CN1206304C - 被整理后赋予抗静电性的聚氨酯和弹性纤维 - Google Patents
被整理后赋予抗静电性的聚氨酯和弹性纤维 Download PDFInfo
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- CN1206304C CN1206304C CNB031077951A CN03107795A CN1206304C CN 1206304 C CN1206304 C CN 1206304C CN B031077951 A CNB031077951 A CN B031077951A CN 03107795 A CN03107795 A CN 03107795A CN 1206304 C CN1206304 C CN 1206304C
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- Prior art keywords
- dialkyl sulfosuccinate
- poly
- alkylsiloxane
- spinning
- fiber
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Classifications
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- D—TEXTILES; PAPER
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Abstract
本发明涉及聚氨酯组合物,和尤其涉及从其得到的弹性聚氨酯纤维,它们含有磺基琥珀酸二烷基酯作为添加剂和/或它们用聚二烷基硅氧烷、磺基琥珀酸二烷基酯和,任选地,矿物油整理。通过添加磺基琥珀酸二烷基酯或者用它制备聚氨酯组合物或弹性聚氨酯纤维抑制了聚合物的静电带电性,这一带电现象是在例如由聚氨酯纤维制得的经编织物的加工过程中发生。
Description
本申请是专利申请号为99102160.6的专利申请的分案申请。
技术领域
本发明涉及聚氨酯组合物,和尤其涉及从其得到的弹性聚氨酯纤维,它们含有磺基琥珀酸二烷基酯作为添加剂和/或它们用包括聚二烷基硅氧烷、磺基琥珀酸二烷基酯和选择性使用的矿物油的混合物整理。通过添加磺基琥珀酸二烷基酯或者用它制备聚氨酯组合物或弹性聚氨酯纤维抑制了聚合物的静电带电性,这一带电现象例如是在由聚氨酯纤维制得的经编织物的加工过程中发生。在极端的情况下,静电带电现象能够因放电而导致火花。
背景技术
在本说明书上下文中使用的术语“纤维”包括由纺丝方法(其原理一般已知)如干纺丝方法,湿纺丝方法或熔融纺丝方法制得的短纤维和连续长丝纤维。
这些方法描述在,例如,“聚氨酯弹性体”,H.Gall和M.Kausch,Kunststoff-handbuch 7,聚氨酯分册,编辑者:G.Oertel,Carl HanseerVerlag,Munich,Vienna,1993,679-694页中。
包括长链合成聚合物的弹性聚氨酯纤维,其中至少85%是从基于聚醚、聚酯和/或聚碳酸酯的链段化聚氨酯合成的。由纤维制得的纱如用于生产片状制品或机织纺织品或某些物品的那些纱,这些物品进而适合于全帮(foundation garments),袜子和运动服,如游泳服或浴裤。经编方法是加工聚氨酯纤维形成片状制品的一种形式。在经编工艺中高加工速率将导致经向纤维卷曲,因此而严重地影响了加工工艺,这最终能够导致机器停工。
在经编织物加工过程中,这些问题的一个起因是纤维材料的静电带电。在一些情况下, 因强烈的放电现象导致火花。从实际的情况来看,在经编织物的加工过程中,这些问题是不可接受的,因为它们需要放慢加工速度或在加工机器上耗资安装喷杆,为的是使电荷耗散。
在聚氨酯纤维加工过程中,静电带电的一个解决方法描述在日本专利申请JP 9-49167中。该专利公开了整理组合物(制剂),它们含有链烷醇铵-和碱金属-磷酸酯的盐类的混合物作为添加剂,用它来使纤维具有抗静电性。在该文献中描述的磷酸酯的盐类的混合物的缺点限制了这些盐在前处理油(preparation oil或preparations)中的溶解度,该前处理油由聚二甲基硅氧烷和矿物油的混合物组成。由于这一原因,为了使前处理油沉积在聚氨酯纤维上需要特殊的和技术上花费大的前处理技术,以确保前处理油的均匀沉积。这一已知前处理油的另一缺点是在该前处理油中含有磷酸酯的盐类,当被引入生产废水中时,限制了生物操作废水处理厂的操作模式。因此,在聚氨酯纤维借助于洗涤和染整工艺的进一步处理中形成了大量的含盐的废料并因此需要单独处理。
US 32 96 063描述了用于保护聚氨酯纤维不受静电带电影响的前处理油的应用,该油是由低粘度聚二甲基硅氧烷或矿物油和聚戊基硅氧烷的混合物组成。然而,所述前处理油体系的缺点是它对静电带电现象的保护不令人满意。
US 42 96 174和US 51 35 575描述了用于聚氨酯纤维的前处理油的,由聚二甲基硅氧烷、聚戊基硅氧烷和脂肪酸盐组成的混合物。然而,所述前处理油体系也具有对静电带电现象保护得不令人满意的缺点。
由氨基聚硅氧烷和磺基琥珀酸二烷基酯组成的前处理油体系从EP493 766 A1中已知。这一水溶性混合物据称在丙烯酸纤维进一步处理形成碳纤维的过程中能够保护碳纤维不带电,并在丙烯酸纤维的氧化和石墨化形成碳纤维时完全分解。然而,所述前处理油体系具有氨基聚硅氧烷的氨基与聚氨酯组合物反应的缺点。这将导致弹性纤维的溶胀,例如,对纤维的加工性能有不利的影响。而且,由洗涤除去前处理油(这是在弹性纤维的染色之前所必要的)变得更加困难或不可能。因此,很难或甚至妨碍了对纤维进行均匀的染色。所述前处理油的严重缺点是氨基聚硅氧烷被吸入导致中毒。所以,纤维的制备和进一步加工必须在耗资巨大的封闭设备中进行。对于形成碳纤维的进一步加工(描述在EP493 766),这一缺点对于中间产品的生产是可以接受的。
发明内容
本发明的首要目的是提供聚氨酯纤维,与已知聚氨酯纤维相比,其改进了抗静电性。在用于生产全帮或游泳衣的经编织物的处理过程中,抗静电性能将使该处理工艺不受到静电带电的损害。
这一目的是根据本发明通过向聚氨酯组合物中添加有效量的磺基琥珀酸二烷基酯作为具有抗静电效果的物质,和/或将该物质作为外处理油的合适形式沉积在弹性纤维上来实现。
本发明涉及具有改进抗静电性能的聚氨酯组合物,其特征在于它包括:
A)99.98-65wt%,特别99.95-80wt%,最优选99.9-85wt%的聚氨酯,
B)0.02-15wt%,特别0.05-5wt%,最优选0.1-3wt%的对应于通式(1)的磺基琥珀酸二烷基酯:
其中
R1和R2相互独立并可以相同或不同,表示氢或包含1-30个碳原子的烷基,和优选表示包含4-18个碳原子的烷基,和M+是H+,Li+,Na+,K+或NH4 +,
和
C)0-20wt%,特别0-15wt%的添加剂。
由于在聚氨酯纤维的静电性能方面得到了改进,这样能够在采用例如经编织物工艺的纤维加工时获得改进。
本发明进一步涉及一种聚氨酯纤维,它们经过整理后赋予了抗静电性,和它们是以热塑性聚氨酯或以包括至少85wt%链段化聚氨酯的聚合物为基础的,含有0.02-15wt%,特别0.05-5wt%,最优选0.1-3wt%的对应于通式(1)的磺基琥珀酸二烷基酯:
其中
R1和R2相互独立并可以相同或不同,表示氢或包含1-30个碳原子的烷基,和优选表示包含4-18个碳原子的烷基,和M+是H+,Li+,Na+,K+或NH4 +,
其中特别地磺基琥珀酸二烷基酯精细地分散在纤维中和/或分布在纤维表面上。
磺基琥珀酸二烷基酯可以按照文献C.R.Carly,Ind.Eng.Chem.,31卷,45页,1939年中所述来制备。
特别优选的磺基琥珀酸二烷基酯是磺基琥珀酸二异丁基酯钠,磺基琥珀酸二辛基酯钠,磺基琥珀酸二己基酯钠,磺基琥珀酸二戊基酯钠和磺基琥珀酸二环己基酯钠。
更优选的磺基琥珀酸二烷基酯是磺基琥珀酸二辛基酯钠和磺基琥珀酸二己基酯钠。
最优选的磺基琥珀酸二烷基酯是磺基琥珀酸二辛基酯钠。
用于改进静电性能的磺基琥珀酸二烷基酯能够以单种物质或以多种磺基琥珀酸二烷基酯的混合物形式使用。
磺基琥珀酸二烷基酯能够加入到聚氨酯组合物中,例如在聚氨酯纤维的生产过程中,在组合物加工中的任何时刻。例如磺基琥珀酸二烷基酯能够以溶液或淤浆的形式加入到其它聚氨酯或PU纤维添加剂的溶液或分散液中。在形成纤维的加工操作过程中,它们能够与聚合物溶液混合或被注射到后者的纤维喷丝板的上游中。磺基琥珀酸二烷基酯当然也能够单独地加入到聚合物(纺丝)溶液中,以蜡形式或以在合适介质中的溶液或淤浆形式。而且,在聚氨酯的常规生产工艺中,磺基琥珀酸二烷基酯能够以前述配制剂的形式加入。
在聚氨酯纤维的生产过程中,磺基琥珀酸二烷基酯也能够作为整理剂沉积下来。例如,磺基琥珀酸二烷基酯能够以蜡状物或以在合适溶剂中的淤浆或溶液形式引入到原则上已知用于聚氨酯纤维整理的低粘度聚二烷基硅氧烷或矿物油中。
由于磺基琥珀酸二烷基酯在聚二烷基硅氧烷或矿物油中的良好溶解性,能够形成均匀的溶液,通过常规的前处理技术如经过前处理辊或纤维导轮或通过喷雾使溶液沉积在聚氨酯纤维上。
可以任选地加入矿物油以改进磺基琥珀酸二烷基酯在聚二烷基硅氧烷中的溶解度。这些物质的混合物是优选使用的。
所以,本发明还涉及抗静电组合物,它含有至少:
D)0.02-15wt%,特别0.05-5wt%,最优选0.1-3wt%的对应于通式(1)的磺基琥珀酸二烷基酯:
其中
R1和R2相互独立并可以相同或不同,表示氢或包含1-30个碳原子的烷基,和优选表示包含4-18个碳原子的烷基,和M+是H+,Li+,Na+,K+或NH4 +,
和
E)85-99.98wt%,特别95-99.95wt%,最优选97-99.9wt%的聚烷基硅氧烷和/或烷氧基化聚烷基硅氧烷,特别是聚二甲基硅氧烷和/或乙氧基化聚二甲基硅氧烷,其粘度为2-100mPa.s(25℃),特别2.5-50mPa.s(25℃),最优选2.5-30mPa.s(25℃),或粘度为2-2500mPa.s(25℃),特别2.5-2000mPa.s(25℃),最优选3-1500mPa.s(25℃)的矿物油,或该矿物油与以上E)下列举的聚烷基硅氧烷的任意混合物。
还有,磺基琥珀酸二烷基酯钠也能够以常常用于聚氨酯纤维的整理中的前处理油形式添加,除了聚二烷基硅氧烷和矿物油外该前处理油还含有其它辅助物质如脂肪酸的金属盐类,例如硬脂酸、油酸或棕榈酸的Mg、Ca、Zn或Al盐,改性聚有机基硅氧烷,例如支化或交联聚有机基硅氧烷,脂肪酸的酯类或其它乳化剂。该前处理油也能够以分散体的形式存在,例如与脂肪酸的盐混合的形式。由于磺基琥珀酸二烷基酯在聚二烷基硅氧烷中的良好溶解性,任选地加入矿物油,这些前处理油的沉积在改进聚氨酯纤维的静电性能同时没有改变,并能够借助于现有的前处理油技术来进行。
本发明的聚氨酯组合物或从其制备的聚氨酯纤维可以含有作为满足各种目的的添加剂C)的物质,如消光剂,填料,抗氧化剂,色料,颜料,媒染剂,和抵抗热、光、UV辐射和蒸汽的作用的稳定剂。尤其,这些添加剂以计量的用量添加,以使它们不起与磺基琥珀酸二烷基酯相反的作用,后者是作为内添加剂引入或后者随前处理油一起外部沉积。
抗氧化剂和抵抗热、光或UV辐射的稳定剂的例子包括选自位阻酚类,HALS稳定剂(位阻胺光稳定剂),三嗪,二苯甲酮和苯并三唑的稳定剂类。颜料和消光剂的例子包括二氧化钛,氧化锌和硫酸钡。色料的例子包括酸性染料,分散和颜料染料和荧光增白剂。
该添加剂以计量的用量添加,以使它们不起与磺基琥珀酸二烷基酯相反的作用,后者是作为内添加剂引入或后者随前处理油一起外部沉积。
除了被加工形成纤维,用磺基琥珀酸二烷基酯整理已赋予抗静电性的聚氨酯还能够用于生产模制品,膜材,弹性体,发泡剂等。
本发明还涉及通过熔融纺丝法、干纺丝法或湿纺丝法,尤其通过干纺丝法或湿纺丝法,生产聚氨酯纤维的方法,该纤维通过整理而赋予抗静电性,该方法的特征在于:0.02-15wt%,优选0.05-5wt%,最优选0.1-3wt%的对应于通式(1)的磺基琥珀酸二烷基酯
其中
R1和R2相互独立并可以相同或不同,表示氢或包含1-30个碳原子的烷基,和优选表示包含4-18个碳原子的烷基,和M+是H+,Li+,Na+,K+或NH4 +,与聚氨酯熔体或聚氨酯溶液,尤其聚氨酯溶液,在将熔体或溶液纺丝形成聚氨酯纤维之前,进行混合。
如果低于0.02wt%的磺基琥珀酸二烷基酯分布在单丝纤维中或单丝纤维表面上,静电带电的减少并不总是令人满意的。在单丝纤维中引入15wt%以上的磺基琥珀酸二烷基酯将导致纤维的性能下降,所以不是推荐的。
除了通过将磺基琥珀酸二烷基酯引入聚氨酯组合物中来将磺基琥珀酸二烷基酯掺入聚氨酯纤维中外,该磺基琥珀酸二烷基酯也能够与例如前处理油混合通过外部途径沉积下来,为的是改进聚氨酯纤维的静电性能。
通过熔融纺丝法、干纺丝法或湿纺丝法,尤其通过干纺丝法或湿纺丝法,生产被整理而赋予抗静电性的聚氨酯纤维的方法的一种独立变化形式的特征在于:将含0.02-15wt%,特别0.05-5wt%,最优选0.1-3wt%的对应于通式(1)的磺基琥珀酸二烷基酯
其中
R1和R2相互独立并可以相同或不同,表示氢或包含1-30个碳原子的烷基,和优选表示包含4-18个碳原子的烷基,和M+是H+,Li+,Na+,K+或NH4 +,的前处理油作为外用涂料在前处理位置被施涂到纺丝的、固化的聚氨酯纤维上。
本发明的抗静电组合物是通过,例如,将有效量,即0.02wt%-15wt%,特别0.05wt%-5wt%,和最优选0.10wt%-3wt%(相对于前处理油的重量)的磺基琥珀酸二烷基酯加入或溶解于聚烷基硅氧烷,优选聚二甲基硅氧烷中来制备,后者具有粘度2-100mPa.s(25℃),优选具有粘度2.5-50mPa.s(25℃),和最优选具有粘度2.5-30mPa.s(25℃)。为了改进磺基琥珀酸二烷基酯在前处理油中的溶解性,聚烷基硅氧烷可以用粘度为2-2500mPa.s(25℃),优选粘度为2.5-2000mPa.s(25℃),和最优选粘度为3-1500mPa.s(25℃)的矿物油替代,或该矿物油可以以0.1wt%-95wt%,优选以0.3wt%-50wt%,和最优选以0.5wt%-少于25wt%(相对于前处理油的重量)的量添加。而且,前处理油还可含有任何已知用于整理聚氨酯纤维的添加剂,如少于或等于5wt%的脂肪酸金属盐,少于或等于15wt%的改性聚有机基硅氧烷,和少于或等于30wt%的脂肪酸酯,它们全部相对于前处理油的重量计。矿物油进一步特征是,密度为805-910kg/m3(15℃)和根据DIN 51378测得的粘度-密度常数(VDC)为0.770-0.825。
前处理油的沉积量是1-15wt%,优选2-10wt%,和最优选3-8wt%,它相对于纤维重量计。
本发明的聚氨酯纤维由链段化聚氨酯聚合物组成,例如基于聚醚、聚酯、聚醚酯、聚碳酸酯或其混合物的那些。这一类型的纤维能够由一般已知的方法制备,如通过US 2 929 804,US 3 097 192,US 3 428 711,US3 553 290和US 3 555 115和WO 9309174中描述的方法制备。而且,聚氨酯纤维可由热塑性聚氨酯组成,其制备方法描述在例如US 5 565270中。当这些纤维通过经编织物工艺加工形成全帮或游泳衣时,如果它们不用抗静电剂处理或用常规的抗静电剂处理的话,所有这些聚合物将因静电带电现象而显示出纤维经线的卷曲。因此,本发明经过整理而赋予抗静电性的纤维包括所有列举的纤维。
磺基琥珀酸二烷基酯是能够掺入聚氨酯纤维中和/或随前处理油一起经过外部途径沉积在纤维上的添加剂。令人惊奇的是,现已发现,磺基琥珀酸二烷基酯易溶于通常用于聚氨酯纤维的前处理的油中,如聚二烷基硅氧烷和/或矿物油,这样能够形成均匀的溶液。甚至以少量添加时,也能够在不需进一步添加其它盐类如链烷醇铵盐或碱金属卤化物的情况下能够显著改进抗静电性。它们可以由已知的前处理技术,例如借助于前处理辊、纤维导轮或通过喷雾,用作为外用涂料的前处理油进行处理。磺基琥珀酸二烷基酯不含重金属且从毒理学和生态-毒理学观点来说也是无害的,所以是非常合适的。在进一步处理过程中,例如在染色过程中,不会产生具有高的盐含量的废水,后者将降低或甚至损害生物操作性废水处理设备的作用模式。
如以下实施例中所揭示的那样,磺基琥珀酸二烷基酯随前处理油一起掺入到聚氨酯纤维中和/或沉积到聚氨酯纤维上的进一步结果是处理过的聚氨酯纤维的静电性能,例如它们的体积电阻率,得到显著改进。不管磺基琥珀酸二烷基酯被掺入聚氨酯组合物中还是随前处理油一起通过外部途径沉积上去,都将使体积电阻率降低。体积电阻率的测量结果是聚氨酯纤维的静电性能的量度。通过降低体积电阻率,可以改进聚氨酯纤维的静电性能。因此,在经编织物的处理过程中抑制了经向纤维的卷曲。由本发明的聚氨酯纤维阻止了在经编织物的处理过程中的停机现象,并提高了处理操作的速度和与其相关的生产率。
尤其,本发明的聚氨酯组合物中的聚氨酯,也包括链段化聚氨酯,能够从在每种情况下分子端部包含羟基的和具有分子量600-4000g/mol的线性均或共聚物制备,后者例如是聚醚二醇,聚酯二醇,聚酯酰胺基二醇,聚碳酸酯二醇,聚丙烯酸二醇,聚硫代酯二醇,聚硫醚二醇,聚烃二醇或它们的混合物或它们的共聚物。而且,聚氨酯尤其是以有机二异氰酸酯和包括多个活性氢原子的扩链剂,如二醇和多元醇,二-和多胺,羟基胺,肼类,聚酰肼类,聚半卡巴肼类,水或这些组分的混合物为基础的。二醇的例子包括乙二醇,1,2-丙二醇,丁二醇或己二醇。二胺的例子包括乙二胺,1,2-丙二胺,2-甲基-1,5-二氨基戊烷,1,3-二氨基环己烷,1-甲基-2,4-二氨基-环己烷或1,2-二氨基环己烷。
磺基琥珀酸二烷基酯可以与其它常用的添加剂C)一起或独立地掺入本发明的聚氨酯组合物中,这些添加剂例如是UV稳定剂,抗氧化剂,媒染添加剂,内润滑剂,色料,填料,消光剂等。而且,磺基琥珀酸二烷基酯能够通过外部途径,例如与整理剂一起,沉积在聚氨酯上。
本发明的聚氨酯纤维能够用于制备弹性机织织物,编织织物,袜子和其它纺织品,尤其用于游泳衣领域中的那些。
本发明的前处理油的使用并不仅仅限于聚氨酯纤维;该前处理油一般能够用于聚合物的抗静电涂料。
本发明的抗静电的聚氨酯组合物能够加工成模制品,膜材或条材,也能够加工成纤维,如前面所述。
下面所述的测试方法被用于测量聚合物的电性能。
聚氨酯组合物的导电性的变化是通过按照DIN54 345中所述测量体积电阻率来测定的。
具体实施方式
本发明借助下面的实施例来进一步解释,然而这些实施例并不构成对本发明的限制。
从给出的实施例中得知,通过在聚氨酯中掺入磺基琥珀酸二烷基酯或通过将磺基琥珀酸二烷基酯沉积在聚氨酯的表面上能够显著地降低体积电阻率。在这方面,磺基琥珀酸二烷基酯的效果显著优越于其他物质如磷酸酯或聚戊基硅氧烷的效果。不可能进行对比实施例来将本发明的前处理油与基于氨基聚硅氧烷的前处理油(EP493 766A1)比较,因为由于氨基聚硅氧烷的毒性而使测试装置需要附加高得多的技术花费。由于聚氨酯的体积电阻率的显著降低和因此获得的静电性能的改进,这样,在例如由弹性聚氨酯纤维制得的经编织物的处理过程中能够防止静电带电现象,从而改进处理工艺。
实施例1
本实施例说明了磺基琥珀酸二烷基酯在基于聚醚二醇的聚氨酯组合物中作为抗静电剂的效率。将用作抗静电剂的磺基琥珀酸二烷基酯以内添加剂形式加入到聚氨酯组合物中。
聚氨酯组合物是从由平均分子量2000g/mol的聚四氢呋喃(PTHF)组成的聚醚二醇生产的。分子量是以数均分子量给出。二醇用亚甲基-双(4-苯基-二异氰酸酯)(MDI)按照摩尔比1-1.8加以封端,然后用乙二胺(EDA)和二乙基胺(DEA)按重量比97∶3的混合物在二甲基乙酰胺中的溶液进行扩链。(在所有实施例中扩链剂和链终止剂的量与预聚物中未反应异氰酸酯的量之比是1.075)。
之后,将添加剂的母料与聚合物混合。该母料由62.6wt%的二甲基乙酰胺(DMAC)、10.3wt%的Cyanox 1790(1,3,5-三(4-叔丁基-3-羟基-2,5-二甲基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮;American Cyanamid的产品),27.0wt%的30%纺丝溶液和0.001wt%的染料Makrolexviolett(Bayer AG的产品)组成。这一母料被加入到聚氨酯组合物中,这样Cyanox 1790的含量是相对于总固体含量的1.0wt%。
将第二种母料与这一聚氨酯组合物混合。该第二母料由30.9wt%的二氧化钛Type RKB2(Bayer AG的产品),44.5wt%的DMAC和24.6wt%的30%纺丝溶液组成,这样最终的纺丝溶液的二氧化钛含量是0.05wt%(相对于聚氨酯-脲聚合物)。
然后将第三种母料与这一聚氨酯组合物混合。该第三种母料由5.5wt%Silwet L 7607(聚烷氧基改性的聚二甲基硅氧烷;粘度:50mPa.s(在25℃下),分子量1000g/mol,OSI Specialties的产品),5.5wt%的硬脂酸镁,45.0wt%的DMAC和44.0wt%的30%纺丝溶液组成,加入之,以使硬脂酸镁的含量是0.25wt%(相对于聚氨酯-脲聚合物)。
第四种母料与聚氨酯组合物混合。第四种母料由15.0wt%的表1中所示磺基琥珀酸二烷基酯,54.0wt%二甲基乙酰胺和31.0wt%的30%纺丝溶液组成,这样在最终聚氨酯组合物中磺基琥珀酸二烷基酯含量(相对于聚氨酯-脲聚合物)给出在表1中。
用刮刀将聚氨酯组合物刮出一层膜。在处于100℃下的循环空气干燥烘箱中蒸发溶剂达2小时。最终的膜具有层厚1mm。
体积电阻率的测量结果示于表1中。很显然的是,甚至向聚氨酯组合物中添加0.1wt%的磺基琥珀酸二辛基酯钠也能够显著降低体积电阻率。该物质作为抗静电剂的效果因此得到证实。通过向聚氨酯组合物中添加较大量的抗静电剂,体积电阻率进一步降低和作为抗静电剂的添加剂的效果因此得到提高。
表1
实验 | 琥珀酸二烷基酯 | 琥珀酸二烷基酯在膜中的含量(wt%) | 体积电阻率(109ohm)[DC测量电压:100V] |
1a | 磺基琥珀酸二辛基酯钠 | 0 | 6.3 |
1b | 磺基琥珀酸二辛基酯钠 | 0.1 | 0.45 |
1c | 磺基琥珀酸二辛基酯钠 | 0.3 | 0.16 |
1d | 磺基琥珀酸二辛基酯钠 | 1 | 0.12 |
实施例2
这一实施例给出了磺基琥珀酸二烷基酯作为抗静电剂在由基于聚酯二醇生产的聚氨酯组合物中的效果。作为抗静电剂的磺基琥珀酸二烷基酯是以内添加剂的形式加入到聚氨酯组合物中。
聚氨酯组合物是从由30.5wt%的1,6-己烷二醇,14.5wt%的新戊基二醇和55.0wt%的己二酸组成的、平均分子量(数均)为2000g/mol的聚酯二醇制得的。该二醇是用亚甲基-双(4-苯基二异氰酸酯)(MDI)按摩尔比1-1.85加以封端,然后用乙二胺(EDA)和二乙基胺(DEA)按重量比98∶2的混合物在二甲基乙酰胺中的溶液进行扩链。
按照与以上实施例1所述同样方式来添加母料和制备膜。
被加入到聚氨酯组合物中的磺基琥珀酸二烷基酯的量(相对于聚氨酯-脲聚合物)示于表2中。很显然,甚至添加少量的磺基琥珀酸二辛基酯钠也能够显著降低聚氨酯组合物的体积电阻率,该物质作为抗静电剂的效果因此得到证实。而且,在对比实验中表明磺基琥珀酸二烷基酯作为抗静电剂的效果显著高于磷酸酯的效果。
表2
实验 | 琥珀酸二烷基酯 | 在膜中的含量(wt%) | 体积电阻率(109ohm)100V** |
2a | 磺基琥珀酸二辛基酯钠 | 0 | 10 |
2b | 磺基琥珀酸二辛基酯钠 | 1 | 0.9 |
2c(对比) | 磷酸酯* | 1.2 | 5 |
*制备DEZ 2;Bayer AG的产物
**DC测量电压
实施例3
这一实施例揭示磺基琥珀酸二烷基酯作为抗静电剂在由基于聚醚二醇制得的聚氨酯纤维中的效果。用作抗静电剂的磺基琥珀酸二烷基酯是作为添加剂与前处理油一起沉积在聚氨酯纤维上。
聚氨酯纤维是从由平均分子量(数均)2000g/mol的聚四氢呋喃组成的聚醚二醇生产的。该二醇是用亚甲基-双(4-苯基二异氰酸酯)(MDI)按摩尔比1-1.7加以封端,然后用乙二胺(EDA)和二乙基胺(DEA)按重量比97∶3在二甲基乙酰胺中的混合物进行扩链。
之后,将如以上实施例1中所述的母料1和2与纺丝溶液混合。使用二甲基乙酰胺代替母料3中的Silwet L 7607。按照这种方式制得的母料同样与纺丝溶液混合。
最终的纺丝溶液是在纺丝装置(为干纺丝方法所使用的典型装置)中通过喷丝板进行干纺丝,形成11旦纤度的单丝纤维,其中在每一种情况下四根单丝纤维结合形成凝集长丝线材。纤维前处理油(由表3中列出的前处理油组成)用前处理辊沉积,其中沉积4wt%的量(相对于聚氨酯纤维的重量)。聚氨酯纤维随后以800m/min的速度卷取。
磺基琥珀酸二烷基酯加入到基于聚醚二醇的聚氨酯纤维的前处理油中的量,和在用各种前处理油整理之后聚氨酯纤维的体积电阻率,示于表3中。显然,在使用硅油的整理操作之后聚氨酯纤维的体积电阻率是较高的,因此根本不会有什么抗静电效果。前处理油Silicone Y 7769也是这种情况,它含有10wt%比例的聚戊基硅氧烷。在每一种情况下甚至向前处理油中添加少量的磺基琥珀酸二烷基酯也将导致聚氨酯纤维的体积电阻率显著降低。磺基琥珀酸二烷基酯作为抗静电剂的效果因此得到证实。
表3:
实验 | 前处理油的组成,wt% | 体积电阻率(1011ohm) | |||
硅油% | 链烷烃 | 磺基琥珀酸二辛基酯钠 | 100V* | 1000V* | |
3a | 100** | 0 | 0 | 4 | 4 |
3b | 93.5** | 6+ | 0.5 | 1.6 | 1.5 |
3c | 92** | 6+ | 2 | 1 | 1.2 |
3d | 100++ | 0 | 0 | 3.5 | 3.2 |
3e | 89.5++ | 10+ | 0.5 | 3 | 3 |
3f | 78++ | 20+ | 2 | 2.5 | 2 |
*DC测量电压
**Silicone Y 7769,OSI Specialties的产品
+BP Enerpar M 2520,BP Oil的产品
++Baysilone oil M 20,Bayer AG的产品
实施例4
这一实施例揭示了磺基琥珀酸二烷基酯作为抗静电剂在由基于聚酯二醇制得的聚氨酯纤维中的效果。用作抗静电剂的磺基琥珀酸二烷基酯作为添加剂随前处理油一起沉积在聚氨酯纤维上,如实施例3中所述。
聚氨酯纤维是从由30.5wt%的1,6-己二醇,14.5wt%的新戊二醇和55.0wt%的己二酸组成的、平均分子量(数均)为2000g/mol的聚酯二醇制备的。该二醇是用亚甲基-双(4-苯基二异氰酸酯)(MDI)按摩尔比1-1.85加以封端,然后用乙二胺(EDA)和二乙基胺(DEA)按重量比98∶2在二甲基乙酰胺中的混合物进行扩链。
之后,如实施例1中所述的母料1和2与纺丝溶液混合。使用二甲基乙酰胺代替母料3中的Silwet L 7607。以这种方式制得的母料同样与纺丝溶液混合。
按照实施例3中所述,最终的纺丝溶液由干纺丝法进行干法纺丝。聚氨酯纤维随后以800m/min的速度卷取。
磺基琥珀酸二烷基酯加入到用于基于聚酯二醇的聚氨酯纤维的前处理油中的量,和在用各种前处理油整理之后聚氨酯纤维的体积电阻率,示于表4中。显然,在使用硅油的整理操作之后聚氨酯纤维的体积电阻率是较高的,因此根本不会有什么抗静电效果。对于前处理油Silicone Y 7769也是这种情况,它含有10wt%比例的聚戊基硅氧烷。在每一种情况下甚至向前处理油中添加少量的磺基琥珀酸二烷基酯也将导致聚氨酯纤维的体积电阻率显著降低。磺基琥珀酸二烷基酯作为抗静电剂的效果因此再次得到证实。
表4:
实验 | 前处理油的组成,wt% | 体积电阻率(1011ohm) | |||
硅油% | 链烷烃 | 磺基琥珀酸二辛基酯钠 | 100V* | 1000V* | |
4a | 100** | 0 | 0 | 9 | 9.5 |
4b | 93.5** | 6+ | 0.5 | 5 | 5 |
4c | 92** | 6+ | 2 | 4 | 4 |
4d | 100++ | 0 | 0 | 3.8 | 3.6 |
4e | 89.5++ | 10+ | 0.5 | 2.7 | 2.7 |
4f | 78++ | 20+ | 2 | 1.7 | 1.7 |
*DC测量电压
**Silicone Y 7769,OSI Specialties的产品
+BP Enerpar M 2520,BP Oil的产品
++Baysilone oil M 20,Bayer AG的产品。
Claims (21)
2.权利要求1的抗静电组合物,其中磺基琥珀酸二烷基酯的含量为0.05-5wt%。
3.权利要求1的抗静电组合物,其中磺基琥珀酸二烷基酯的含量为0.1-3wt%。
4.权利要求1的抗静电组合物,其中R1和R2表示包含4-18个碳原子的烷基。
5.权利要求1的抗静电组合物,其中聚烷基硅氧烷是聚二甲基硅氧烷。
6.权利要求1的抗静电组合物,其中烷氧基化聚烷基硅氧烷是乙氧基化聚二甲基硅氧烷。
7.权利要求1的抗静电组合物,其中聚烷基硅氧烷和/或烷氧基化聚烷基硅氧烷的含量是95-99.95wt%。
8.权利要求1的抗静电组合物,其中聚烷基硅氧烷和/或烷氧基化聚烷基硅氧烷的含量是97-99.9wt%。
9.权利要求1的抗静电组合物,其中聚烷基硅氧烷和/或烷氧基化聚烷基硅氧烷的粘度为2.5-50mPa.s(25℃)。
10.权利要求1的抗静电组合物,其中聚烷基硅氧烷和/或烷氧基化聚烷基硅氧烷的粘度为2.5-30mPa.s(25℃)。
11.权利要求1的抗静电组合物,其中矿物油的粘度为2.5-2000mPa.s(25℃)。
12.权利要求1的抗静电组合物,其中矿物油的粘度为3-1500mPa.s(25℃)
13.一种通过熔融纺丝法生产聚氨酯纤维的方法,该纤维通过整理而赋予抗静电性,该方法包括生产纺丝用的熔体、将熔体纺丝、在喷丝板的下方形成线材,冷却线材,任选地拉伸所形成的线材,以及对线材进行前处理和卷绕,其特征在于将含有0.02-15wt%的对应于通式(1)的磺基琥珀酸二烷基酯
其中
R1和R2相互独立并可以相同或不同,表示氢或包含1-30个碳原子的烷基,
M+是H+,Li+,Na+,K+或NH4 +,
的前处理油作为外用涂料在前处理位置被施涂到纺丝的、固化的聚氨酯纤维上。
14.权利要求13的方法,其中磺基琥珀酸二烷基酯的含量为0.05-5wt%。
15.权利要求13的方法,其中磺基琥珀酸二烷基酯的含量为0.1-3wt%。
16.权利要求13的方法,其中R1和R2表示包含4-18个碳原子的烷基。
18.权利要求17的方法,其中磺基琥珀酸二烷基酯的含量为0.05-5wt%。
19.权利要求17的方法,其中磺基琥珀酸二烷基酯的含量为0.1-3wt%。
20.权利要求17的方法,其中R1和R2表示包含4-18个碳原子的烷基。
21.根据权利要求13或17的方法,其特征在于包含磺基琥珀酸二烷基酯的前处理油是权利要求1的抗静电组合物。
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DE19805130.1 | 1998-02-09 | ||
DE19805130A DE19805130A1 (de) | 1998-02-09 | 1998-02-09 | Antistatisch ausgerüstete Polyurethane und Elastan-Fasern |
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CNB031077951A Expired - Fee Related CN1206304C (zh) | 1998-02-09 | 2003-04-02 | 被整理后赋予抗静电性的聚氨酯和弹性纤维 |
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EP (1) | EP0934978A1 (zh) |
JP (1) | JPH11315202A (zh) |
KR (1) | KR100573337B1 (zh) |
CN (2) | CN1124313C (zh) |
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DE (1) | DE19805130A1 (zh) |
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DE19931255A1 (de) * | 1999-07-07 | 2001-01-11 | Bayer Ag | Polyurethanharnstoffasern mit erhöhter Festigkeit |
US20050228089A1 (en) * | 2002-02-28 | 2005-10-13 | Ikunori Azuse | Lubricant for treating elastic fiber |
WO2004067687A2 (en) * | 2003-01-17 | 2004-08-12 | Kollin Edward B | Lubricants for run-flat tire systems |
US7259206B2 (en) * | 2003-09-04 | 2007-08-21 | Nippon Paint Co., Ltd. | Water-borne resin composition and electrocoating composition |
US20050199332A1 (en) * | 2004-02-24 | 2005-09-15 | Scott Deborah C. | Hosiery mending composition and method |
DE102004029274A1 (de) * | 2004-06-17 | 2006-01-05 | Dorlastan Fibers & Monofil Gmbh | Gegen Farbänderung geschützte chlorbeständige Elastanfasern |
US20070129524A1 (en) * | 2005-12-06 | 2007-06-07 | Sunkara Hari B | Thermoplastic polyurethanes comprising polytrimethylene ether soft segments |
CN100372906C (zh) * | 2006-02-28 | 2008-03-05 | 黄晖 | 一种防静电包装材料 |
EP2094889A2 (de) * | 2006-11-23 | 2009-09-02 | Basf Se | Verfahren zur herstellung von fasern |
CN101586257B (zh) * | 2008-05-19 | 2011-02-16 | 北京化工大学 | 控制纤维粘连的静电纺丝方法及装置 |
KR101219986B1 (ko) * | 2010-12-29 | 2013-01-08 | 주식회사 효성 | 멀티필라멘트 탄성섬유의 필라멘트간 접착력이 우수한 폴리우레탄 섬유 및 이의 제조방법 |
KR101684792B1 (ko) * | 2015-07-10 | 2016-12-21 | 주식회사 효성 | 내염소성이 우수한 스판덱스 섬유 |
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CN107858766B (zh) * | 2017-12-08 | 2021-08-20 | 华峰重庆氨纶有限公司 | 一种抗静电易着色聚氨酯弹性纤维的制备方法 |
TWI809315B (zh) * | 2019-09-24 | 2023-07-21 | 日商旭化成股份有限公司 | 再生聚胺酯彈性纖維、其製法、含有該再生聚胺酯彈性纖維之纖維構造物、皺褶部件、及衛生材料 |
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DE1174739B (de) * | 1962-02-19 | 1964-07-30 | Boehme Fettchemie Gmbh | Verfahren zur antistatischen Ausruestung von geformten Gebilden |
US3296063A (en) | 1963-11-12 | 1967-01-03 | Du Pont | Synthetic elastomeric lubricated filament |
GB1132594A (en) * | 1964-08-13 | 1968-11-06 | Porous Plastics Ltd | Improvements relating to artificial leather |
GB1293940A (en) * | 1968-11-08 | 1972-10-25 | Asahi Chemical Ind | Preparation of polyurethane composiitons |
JPS5125484A (en) * | 1974-08-27 | 1976-03-02 | Showa Denko Kk | Taidenboshiseijukiekitaisoseibutsu |
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US4296174A (en) | 1980-08-08 | 1981-10-20 | E. I. Du Pont De Nemours And Company | Spandex filaments containing certain metallic soaps |
CA1179105A (en) * | 1981-10-30 | 1984-12-11 | Robert M. Marshall | Stabilized finish composition |
DE3736749A1 (de) * | 1987-10-30 | 1989-05-11 | Bayer Ag | Verwendung von alkali- oder erdalkalisalzen von sulfobernsteinsaeureestern als interne antistatika, abzieh- und wickelhilfen fuer transparente polycarbonatfolien |
US4844824A (en) * | 1988-02-08 | 1989-07-04 | The Procter & Gamble Company | Stable heavy duty liquid detergent compositions which contain a softener and antistatic agent |
ES2070149T3 (es) | 1988-07-06 | 1995-06-01 | Osi Specialties Inc | Metodo para formar dispersiones estables de particulas solidas. |
US4895902A (en) * | 1988-07-28 | 1990-01-23 | E. I. Dupont De Nemours And Company | Hindered tertiary amine aminoalkyl methacrylate stabilizer for spandex |
DE3844435C1 (zh) * | 1988-12-31 | 1990-08-23 | Kurz, Geb. Sendtko, Waldtraud, 8011 Vaterstetten, De | |
JP2589219B2 (ja) | 1990-12-22 | 1997-03-12 | 東邦レーヨン株式会社 | 炭素繊維製造用プレカ−サ−及びその製造法、並びにそのプレカ−サ−から炭素繊維を製造する方法 |
JP2958629B2 (ja) * | 1997-04-21 | 1999-10-06 | 三洋化成工業株式会社 | 弾性繊維用油剤 |
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- 1999-02-08 BR BR9900547-6A patent/BR9900547A/pt not_active Application Discontinuation
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Publication number | Publication date |
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JPH11315202A (ja) | 1999-11-16 |
HUP9900274A2 (hu) | 1999-10-28 |
TR200400944A1 (tr) | 2005-02-21 |
IL128395A (en) | 2004-06-20 |
BR9900547A (pt) | 2000-02-01 |
TR199900253A2 (xx) | 1999-09-21 |
IL128395A0 (en) | 2000-01-31 |
HU9900274D0 (en) | 1999-04-28 |
AR016979A1 (es) | 2001-08-01 |
KR100573337B1 (ko) | 2006-04-24 |
TW425417B (en) | 2001-03-11 |
KR19990072495A (ko) | 1999-09-27 |
CN1226577A (zh) | 1999-08-25 |
SG77218A1 (en) | 2000-12-19 |
CN1124313C (zh) | 2003-10-15 |
HK1022163A1 (en) | 2000-07-28 |
DE19805130A1 (de) | 1999-08-12 |
US6329452B1 (en) | 2001-12-11 |
CO5040171A1 (es) | 2001-05-29 |
HUP9900274A3 (en) | 2000-10-30 |
EP0934978A1 (de) | 1999-08-11 |
CA2260760A1 (en) | 1999-08-09 |
PL331308A1 (en) | 1999-08-16 |
CN1442462A (zh) | 2003-09-17 |
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