CN101547787A - 多轴向聚乙烯织物和层压体 - Google Patents

多轴向聚乙烯织物和层压体 Download PDF

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CN101547787A
CN101547787A CNA2007800435938A CN200780043593A CN101547787A CN 101547787 A CN101547787 A CN 101547787A CN A2007800435938 A CNA2007800435938 A CN A2007800435938A CN 200780043593 A CN200780043593 A CN 200780043593A CN 101547787 A CN101547787 A CN 101547787A
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fabric
layer
polyethylene
yarn
ground floor
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CN101547787B (zh
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M·J·仇
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D11/00Double or multi-ply fabrics not otherwise provided for
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/08Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/086Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/10Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/12Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/10Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/20Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
    • B29C70/202Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres arranged in parallel planes or structures of fibres crossing at substantial angles, e.g. cross-moulding compound [XMC]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/12Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/04Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments in rectilinear paths, e.g. crossing at right angles
    • D04H3/045Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments in rectilinear paths, e.g. crossing at right angles for net manufacturing
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/10Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between yarns or filaments made mechanically
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41WEAPONS
    • F41HARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00Armour; Armour plates
    • F41H5/02Plate construction
    • F41H5/04Plate construction composed of more than one layer
    • F41H5/0471Layered armour containing fibre- or fabric-reinforced layers
    • F41H5/0478Fibre- or fabric-reinforced layers in combination with plastics layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • B32B2262/0253Polyolefin fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02Synthetic macromolecular fibres
    • B32B2262/0261Polyamide fibres
    • B32B2262/0269Aromatic polyamide fibres
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24058Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2369Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2615Coating or impregnation is resistant to penetration by solid implements
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2615Coating or impregnation is resistant to penetration by solid implements
    • Y10T442/2623Ballistic resistant
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2631Coating or impregnation provides heat or fire protection

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Abstract

本发明提供了多轴向织物,所述织物包含第一层,所述第一层包含多根取向为第一方向的基本上平行且不含树脂的聚乙烯纱线;第二层,所述第二层包含取向为第二个方向的基本上平行且不含树脂的聚乙烯纱线,所述第一和第二方向彼此相对歪斜;插置在第一和第二层之间并且与所述第一和第二层接触的层,所述层含有热塑性或热固性薄膜;在所述多轴向织物的各层间横向交织的纱线。

Description

多轴向聚乙烯织物和层压体
发明领域
本发明涉及用于防弹应用的多轴向织物。
发明背景
人体防弹衣,例如防弹背心、头盔以及其他制品,通常由用于阻挡子弹或其他投射体、以及任何受迫施加到防弹衣上的其他物体例如刀子侵彻的材料制成。这类制品可用于武装部队、警察和民用。提高战斗环境下士兵和警察所用的防弹系统的耐磨损性和整体效能的需求日益增加。防弹系统的总体厚度和重量可影响耐磨损性,但是在当前已知的系统中,降低这些参数会损害防弹衣的抗侵彻效力。
某些构造在本领域中是已知的。参见例如美国专利申请2002/0164911、2003/0228815、2004/0045428、2004/0132368和2005/0081571以及美国专利4,183,993、5,160,776、5,677,029和5,935,678。
虽然上述专利和申请提出了众多优势,但是仍然需要能够以高生产率和简化的制造工艺生产的交叉层叠式防弹材料。
发明概述
本发明提供了多轴向织物,所述织物包含第一层,所述第一层包含多根在第一方向上基本平行的不含树脂的聚乙烯纱线;第二层,所述第二层包含多根在第二方向上基本平行且相对于第一层的聚乙烯纱线歪斜或偏置的不含树脂的聚乙烯纱线;插置在所述第一和第二层之间并与这两个层接触的层,该层包含热塑性或热固性薄膜;以及横向交织的横向纱线。纱线的第一和第二层基本上不含树脂。
本发明还提供了生产此类织物的方法。
附图说明
结合附图对实施方案进行了说明以便更好地理解本文提出的概念。
图1包括在多轴向织物构造中使用多个单向层和横向纤维的图示。
技术人员了解附图中的物体是以简洁明了的方式示出的,未必按比例绘制。例如,可相对于其他物体来放大图中某些物体的尺寸以便更好地理解实施方案。
例证性实施方案详述
本发明提供了多轴向织物,该多轴向织物包含:
第一层,其包含取向为第一方向的基本上平行且基本上不含树脂的聚乙烯纱线;
第二层,其包含取向为第二方向的基本上平行且基本上不含树脂的聚乙烯纱线,第一方向和第二方向彼此相对歪斜;
插置在第一和第二层之间并且与这两层接触的层,该层包含热塑性或热固性薄膜;和
在多轴向织物的各层间横向交织的纱线。
在一些实施方案中,所述织物可任选地涂覆有聚合物,所述聚合物具有-40至0℃的玻璃化转变温度,以及在20℃下2×106至1013泊的零剪切熔体粘度。一些薄膜包含聚乙烯。
在一些织物中,第二层的纱线相对于第一层的纱线呈90°角歪斜。
在某些实施方案中,聚乙烯具有至少1百万的数均分子量。
织物可任选地包含作为背衬层放置的附加层,所述层包含芳族聚酰胺毡。在一些实施方案中,芳族聚酰胺毡包含芳族聚酰胺人造短纤维。在一些实施方案中,芳族聚酰胺毡包含聚(对苯二甲酰对苯二胺)人造短纤维。
某些织物可任选地包含作为背衬层放置的附加层,所述层包含聚吡啶并二咪唑。一种可用的聚吡啶并二咪唑为聚[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]。
在其他实施方案中,任选的背衬层包含聚烯烃毡。在一些实施方案中,聚烯烃毡包含聚烯烃人造短纤维。在一些实施方案中,聚烯烃毡包含聚乙烯人造短纤维。
在某些实施方案中,横向纱线包含聚乙烯纤维。
织物可包括附加的层。在一个实施方案中,织物另外包含一个或多个层,这些层被构造成形成交替的层的形式,其包含(i)基本上平行的不含树脂的聚乙烯纱线,其中所述另外的聚乙烯纱线相对于各相邻层中的纱线歪斜,和(ii)热塑性或热固性薄膜。
在一些实施方案中,聚乙烯纱线的层数足以通过NIJ防弹标准0101.04的II级和IIIA级。在一些实施方案中,织物包含至少10层聚乙烯纱线。
本发明的其他方面涉及包含本文所述织物的衣服或制品。
还提供了用于制造多轴向织物的方法,该方法包括:
提供热塑性或热固性薄膜;所述薄膜具有第一和第二表面;
使第一层与薄膜的第一表面接触,所述第一层包含多根在第一方向上基本平行的基本上不含树脂的第一聚乙烯纱线;
使薄膜与第二层接触,所述第二层包含多根基本上不含树脂的聚乙烯纱线,所述聚乙烯纱线在第二方向上基本平行并且相对于第一聚乙烯纱线歪斜或偏置,其中第二层与该薄膜在薄膜的第二表面接触;并且
在多轴向织物内横向交织横向纱线。
通过将织物暴露于高温和压力下以形成层压体,从而将其紧缩。
参考以下对例示和优选实施方案的详细说明,可更容易理解本发明,所述详细说明构成了本公开的一部分。应当理解,权利要求的范围并不限于本文所述和/或示出的具体装置、方法、条件或参数,并且本文所用术语的目的仅在于以举例的方式描述具体实施方案,并非旨在限制受权利要求书保护的本发明。而且如包括所附权利要求的说明书中所用,单数形式“一种”、“一个”和“该”包括复数形式,并且提及的具体数值至少包括该具体值,除非上下文清楚地另有指明。当表述数值的范围时,另一个实施方案包括从一个具体值和/或到另一个具体值。类似地,当采用先行词“约”将数值表述为近似值时,应当理解,该具体值也构成了另一个实施方案。所有范围均具有包含性和组合性。
多种热塑性和热固性薄膜是本领域的技术人员已知的。可用的热塑性材料包括聚烯烃例如聚乙烯和聚丙烯、聚酰胺、聚酯、或它们的混合物。热固性材料包括环氧树脂、聚酯树脂、酚醛树脂、乙烯基酯树脂等。在一些实施方案中,热塑性或热固性薄膜包含聚乙烯。
为了本文的目的,术语“纤维”被定义为相对柔韧、宏观上均匀并且在沿其长度方向竖直的横截面上具有高的长宽比的主体。纤维横截面可为任何形状,但通常为圆形。纤维能够以未涂覆的、涂覆的、或其他预处理过的(例如,预拉伸或热处理的)形式存在。本文中,术语“长丝”可与术语“纤维”互换使用。
如本文所用,术语“人造短纤维”是指切割成所需长度的纤维,或是在沿其长度方向竖直的横截面上天然存在或天然具有比长丝低的长宽比的纤维。长度可在约0.1英寸至数英尺之间变化。在一些实施方案中,长度介于0.1英寸至约8英寸之间。可将人造短纤维切割成适于在棉纺、毛纺或精纺毛纱纺丝设备上进行处理的长度。
人造短纤维可具有(a)基本上均匀的长度,(b)变化或无规的长度,或(c)人造短纤维的一些子集具有基本均匀的长度,而人造短纤维的其余子集长度不同,这些子集中的人造短纤维混合在一起,形成基本上均匀的分布。
在一些实施方案中,合适的人造短纤维具有1至30厘米的长度。通过短纤维方法制造的人造短纤维具有1至6厘米的纤维长度。
可通过任何方法制造人造短纤维。人造短纤维可通过以下方式形成:拉断连续的纤维以形成具有充当褶皱的变形部分的人造短纤维。可使用旋转切割机或铡刀式切割机切割连续的直纤维来形成人造短纤维,所得的是直的(即不卷曲的)人造短纤维,或另外地从卷曲的连续纤维上切割来形成人造短纤维,所述卷曲的连续纤维在沿着人造短纤维的长度方向上具有锯齿状的褶皱,其中褶皱(即重复的弯曲)频率为每厘米上的褶皱数不超过8个。
可通过在拉断操作期间拉断一束或一捆连续长丝来制造拉断人造短纤维,所述连续长丝具有一个或多个预先确定了距离的断裂区,从而形成大量无规变化的纤维,所述纤维的平均切断长度可以通过调节断裂区进行控制。
可使用本领域所熟知的传统的长绒短纤维环锭纺纱工艺,将本发明的人造短纤维纺成纱线。对于短纤维,通常使用长度为3/4英寸至2又1/4英寸(即1.9至5.7cm。)的棉纺系统来纺纱纤维。对于长绒,通常使用最大长度为6又1/2英寸(即16.5cm)的精纺或毛纺系统来纺纱纤维。然而,这并非旨在限制为环锭纺纱,因为还可使用喷气纺纱、自由端纺纱、以及很多其他类型的可将人造短纤维纺成可用纱线的纺纱工艺来纺制纱线。
拉断人造短纤维通常具有最大为7英寸(即17.8cm)的长度,并且可使用传统的拉断丝束直接成条方法来制成。通过例如在PCT专利申请WO0077283中描述的方法,人造短纤维具有最多可约20英寸(即51cm)的最大长度。使用采用喷气流的长丝缠结,通过将纤维加固为纺纱而制成纱线,该纱线具有在3至7克/分特范围内的韧度。这些纱线可进行二次捻线,即可在它们形成之后对它们加捻以赋予纱线更高的韧度,在该情况下,韧度可在10至18克/旦尼尔(即9至17克/分特)的范围内。由于该方法赋予了纤维一定程度的褶皱,因此拉断人造短纤维通常无需褶皱。
术语“连续长丝”是指具有相对较小直径的柔韧纤维,其长度大于指示人造短纤维的长度。可通过本领域的技术人员熟知的方法将连续长丝纤维转变为复丝。
如本文所定义,“纱线”是指连续长度的两根或更多根纤维,其中纤维如本文所定义。
“织物”是指任何织造、针织或非织造结构。在一些实施方案中,织物为非织造材料。“非织造材料”是指包括单向纤维、毡等的纤维网络。
如本文所用,术语“偏置”仅指不是位于正上方。术语“歪斜”在涉及两组多根纱线时是指两组纱线相对于彼此处于不同的角度。可以使用能提供可接受性能的任何角度。本领域的技术人员能够确定具体构造的最佳歪斜。例如,对于两层而言,两组纱线可处于0度和90度。其他实例为0度/45度/90度和0度/45度/90度/45度。
优选的聚烯烃包括聚乙烯和聚丙烯。所谓聚乙烯是指主要为线性的聚乙烯材料,重均分子量为至少150,000。在一些实施方案中,重均分子量等于或大于一百万、两百万或五百万。这些高分子量纤维可在溶液中制备(参阅美国专利4,137,394和4,356,138),或者可从溶液中进行纺丝以形成凝胶(参见美国专利4,413,110),或者可通过轧制和拉伸方法来制备(参阅美国专利5,702,657)。
聚乙烯链可任选地包含少量的每100个主链碳原子具有不超过5个修饰单元的链分支或共聚单体。聚合物还可以包含与其混合的不超过约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、丙烯等,或是低分子量添加剂,例如经常掺入的抗氧化剂、润滑剂、紫外线屏蔽剂、着色剂等。此类聚合物通常被称为伸展链聚乙烯(ECPE)。
本领域的技术人员可通过成形技术、拉伸比和温度等的变型来提供具有不同属性的聚烯烃纤维。
在优选的实施方案中,纤维的韧度应该为至少15克/旦尼尔、20克/旦尼尔、25克/旦尼尔或30克/旦尼尔。类似地,通过拉伸实验机测量,纤维的初始抗拉模量为至少300克/旦尼尔、500克/旦尼尔、1,000克/旦尼尔或1,200克/旦尼尔。
重均分子量为约十五万至两百万的聚乙烯绝大多数通常具有约138℃的熔点。高取向的聚乙烯长丝由这样的材料制成,但长丝的熔点高出约7至约13℃。这种熔点的升高据信反映出了与本体聚合物相比长丝的结晶完整性和更高的结晶取向。
类似地,聚丙烯是主要为线性的聚丙烯材料,其具有的分子量和其他属性类似于针对聚乙烯所讨论的那些。
高分子量线性聚烯烃纤维可商购获得。在美国专利4,457,985中讨论了包括聚乙烯和聚丙烯的聚烯烃纤维的制备。
可用于背衬层中的合适的纤维的实例包括由下列聚合物制成的那些纤维:例如聚烯烃(例如聚乙烯或聚丙烯)、聚酰亚胺、聚酯、聚(乙烯醇)、聚苯并唑例如聚苯并咪唑(PBI))、芳族聚酰胺(例如聚对苯二甲酰对苯二胺,其由E.I.du Pont de Nemours and Company(DuPont),Wilmington,DE以商品名
Figure A200780043593D0009134216QIETU
销售)以及聚吡啶并唑(例如聚吡啶并二咪唑,可以商品名
Figure A200780043593D0009134219QIETU
得自Magellan Systems International,Richmond VA)。根据ASTM D-885,纤维的韧度应该至少为约900MPa,以提供优异的抗弹道侵彻性。优选地,纤维还具有至少约10GPa的模量。
当聚合物为聚酰胺时,芳族聚酰胺是优选的。所谓“芳族聚酰胺”是指其中至少85%的酰胺(-CO-NH-)键直接连接到两个芳族环上的聚酰胺。合适的芳族聚酰胺纤维在Man-Made Fibers-Science and Technology,第2卷标题为“Fiber-Forming Aromatic Polyamides”的部分第297页,W.Black等人,Interscience Publishers,1968)中有所描述。芳族聚酰胺纤维也在美国专利4,172,938、3,869,429、3,819,587、3,673,143、3,354,127和3,094,511中有所公开。添加剂可以与芳族聚酰胺一起使用,并且已发现,可将高达10重量%的其他聚合物材料与芳族聚酰胺共混,或者可使用具有多达10%的其他二胺(其取代了芳族聚酰胺的二胺)或多达10%的其他二甲酰氯(其取代了芳族聚酰胺的二甲酰氯)的共聚物。
优选的芳族聚酰胺为对位芳族聚酰胺,而优选的对位芳族聚酰胺为聚对苯二甲酰对苯二胺(PPD-T)。所谓PPD-T是指由对苯二胺和对苯二甲酰氯以大约等摩尔比进行聚合反应所得的均聚物,以及少量其他二胺与对苯二胺和少量其他二甲酰氯与对苯二甲酰氯结合所得的共聚物。作为一般原则,其他二胺和其他二甲酰氯的使用量可高达对苯二胺或对苯二甲酰氯的约10摩尔%,或者可能略高,唯一的前提条件是其他二胺和二甲酰氯不含干扰聚合反应的活性基团。PPD-T也指由其他芳族二胺和其他芳族二甲酰氯结合所得的共聚物,所述二酰氯为例如2,6-萘二甲酰氯或者氯代或二氯对苯二甲酰氯或3,4′-二氨基二苯醚。
当聚合物为聚烯烃时,聚乙烯或聚丙烯是优选的。所谓聚乙烯是指分子量优选大于一百万的并主要为线性的聚乙烯材料,该材料可以包含少量的每100个主链碳原子具有不超过5个修饰单元的链分支或共聚单体,而且还可以包含与其混合的不超过约50重量%的一种或多种聚合物添加剂,例如烯烃-1-聚合物,尤其为低密度聚乙烯、丙烯等,或低分子量添加剂,例如经常掺入的抗氧化剂、润滑剂、紫外线屏蔽剂、着色剂等。一种这样的聚合物通常被称为伸展链聚乙烯(ECPE)。类似地,聚丙烯优选为主要为线性的分子量大于一百万的聚丙烯材料。高分子量线性聚烯烃纤维可商购获得。在美国专利4,457,985中讨论了聚烯烃纤维的制备。
聚芳烃唑聚合物(例如聚苯并唑和聚吡啶并唑)可通过使干燥成分的混合物与多磷酸(PPA)溶液进行反应来制得。干燥成分可包含形成唑的单体和金属粉末。准确称重批次的这些干燥成分可以通过采用本发明的至少一些优选实施方案获得。
示例性的形成唑的单体包括2,5-二巯基-对苯二胺、对苯二甲酸、双-(4-苯甲酸)、氧基-双-(4-苯甲酸)、2,5-二羟基对苯二甲酸、间苯二甲酸、2,5-吡啶二甲酸、2,6-萘二甲酸、2,6-喹啉二甲酸、2,6-双(4-羧基苯基)吡啶并双咪唑、2,3,5,6-四氨基吡啶、4,6-二氨基间苯二酚、2,5-二氨基对苯二酚、1,4-二氨基-2,5-二巯基苯、或它们的任何组合。优选地,形成唑的单体包括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,优选的是形成唑的单体为磷酸化的。优选地,磷酸化的形成唑的单体在存在多磷酸和金属催化剂的情况下聚合。
可使用金属粉末来帮助堆积最终聚合物的分子量。金属粉末通常包括铁粉、锡粉、钒粉、铬粉、以及它们的任何组合。
使形成唑的单体和金属粉末混合,然后使混合物与多磷酸反应以形成聚芳烃唑聚合物溶液。如果需要,可将另外的多磷酸加入到聚合物溶液中。通常将聚合物溶液通过模具或喷丝头挤出或纺丝来制备或纺成长丝。
聚苯并噁唑(PBO)和聚苯并噻唑(PBZ)为两种合适的聚苯并唑聚合物。这些聚合物在PCT专利申请WO 93/20400中有所描述。聚苯并噁唑和聚苯并噻唑优选由下列结构的重复单元构成:
Figure A200780043593D00111
Figure A200780043593D00121
当显示接合到氮原子上的芳族基团可以为杂环时,它们优选为碳环;而当它们可以为稠合或未稠合的多环体系时,它们优选为单一的六元环。当双唑主链中所示的基团为优选的对亚苯基时,该基团可用不干扰聚合物制备的任何二价有机基团取代,或根本不用基团取代。例如,该基团可为最多十二个碳原子的脂族、甲苯基、亚联苯基、双亚苯基醚等等。
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,优选至少100个重复单元。这些聚合物的制备以及这些聚合物的纺丝在PCT专利申请WO 93/20400中有所公开。
由聚(吡啶并唑)聚合物制成的纤维适用于本发明。这些聚合物包括聚(吡啶并咪唑)、聚(吡啶并噻唑)、聚(吡啶并噁唑)、聚(吡啶并双咪唑)、聚(吡啶并二噻唑)和聚(吡啶并二噁唑)。
聚(吡啶并双咪唑)是一种具有高强度的刚棒聚合物。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的特性粘度。此类纤维包括PIPD纤维(也称为
Figure A200780043593D0012134340QIETU
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]制成的纤维)。PIPD纤维基于下列结构:
Figure A200780043593D00122
聚(吡啶并双咪唑)纤维可与熟知的可商购获得的PBI纤维或聚(苯并咪唑)纤维不同,因为聚(苯并咪唑)纤维是聚(双苯并咪唑)。聚(双苯并咪唑)纤维不是刚棒聚合物,并且与聚(吡啶并双咪唑)相比,其纤维强度和抗拉模量均较低。
已报道PIPD纤维具有拥有约310GPa(2100克/旦尼尔)的平均模量和最多约5.8GPa(39.6克/旦尼尔)的平均韧度的潜力。这些纤维在下列文献中有所描述:Brew等人,“Composites Science and Technology”1999,59,1109;Van der Jagt和Beukers,“Polymer”1999,40,1035;Sikkema,“Polymer”1998,39,5981;Klop和Lammers,“Polymer”,1998,39,5987;Hageman,等人,“Polymer”1999,40,1313。
如本文所用,如果层被描述为具有“基本上不含树脂的聚乙烯纱线”,其是指所述层包含小于10重量%的树脂。在一些实施方案中,所述层包含小于5重量%的树脂。在其他实施方案中,所述层包含小于1重量%的树脂,甚至不含树脂。
保护性防弹衣是本发明的一个主要应用。通过标准背心制造方法例如缝合可将高性能纤维结构制造到防弹衣中。防弹衣由制造商构造,以符合抗侵彻、抗钝伤要求,并且符合美国国家司法研究所(National Instituteof Justice)在NIJ 100-98中规定的其他要求。根据NIJ 100-98,将防弹板组装成单一部件的方式因制造商而异。在一些情况下,多个层是沿着板的整个边缘斜缝的;在其他情况下,这些层是在几个位置粗缝在一起的。某些制造商采用一排排垂直或水平的缝合线来组装织物;有一些甚至将整个防弹板缝入。没有证据表明缝合会削弱防弹板的防弹性能。相反,缝合趋于改善总体性能,尤其是在防钝伤的情况下,具体情况取决于所用织物的类型。
通过以下实施例例证了本发明,这些实施例并非旨在限制本发明的范围。
实施例
本发明现在将由以下具体实施例说明:
比较实施例
在比较实施例1中,使用可以商标
Figure A200780043593D00131
 Plus得自Honeywell的聚乙烯交叉层叠单向层。Spectrashield Plus通过以下几个主要步骤制成:(1)制备单向层,其中每层中的纤维几乎平行排列,并且基本上涂覆有树脂基质;(2)通过切割并且分件地将一个单向层垂直于第二单向层放置来交叉层叠两个单向层,所述单向层的双面均覆盖有聚乙烯薄膜;并且(3)在高温和压力下挤压交叉层叠的单向层(美国专利5,173,138)。Spectrashield Plus的面密度为约114g/m2
大小为约15’×15”、总的面密度为约4.1kg/m2的三十六层Spectrashield Plus只在四个角上进行粗缝。然后用.357magnum子弹测试该组合件,以根据NIJ标准-0101.04确定弹速V50。弹速V50为约485m/s。
实施例
在本发明的实施例1中,双轴向织物层由1440分特的高强度聚乙烯纤维制成,该织物层可以商标
Figure A200780043593D00141
 1000得自Honeywell。构造每层双轴向织物的方法为:以11.6根/厘米排布的不含树脂的第一组平行纱线、面密度为约7.8g/m2的低密度聚乙烯薄膜薄层(约9μ),得自RavenIndustries Inc.,然后将以11.6根/厘米排布的不含树脂的第二组平行纱线垂直于第一组纱线布置,之后将由110分特聚酯纱线制成的第三组成圈纱线横穿第一组纱线、薄膜以及第二组纱线,以稳定双轴向织物。本发明的双轴向层的面密度为约342g/m2,其比Spectrashield plus的面密度重约三倍。本发明的双轴向织物(其中薄膜夹在第一和第二组纱线之间)仅由一个步骤制成,具有高生产率和任何所需的宽度。本发明的双轴向织物被切割为约15”×15”大小的层,并在约110℃和0.5MPa的条件下热压约10分钟以进一步紧缩,每个层均由隔离膜分隔。将十二层紧缩的本发明的双轴向织物(总的面密度为约4.1kg/m2)仅在四个角进行粗缝,然后按照NIJ防弹标准0101.04用.357magnum子弹进行测试,以确定弹速V50。期望在层数明显少于比较实施例1(即用比较实施例1的约三分之一的层数)并且以更低的成本组装本发明制造的防弹制品的情况下,获得至少相等的结果。

Claims (20)

1.一种多轴向织物,所述织物包含:
第一层,所述第一层包含取向为第一方向的基本上平行且基本上不含树脂的聚乙烯纱线;
第二层,所述第二层包含取向为第二方向的基本上平行且基本上不含树脂的聚乙烯纱线,所述第一方向和所述第二方向彼此相对歪斜;
插置在所述第一层和所述第二层之间并且与这两层接触的层,所述层包含热塑性或热固性薄膜;和
在所述多轴向织物的各层间横向交织的纱线。
2.权利要求1的织物,其中所述第二层的纱线相对于所述第一层的纱线呈90°角歪斜。
3.权利要求1的织物,其中所述聚乙烯具有至少1百万的数均分子量。
4.权利要求1的织物,其中所述热塑性或热固性薄膜包含聚乙烯。
5.权利要求1的织物,其中:
所述织物可任选地涂覆有高粘度聚合物,所述聚合物具有在-40至0℃范围内的玻璃化转变温度,以及在20℃下2×106至1013泊的零剪切熔体粘度;
所述第二层的纱线相对于所述第一层的纱线呈90°角歪斜;并且
所述聚乙烯具有至少1百万的数均分子量。
6.权利要求1的织物,所述织物包含作为背衬层放置的附加层,所述层包含芳族聚酰胺毡。
7.权利要求6的织物,其中所述芳族聚酰胺毡包含芳族聚酰胺人造短纤维。
8.权利要求6的织物,其中所述芳族聚酰胺毡包含聚(对苯二甲酰对苯二胺)人造短纤维。
9.权利要求1的织物,所述织物包含作为背衬层放置的附加层,所述层包含聚吡啶并二咪唑。
10.权利要求9的织物,其中所述聚吡啶并二咪唑为聚[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]。
11.权利要求1的织物,所述织物包含作为背衬层放置的附加层,所述层包含聚烯烃毡。
12.权利要求11的织物,其中所述聚烯烃毡包含聚烯烃人造短纤维。
13.权利要求11的织物,其中所述聚烯烃毡包含聚乙烯人造短纤维。
14.权利要求1的织物,其中所述横向纱线包含聚乙烯纤维。
15.权利要求1的织物,所述织物另外包含一个或多个层,所述多个层被构造成提供交替的层,所述交替的层包含(i)基本上不含树脂且基本平行的聚乙烯纱线,其中所述另外的聚乙烯纱线相对于各相邻层中的纱线歪斜,和(ii)热塑性或热固性薄膜。
16.权利要求15的织物,所述织物包含至少10层聚乙烯纱线。
17.一种包含权利要求1的织物的衣服。
18.一种包含权利要求1的织物的制品。
19.一种制造多轴向织物的方法,所述方法包括:
提供热塑性或热固性薄膜;所述薄膜具有第一和第二表面;
使第一层与所述薄膜的第一表面接触,所述第一层包含多根在第一方向上基本平行的基本上不含树脂的聚乙烯纱线;
使第二层与所述薄膜接触,所述第二层包含多根基本上不含树脂的聚乙烯纱线,所述纱线在第二方向上基本平行并且相对于所述第一层的聚乙烯纱线歪斜或偏置,其中所述第二层与薄膜在所述薄膜的第二表面上接触;并且
在所述多轴向织物内横向交织横向纱线。
20.权利要求19的方法,其中所述织物可任选地涂覆有高粘度聚合物,所述聚合物具有在-40至0℃范围内的玻璃化转变温度,以及在20℃下2×106至1013泊的零剪切熔体粘度;
所述第二层的纱线相对于所述第一层的纱线呈90°角歪斜;并且所述聚乙烯具有至少1百万的数均分子量。
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