CN1930334B - 防电弧和防火的变性聚丙烯腈/棉/芳族聚酰胺纤维共混物 - Google Patents

防电弧和防火的变性聚丙烯腈/棉/芳族聚酰胺纤维共混物 Download PDF

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CN1930334B
CN1930334B CN2005800071947A CN200580007194A CN1930334B CN 1930334 B CN1930334 B CN 1930334B CN 2005800071947 A CN2005800071947 A CN 2005800071947A CN 200580007194 A CN200580007194 A CN 200580007194A CN 1930334 B CN1930334 B CN 1930334B
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R·朱
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DuPont Safety and Construction Inc
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    • D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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Abstract

适用于防电弧和防火的纱线、织物和衣服含有变性聚丙烯腈、棉和芳族聚酰胺纤维。

Description

防电弧和防火的变性聚丙烯腈/棉/芳族聚酰胺纤维共混物 
技术领域
本发明涉及适用于生产具有防电弧性能和防火性能的织物的共混纱线。本发明还涉及由该织物生产的衣服。 
背景技术
靠近激励电气设备的工作人员和应对激励设备附近突发事件的救灾人员要冒电弧和可能因电弧事件引起的火灾的危险。电弧一般是涉及数千伏特和数千安培电流的极其凶险的事件。电弧是当空气中两个电极之间的电位差(即电压)使空气中的原子离子化而变成能导电时形成的。 
防电弧和阻燃衣服一般穿起来不舒服，因为其中所加入的防护性纤维具有不良的湿气传输性。穿防护服的人一般都因防护服内所加入的防护性纤维而经受触觉上的不舒适性和热应力。 
授予Ichibori等的美国专利5,208,105公开了包含内有大量锑化合物的含卤纤维和至少一种纤维选自天然纤维和化学纤维的阻燃复合材料纤维共混物。把纤维共混物织造成织物，然后试验其极限氧指数，作为其阻燃性的量度。 
授予Green的美国专利5,223,334公开了提供防护电弧引起辐射能的织物。Green未公开在共混纱线中使用变性聚丙烯腈纱线。此外，Green也未公开由棉含量低于50％的纱线形成的防护性织物。 
目前需要在材料暴露于电弧中时提供高度防护性并阻燃以保护穿戴者免受二次效应的纱线织物和衣服。 
发明内容
本发明涉及适用于防电弧和防热织物和衣服的纱线，包含： 
(a)40～75重量％变性聚丙烯腈纤维， 
(b)10～40重量％棉纤维和 
(c)1～25重量％芳族聚酰胺纤维， 
所述百分数都以组分(a)、(b)和(c)之和为基准计算。 
这种纱线适合于加进耐热和耐电弧的织物和衣服中，尤其适合于保护工人抗电弧。此外，这种织物和衣服可提供抗开裂性、阻燃性和耐磨性。 
发明详述 
本发明涉及提供防电弧性和阻燃性都更高的纱线、织物和衣服。包含低拉伸强度阻燃纤维的织物和衣服，在暴露于电弧的强热应力中时会开裂，从而使穿戴者因入射能而受额外伤害。电弧一般涉及数千伏特和数千安培电流。电弧比来自骤燃之类的入射能强得多。为了对穿戴者提供保护，衣服或织物必须阻止能量穿透、转移到穿戴者身上。相信这一点是靠织物吸收一部分入射能和织物抗开裂实现的。在开裂期间，织物中形成孔洞，把穿戴者的表面直接暴露于入射能。 
本发明的纱线、织物和衣服，在暴露于电弧的强热应力时，阻止能量传移。相信本发明减少能量传移的机制是吸收一部分入射能并通过炭化减少透射能。 
本发明的纱线包含变性聚丙烯腈纤维、棉纤维和芳族聚酰胺纤维的共混物。本发明的纱线一般包含40～75重量％变性聚丙烯腈纤维、10～40重量％棉纤维和1～40重量％芳族聚酰胺纤维。优选本发明的纱线包含45～65重量％变性聚丙烯腈纤维、15～35重量％棉纤维和5～30重量％芳族聚酰胺纤维。上述百分数均以这3种命名组分之和为基准计算。 
所谓“纱线”是指纺丝或加捻在一起形成连续股的纤维的集合，它们能用于织造、针织、编结或添纱，或制成纺织材料或织物。 
所谓变性聚丙烯腈纤维是指由主要包含聚丙烯腈的聚合物制成的丙烯酸合成纤维。优选该聚合物是包含30～70重量％聚丙烯腈和70～30含卤乙烯基单体的共聚物。含卤乙烯基单体是至少一种选自如下一组的单体：氯乙烯、偏氯乙烯、溴乙烯、偏溴乙烯等。可共聚乙烯基单体的实例是丙烯酸、甲基丙烯酸、这类酸的盐或酯、丙烯酰胺、甲基丙烯酰胺、醋酸乙烯酯等。 
本发明的优选变性聚丙烯腈纤维是丙烯腈与偏氯乙烯组合的共聚物，为了提高阻燃性，该共聚物还含有一种或多种氧化锑。这类适用 的变性聚丙烯腈纤维包括，但不限于，美国专利3,193,602所公开的含2重量％三氧化锑的纤维、美国专利3,748,302所公开的用存在量至少2重量％且优选不超过8重量％的多种氧化锑制成的纤维，以及美国专利5,208,105和5,506,042所公开的含8～40重量％锑化合物的纤维。 
在本发明的纱线内，变性聚丙烯腈纤维提供阻燃的焦炭形成纤维，其LOI一般至少为28，随锑衍生物的掺入量而变。变性聚丙烯腈纤维也阻止因暴露于火中所引起的纤维损伤的扩展。变性聚丙烯腈纤维虽然非常阻燃，但其本身提供的拉伸强度不足以为纱线或由这种纱线制成的织物提供暴露于电弧中时所需的抗开裂能力。 
如本文所用，“芳族聚酰胺”是指下述聚酰胺：至少85％的酰胺键(-CONH-)直接连接在2个芳环上。芳族聚酰胺可以与添加剂一起使用，实际上已发现，可以用多达10％的其它聚合物与芳族聚酰胺进行共混，也可以用多达10％的其它二胺取代芳族聚酰胺中的二胺或多达10重量％的其它二酰基氯取代芳族聚酰胺中的二酰基氯。适用的芳族聚酰胺纤维已描述在Interscience出版社1968年出版的W.Black等所著的Man-Made Fibers-Science and Technology，Volume 2，page297(人造纤维-科学与技术，第二卷，297页)，题为Fiber-FormingAromatic Polyamides(成纤芳族聚酰胺)的部分中。芳族聚酰胺纤维也公开在美国专利4,172,938；3,869,429；3,819,587；3,673,143；3,354,127和3,094,511中。对位-芳族聚酰胺是酰胺键在对位上彼此相对的芳族聚酰胺，而间位-芳族聚酰胺是酰胺键在间位上彼此相对的芳族聚酰胺。在实践本发明时，最常用的芳族聚酰胺是聚对苯二甲酰对苯二胺和聚间苯二甲酰间苯二胺。 
正是在本发明范围内，可以用单一型芳族聚酰胺。例如，能或者用间位-芳族聚酰胺，或者用对位-芳族聚酰胺。 
但是，在优选模式中，要同时使用对位-芳族聚酰胺和间位-芳族聚酰胺。典型的百分数是20～40重量％对位-芳族聚酰胺和60～80间位-芳族聚酰胺。上述百分数仅以芳族聚酰胺为基准。这两种芳族聚酰胺的优选范围是25～35重量％对位-芳族聚酰胺和65～75重量％间位-芳族聚酰胺。 
在本发明的纱线中，棉纤维提供阻燃纤维，它们提供纱线内的湿传输。包含棉纤维的衣服靠吸去来自穿戴者的湿气而使穿戴者更舒 服。通过允许排汗，就减少了穿戴者本身给自己所施的热应力。 
此外，在本发明的纱线、织物或衣服中还可加入抗静电组分如，钢纤维、碳纤维或已有纤维上的碳涂层。当碳或金属如钢被加进本发明的纱线、织物或衣服中时，它们的导电性就为有助于耗散静电的积聚提供电导。静电放电对于使用敏感电气设备或靠近可燃蒸气的工作人员可能是很危险的。 
本发明的纱线可以用本领域熟知的任何纺纱技术来生产，例如，但不限于，环绽纺纱、包芯纺纱和气流喷射纺纱或更高的气流喷射纺纱，如用空气把短纤维加捻成纱线的Murata气流喷射纺纱。然后，一般要在把由任何普通技术生产的单一型纱线合股在一起以形成包含至少两种单一型纱线的合股-加捻纱线之后转化为织物。 
为提供免遭电弧造成的强热应力的防护，希望防电弧织物和由该织物制成的衣服具有如下特点：高于空气中氧浓度的LOI以阻燃，短焦炭长度表明织物损伤慢扩展和良好的抗开裂性以防入射能量直接冲击到保护层之下的表面。 
热防护衣服，如消防员的消防服一般都能抵制明火所产生的对流热。这类防护服在暴露于由电弧产生的强能量中时会开裂(即织物中形成开口)，使能量穿透衣服并使穿戴者严重受伤。本发明的织物，在暴露于电弧中时，既能防明火的对流热，又提供更好的抗开裂性和能量转移能力。织物的厚度以及防护服，如消防员常穿的消防服，的总重量，会因包裹体热和皮下出汗而对穿戴者造成热应力。本发明的织物在织物纱线内含有湿传输纤维如棉纤维，以提供从穿戴者吸去汗湿而提高舒适性并减少热应力的机制。 
基础重量是单位面积重量的量度。典型的单位包括盎司/码2或g/cm2。本说明书中报告的基础重量以盎司/码2(OPSY)报告。随单位面积织物量的增加，潜在危险与受保护者之间的材料量就增加。材料基础重量的增加意味着将观察到防护性的相应增加。本发明织物基础重量的增加导致更高的抗开裂性、更高的防热因子和更好的防电弧性。本发明织物的基础重量一般都大于约8.0opsy，优选大于约8.7opsy，以及非常优选大于约9.5opsy。相信基础重量大于12opsy的本发明织物会表现出更高的刚度并因此会降低由这种织物制成衣服的舒适性。 
焦炭长度是纺织物阻燃性的量度。焦炭定义为因热解或不完全燃 烧所形成的炭素残渣。在ASTM 6413-99试验条件下织物的焦炭长度，如本说明书中报告，定义为受特定撕力后自直接暴露于火烟中的织物边缘至最远可见织物损伤点的距离。优选本发明织物的焦炭长度小于6英寸，优选小于4.5英寸。 
本发明的织物可作为单层使用或作为多层防护服的一部分使用。本发明的纱线可存在于织物的经纱或纬纱中。优选本发明的纱线同时存在于所得织物的经纱和纬纱中。 
试验方法 
磨耗试验 
本发明织物的磨耗性按ASTM D-3884-01“纺织品耐磨性标准指南(旋转平台，双头法)”。 
耐电弧试验 
本发明织物的耐电弧性按ASTM F-1959-99“测定服装材料电孤热性能值的标准试验方法”测定。优选本发明织物的耐电弧性至少为0.8卡/cm2·opsy，更优选至少1.2卡/cm2·opsy。 
抓样强力试验 
本发明织物的耐抓性按ASTM D-5034-95“织物断裂强度和伸长率的标准试验方法(抓样强力试验)”测定。 
极限氧指数试验 
本发明织物的极限氧指数(LOI)按ASTM G-125-00“测定液体和固体材料在气态氧化剂中着火极限的标准试验方法”测定。 
撕裂试验 
本发明织物的抗撕裂性按ASTM D-5587-03“Trapezoid法织物撕裂的标准试验方法”。 
防热性试验 
本发明织物的防热性按NFPA 2112“保护工人免受骤燃的阻燃服的标准”测定。 
垂直燃烧试验 
本发明织物的焦炭长度按ASTM D-6413-99“纺织品阻燃性标准试验方法(垂直法)”测定。 
术语防热性(TPP)涉及在织物暴露于直接火烟或辐射热中时，织物对织物下穿戴者皮肤提供持续和可靠防护的能力。 
极限氧指数(LOI) 
按ASTM G125/D2863 
在ASTM D2863的条件下氧氮混合物刚好支持一开始在室温下的材料燃烧的最低氧浓度，以体积百分数表示。 
为说明本发明，提供下列实施例。所有份数和百分数都以重量计，温度是摄氏度，除非另有说明。 
具体实施方式
实施例 
变性聚丙烯腈/棉/芳族聚酰胺织物 
实施例1 
制备经纱和纬纱中都有 
Figure DEST_PATH_GA20169980200580007194701D00021
462型、 29、变性聚丙烯腈和棉的均匀共混物的环绽纺纱的舒适且耐久的织物。 
Figure DEST_PATH_GA20169980200580007194701D00023
462型是93％聚间苯二甲酰间苯二胺(MPD-1)、5％聚对苯二甲酰对苯二胺(PPD-T)和2％去静电纤维(杜邦公司的P-140)，变性聚丙烯腈是含15％锑的ACN/聚偏氯乙烯共聚物(商品名为 
Figure DEST_PATH_GA20169980200580007194701D00024
M)，以及Kevlar29是聚对苯二甲酰对苯二胺(PPD-T)。 
制备含10重量％ 462型、10重量％ 
Figure DEST_PATH_GA20169980200580007194701D00026
29、55重量％变性聚丙烯腈和25重量％棉的清棉混条，并用环锭细纺机以传统的棉体系加工成捻度为3.7的纺纱。由此制成的纱线是24.6特(24棉纱支数)单纱。然后在合股机上将两股单纱进行合股以制成双股纱。用类似的方法以及相同的捻度和共混比制成32.8特(18棉纱支数)纱线，作纬纱用。然后把这两种纱合股成合股纱。 
在梭织机上把 变性聚丙烯腈/棉纱线作为经纱和纬纱用于3×1斜纹结构中。该本色斜纹织物的结构是24经纱×15纬纱/cm(60经纱×39纬纱/英寸)，基础重量为271.3g/m2(8盎司/码2)。把如上所述制成的本色斜纹织物浸在热水中煮炼并在低张力下干燥之。然后用碱性染料喷染该煮炼过的织物。 
实施例2 
制备经纱和纬纱中都有Nomex462型、Kevlar29、变性聚丙烯腈和棉的均匀共混物的环绽纺纱的舒适且耐久的织物。Nomex462型是93％聚间苯二甲酰间苯二胺(MPD-1)、5％聚对苯二甲酰对苯二胺(PPD-T)和2％去静电纤维(杜邦公司的P-140)，变性聚丙烯腈是含15％锑的ACN/聚偏氯乙烯共聚物(商品名为ProtexM)，以及Kevlar29是聚对苯二甲酰对苯二胺(PPD-T)。 
制备含10重量％Nomex
Figure 058071947_12
462型、10重量％Kevlar29、45重量％变性聚丙烯腈和35重量％棉的清棉混条，并用环锭细纺机以传统的棉体系加工成捻度为3.7的纺纱。由此制成的纱线是24.6特(24棉纱支数)单纱。然后在合股机上将两股单纱进行合股以制成双股纱。用类似的方法以及相同的捻度和共混比制成32.8特(18棉纱支数)含50/50Nomex462/变性聚丙烯腈的纱线，作纬纱用。然后把这两种纱合股成合股纱。 
在梭织机上把Nomex
Figure 058071947_15
/Kevlar
Figure 058071947_16
/变性聚丙烯腈纤维/棉纱线作为经纱和纬纱用于3×1斜纹结构中。该本色斜纹织物的结构是23经纱×16纬纱/cm(58经纱×40纬纱/英寸)，基础重量为264.5g/m2(7.8盎司/码2)。把如上所述制成的本色斜纹织物浸在热水中煮炼并在低张力下干燥之。然后用碱性染料喷染该煮炼过的织物。 
下表示意对实施例1和2测定的性能。 
    实施例1     实施例2
    织物组成
    织物结构     2×1斜纹     2×1斜纹
    基础重量(opsy)     6.7     6.7
    焦炭长度(英寸)    经纱×纬纱     4×4     3.3×3.6
    TPP值    (卡/cm2)     11.8     12.5
    抓样强度(磅力)    经纱×纬纱     100×96     118×89
    Trap撕裂强度(磅力)    经纱×纬纱     13.6×11.7     13.8×10.8
    Taber磨耗    (次数)CS-10/1000g     352     317

Claims (20)

1.适合提供防电弧性和防火性的纱线，包含：
(a)40～75重量％变性聚丙烯腈纤维，
(b)10～40重量％棉纤维和
(c)1～40重量％芳族聚酰胺纤维，
所述百分数都以组分(a)、(b)和(c)之和为基准计算。
2.权利要求1的纱线，包含
(a)45～60重量％变性聚丙烯腈纤维，
(b)15～35重量％棉纤维和
(c)5～30重量％芳族聚酰胺纤维。
3.权利要求1的纱线，其中所述纤维同时包括对位-和间位-芳族聚酰胺纤维。
4.权利要求3的纱线，其中，在芳族聚酰胺纤维总量中，对位-芳族聚酰胺纤维的存在量为20～40重量％以及间位-芳族聚酰胺纤维的存在量为60～80重量％。
5.权利要求4的纱线，其中对位-芳族聚酰胺纤维的存在量为25～35重量％以及间位-芳族聚酰胺纤维的存在量为65～75重量％。
6.权利要求5的纱线，还含有抗静电组分。
7.权利要求6的纱线，其中抗静电组分是碳或金属。
8.权利要求7的纱线，其中抗静电组分是碳。
9.权利要求1的纱线，还含有抗静电组分。
10.权利要求9的纱线，其中抗静电组分是碳。
11.适合提供防电弧性和防热性的织物，包含：
(a)40～75重量％变性聚丙烯腈纤维，
(b)10～40重量％棉纤维和
(c)1～40重量％芳族聚酰胺纤维，
所述百分数都以组分(a)、(b)和(c)之和为基准。
12.权利要求11的织物，包含：
(a)45～60重量％变性聚丙烯腈纤维，
(b)15～35重量％棉纤维和
(c)5～30重量％芳族聚酰胺纤维。
13.权利要求11的织物，其中按ASTM D-6413-99测得的焦炭长度小于6英寸。
14.权利要求11的织物，其中按ASTM D-6413-99测得的焦炭长度小于4.5英寸。
15.权利要求11的织物，其中所述织物包括对位-和间位-芳族聚酰胺。
16.权利要求15的织物，其中，在芳族聚酰胺纤维总量中，对位-芳族聚酰胺纤维的存在量为20～40重量％以及间位-芳族聚酰胺纤维的存在量为60～80重量％。
17.权利要求16的织物，其中对位-芳族聚酰胺纤维的存在量为25～35重量％以及间位-芳族聚酰胺纤维的存在量为65～75重量％。
18.权利要求11的织物，还包含抗静电组分。
19.适合提供防电弧性和防热性的衣服，包含：
(a)40～75重量％变性聚丙烯腈纤维，
(b)10～40重量％棉纤维和
(c)1～40重量％芳族聚酰胺纤维，
所述百分数以组分(a)、(b)和(c)之和为基准计算。
20.权利要求19的衣服，包含：
(a)45～60重量％变性聚丙烯腈纤维，
(b)15～35重量％棉纤维和
(c)5～30重量％芳族聚酰胺纤维。
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WO2005090660A1 (en) 2005-09-29
EP1725704B1 (en) 2008-05-28
BRPI0508166B1 (pt) 2015-12-01
US20050208855A1 (en) 2005-09-22
BRPI0508166A (pt) 2007-08-07
BRPI0508166B8 (pt) 2023-01-31
JP2007529649A (ja) 2007-10-25
CN1930334A (zh) 2007-03-14
CA2557185A1 (en) 2005-09-29
DE602005007193D1 (de) 2008-07-10
KR20060124761A (ko) 2006-12-05

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