CN101330843B - 包含柔软高耐热性聚苯并咪唑和聚吡啶并双咪唑纤维外层面料的服装 - Google Patents

包含柔软高耐热性聚苯并咪唑和聚吡啶并双咪唑纤维外层面料的服装 Download PDF

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CN101330843B
CN101330843B CN200680047210.XA CN200680047210A CN101330843B CN 101330843 B CN101330843 B CN 101330843B CN 200680047210 A CN200680047210 A CN 200680047210A CN 101330843 B CN101330843 B CN 101330843B
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fiber
polypyridobisimidazo
flame
outer shell
resistant garment
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CN101330843A (zh
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R·H·朱
R·杨
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • B32B5/02Layered 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
    • B32B5/08Layered 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 the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00Materials specially adapted for outerwear
    • A41D31/04Materials specially adapted for outerwear characterised by special function or use
    • A41D31/08Heat resistant; Fire retardant
    • AHUMAN NECESSITIES
    • A41WEARING APPAREL
    • A41DOUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00Materials specially adapted for outerwear
    • A41D31/04Materials specially adapted for outerwear characterised by special function or use
    • A41D31/08Heat resistant; Fire retardant
    • A41D31/085Heat resistant; Fire retardant using layered materials
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62BDEVICES, APPARATUS OR METHODS FOR LIFE-SAVING
    • A62B17/00Protective clothing affording protection against heat or harmful chemical agents or for use at high altitudes
    • A62B17/003Fire-resistant or fire-fighters' clothes
    • 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
    • B32B5/02Layered 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
    • B32B5/024Woven fabric
    • 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
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/74Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent 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
    • D01F6/94Monocomponent 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 other polycondensation products
    • DTEXTILES; PAPER
    • D02YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02GCRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443Heat-resistant, fireproof or flame-retardant yarns or threads
    • DTEXTILES; PAPER
    • D03WEAVING
    • D03DWOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D03D15/513Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
    • 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • 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
    • 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
    • B32B2262/14Mixture of at least two fibres made of different materials
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/726Permeability to liquids, absorption
    • B32B2307/7265Non-permeable
    • 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
    • B32B2437/00Clothing
    • 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
    • B32B2571/00Protective equipment
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/14Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
    • 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
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/92Fire or heat protection feature
    • 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
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/92Fire or heat protection feature
    • Y10S428/921Fire or flameproofing
    • 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
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904Staple length fiber
    • 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
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • 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.]
    • Y10T442/30Woven fabric [i.e., woven strand or strip material]
    • Y10T442/3976Including strand which is stated to have specific attributes [e.g., heat or fire resistance, chemical or solvent resistance, high absorption for aqueous composition, water solubility, heat shrinkability, etc.]
    • 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.]
    • Y10T442/40Knit fabric [i.e., knit strand or strip material]
    • Y10T442/45Knit fabric is characterized by a particular or differential knit pattern other than open knit fabric or a fabric in which the strand denier is specified
    • Y10T442/456Including additional strand inserted within knit fabric
    • Y10T442/463Warp knit insert strand

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  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Toxicology (AREA)
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  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Professional, Industrial, Or Sporting Protective Garments (AREA)
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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明涉及一种具有外层面料的阻燃服装,所述外层面料包含5-50重量份比浓对数粘度大于20dl/g的聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维。

Description

包含柔软高耐热性聚苯并咪唑和聚吡啶并双咪唑纤维外层面料的服装
发明领域
本发明涉及一种具有外层面料的阻燃服装,所述外层面料包含聚吡啶并双咪唑纤维和聚苯并咪唑纤维。
发明背景
聚吡啶并双咪唑聚合物为刚性棒状聚合物。已知用该聚合物(其一种聚合物组合物被称为PIPD且已知作为用于制备M5纤维的聚合物)制备的纤维用于耐切割和阻燃防护服装。例如参见PCT申请WO199902169和WO2005002376。用聚合物链之间具有强氢键的刚性棒状聚合物(例如聚吡啶并双咪唑)制备的纤维见述于授权予Sikkema等人的美国专利5,674,969。聚吡啶并双咪唑的实例包括聚(1,4-(2,5-二羟基)亚苯基-2,6-吡啶并[2,3-d:5,6-d’]双咪唑),该物质可通过四氨基吡啶与2,5-二羟基对苯二甲酸在多磷酸中缩聚制备。Sikkema描述到,在制备一维或二维物体(例如纤维、膜、带等)时,希望聚吡啶并双咪唑具有高分子量,所述分子量对应于25℃在甲磺酸中以0.25g/dl的聚合物浓度测定的相对粘度(“Vrel”或“ηrel”)为至少约3.5,优选至少约5,更特别是等于或大于约10。Sikkema还公开了使用相对粘度大于约12的聚[吡啶并双咪唑-2,6-二基(2,5-二羟基-对亚苯基)]得到良好的纤维纺纱结果,且可达到超过50的相对粘度(对应于比浓对数粘度大于约15.6dl/g)。
已公开的美国专利申请US20030228812和US20040216215以及美国专利6,624,096公开了由Kevlar和聚苯并咪唑(PBI)的混合物制备的防护织物和服装。美国专利申请2003/0228812公开了聚苯并咪唑(PBI)和PBO纤维在防护服装中的用途。PCT专利申请WO2004023909公开了聚苯并咪唑和聚(对亚苯基苯并双噁唑)纤维和长丝在织物中的用途。
上述聚苯并咪唑为聚联苯并咪唑组合物,聚联苯并咪唑不是刚性棒状聚合物。因此,由该聚合物制备的纤维具有低纤维强度。
耐热阻燃防护服装已被消防队员、应急人员、军人和竞赛人员用来挽救生命并降低由于火和其他热事件引起的伤害。聚吡啶并双咪唑纤维具有优良的阻燃性,在许多方面比大多数其他纤维优异,且由于该聚合物的刚性棒状性质,由聚吡啶并双咪唑制备的纤维具有异常高的强度。但是,希望将聚吡啶并双咪唑纤维的优异阻燃性结合到防护服装的外层面料中以利用其优异的阻燃性。使用这种纤维时的一种顾虑为这种纤维具有高拉伸模量并且制成的织物较硬且穿着不舒服。因此,需要一种具有既柔软且较舒适又能提供良好阻燃性的包含聚吡啶并双咪唑的外层面料的服装。
发明概述
在一些实施方案中,本发明涉及具有外层的阻燃服装,所述外层包含聚吡啶并双咪唑纤维和聚苯并咪唑纤维。在某些实施方案中,本发明涉及一种包含5-50重量份比浓对数粘度大于20dl/g的聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维。
在一些实施方案中,所述聚吡啶并双咪唑纤维的比浓对数粘度大于25dl/g。在其他实施方案中,所述聚吡啶并双咪唑纤维的比浓对数粘度大于28dl/g。
本发明的一些阻燃服装包含35-50重量份聚吡啶并双咪唑纤维和50-65重量份聚苯并咪唑纤维。
在一些实施方案中,所述聚吡啶并双咪唑和聚苯并咪唑纤维为短纤维。在某些实施方案中,所述聚吡啶并双咪唑和聚苯并咪唑纤维为长丝。
一种优选的聚吡啶并双咪唑聚合物为聚[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]。
在一些实施方案中,所述聚苯并咪唑纤维包括聚联苯并咪唑聚合物。在某些实施方案中,所述聚联苯并咪唑聚合物为聚(2,2’-(间亚苯基)-5,5’-联苯并咪唑)聚合物。
在一些实施方案中,所述聚吡啶并双咪唑和聚联苯并咪唑纤维在服装的外层面料中。
在另一方面,本发明涉及一种阻燃服装,所述阻燃服装依次包含(a)内层耐热衬里、(b)液体阻挡层和(c)外层面料,所述外层面料(c)包含5-50重量份聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维;所述聚吡啶并双咪唑纤维的比浓对数粘度大于20dl/g。
本发明的其他实施方案涉及生产具有内层耐热衬里、液体阻挡层和外层面料的阻燃服装的方法,所述方法包括将外层面料结合到服装中,所述外层面料包含5-50重量份聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维;所述聚吡啶并双咪唑纤维的比浓对数粘度大于20dl/g。
示例性实施方案的详细描述
参考构成本公开的一部分的示例性和优选实施方案的以下详细说明可更容易地理解本发明。应理解的是,要保护的范围不限于本文所述和/或所示的具体装置、方法、条件或参数,且本文使用的术语仅通过举例的方式用于描述具体实施方案,并不是要局限本发明要求保护的范围。同样,在包括附随的权利要求书的说明书中,除非上下文明确说明,否则单数形式包括复数形式,且提到的具体数值包括至少该具体值。当表述一定范围的数值时,另一个实施方案包括从一个具体值和/或至另一个具体值。同样,当使用前缀“约”以近似值表示数值时,应理解的是该具体值构成另一个实施方案。包括所有的范围且可将其组合使用。
在一个实施方案中,本发明涉及一种具有外层面料的阻燃服装,所述外层面料包含5-50重量份比浓对数粘度大于20dl/g的聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维。本发明涉及一种依次包含内层耐热衬里、液体阻挡层和外层面料的阻燃服装,所述外层面料包含5-50重量份比浓对数粘度大于20dl/g的聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维。
在一些实施方案中,所述聚吡啶并双咪唑纤维的比浓对数粘度大于25dl/g。在其他实施方案中,所述聚吡啶并双咪唑纤维的比浓对数粘度大于28dl/g。
本发明的一些阻燃服装包含35-50重量份聚吡啶并双咪唑纤维和50-65重量份聚苯并咪唑纤维。
在一些实施方案中,所述聚吡啶并双咪唑和聚苯并咪唑纤维为短纤维。在某些实施方案中,所述聚吡啶并双咪唑和聚苯并咪唑纤维为长丝。
一种优选的聚吡啶并双咪唑(polypyridimidazole)聚合物为聚[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]。
在一些实施方案中,所述聚苯并咪唑纤维包括聚联苯并咪唑纤维。在某些实施方案中,所述聚联苯并咪唑纤维为聚(2,2’-(间亚苯基)-5,5’-联苯并咪唑)聚合物。
在另一方面,本发明涉及一种阻燃服装,所述阻燃服装依次包含(a)内层耐热衬里、(b)液体阻挡层和(c)外层面料,所述外层面料(c)包含5-50重量份聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维;所述聚吡啶并双咪唑纤维的比浓对数粘度大于20dl/g。
本发明的其他实施方案涉及生产具有内层耐热衬里、液体阻挡层和外层面料的阻燃服装的方法,所述方法包括将外层面料结合到服装中,所述外层面料包含5-50重量份聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维;所述聚吡啶并双咪唑纤维的比浓对数粘度大于20dl/g。
按照本文意图,术语“纤维”定义为较柔软的宏观均匀体,其长度与垂直于其长度的横截面的宽度之比大。纤维的横截面可为任何形状,但通常为圆形。本文中,术语“丝”或“长丝”与术语“纤维”可互换使用。
本文使用的术语“短纤维”是指切成所需长度或拉断的纤维,或与长丝比较时具有或天然具有低的长度与垂直于其长度的横截面的宽度之比的天然存在的纤维。长度可从约0.1英寸至数英尺不等。在一些实施方案中,长度为0.1英寸至约8英寸。将人造短纤维切成适于在棉、毛或精纺纱纺纱设备上加工的长度。
短纤维可具有(a)基本均匀的长度、(b)可变或无规的长度或(c)短纤维子集具有基本均匀长度而其他子集中的短纤维具有不同的长度,将各子集中的短纤维混合在一起形成基本均匀的分布。
在一些实施方案中,合适的短纤维长度为1-30厘米。通过短切法制备的短纤维的纤维长度为1-6厘米。
可通过任何方法制备短纤维。可通过拉断连续纤维形成短纤维,使得短纤维具有作为卷曲的变形部分。可使用旋转切割机或截切机从连续直纤维切下短纤维得到直的(即非卷曲的)短纤维,或再从沿着短纤维长度具有锯齿形卷曲(卷曲(或重复弯曲)频率不到8个卷曲/厘米)的卷曲连续纤维切下短纤维。
可通过在拉断工序中使一束长丝断裂产生质量随机变化的纤维来制备拉断短纤维,所述拉断工序具有一个或多个规定距离的断裂区,所述拉断短纤维的平均切断长度受到断裂区调节控制。
可采用本领域中众所周知的传统长短纤维环锭纺纱法将本发明短纤维转变成纱。就短纤维而言,通常使用棉纺体系将长度为3/4英寸至2-1/4英寸(即1.9-5.7cm)的纤维纺纱。就长纤维而言,通常使用精纺或毛纺体系将至多6-1/2英寸(即16.5cm)的纤维纺纱。然而,这并不局限于环锭纺,因为纱线还可采用喷气纺、自由端纺纱和将短纤维转变成有用纱的许多其他纺纱法进行纺制。
通常拉断短纤维的长度至多7英寸(即17.8cm)长且可采用传统拉断丝束成条短纤维法制备。最大长度至多约20英寸(即51cm)的短纤维可通过例如在PCT专利申请WO 0077283中所述的方法制备。可通过采用气流喷射进行长丝缠结将纤维压结成短纤纱,制备强度为3-7克/分特的纱线。这些纱线可具有复捻,也就是说,它们可在成形后经过加捻来赋予所得纱更大的强度,在这种情况下,强度可为10-18克/旦尼尔(即9-17g/dtex)。拉断短纤维通常不需要卷曲,这是由于拉断法赋予所得纤维一定程度的卷曲。
术语“长丝”是指具有较小直径的柔软纤维,其长度比短纤维长。长丝纤维和长丝的复丝可通过本领域技术人员众所周知的方法制备。
本发明的织物可具有许多结构,包括但不局限于针织或机织织物或非织造结构。这种织物结构对本领域技术人员而言是众所周知的。
“非织造”织物是指纤维网,包括单向(如果包含在基质树脂内)、毡、纤维絮垫等。
“织造”织物是指采用任何织物组织如平纹组织、四经破缎纹、方平组织、缎纹组织、斜纹组织等的机织织物。认为平纹和斜纹组织是本行业中最常用的组织。
本发明利用聚吡啶并双咪唑纤维。这种纤维为高强度的刚性棒状聚合物。所述聚吡啶并双咪唑纤维的比浓对数粘度为至少20dl/g或至少25dl/g或至少28dl/g。这种纤维包括PIPD纤维(也被称为M5纤维,该纤维由聚[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]制成)。PIPD纤维基于以下结构:
聚吡啶并双咪唑纤维与公知的市售PBI纤维即聚苯并咪唑纤维的区别在于聚苯并咪唑纤维为聚联苯并咪唑。聚联苯并咪唑纤维不是刚性棒状聚合物,并且与聚吡啶并双咪唑比较,具有低纤维强度和低拉伸模量。
已报道PIPD纤维能够具有约310GPa(2100克/旦尼尔)的平均模量和至多约5.8GPa(39.6克/旦尼尔)的平均强度。这些纤维已由Brew等人,Composites Science and Technology 1999,59,1109;Vander 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描述。
制备刚性棒状聚吡啶并咪唑聚合物的一种方法详细公开于授权予Sikkema等人的美国专利5,674,969。聚吡啶并咪唑聚合物可通过干燥各种成分的混合物与多磷酸(PPA)溶液的反应制得。干燥成分可包括形成吡啶并双咪唑的单体和金属粉末。制备用于本发明织物的刚性棒状纤维所用的聚吡啶并双咪唑聚合物应具有至少25个且优选至少100个重复单元。
按照本发明意图,聚吡啶并咪唑聚合物的相对分子量适合由以下方法表征,用适合溶剂(如甲磺酸)将聚合物产物稀释到聚合物浓度为0.05g/dl,并且在30℃测定一个或多个稀溶液的粘度。本发明的聚吡啶并咪唑聚合物的分子量的大小适合通过测定一个或多个稀溶液的粘度来监测并且与之成对应关系。因此,通常通过测定稀溶液的相对粘度(“Vrel”或“ηrel”或“nrel”)和比浓对数粘度(“Vinh”或“ηinh”或“ninh”)来监测聚合物分子量。稀聚合物溶液的相对粘度和比浓对数粘度根据以下表达式关联:
Vinh=ln(Vrel)/C,
其中ln为自然对数函数,C为聚合物溶液的浓度。Vrel为聚合物溶液粘度与不含聚合物的溶剂粘度的无量纲比值,因此,Vinh用浓度倒数的单位表示,通常为分升/克(“dl/g”)。因此,在本发明的某些方面,所制备聚吡啶并咪唑聚合物的特征为提供在30℃下在甲磺酸中聚合物浓度为0.05g/dl时比浓对数粘度为至少约20dl/g的聚合物溶液。由于本发明较高分子量聚合物产生粘性聚合物溶液,因此可采用聚合物在甲磺酸中浓度为约0.05g/dl的聚合物/甲磺酸溶液以在合理时间内测定比浓对数粘度。
本发明所用的形成吡啶并双咪唑的示例性单体包括2,3,5,6-四氨基吡啶和各种酸,包括对苯二甲酸、联-(4-苯甲酸)、氧联-(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-喹啉二甲酸或其任何组合。形成吡啶并双咪唑的单体优选包括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,优选形成吡啶并咪唑的单体经磷酸化。磷酸化的形成吡啶并咪唑的单体优选在多磷酸和金属催化剂存在下聚合。
可用金属粉末帮助构建最终聚合物的分子量。金属粉末一般包括铁粉、锡粉、钒粉、铬粉及其任何组合。
可使形成吡啶并双咪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吡啶并咪唑聚合物溶液。如果需要,可将另外的多磷酸加入到聚合物溶液。通常将聚合物溶液通过模具或喷丝头挤出或纺丝以制备或纺成长丝。
用于制备用于本发明的PBI纤维的聚联苯并咪唑聚合物可通过在美国专利2,895,948和美国再颁专利26,065中公开的方法制备。聚联苯并咪唑纤维可通过例如在美国专利3,441,640和美国专利4,263,245中公开的已知方法制备。
在一些实施方案中,所述聚苯并咪唑(PBI)纤维包括聚联苯并咪唑聚合物。一种可用的聚联苯并咪唑聚合物为聚(2,2’-(间亚苯基)-5,5’-联苯并咪唑)聚合物。一种商品PBI聚合物由四氨基联苯和间苯二甲酸二苯酯制备,使用二甲基乙酰胺作为溶剂,通过干纺纱法形成纤维。
作为本发明某些特别有用实施方案的说明,阻燃服装可实质上具有一层,该层为外层面料,这种服装例如消防队员或军人用的跳伞服。这种服装通常用在消防队员服装上,且可用于跳伞进入某区域来扑灭森林火灾。
在本发明的其他实施方案中,所述阻燃服装为多层服装,这种多层服装具有例如在美国专利5,468,537中所公开的通用结构,该专利通过引用结合到本文中。这种服装通常具有三层或三种类型的织物结构,各层或织物结构具有不同的作用。存在为消防战士提供阻燃防护并作为主要防火物的外层面料。与外层面料相邻的是湿气阻挡层,该阻挡层通常为液体阻挡层,但可选择阻挡层允许湿气通过阻挡层。在纤维非织造或织造聚间芳酰胺(meta-aramid)组织稀松织物上的Gore-TexPTFE膜或Neoprene膜的层压材料为通常用于该结构的湿气阻挡层。与湿气阻挡层相邻的是耐热衬里,耐热衬里通常包括附着在内层面料上的耐热纤维絮垫。湿气阻挡层使耐热衬里保持干燥,耐热衬里保护穿戴者免受来自火的热胁迫或穿戴者感到的热威胁。
基于两种纤维为100重量份计算,本发明服装的外层面料含有5-50重量份聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维。认为该组成范围提供了两种纤维的最佳性能组合。在一些优选实施方案中,基于两种纤维为100重量份计算,本发明服装的外层面料的组成范围为35-50重量份聚吡啶并双咪唑纤维和50-65重量份聚苯并咪唑纤维。
本发明的服装具有改进的外层面料,使得纤维防护服装具有高柔软性和高阻燃性的外层面料。其中希望由高强度刚性棒状纤维(例如聚吡啶并双咪唑)制备的织物。但是,刚性棒状聚吡啶并双咪唑纱通常具有非常高的拉伸模量,通常为约600-2300克/旦尼尔。在用于服装的一些优选实施方案中,拉伸模量为1000-1800克/旦尼尔。在许多情况下,具有高拉伸模量的纱转变为较硬的织物,因此,完全由高模量聚吡啶并双咪唑纱制成的织物的纤维拉伸模量高,认为这种织物太硬以至于在许多情况下使得服装不舒适。
另一方面,虽然聚苯并咪唑纤维具有阻燃性,但为强度差的纤维,且这种类型的纤维通常具有约30-60克/旦尼尔的低得多的拉伸模量。认为加入即使少量的较高强度和较高模量的聚吡啶并双咪唑纤维(约5%重量)可有利于提高织物强度,且在一些实施方案中,大于约35%但不大于50%重量的聚吡啶并双咪唑纤维可提供用于防护服装的优选织物。这种织物具有较低的硬度,因此比起完全由较高含量的高模量聚吡啶并双咪唑纤维制备的织物更柔软。
聚吡啶并双咪唑和聚苯并咪唑纤维均具有高阻燃性,因此,占多数的较低强度但非常柔软的聚苯并咪唑纤维与占少数的高强度且高模量聚吡啶并双咪唑纤维的组合确保所得阻燃织物制得的服装对需要阻燃性和舒适性的环境提供柔软的外层面料。
在本发明的一个优选实施方案中,外层面料为织造物。可使用纤维的均匀混合物的短纤纱将纤维结合到外层面料中。术语“均匀混合物”是指混合物中的各种短纤维形成相当均匀的纤维混合物。如果需要,其他短纤维可与短纤维的这种相当均匀的混合物合并。可通过本领域已知的各种方式进行共混,包括将多筒连续丝退卷同时切断所述两种或多种纤维来形成切断短纤维的混合物的方法;或包括打开不同短纤维包,然后开松并混合开松机、混合器和梳理机中的各种纤维的方法;或形成各短纤维长条,然后进一步加工成混合物,如在梳理机中形成纤维混合物长条的方法。制备均匀纤维混合物的其他方法是可能的,只要各种不同纤维相当均匀地分布于混合物中。如果采用所述混合物制备纱线,所得纱也具有相当均匀的短纤维混合物。通常,在最优选实施方案中,将各短纤维开松或分开至纤维加工成有用织物的通常程度,从而由于短纤维没开松好导致纤维结或粗结和其他主要缺陷存在的量不会降低最终织物质量。
或者,本发明一些织造织物可通过将各条聚吡啶并双咪唑纤维短纤纱和各条聚苯并咪唑纤维短纤纱一起机织来制备。这可通过若干方式实现,如将两种不同短纤纱合股在一起或通过将一种短纤维织入经纱和将另一种短纤维织入纬纱来织成织物的一部分。
或者,本发明一些织造织物可采用复丝连续纱制备,所述复丝为不同长丝的混合物,或如上针对不同短纤纱所述,采用各条不同复丝纱织造。
本发明还涉及一种生产具有内层耐热衬里、液体阻挡层和外层面料的阻燃服装的方法,所述方法包括将外层面料结合到服装中,所述外层面料包含5-50重量份聚吡啶并双咪唑纤维和50-95重量份聚苯并咪唑纤维,所述聚吡啶并双咪唑纤维的比浓对数粘度大于20dl/g。在一些优选实施方案中,所述聚吡啶并双咪唑纤维包括聚[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]。
实施例
通过以下实施例来说明本发明,但不局限于此。
实施例1
制备防热耐用织物,所述织物的经、纬环锭纺纱线中都具有聚苯并咪唑纤维、聚吡啶并双咪唑短纤维和抗静电短纤维的均匀混合物。聚苯并咪唑短纤维由聚(2,2’-(间亚苯基)-5,5’-联苯并咪唑)聚合物制备,以常用名PBI纤维(得自PBI Performance Products,Charlotte,NC)为人们所知;聚吡啶并双咪唑短纤维由PIPD聚合物制成,由Magellan Systems International公司以商标为M5的纤维销售;抗静电短纤维具有尼龙皮和碳芯,并作为P-140尼龙纤维(得自Invista)为人们所知。
通过常规棉纺设备制备和加工40%重量聚吡啶并双咪唑纤维、58%重量聚苯并咪唑和2%重量抗静电纤维的清棉机混合物条,然后采用环锭细纱机纺纱成捻度系数为4.0、单纱支数为约21特(28英制棉纱支数)的短纤纱。然后在合股机上将两单纱合股来制备双股纱。采用类似方法和相同捻度及混合比,制备24特(24英制棉纱支数)纱以用作纬纱。同上,将两股单纱合股成双股纱。
然后将聚苯并咪唑/聚吡啶并双咪唑/抗静电混纺纱用作经纱和纬纱并在有梭织机上织成织物,制备具有2×1斜纹组织和26经纱×17纬纱/cm(72经纱×52纬纱/英寸)结构和基重为约215g/m2(6.5oz/yd2)的坯布。然后在热水中洗净所得斜纹坯布并低张力干燥。接着采用碱性染料将洗净织物喷射染色。成品织物的基重为约231g/m2(7oz/yd2)。然后将成品织物用作三层复合织物的外层面料,所述三层复合织物还包括湿气阻挡层和耐热衬里。所述湿气阻挡层为具有无纺MPD-I/PPD-T纤维基底(2.7oz/yd2)的Goretex(0.5-0.8oz/yd2),耐热衬里为缝到3.2oz/yd2MPD-I短纤维稀纱布上的三层射流喷网法1.5oz/yd2片。然后采用该复合织物制备防护服装如消防员战斗服。
实施例2
或者,通过将所述织物按照图案裁剪成织物形状并将这些形状缝在一起形成用作工业防护服的防护连衣裤,将实施例1的成品织物制备成防护制品,包括服装。同样,将该织物裁剪成织物形状并将这些形状缝在一起来制成包括防护衫和防护裤的防护服组合。如果需要,将所述织物裁剪并缝合来制备其他防护服组成部分如头巾、袖子和围裙。

Claims (2)

1.一种具有外层面料的阻燃服装,所述外层面料包含:
5-50重量份比浓对数粘度大于20dl/g的聚吡啶并双咪唑纤维,和
50-95重量份聚苯并咪唑纤维。
2.权利要求1的阻燃服装,其中所述聚吡啶并双咪唑纤维的比浓对数粘度大于25dl/g。
3. 权利要求1的阻燃服装,其中所述聚吡啶并双咪唑纤维的比浓对数粘度大于28dl/g。
4. 权利要求1的阻燃服装,其中所述外层面料包含:
35-50重量份聚吡啶并双咪唑纤维,和
50-65重量份聚苯并咪唑纤维。
5. 权利要求1的阻燃服装,其中所述聚吡啶并双咪唑和聚苯并咪唑纤维以短纤维的形式存在。
6. 权利要求5的阻燃服装,其中所述聚吡啶并双咪唑聚合物为聚[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]。
7. 权利要求1的阻燃服装,其中所述聚苯并咪唑纤维包括聚联苯并咪唑聚合物。
8. 权利要求7的阻燃服装,其中所述聚联苯并咪唑聚合物为聚(2,2’-(间亚苯基)-5,5’-联苯并咪唑)聚合物。
9. 权利要求1的阻燃服装,其中所述聚吡啶并双咪唑和聚苯并咪唑纤维以长丝的形式存在。
10. 一种阻燃服装,所述阻燃服装依次包含:
a)内层耐热衬里,
b)液体阻挡层,和
c)外层面料,
所述外层面料包含:
5-50重量份比浓对数粘度大于20dl/g的聚吡啶并双咪唑纤维,和
50-95重量份聚苯并咪唑纤维。
11. 权利要求10的阻燃服装,其中所述聚吡啶并双咪唑纤维的比浓对数粘度大于25dl/g。
12. 权利要求10的阻燃服装,其中所述聚吡啶并双咪唑纤维的比浓对数粘度大于28dl/g。
13. 权利要求10的阻燃服装,其中所述外层面料包含:
35-50重量份聚吡啶并双咪唑纤维,和
50-65重量份聚苯并咪唑纤维。
14. 权利要求10的阻燃服装,其中所述聚吡啶并双咪唑和聚苯并咪唑纤维以短纤维的形式存在。
15. 权利要求14的阻燃服装,其中所述聚吡啶并双咪唑聚合物为聚[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]。
16. 权利要求10的阻燃服装,其中所述聚苯并咪唑纤维包括聚联苯并咪唑聚合物。
17. 权利要求16的阻燃服装,其中所述聚联苯并咪唑聚合物为聚(2,2’-(间亚苯基)-5,5’-联苯并咪唑)聚合物。
18. 权利要求10的阻燃服装,其中所述聚吡啶并双咪唑和聚苯并咪唑纤维以长丝的形式存在。
19. 一种生产具有内层耐热衬里、液体阻挡层和外层面料的阻燃服装的方法,所述方法包括将外层面料结合到服装中,所述外层面料包含:
5-50重量份比浓对数粘度大于20dl/g的聚吡啶并双咪唑纤维,和
50-95重量份聚苯并咪唑纤维。
20. 权利要求19的方法,其中所述聚吡啶并双咪唑纤维包括聚[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]。
CN200680047210.XA 2005-12-16 2006-12-13 包含柔软高耐热性聚苯并咪唑和聚吡啶并双咪唑纤维外层面料的服装 Expired - Fee Related CN101330843B (zh)

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