CN1156485A - 柔软强力热塑性聚合物纤维和由其制造的非织造织物 - Google Patents

柔软强力热塑性聚合物纤维和由其制造的非织造织物 Download PDF

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CN1156485A
CN1156485A CN95194765A CN95194765A CN1156485A CN 1156485 A CN1156485 A CN 1156485A CN 95194765 A CN95194765 A CN 95194765A CN 95194765 A CN95194765 A CN 95194765A CN 1156485 A CN1156485 A CN 1156485A
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P·M·科贝利维克
S·K·奥弗苏
S·E·肖华
R·L·兰斯
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Abstract

提供了一种非织造纤维和织物,其中该织物具有与传统织物相差不大的强度特性,但却较柔软。该纤维是高结晶度聚丙烯聚合物和聚丙烯聚乙烯的无规嵌段共聚物的混合物。本发明的织物可以与另一个纺粘层、熔喷非织造织物或薄膜层压。本发明的非织造织物可以用于若干产品,例如衣服、个人护理用品、医用产品、防护罩和户外用织物。

Description

柔软强力热塑性聚合物纤维 和由其制造的非织造织物
                    发明背景
概括地说,本发明涉及热塑性树脂纤维和从这种纤维形成的非织造织物或纤维网,以及用这种纤维网作为一个组成部分的层压制品。
将热塑性树脂挤压,形成纤维、织物和纤维网的技术已经有许多年历史。适于这种用途的最普通的热塑性塑料是聚烯烃,尤其是聚丙烯。其他材料如聚酯、聚醚酯、聚酰胺和聚氨酯也适用于形成非织造织物。
非织造织物或纤维网可用于各种用途如尿布、妇女卫生用品、毛巾和休闲或防护织物。用于这些用途的非织造织物通常为层压制品如纺粘/熔喷/纺粘(SMS)层压制品的形式。非织造织物的强度是最需要的特性之一。纤维网强度较高,使用较薄层的材料就可以得到相当于较厚层的强度,从而使一部分结构为纤维网的任何制品的消费者能节省费用、减小制品体积和重量。此外,最理想的是这类纤维网,尤其是当用于消费产品如尿布或妇女卫生用品时必须是非常柔软的。
本发明的一个目的是提供一种强度很高而且非常柔软的聚丙烯非织造织物或纤维网。
                    发明概述
提供了一种强度很高而且柔软的非织造聚丙烯纤维。也提供了一种织物,该织物是由聚烯烃聚合物的共混物生产的纤维的纤维网。一种聚合物是高结晶度的聚丙烯。另一种聚合物是聚丙烯和聚乙烯的共聚物,其中乙烯为无规嵌段分布,因此它是一种“无规嵌段共聚物”。
从上述共混物的纤维制成的织物的强度高得令人惊奇,发明者认为,这是由于聚丙烯的结晶度高,在粘合时粘合点没有完全熔融所致。
把本发明的非织造织物可应用于一些产品,例如衣服、个人护理用品、医用产品、防护罩和户外用织物。
                          定义
本文所使用的术语“非织造织物或纤维网”意指结构为单根纤维或丝交互铺置,而不是象针织物那样以规则重复的方式铺置的一种纤维网。非织造织物或纤维网现已能用许多方法制成,例如熔喷法、纺粘法和梳理机纤维网粘合法。非织造织物的单位重量通常以每平方码材料的盎司数(osy)或以每平方米的克数(gsm)表示,纤维有效直径通常以微米表示。(注:从osy换算成gsm的方法为osy×33.91)。
本文使用的术语“微纤维”意指平均直径不大于约50微米的小直径纤维,例如:平均直径约为0.5~50微米,或者更具体地说,微纤维平均直径可约为2~40微米。直径,例如以微米为单位给出的聚丙烯纤维的直径,可以通过将该直径数值平方,再将所得结果乘以0.00629,换算成旦数,例如,15微米的聚丙烯纤维,约为1.42旦(152×0.00629=1.415)。
本文所使用的术语“纺粘纤维”指的是将熔融热塑性材料从喷丝板的许多细的通常为圆形的具有挤压长丝直径的毛细管中以长丝的形式挤压出来形成的直径很小的纤维,然后迅速按以下专利所述方法处理,例如Appel等人的美国专利4,340,563、Dorschner等人的美国专利3,692,618、Matsuki等人的美国专利3,802,817、Kinney的美国专利3,338,992和3,341,394、Lery的美国专利3,502,763和3,909,009,以及Dobo等人的美国专利3,542,615。纺粘纤维通常是连续的、并且直径大于7微米。更具体地说,直径通常约为10~20微米。
本文所使用的术语“熔喷纤维”意指按如下方法形成的纤维,将熔融热塑性材料经许多细的、通常为圆形的喷丝头毛细管挤出,以熔融纤维或丝的形式进入会聚高速气流(例如空气),使熔融热塑性材料的丝变细来减少其直径,可以达到微纤维直径。此后,高速气流携带熔喷纤维,置于一收集表面上,形成无规分布的熔喷纤维网。这种方法公开于例如Butin的美国专利3,849,241中。熔喷纤维通常是直径小于10微米的微纤维。
本文所使用的术语“双组分”指的是将至少两种聚合物从各个挤出机挤出,而且将它们一起纺成一根纤维所形成的纤维。这种双组分纤维的结构可以是例如:一种聚合物围绕另一种聚合物的皮/芯排列,或者可以是如Kaneko等人的美国专利5,108,820说明的并列排列或者为“海岛”排列。聚合物的比例为75/25,50/50,25/75或任何其他要求的比例。
本文所使用的术语“双成分纤维”指的是从同一台挤出机以共混物的形式挤出的至少两种聚合物形成的纤维。双成分纤维有时称为多成分纤维,并且通常在一种主要聚合物的基质中有一种聚合物的原纤维。这种通用型纤维,例如Gessner的美国专利5,108,827已有详述。
本文中所使用的术语“共混物”意指两种或两种以上聚合物的混合物,而术语“合金”意指共混物的一个子类,其中各组分不溶混,但是已被相容。“溶混性”和“不溶混性”分别被定义为具有负值和正值混合自由能的共混物。另外,“相容作用”被定义为为了制造合金,改善不溶混的聚合物共混物的界面性能的过程。注意从聚合物的共混物形成的纤维不必具备双成分纤维的原纤维特性。
本文所使用的术语“机器方向”或MD意指随着生产织物而得到的织物长度方向。术语“机器横向”或CD意指织物的宽度方向,即通常指垂直于MD的方向。
本文使用的“衣服”这个词意指可以穿着的任何类型的服装。包括工业工作服和衣裤相连的工作服、内衣、裤子、衬衣、夹克、手套和短袜等。
本文所使用的“医用产品”这个用语意指医用、牙科用或兽医用的外科手术服和窗帘、面具、头套、鞋套绷带、绷带和灭菌外衣等。
本文所使用的“个人护理用品”这个用语意指擦布、尿布、运动短裤、吸湿衬裤、残疾人用品以及妇女卫生用品。
本文所使用的“防护罩”这个用语意指运载工具的罩,如汽车、卡车、船、飞机、摩托车、自行车和高尔夫车等;经常置于室外的设备的罩,如烤架、庭院和花园机具(割草机、旋转碎土器等)和草地设备,以及地毯、桌布和野餐区覆盖物。
本文所使用的“户外用织物”这个用语意指主要的,但不排除其它,户外应用的织物。户外用织物包括应用于如下方面的织物,如:防护罩、野营者/追猎者用的织物、帆布、篷帐布、天篷、帐幕、农用织物和户外服装如头套、工业工作服和衣裤相连的工作服、裤、衬衣、夹克、手套、短袜和鞋套等。
                      实验方法
压杯值(Cup Crush):非织造织物的柔软度可按照“压杯”试验测定。压杯值较低表示材料较柔软。压杯试验是通过测量,直径为4.5厘米的半球形底座将一块23厘米×23厘米的织物压成直径约6.5厘米高约6.5厘米的倒转杯形,所需要的最大负荷来评价织物的柔软度,进行上述测量时,杯形织物用一个直径约为6.5厘米的圆筒围绕,以便保持其均匀变形。底座和杯对齐,以避免杯壁和底座接触而影响最大负荷。当底座以每秒0.25英寸(每分钟38厘米)的速度下降时,测量最大负荷。测量压杯值适用的装置是Schaeritz公司(Pennsauken,新泽西州)供应的FTD-G-500型测压仪(量程500克)。压杯值以克计量。
强度:织物断裂强度可以按照ASTM试验D-1682-64测量。该试验测量的最大强度以磅计,伸长以织物百分数计。
熔体流动速率:熔体流动速率(MFR)是聚合物粘度的一种度量。MFR以在规定负荷或切变速率下在测定时间内从已知尺寸的毛细管流出的材料重量表示,按照,例如:ASTM试验1238条件E,在230℃下测量,以克/10分钟表示。
                   附图简述
图1是希蒙特(Himont)KSO-050的碳13核磁共振波谱图,以0~60ppm作横轴,用四甲基硅烷作载体,采用本领域中已知的方法用Bruker AC-250 NMR波谱仪进行实验。
图2是希蒙特(Himont)KSO-050无规嵌段共聚物红外扫描或曲线图。以波数400~2000作横轴,以透射率百分数35~101作纵轴。
                    详述
优选的是,本发明的纤维和非织造织物采用纺粘法生产。本发明的纤维和织物用高结晶聚丙烯和无规嵌段共聚物制成,两者的量分别约为95%重量和5%重量至50%重量和50%重量。
纺粘法中使用的聚烯烃的重要性质对本领域的技术人员来说是已知的。熔体流动速率、粘度、二甲苯不溶物和等规聚合物对聚合物总量的百分率在表征聚合物的特性中都是相当重要的。
熔体流动速率与聚合物的粘度有关,其数值较高表示粘度较低。关于熔体流动速率的试验上文已做详细说明。
二甲苯不溶物测量聚合物中低分子量等规物和中分子量无规物的量。分子量分布中的二甲苯不溶部分在纤维成形期间不结晶,并且认为在气动拉细纤维成形过程中有助于纤维的拉伸过程。已经发现,实施本发明使用的聚合物必须含有二甲苯不溶物,最大约为2%。
聚合物结晶度的另一种度量是等规聚合物对聚合物总量的百分数。称之为等规度或等规指数,它可以从聚合物的核磁共振波谱计算出。已经发现实施本发明使用的聚合物等规度必须至少约为98%。
可以认为,与常用聚丙烯比较,结晶度较高的聚丙烯最高熔融温度向高移动6~7℃,热函约增加20%。这种增加使足够的材料熔融来参与粘合过程,但是也保持纤维有足够的性能以维持其强度。
纺粘法一般使用一个漏斗,将聚合物进料到加热了的挤压机中。挤压机将熔融聚合物输送到喷丝板,聚合物通过喷丝板中排成一行或多行的细小孔,被纤维化,形成丝幕。丝条通常以低压空气骤冷,拉伸,通常以气动方法置于运动着的有小孔的垫上、运输带或“成形金属丝网”上,形成非织造织物。纺粘法常用的聚合物加工温度通常为约350~约610 °F(175~320℃)。
用纺粘法生产的纤维,直径依加工条件和从这些纤维生产的织物的预期最终用途而异,通常为约10~20微米。例如:由于增加聚合物分子量或降低加工温度,使纤维直径增大。骤冷气流温度和气流拉伸压力的变化也会影响纤维直径。在本发明中所使用的具体聚合物生产的纤维的直径可以比纺粘法通常生产的小。
通常将纺粘纤维粘合在一起,压实成粘结层。在实施本发明中优选的粘合方法是热粘合和超声粘合,但是也可以使用其他方法如流体缠结、针刺粘结和粘合剂粘合法。即使高结晶度聚丙烯的熔点较纺粘织物常用的聚丙烯高,但是在制造本发明织物中也不必使用特殊的粘合条件,粘合仍在大约与传统聚丙烯相同的温度下进行。本发明者认为,低熔点无规嵌段共聚物在粘合点优先熔融粘合,而高结晶度聚丙烯熔融较少,以便有助于保持纤维网的强度;但他们并不希望其发明受这种看法的约束。这既保证得到了强力织物,又提供了足够的粘合面积用于将织物结合在一起。
本发明的织物能以织物单位重量约为0.3~3.5osy(10~119gsm)的单层实施方案使用,或者作为织物单位重量高得多的多层层压制品的一个组分使用。这种层压制品可以包括另一个纺粘层、熔喷层、薄膜、玻璃纤维、短纤维、纸以及本领域技术人员已知的其他常用材料。
假如织物与薄膜或熔喷层一起层压,那末薄膜或熔喷层可由聚氨酯、聚酯、聚醚酯、聚酰胺或聚烯烃构成,且可以是弹性体。可以用于薄膜和熔喷织物的商品弹性体聚合物的具体实例包括苯乙烯嵌段聚烯烃共聚物如壳牌化学公司(得克萨斯州休斯敦)供应的通称为KRATON的材料,聚氨酯弹性体材料如B.F.Goodrich公司的称为ESTANE的材料,聚酰胺弹性体材料如Rilasn公司以商标名PEBAX供应的材料,聚酯弹性体材料如杜邦公司以商标名HYTREL供应的材料。
多层层压制品可以采用许多不同技术制成,包括,但不只限于,使用粘合剂、针刺、超声粘合、热轧光和本领域已知的任何其它方法。Brock等人的美国专利4,041,203和Collier等人的美国专利5,169,706公开了一个多层层压制品的实施方案,其中,一些层是纺粘,一些层是熔喷,如纺粘/熔喷/纺粘(SMS)层压制品。这样一种层压制品可以通过如下方法制造,在移动的输送带或成形金属丝网上顺序放置,先是纺粘织物层,然后是熔喷织物层,最后是另一层纺粘层,再用上述方法将该层压制品粘合。或者,可以分别单独制造这三层织物,叠合于压辊上,然后在单独的粘合步骤中结合。
可以使用本发明织物的领域是衣服、医用产品、个人护理用品和户外用织物。
正如以上所述,用于本发明的聚丙烯聚合物必须具有高结晶度,即这种聚丙烯聚合物的等规度必须至少为98%。全世界的许多制造厂均可供应这种聚丙烯聚合物。其中一个供应厂商是埃克森(Exxon)化学公司(得克萨斯州,贝敦),它可供应在结晶度规格范围内的实验聚丙烯聚合物。
本发明的纤维是共混热塑性聚合物纤维,所以用于本发明的无规嵌段共聚物必须与高结晶度聚丙烯聚合物溶混,并保留在半结晶纤维的非结晶相内。优选不使用相容剂。为了符合这些规定,适用的无规嵌段共聚物的熔融温度必须低于160℃(320 °F)。适用的无规嵌段共聚物可得自希蒙特公司(特拉华州威明顿),其商品名为KSO-57P。按照Bill Publications(355 Park Ave.South,N.Y.,N.Y.,10010)的塑料工艺制造商手册和买方指南(Plastic Technology′s  ManufacturersHandbook&Buyer′s Guide)1994/95第673页,希蒙特的KSO-57P熔体流动速率为30,密度为0.9克/厘米3
聚合物的特征可用许多方法表示,其中两种是核磁共振扫描法(NMR)和红外扫描(IR)。图1和图2表示实施本发明中优选的无规嵌段共聚物希蒙特公司的KSO-050在过氧化物裂解生产KSO-57P之前的扫描结果。过氧化物裂解是一种提高聚合物熔体流动速率的方法。Timmons的美国专利5,271,883叙述了该方法的一个实例。
该聚合物的NMR波谱和IR曲线表明:KSO-57P含有约3%无规乙烯分子和9~10%嵌段乙烯分子,因此称为前文已述的“无规嵌段共聚物”。
以下实例说明,由符合本发明要求的聚合物生产的纤维(实例2、3、5和6)与不符合本发明要求的聚合物生产的纤维的特性的比较。结果示于表1。
                    实例1
生产了织物单位重量(BW)为0.7osy(24gsm)的纺粘非织造织物。该纤维由埃克森化学公司的商品聚丙烯Escorene3445制成。其纺丝温度约为430°F(221℃)。喷丝板孔径为0.6毫米,原料通过量约为0.7克/孔·分(ghm),所产生的纤维直径约为15微米(1.4旦)。使纤维网通过温度为305 °F(152℃)的热轧光机,将纤维热粘合,粘合面积约为15%。
                       实例2
生产了织物单位重量为0.7osy(24gsm)的纺粘非织造织物。该纤维由埃克森化学公司的高结晶度实验聚丙烯(HCP)和希蒙特的KSO-57P无规嵌段共聚物以80/20比例的混合物制成。其纺丝温度约为430°F(221℃),喷丝板孔径为0.6毫米,原料通过量为0.7~0.9克/孔·分(ghm),所生产的纤维直径为15.4微米(1.5旦)。使纤维网通过温度为305°F(152℃)的热轧光机,将纤维热粘合,粘合面积约为15%。
                   实例3
生产了织物单位重量为0.7osy(24gsm)的纺粘非织造织物。该纤维由埃克森化学公司的高结晶度实验聚丙烯和希蒙特的KSO-57P无规嵌段共聚物以60/40比例的混合物制成。其纺丝温度约为430°F(221℃)。喷丝板孔径为0.6毫米,原料通过量约为0.7克/孔·分(ghm),所生产的纤维直径为15.4微米(1.5旦)。使纤维网通过温度为305°F(152℃)的热轧光机,将纤维热粘合,粘合面积约为15%。
                   实例4
生产了织物单位重量为1.6osy(54gsm)的纺粘非织造织物。该纤维由埃克森化学公司的Escorene3445聚丙烯制成。其纺丝温度约为430°F(221℃)。喷丝板孔径为0.6毫米,原料通过量约为0.7克/孔·分(ghm),所生产的纤维直径为15微米(1.4旦)。使纤维网通过温度为305°F(152℃)的热轧光机,将该纤维热粘合,粘合面积约为15%。
                        实例5
生产了织物单位重量为1.6osy(54gsm)的纺粘非织造织物。该纤维由埃克森化学公司的高结晶度实验聚丙烯和希蒙特的KSO-57P无规嵌段共聚物以80/20比例的混合物制成。其纺丝温度约为430°F(221℃)。喷丝板孔径为0.6毫米,原料通过量约为0.7克/孔·分(ghm),所生产的纤维直径为15.4微米(1.5旦)。使纤维网通过温度为305°F(152℃)的热轧光机,将该纤维热粘合,粘合面积约为15%。
                     实例6
生产了织物单位重量为1.6osy(54gsm)的纺粘非织造织物。该纤维由埃克森化学公司的高结晶度实验聚丙烯和希蒙特的KSO-57P无规嵌段共聚物以60/40比例的混合物制成。其纺丝温度约为430°F(221℃)。喷丝板孔径为0.6毫米,原料通过量约为0.7克/孔·分(ghm),所生产的纤维直径为15微米(1.4旦)。使纤维网通过温度为305°F(152℃)的热轧光机,将该纤维热粘合,粘合面积约为15%。
                            表1
                           压杯值               CD                        MD序号  样品名称             BW   能量  负荷   最大负荷 伸长   断裂能  最大负荷 伸长    断裂能1    Escorene3445      0.7  1527   77.4  13.699   62.05  23.731  18.257   54.27   24.2092    80/20(HCP,KSO57P)   0.7  1094   55.6  12.768   62.3   19.541  14.955   55.5    24.5813    60/40(HCP,KSO57P)   0.7   612   34     8.591   69.83  14.453   9.928   54.75   19.0564    Escorene3445      1.6  7094  378    27.636   61.26  67.098  40.7     44.2    68.75    80/20(HCP,KSO57P)   1.6  5460  280    37.53    94.75  85.568  45.18    69.428  82.1696    60/40(HCP,KSO57P)   1.6  3282  181    30.346   97.85  68.847  30.34    64.43   61.09
该数据表明,按照本发明制成的纺粘型织物,当织物单位重量较低时,强度和常规纤维网不相上下,而当织物单位重量较高时,强度则令人惊奇地优于常规纤维网。当压杯值基本上较低时,呈现出这样的强度,说明柔软度大大改善。事实上,按照本发明制成的织物的柔软度至少比传统聚丙烯织物在25%,即其压杯值至少比单独由聚丙烯制成的非织造纤维网低25%。
这些结果表明,由高结晶度聚丙烯和具有特定特性的无规嵌段共聚物的独特组合纺成的纤维制成的纺粘型织物的物理性能与传统聚丙烯纺粘型织物相差不大,但其柔软性却较好。

Claims (20)

1.可粘合的热塑性聚合物纤维,它由结晶度至少为98%的聚丙烯聚合物和熔点低于160℃的聚丙烯和聚乙烯无规嵌段共聚物的共混物构成。
2.权利要求1的纤维,它基本上不含相容剂。
3.权利要求1的纤维,它是由选自纺粘法和熔喷法的方法生产的。
4.权利要求3的纤维,其中所述的方法是纺粘法。
5.权利要求1的热塑性聚合物纤维,其中所述的无规嵌段共聚物具有图1所示的NMR波谱。
6.一种非织造织物,包含权利要求1的热塑性聚合物纤维的纤维网。
7.权利要求6的非织造织物,其织物单位重量为约0.3~约3.5osy。
8.权利要求6的非织造织物,它是由选自纺粘法和熔喷法的方法生产的。
9.权利要求8的织物,其中所述的方法是纺粘法。
10.权利要求9的非织造聚丙烯织物,它另外还包含第二层纺粘聚丙烯。
11.权利要求10的非织造织物,其中所述的非织造纺粘层之间至少有一层选自熔喷非织造织物和薄膜的中间材料。
12.权利要求11的非织造织物,其中所述的中间材料是一种弹性体熔喷非织造织物,它是由选自苯乙烯嵌段共聚物、聚烯烃、聚氨酯、聚酯、聚醚酯和聚酰胺的一种材料制成的。
13.权利要求11的非织造织物,其中所述的中间材料是一种弹性体薄膜,它是由选自苯乙烯嵌段共聚物、聚烯烃、聚氨酯、聚酯、聚醚酯和聚酰胺的成膜聚合物制成的。
14.权利要求11的非织造织物,其中所述的层是采用选自热粘合、超声粘合、流体缠结、针刺粘合和粘合剂粘合等方法中的一种方法粘在一起,而形成层压制品的。
15.权利要求14的层压制品,其形式可为医用产品、个人护理用品和户外用织物。
16.权利要求14的层压制品,其中所述的产品是个人护理用品,而所述的个人护理用品是尿布。
17.权利要求14的层压制品,其中所述的产品是个人护理用品,而所述的个人护理用品是妇女卫生用品。
18.权利要求14的层压制品,其中所述的产品是医用产品,而所述的医用产品是外科手术服。
19.权利要求14的层压制品,其中所述的产品是医用产品,而所述的医用产品是面具。
20.权利要求14的层压制品,其中所述的产品是个人护理用品,而所述的个人护理用品是擦布。
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CN105586719B (zh) * 2014-10-24 2019-04-05 张家港骏马无纺布有限公司 一种柔软高强力涤纶sms复合非织造材料及其制备方法
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CN113164303B (zh) * 2018-11-30 2023-11-17 金伯利-克拉克环球有限公司 三维非织造材料及其制造方法
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US6224977B1 (en) 2001-05-01
US5607798A (en) 1997-03-04
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MX9701434A (es) 1997-05-31
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CA2154496C (en) 2004-09-14
AU3151295A (en) 1996-03-14
CN1066784C (zh) 2001-06-06
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AU687599B2 (en) 1998-02-26

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