中,至少一重多个纱线(at least one plurality ofyarns)包含芳族聚酰胺纤维。在某些实施方案中,至少一重多个纱线包含聚双哒唑(polybispyridazole)纤维。一种优选的聚双哒唑为聚[2,6-二咪唑[4,5-b:4,5-e]-吡啶亚基-1,4(2,5-二羟基)亚苯基](poly[2,6-dimidazo[4,5-b;4,5-e]-pyridinylene-1,4(2,5-dihydroxy)phenylene])。
合适的高粘度聚合物包括一种或多种氰基丙烯酸酯粘合剂、氨基甲酸乙酯粘合剂、脂族胺环氧树脂、芳族胺环氧树脂、聚(丙酸乙烯基酯)、聚(甲基丙烯酸己酯)、聚(丙烯酸异丙酯)、及乙烯/丙烯酸甲酯共聚物。
在一些实施方案中,所述横向纱线包含聚酯纤维、聚乙烯纤维、聚酰胺纤维、芳族聚酰胺纤维、聚芳烃唑(polyareneazoles)纤维、聚哒唑(polypyridazoles)纤维、或聚吡啶并双咪唑(polypyridobismidazole)纤维。
在某些实施方案中,所述织物还包含第三纱线层,该层包含多个在第三方向上基本平行并相对于第一和第二纱线呈斜向或偏移的纱线。在一些实施方案中,所述织物还包含第四纱线层,该层包含多个在第四方向上基本平行并相对于第一、第二和第三纱线呈斜向或偏移的纱线。
本发明还提供了包含在此所述的织物的制品和服装。
本发明还涉及制备织物的方法,该方法包括:
将包含多个在第一方向上基本平行的第一纱线的第一层与第二层接触,所述第二层包含多个在第二方向上基本平行并相对于第一纱线呈斜向或偏移的第二纱线;和
横向交织纱线与层以形成多轴向织物;
其中,每一层以高粘度聚合物涂覆,所述聚合物具有约-40至约0℃范围的Tg,及20℃的零剪切粘度为约2×106至约1013泊。
参考下面形成本公开的一部分的示例性及优选实施方案的详细描述,可以更好地理解本发明。应该理解,权利要求的保护范围并不限于在此描述和/或呈现的具体装置、方法、条件及参数,并且,用于本文的术语仅是通过例子用于描述具体的实施方案,并非旨在成为所要求保护的发明的限定。同样,如用在包括所附的权利要求书的说明书中,除非上下文清楚地相反地指出,单数形式“a”、“an”和“the”包含复数,并且具体数值的提及包含至少该具体数值。当表示数值范围时,另一实施方案包含从一个具体数值和/或至另一个具体数值。类似地,当数值通过使用先行词“约”而以近似值表示时,应该理解为该具体数值形成另一个实施方案。所有范围都是包含的和可合并的。
在此所用的术语“偏移”简单地是指不是正好在上面。术语“斜向”当指两重纱线时意味着所述重相对于彼此处于不同的角度。可以采用提供可接受性能的任意角度。本领域技术人员能够确定用于特定构造的最佳倾斜方向。例如,具有两层时,所述重可以处于0°和90°。其它的例子是0°/45°/90°和0°/45°/90°/45°。
本发明涉及多轴向织物,该织物包含第一层,该层包含多个在第一方向上基本平行的第一纱线,和第二层,该层包含多个在第二方向上基本平行并相对于第一纱线呈斜向的第二纱线。织物采用在所述层间横向交织的纱线。所述层可以以任意顺序放置并可以任选地涂覆以高粘度聚合物,所述聚合物具有约-40至约0℃的范围的Tg,约20000-100000的分子量及20℃的零剪切粘度为约2×106至约1013泊。
本发明还可以包含另外的层。所述层包括第三纱线层,该层包含多个在第三方向上基本平行并相对于第一和第二纱线呈斜向的第三纱线。其它的层包括第四纱线层,该层包含多个在第四方向上基本平行并相对于第一、第二和第三纱线呈斜向的第四纱线。
合适的用于所述层的纤维的例子包括由聚合物如聚烯烃(例如,聚乙烯或聚丙烯)、聚酰亚胺、聚酯、聚(乙烯醇)、聚吲哚如聚苯并咪唑(PBI)、聚芳酰胺如聚(对苯二甲酰对苯二胺)(poly(paraphenyleneterephthalamide))(由E.I.du Pont de Nemours and Company(DuPont),Wilmington,DE以商品名KEVLAR出售)、及聚哒唑如聚吡啶并双咪唑(可购自Magellan Systems International,Richmond VA,商品名M5)制成的那些。根据ASTM-D885,纤维的韧度应为至少约900MPa以提供优异的弹道抗刺穿性。优选地,纤维还具有至少约10GPa的模量。
当聚合物是聚酰胺时,芳族聚酰胺为优选。“芳族聚酰胺”是指一种聚酰胺,其中至少85%的酰胺(-CO-NH-)链直接与两个芳环连接。在Man-Made Fibers-Science and Technology,Volume 2,Second标题为Fiber-Forming Aromatic Polyamides,297页,W.Black等,IntersciencePublishers,1968,描述了合适的芳族聚酰胺纤维。同样,在美国专利4,172,938、3,869,429、3,819,587、3,673,143、3,354,127及3,094,511中,也公开了芳族聚酰胺纤维。添加剂可以与芳族聚酰胺一起使用,并且,已经发现多达10%重量的其它聚合物材料可以与芳族聚酰胺混合,或者可以使用具有多至10%重量的取代了芳族聚酰胺的二胺的其它二胺或多至10%重量的取代了芳族聚酰胺的二酰氯的其它二酰氯的共聚物。
优选的芳族聚酰胺是对芳族聚酰胺及优选的对芳族聚酰胺是聚(对苯二甲酰对苯二胺)(PPD-T)。PPD-T是指由对苯二胺和对苯二酰氯的大致摩尔对摩尔聚合而得的均聚物,和同样由引入少量其它二胺与所述对苯撑二胺一起和引入少量其它二酰氯与所述对苯二酰氯一起而得的共聚物。作为通用的原则,如果所述其它二胺和其它二酰氯没有干扰聚合反应的反应基团,则其它二胺和其它二酰氯的用量可达所述对苯撑二胺或对苯二酰氯的约10mol%,或可稍高。PPD-T也指由引入其它芳族二胺和其它芳族二酰氯例如2,6-萘二酰氯或氯-或二氯对苯二酰氯或3,4’-二氨基二苯醚所得的共聚物。
当聚合物是聚烯烃时,优选为聚乙烯或聚丙烯。聚乙烯是指优选大于1,000,000分子量的线型聚乙烯占主导的材料,该材料每100个主链碳原子可以包含不超过5个修改单元的少量支链或共聚物,还可以包含与其混合的不超过大约50%重量的一种或多种聚合物添加剂,例如烯烃-1-聚合物,尤其是低密度聚乙烯、聚丙烯等,或低分子量添加剂如抗氧化剂、润滑剂、紫外掩蔽剂、着色剂等通常加入的添加剂。一种此类聚合物公知为扩增链聚乙烯(ECPE)。类似地,聚丙烯优选为大于1,000,000分子量的线型聚丙烯占主导的材料。高分子量线型聚烯烃纤维可以商购获得。在美国专利4,457,985中论述了聚烯烃纤维的制备。
聚芳烃唑聚合物,如聚吲哚和聚哒唑,可以通过将干燥成分的混合物与聚磷酸(PPA)溶液反应制得。所述干燥成分可以包括吡咯生成单体和金属粉末。这些干燥成分的精确称量份可以通过采用至少本发明中的一些优选实施方案获得。
吡咯生成单体的例子包括2,5-二疏基-对-苯撑二胺、对苯二甲酸、双-(4-苯甲酸)、氧-双-(4-苯甲酸)、2,5-二羟基对苯二甲酸、间苯二甲酸、2,5-吡啶并二羧酸、2,6-萘二羧酸、2,6-喹啉二羧酸、2,6-二(4羧基苯基)吡啶并二咪唑、2,3,5,6-四氨基吡啶、4,6-二氨基间苯二酚、2,5-二氨基氢醌、1,4-二氨基-2,5-二硫代苯或其任意组合。优选地,所述吡咯生成单体包括2,3,5,6-四氨基吡啶和2,5-二羟基对苯二甲酸。在某些实施方案中,所述吡咯生成单体优选被磷酸化。优选地,所述磷酸化的吡咯生成单体是在聚磷酸和金属催化剂存在下聚合的。
可以使用金属粉末帮助构建所述最终聚合物的分子量。所述金属粉末典型地包括铁粉末、锡粉末、钒粉末、铬粉末及其任意组合。
所述吡咯-生成单体和金属粉末混合,随后所得混合物与聚磷酸反应制得聚芳烃唑聚合物溶液。如需要可以加入附加的聚磷酸到聚合物溶液中。典型地,所述聚合物溶液被挤出或通过模头或纺丝孔纺丝以制备或纺制长丝。
聚苯并噁唑(PBO)和聚苯并噻唑(PBZ)是两种合适的聚吲哚聚合物。PCT申请WO93/20400描述了这些聚合物。聚苯并噁唑和聚苯并噻唑优选由具有以下结构的重复单元组成:
当所示结合到氮原子的芳香基团可以为杂环时,它们优选为碳环的;当它们可以为稠合或非稠合多环系时,优选为单个六元环。当双-吡咯的主链上所示的基团是优选的对苯撑基团时,该基团可以被任何不会干扰聚合物制备的二价有机基团替代,或根本没有基团。例如,该基团可以是至多12个碳原子的脂族基团、甲代亚苯基、亚联苯基、双-亚苯基醚等。
用于制备本发明的纤维的聚苯并噁唑和聚苯并噻唑应具有至少25个及优选情况下至少100个重复单元。所述聚合物的制备和那些聚合物的纺丝在前面提到的PCT专利申请WO 93/20400中公开。
由聚哒唑聚合物制得的纤维适用于本发明。这些聚合物包括聚吡啶并咪唑(poly(pyridimidazle)),聚吡啶并噻唑poly(pyridothiazole),聚吡啶并噁唑poly(pyridoxazole),聚吡啶并双咪唑,聚吡啶并双噻唑,及聚吡啶并双噁唑。
聚吡啶并双咪唑是具有高强度的刚性杆型聚合物。所述聚吡啶并双咪唑纤维可以具有至少20dl/g或至少25dl/g或至少28dl/g的固有粘度。所述纤维包括PIPD纤维(也称为M5纤维和由聚[2,6-二咪唑并[4,5-b:4,5-e]-亚吡啶基-1,4(2,5-二羟基)亚苯基]制得的纤维)。PIPD纤维是基于下述结构:
聚吡啶并双咪唑纤维可以和公知的可商购的PBI纤维或聚苯并咪唑纤维区分出来,其原因在于聚苯并咪唑纤维是聚双苯并咪唑。与聚吡啶并双咪唑相比,聚双苯并咪唑纤维不是刚性杆型聚合物且具有低纤维强度和低拉伸模量。
已经报告PIPD纤维具有潜能以拥有约310GPa(2100克/旦尼尔)的平均模量和达约5.8GPa(39.6克/旦尼尔)的平均韧度。Brew等,Composites Science and Technology 1999,59,1109;Van Der Jagt andBeukers,Polymer 1999,40,1035;Sikkema,Polymer 1998,39,5981;Klopand Lammers,polymer,1998,39,5987;Hageman等,Polymer 1999,40,1313已经描述了这些纤维。
这些织物、制品、服装等可以具有另外的层或可以具有在本申请中所述的织物,所述织物与其它织物或片相邻。高性能纤维结构可以采用许多形式如针织织物、织造织物、单组织(uniweave)结构、单向片层、多向片层(例如具有以介于约20至90°的角度交叉的纤维的那些),非织造层(例如,毡),或者甚至单纤维。纤维结构可以采用本发明的多于10、20、40或60层的单根纤维结构。
有些层可以以聚合物处理。处理的层可以放置在背面,远离冲击点,或者可以放置在中间,或者以最优化身体防护服中的性能的任何其它形式。每一处理层的聚合物浓度可以相同,或者可以层与层之间变化以提供贯穿组件的理想的刚度变化。处理过的层可以用于由层与层可能不同的类型的织物结构组成的组件中。
身体防护服是本发明的一项主要应用。高性能纤维结构可以通过标准背心制造方法如缝制来制成防护服。防护服由制造商构造以符合由National Institute of Justice通过NIJ100-98制定的刺穿抗性、钝性损伤、及其它规定。根据NIJ100-98,防弹板组装成单个单元的方式因制造商而异。在一些情况下,所述多层被沿着所述板的整体边缘斜缝;在另一些情况下,所述层在数处被粗缝在一起。有些制造商以多行垂直或水平的缝合来组装织物;有些甚至可以绗缝(quilt)整个防弹板。没有缝制损害板抗冲击性能的证据存在。相反,根据所用织物的类型,缝制倾向于改善整体性能,尤其在钝性损伤的情况下。
在本发明的一些实施方案中,一种或多种具有低玻璃转化温度的高粘度聚合物添加剂被涂敷于纤维结构上或浸渍于纤维结构中。所述高粘度聚合物粘合剂可以变化地称为聚合物或粘合剂。同样,当使用术语“浸渍的”时,应该理解为它也旨在包含涂敷。优异的冲击抗性被保存同时提高了钝性损伤抗性。背面变形(BFD)是钝性损伤的指数,也就是,BFD越低,穿着保护装置的人将承受的损伤越少。以低浓度浸渍于纤维结构中的液体粘合剂被认为是,通过改变在弹道冲击情况下织物组织中单丝的滑动摩擦力而主要作为摩擦增长剂起作用。而且,此种材料降低了背面变形,同时保持或稍微提高了在制品如防护服中对刺穿的冲击抗性。BFD以毫米(mm)表示。
在一些实施方案中,本发明还是包含一层或多层以约1至15%重量的高粘度粘合剂浸渍(或涂敷)的高性能纤维结构,所述粘合剂具有介于约-40℃至0℃的Tg。所述玻璃转化温度是使用差示扫描量热法(DSC)在10℃/min的加热率下测得的。选取所述转变的中心点作为Tg。Tg在本申请说明书全文以℃表示。
通常,液体粘合剂相对于固体粘合剂为优选。如同其它刚性更大的添加剂以及由于约15%重量或更多的粘合剂添加剂的存在而刚性太大或摩擦力太高的系统那样,固体粘合剂基质会导致降低的弹道抗刺穿性。如下面所论述的,当多层在受到高速度抛射体冲击时,对其中摩擦力和刚性非常高的浸渍织物来说,可以预料到此种行为。
关于在冲击过程中具有低Tg粘合剂的织物的响应,考虑这些系统的应变率依赖性是很重要的。实验性地理解这一点的一个方法是应用频率依赖动态力学方法。至于试验,惰性玻璃支撑织物(inert glass supportfabrics)浸渍以聚乙烯基丙酸酯(PVP)或聚己基甲基丙烯酸酯(PHM)。将PHM以甲苯从溶液中沉淀出来并去除甲苯。这些样品用于频率依赖动态力学分析(DMA)中。所述试验及装置是标准的并在“Use of aDynamical Mechanical Analyzer to Study Supported polymers”Starkweather,H.W.,Giri,M.R.,J.Appl.Polym.Sci.1982,27,1243中描述。将频率依赖性玻璃转化解析为损失信号中的最大值。分别取所述频率的极值于0.1Hz和30Hz,PHM的Tg的范围介于-18.5℃至-2℃。在相同的频率范围,PVP的Tg介于3℃至12.5℃。这些分别对应于PHM和PVP的活化能40kcal/mol和65kcal/mol。弹道事件的非常高的应变率导致高等价变形频率(>>105Hz)。此升高的应变率容易地将PVP和PHM由液相转变为玻璃态固相。例如,在105Hz,基于所述PHM的活化能的Tg将转移至25℃。这一值表明,在室温下,在由弹道冲击导致的高应变率下,PHM甚至完全成为玻璃相。
本发明所用的高粘度粘合剂的Tg落在约-40℃至约0℃的范围内,优选在约-35℃至约-10℃的范围内。对于这些材料,来自弹道事件的高应变率足以将此频率依赖的Tg转移至室温以上,将粘性粘合剂转化为刚性的玻璃态固体。由于其低Tg和“流体”本质,这些粘合剂提供用于制备在静态条件下舒适的防护背心的柔性织物。如果玻璃转化在约-40℃以下,则所述应变率不足够高以将系统转化为玻璃相。
如上所述,在一些优选实施方案中,所述粘合剂应为高粘度聚合物流体。它们不应为弹性固体、非常高分子量的聚合物、半结晶弹性固体或交联弹性固体。聚合物,例如这些,会降低刺穿抗性且会刚性更大,因此导致舒适性的降低。另外,尤其,以低浓度施用的所述固体粘合剂,不会是自复原的,并且,一旦织物充分变形,会丧失有效性。
这些高粘度粘合剂赋予了中等至相当高的摩擦力。对于具有约-40℃至约0℃范围Tg的高粘度粘合剂,在干燥织物对照样品上的提高的摩擦力与BFD紧密关联并且对有益性能做出贡献。浸渍的添加剂的粘度还与织物刚度有关。
除Tg之外,用于本发明的粘合剂还可以由其分子量(Mw)及粘度表征。所述分子量是重均的,并且典型地通过凝胶渗透色谱法来测定。所述粘性流体聚合物的分子量可以介于例如约20000至400000g/mol(在一些实施方案中20000至100000)。粘性流体聚合物的理想的粘度范围介于约2×106至约1013泊。典型地,粘度在室温下测量,但是通常,在此提供的主题粘合剂的粘度在室温下过高以至于无法按标准技术测量。在这种情况下,通过由高温熔体粘度、熔体流动指数表征或其它定性流变表征进行外推来估量所述粘度。用于聚合物流体的零剪切粘度表征的一种典型方法是锥板流变法或毛细管粘度法。在上述范围之外的低粘度会典型地降低性能,如在具有低Tg的硅氧烷流体的情况下,甚至具有高Mw的那些。这些材料由于润滑而降低摩擦力。如Briscoe,B.J.,Motamedi,F.“The ballistic impact characteristics of aramid fabrics:theinfluence of interface friction”,Wear 1992 158(1-2),229所公开的,这与较差的防弹性能相关联。
具有合适性能的液体粘合剂可以以许多方法制备,包括悬浮、乳液或熔融聚合以及以混合或共聚物的形式。在此用作高粘度粘合剂的聚合物的例子包括聚乙烯基丙酸酯、聚甲基丙烯酸己酯、聚丙烯酸异丙酯,及乙烯/丙烯酸甲酯共聚物(其中乙烯的含量为38%重量和丙烯酸甲酯的含量为62%重量)。
在防弹织物中浸渍高粘度粘合剂,所述粘合剂具有的流动性能和模量性能显著不同于固体弹性体。根据究竟有多少层被处理,以介于约1至约15%重量范围的添加剂量,在聚芳酰胺织物中发现了理想高水平的弹道抗刺穿性及背面变形(钝性损伤的量度)。与在目前使用的织物背心中提供理想的钝性损伤防护所需要的面密度相比,可以确信此种系统将省去约20-30%的重量。用于本发明的高密度粘合剂具有的玻璃转化温度Tg可以使其在本发明中能够提供理想的液体粘合剂性能,并且通过纤维结构中的粘度及摩擦作用控制背面变形。
为了本发明的目的,术语“纤维”定义为较柔性的、宏观均匀的物体,具有高的长度对横穿垂直于其长度的其横截面的宽度的比。所述纤维横截面可以是任意形状,但是典型地为圆形。在此,术语“单丝”或“长丝”与术语“纤维”可互换地使用。
在此所用的术语“短纤维”是指切断成理想长度的纤维或者天然地带有或天然地具有与长丝相比较而言低的长度对横穿垂直于其长度的其横截面的宽度的比。长度可以自约0.1英寸至数英尺改变。在一些实施方案中,所述长度为自0.1英寸至约8英寸。人造短纤维被切断至适于在棉、粗纺羊毛、精纺纱线纺制装置上加工的长度。
所属短纤维可以具有(a)基本一致的长度,(b)可变的或随机的长度,或(c)具有基本一致的长度的子集的短纤维,和在其它具有不同长度的子集中的短纤维,所述在子集中的短纤维混合在一起形成基本一致的分布。
在一些实施方案中,适合的短纤维具有1-30厘米的长度。通过短绒工序的短纤维导致纤维长度为1-6厘米。
可以通过任意方法制备短纤维。通过拉伸断裂的长纤维制备短纤维,导致短纤维具有作为卷曲的变形区。所述短纤维可以使用转刀或切断机自长的直纤维切下,产生直的(即,非卷曲的)短纤维,或者另外地,自卷曲长纤维切下,所述卷曲长纤维沿短纤维长度方向具有锯齿形卷曲,具有每厘米不多于8个卷曲的卷曲(或重复弯曲)频率。
通过在具有一个或多个断裂区(具有预定间距)的拉伸断裂操作中断裂长丝束或簇可以制备拉伸断裂短纤维,从而得到量可以随机变化的具有平均切断长度的纤维,所述平均切断长度通过断裂区调整进行控制。
使用本领域公知的传统的长和短纤维环锭纺工艺,本发明的短纤维可以转变为纱线。对于短纤维,棉系统纺纱典型地使用3/4英寸至2-1/4英寸的纤维长度(即1.9-5.7cm)。对于长纤维,精纺或粗纺系统纺纱,典型地使用达6-1/2英寸的纤维(即16.5cm)。但是,这并非意在对环锭纺的限定,因为所述纱线还可以使用喷气纺纱、自由端纺纱及许多其它类型地将短纤维转变为可使用的纱线的纺纱技术来纺制。
所述拉伸断裂短纤维典型地具有达7英寸(即17.8cm)长的长度,并且使用传统的拉伸断裂丝束成条纤维工艺(stretch-broken tow to topstaple processes)制备可以是15。通过如例如在PCT专利申请WO0077283中描述的方法,具有最大长度达约20英寸的短纤维(即51cm)是可能的。通过使用以气流喷射长丝缠结将纤维合并为短纤纱(spunyarn)制备纱线,具有介于3至7g/dtex范围的韧度。这些纱线可以具有二次捻度,即,在成型后可以加捻以赋予纱线更大的韧度,在此情况下,所述捻度可以介于10至18克/旦尼尔(即,9-17g/dtex)的范围。所述拉伸断裂短纤维通常不需要卷曲,因为此工艺赋予了纤维一定的卷曲度。
术语长丝是指具有相对小直径的弹性纤维,且其长度长于称为短纤维的那些。通过本领域技术人员公知的工艺,长丝纤维可以转变为复丝。
本发明的织物可以采用多种构造,包括,但不限于,针织或织造织物或非织造织物结构。所述织物构造为本领域技术人员所公知。
“非织造”织物是指纤维网,包括单向的(如果包括于基质树脂中)、毡、纤维条等。
“织造”织物是指使用任何织物组织如平纹组织、五经缎纹组织、方平组织、缎纹组织、斜纹组织等织造的织物。可以认为平纹和斜纹组织是商业上使用最常见的组织。
通过以下实施例例证本发明,实施例并非意在限制本发明的范围。
实施例
对比例1
在对比例1中,由930dtex高韧度聚对亚苯基对苯二酰胺长丝纱线制备多轴向织物层,所述纱线的线密度为每根长丝1.66dtex,可以自E.I.DuPont de Nemours and Company按商标Kevlar129商品购得。每层织物由4组以18根经纱/英寸按不同角度铺置的平行纱线构建并通过一组低旦尼尔和低韧度的线圈形成性聚乙烯纱线固定在一起。每多轴向织物层的面密度为约0.27kg/m2。所述用于多轴向织物的四组纱线的拉伸强度为24.3g/dtex,且纤维的密度为1.44g/cm3。所述多轴向织物层的稳定性很差。通过尖锐物体的穿入,多轴向织物层中的纱线会扭曲并被推到旁边。约15”×15”尺寸大小的17层多轴向织物沿边缘及横向缝合缝合在一起以形成具有总面密度约为4.6kg/m2的复合结构。然后,根据NIJ弹道标准0101.04级别II对组件进行抗357mag子弹测试以获得弹道V50及背面变形。由于所述织物层的低结构稳定性,所得结果,尤其是所述复合结构背面变形较差。
实施例1
在本发明的实施例1中,由930dtex高韧度聚对亚苯基对苯二酰胺长丝纱线制备多轴向织物层,所述纱线的线密度为每根长丝1.66dtex,可以商标Kevlar129由E.I.DuPont de Nemours and Company购得。每层织物由4组以18根经纱/英寸按不同角度铺置的平行纱线构建并通过一组低旦尼尔和低韧度的线圈形成性聚乙烯纱线固定在一起。每个多轴向织物层的面密度为约0.27kg/m2。所述用于多轴向织物的四组纱线的拉伸强度为24.3g/dtex,且纤维的密度为1.44g/cm3。所述多轴向织物层进一步以约5wt%的高粘度聚合物涂覆,所述聚合物具有为约-40至约10℃的范围的Tg,及20℃的零剪切熔体粘度为2×106至约1013泊,分子量为约20000至100000。每一涂覆的多轴向织物层的面密度为约0.284kg/m2。本发明的多轴向织物层的结构稳定性非常好。
约15”×15”尺寸大小的本发明的16层涂覆的多轴向织物沿边缘及横向缝合缝合在一起以形成具有总面密度约为4.5kg/m2的复合结构。然后,按NIJ弹道标准0101.04级别II对组件进行抗357mag子弹测试以获得弹道V50及背面变形。所得结果,尤其是所述样品的复合结构的背面变形低于44mm并远远优于在对比例1中描述的技术的结果。
为了清楚起见,应该理解在此分别的实施方案的上下文中描述的具体特征,也可以在单个实施方案中合并提供。相反,为简便起见,在单个实施方案的上下文中描述的各个特征,也可以分别地或以任何子组合形式提供。
Claims (17)
1.多轴向织物,包含:
第一层,该层包含多个在第一方向上基本平行的第一纱线,
第二层,该层包含多个在第二方向上基本平行并相对于第一纱线呈斜向或偏移的第二纱线,
横向纱线,该纱线在所述第一层和第二层内横向交织以将所述第一层和第二层固定在一起;
其中,所述第一层和第二层的每一层以高粘度聚合物涂覆,所述聚合物具有为-40至0℃范围的Tg,及在20℃的零剪切粘度为2×106至1013泊;所述高粘度聚合物包含氰基丙烯酸酯粘合剂、氨基甲酸乙酯粘合剂、脂族胺环氧树脂、芳族胺环氧树脂、聚(丙酸乙烯基酯)、聚(甲基丙烯酸己酯)、聚(丙烯酸异丙酯)、及乙烯/丙烯酸甲酯共聚物中的一种或多种。
2.根据权利要求1所述的织物,其中所述多个纱线中的至少一种包含芳族聚酰胺纤维。
3.根据权利要求1所述的织物,其中所述多个纱线中的至少一种包含聚双哒唑纤维。
4.根据权利要求3所述的织物,其中所述聚双哒唑是聚[2,6-二咪唑并[4,5-b:4,5-e]-吡啶亚基-1,4(2,5-二羟基)亚苯基]。
5.根据权利要求1所述的织物,其中所述横向纱线包含聚酯纤维、聚乙烯纤维、聚酰胺纤维、聚芳烃唑纤维、聚哒唑纤维、或聚吡啶并双咪唑纤维。
6.根据权利要求1所述的织物,其中所述横向纱线包含芳族聚酰胺纤维。
7.根据权利要求1所述的织物,还包含第三纱线层,该层包含多个在第三方向上基本平行并相对于第一和第二纱线呈斜向或偏移的第三纱线。
8.根据权利要求7所述的织物,其中所述多个纱线中的至少一种包含芳族聚酰胺纤维。
9.根据权利要求7所述的织物,其中所述多个纱线中的至少一种包含聚双哒唑纤维。
10.根据权利要求9所述的织物,其中所述聚双哒唑是聚[2,6-二咪唑并[4,5-b:4,5-e]-吡啶亚基-1,4(2,5-二羟基)亚苯基]。
11.根据权利要求7所述的织物,还包含第四纱线层,该层包含多个在第四方向上基本平行并相对于第一、第二和第三纱线呈斜向或偏移的第四纱线。
12.根据权利要求11所述的织物,其中所述多个纱线中的至少一种包含芳族聚酰胺纤维。
13.根据权利要求11所述的织物,其中所述多个纱线中的至少一种包含聚双哒唑纤维。
14.根据权利要求13所述的织物,其中所述聚双哒唑是聚[2,6-二咪唑并[4,5-b:4,5-e]-吡啶亚基-1,4(2,5-二羟基)亚苯基]。
15.包含权利要求1所述的织物的服装。
16.包含权利要求1所述的织物的制品。
17.制备织物的方法,包括:
将包含多个在第一方向上基本平行的第一纱线的第一层与第二层接触,所述第二层包含多个在第二方向上基本平行并相对于第一纱线呈斜向或偏移的第二纱线;和
横向交织纱线与所述第一层和第二层以形成多轴向织物;
其中,每一层以高粘度聚合物涂覆,所述聚合物具有-40至0℃范围的Tg,及在20℃的零剪切粘度为2×106至1013泊;所述高粘度聚合物包含氰基丙烯酸酯粘合剂、氨基甲酸乙酯粘合剂、脂族胺环氧树脂、芳族胺环氧树脂、聚(丙酸乙烯基酯)、聚(甲基丙烯酸己酯)、聚(丙烯酸异丙酯)、及乙烯/丙烯酸甲酯共聚物中的一种或多种。
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US74914705P | 2005-12-08 | 2005-12-08 | |
US60/749,147 | 2005-12-08 | ||
PCT/US2006/061739 WO2007067950A1 (en) | 2005-12-08 | 2006-12-07 | Multiaxial fabric with strain-responsive viscous liquid polymers |
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CN101321618A CN101321618A (zh) | 2008-12-10 |
CN101321618B true CN101321618B (zh) | 2012-07-18 |
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US (1) | US8171569B2 (zh) |
EP (1) | EP1965975B1 (zh) |
JP (1) | JP5102775B2 (zh) |
KR (1) | KR101337052B1 (zh) |
CN (1) | CN101321618B (zh) |
BR (1) | BRPI0620574A2 (zh) |
CA (1) | CA2630153A1 (zh) |
WO (1) | WO2007067950A1 (zh) |
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CA2627901A1 (en) * | 2005-12-08 | 2007-06-14 | E. I. Du Pont De Nemours And Company | Multiaxial fabric for ballistic applications |
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US8256019B2 (en) * | 2007-08-01 | 2012-09-04 | Honeywell International Inc. | Composite ballistic fabric structures for hard armor applications |
US9296174B2 (en) | 2011-01-12 | 2016-03-29 | Compagnie Chomarat | Composite laminated structures and methods for manufacturing and using the same |
ITPN20110046A1 (it) * | 2011-06-20 | 2012-12-21 | Daniele Marino | Protezione dagli agenti atmosferici per veicoli |
US9023450B2 (en) | 2011-09-06 | 2015-05-05 | Honeywell International Inc. | High lap shear strength, low back face signature UD composite and the process of making |
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US9023451B2 (en) | 2011-09-06 | 2015-05-05 | Honeywell International Inc. | Rigid structure UHMWPE UD and composite and the process of making |
US9194662B1 (en) * | 2013-03-15 | 2015-11-24 | Peter D. Poulsen | Article for dispersing energy of a blast or impact |
US20150030805A1 (en) * | 2013-07-29 | 2015-01-29 | Compagnie Chomarat | Composite bi-angle and thin-ply laminate tapes and methods for manufacturing and using the same |
CN103541108A (zh) * | 2013-11-04 | 2014-01-29 | 吴江市祥盛纺织品有限公司 | 一种闪光棉记忆面料 |
CN103726193A (zh) * | 2013-12-30 | 2014-04-16 | 吴江金名来丝绸进出口有限公司 | 一种抗菌面料 |
CN111020780B (zh) * | 2019-12-19 | 2020-11-24 | 界首市华宇纺织有限公司 | 一种高粘度的保暖抗菌纱线及其生产工艺 |
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- 2006-12-07 JP JP2008544653A patent/JP5102775B2/ja not_active Expired - Fee Related
- 2006-12-07 US US12/086,266 patent/US8171569B2/en not_active Expired - Fee Related
- 2006-12-07 WO PCT/US2006/061739 patent/WO2007067950A1/en active Application Filing
- 2006-12-07 BR BRPI0620574-7A patent/BRPI0620574A2/pt active Search and Examination
- 2006-12-07 EP EP06846516.0A patent/EP1965975B1/en not_active Not-in-force
- 2006-12-07 KR KR1020087016438A patent/KR101337052B1/ko active IP Right Grant
- 2006-12-07 CN CN2006800455284A patent/CN101321618B/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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EP1965975B1 (en) | 2015-11-11 |
JP5102775B2 (ja) | 2012-12-19 |
KR101337052B1 (ko) | 2013-12-05 |
BRPI0620574A2 (pt) | 2011-11-16 |
JP2009518526A (ja) | 2009-05-07 |
WO2007067950A1 (en) | 2007-06-14 |
CN101321618A (zh) | 2008-12-10 |
KR20080081957A (ko) | 2008-09-10 |
US20090136706A1 (en) | 2009-05-28 |
US8171569B2 (en) | 2012-05-08 |
EP1965975A1 (en) | 2008-09-10 |
CA2630153A1 (en) | 2007-06-14 |
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