CN1259153A - 拉伸充填微孔膜及其制造方法 - Google Patents
拉伸充填微孔膜及其制造方法 Download PDFInfo
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- CN1259153A CN1259153A CN98805723A CN98805723A CN1259153A CN 1259153 A CN1259153 A CN 1259153A CN 98805723 A CN98805723 A CN 98805723A CN 98805723 A CN98805723 A CN 98805723A CN 1259153 A CN1259153 A CN 1259153A
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Abstract
一种通过挤压制备出可透气的微孔膜,此膜包括约30—70%重量的热塑性聚合物;约30—70%重量的平均粒度小于约10微米的填料;及约100—1000PPM的单官能受阻酚例如α生育酚,然后将此充填膜沿至少一个方向充分地拉伸成使其中形成细孔的网络并具有超过300g/m2/24小时的水蒸汽透过率。
Description
发明领域
本发明涉及拉伸充填膜。更具体地说,本发明涉及改进的拉伸充填微孔膜。
发明背景
当前存在有种种能用作粒状物质、水与其他液体的阻挡层,但仍可使水蒸汽与空气从中通过的织物。这种织物普遍称作为“可透气阻挡层”织物。可透气阻挡层织物已用作户外用织物、防水布、衣着、贴身产品、感染控制产品以及众多的其他制品。此外,可透气阻挡层织物通常最好是在不透气阻挡层材料之上,这是因为可透气阻挡层织物会使俘获于此织物之下的水分作为水蒸汽形式逸出。这样,采用了可透气阻挡层的衣服穿起来普遍较为舒适,因为水蒸汽通过这种织物迁移出有助于减少和/或消除由于相对于皮肤俘获了过多的水份而造成的不舒适。
虽然在先有技术中已知有多种可透气阻挡层织物,但特别有用的可透气阻挡层则包括拉伸充填微孔膜。这类膜通常充填以粒料,然后经压实或拉伸而于膜上普遍形成细孔网络。这种细孔网络允许气体和水蒸汽通过此膜,同时对液体或粒状物质起到阻挡层作用。膜中填料的数量和尺寸以及拉伸度受到控制,用以形成这样的微孔网络,其尺寸和频率能给织物以所需水平的透气率。例如授予Sheth的美国专利No.4777073公开了一种可透气的聚烯烃膜,它充填有按体积计约15-35%的碳酸钙并被拉伸至其原始长度的约4倍。类似地,授于Tapp的美国专利No.5169712公开了一种定向的多孔膜,它包括乙烯-丙烯嵌段共聚物,以成核剂和碳酸钙充填,可拉伸至其原有长度的约7倍,而形成可透气的微孔膜。
虽然充填式微孔膜能提供具有良好阻挡性和透气性的制品,但使这种膜能有效的商品化和实际应用则需要改进拉伸性、强度和提高其能够经受缺陷的能力。在这一方面,拉伸或减薄充填式膜常使它们特别容易出现不均匀性,例如针孔、比膜厚大的胶滞体、粒子污染物和/或不均匀的聚合物分布。虽不会有损于膜的透气性,但拉伸充填膜的阻挡层性质则有可能受到损害,这是由于这些不均匀性常会在膜中形成缺陷(即宏大的孔洞)或低强度区。这在要把此种膜用作对尿、血或其他体液以及与此有关的病菌的阻挡层时关系重大。此外,把充填式膜拉伸到所需程度虽然可用来使膜取向还使其微孔化,但却使由此形式的透气膜的强度和伸长率不利地减小了。考虑到这种膜的许多用途,特别是用作衣着或控制感染产品时,就极其希望有改进了耐用性的透气阻挡层织物,这是由于强度较低的膜势必较易撕裂且同时对于用在需要活动的场所会带来较多的限制。
于是,需要有改进了的充填微孔膜,特别是那些改进了强度和拉伸特性的膜。另外还需要有在拉伸时减少了不均匀程度和/或更能容许这类不均匀性的充填式膜。此外,还需要有制造这种拉伸充填膜的方法,特别是制造使成品膜的物理特性得到了改进和/或减少了产生薄膜缺陷可能性的透气膜的方法。
发明概述
上述需要的实现和内行人士感到困惑的问题的解决是通过本发明的拉伸充填膜而获得的,这种拉伸充填膜包括:(i)约30-70%(重量)的热塑性聚合物;(ii)约30-70%(重量)的平均粒度小于约10微米的填料粒、(iii)约100-1500ppm的单官能受阻酚,其中此拉伸充填膜是可透气阻挡层。在另一方面,这种受阻酚最好包括生育酚例如2,5,7,8-四甲基-2-(4′,8′,12′-三甲基十三烷基)-6-苯并二氢吡喃。在最佳实施例中,单官能受阻酚例如α生育酚在此膜中的存在量可以为约100-600ppm。
在本发明的又一个方面,可透气的拉伸减薄膜的阻挡层按照本发明可按下述步骤制成:形成膜的挤压材料,这种膜料包括约30-70%(重量)的热塑聚合物、约30-70%(重量)的平均粒度小于约10微米的填料粒、以及约100-1000ppm的单官能受阻酚。然后由这种挤压料形成膜,然后,至少在一个方向上充分地拉伸,以赋予此膜料可透气性。这种膜最好按伸长率50-90%拉伸而裂隙形成WVTR超过约300克/米2/24小时(g/m2/24hr)的透气膜。在又一个方面,这种膜可沿机器方向(MD)单轴向拉伸到足以使此拉伸充填膜具有的WVTR至少为1500g/m2/24hr的程度。
附图简要描述
图1是本发明的拉伸充填膜/非织造物层压件的横剖图。
定义
这里所用的词“非织造”织物或织品是指具有各个纤维或纱相互夹层组成但不像针织织物可识别形式的结构的织品。非织造物或织品可以由多种方法形成,例如熔喷法、纺粘法和粘合粗梳织物法。
这里所用的词“纺粘纤维”是指定向聚合材料的小直径纤维。纺粘纤维可以由喷丝板的许多细小的通常为圆形的毛细管将熔融热塑材料挤压成丝,然后对挤出丝快速减径形成,例如可参看下述美国专利:授予Appel等的No.43404563、授予Dorschner等的No.3692618、授予Matsuki等的No.3802817、授予Kinney的No.3338992与No.3341394、授予Hartmon的No.3502763、授予Dobo等的3542615、授予Pike等的No.5418045。纺粘纤维在其沉积于凝聚面上时一般无粘性而且是连续的。细纤维的纺粘织物例如可以由共同转让的美国专利申请No.08/756426中所述的可分纤维制成,这类织物同样也属于这里所说的纺粘纤维。
这里所用的词“熔喷纤维”是指低取向聚合材料(相对纺粘纤维而言)的微纤维,而且这种微纤维可以通过将熔融热塑性材料经由许多细小的通常为圆形的型模毛细孔挤压成熔融的丝线或丝,进入会聚的高速的常常是热的气体例如空气流中,该气流将熔融的热塑纤维扩散,以对其减径,这主要是微纤维。然后可以用高速气流将这种熔喷纤维载运并沉积到凝聚面上形成无规散布的熔喷纤维织物。上述方法公开了例如授予Butin等的美国专利No.3849241中,它的整个内容已综合于此供参考。熔喷纤维是连续或不连续的微纤维,平均直径一般小于10微米且在沉积于凝聚面上时一般是粘性的。
这里所用的词“多层层压件”指这样的夹层件,其中一些层是纺粘的而一些层是熔喷的,例如纺粘/熔喷/纺粘(SMS)层压件,其他的例如公开于下述美国专利中:No.4041203(Brock等)、No.5169706(Collier等)、No.5145727(Potts等)、No.5178931(Perkins等)、No.5188885(Timmons等),这些专利的整个内容已综合于此供参考。形成这种层压件时,可以于运动的成形带上顺序地沉积首先是纺粘织物层、然后是熔喷织物层而最后是另一纺粘层,此后再由下述的热点粘合法粘合这种层压件。另外也可独立地制成各织物层,集合成卷并按独立的粘合步骤结合。
这里所用的词“聚合物”一般包括但不限于均聚物、共聚物,例如嵌段、接枝、无规和交错的共聚物、三无共聚物等以及它们的混合物和改性物。此外,除非另加限制,“聚合物”一词还将包括它们所有可能的分子几何构型。这些构型包括但不限于等规的、间同立构的和无规的对称的。
这里所用的词“机器方向”或MD是指织物在生产中其长度所在的方向,而“横切机器方向”或CD则是指织物在生产中其宽度所在的方向,即一般垂直于MD的方向。
这里所用的词“混合物”是指两种或多种聚合物的混合物,而词“渗混物”则是指混合物的子类,其中的组份是不溶混的但是是混用的。“可混性”和“不溶混性”定义为对于混合的自由能分别具有负值和正值的混合性质。此外,“混用化”定义为改进不溶混聚合物混合物界面性质使其成为掺混物的方法。
这里所用的词“超声粘合”是指所采用的一种工艺,例如美国专利No.43748888(Bornslaeger)所述的,使织物通过集音器与砧辊之间的工艺。
这里所用的词“点粘合”是指在多个离散的分开区域上粘合层压件的一层或多层。作为具体的例子,“热点粘合”可以包括使待粘合的层压件的一层或多层通过加热的刻花辊和光滑的压光辊之间的步骤。刻花辊可用某种方式形成花纹,使得整个织物并不在其整个表面上被粘合,而砧辊通常则具有平的表面。为此,出于功能的功能方面和美观方面的考虑,已为压光辊开发了种种花纹。这种花纹的例子之一是具有许多的点,并且是所谓Hansen Pennings或“H&P”花纹,根据美国专利No.3855046(Hansen与Pennings)指出,对于新的花纹有约30%的粘合面积,计约200粘合点/英寸2。H&P花纹具有方形点或针点粘合区,其中每个方形针点的边长为0.038英寸(0.965mm)、针点间距为0.070英寸(1.778mm),粘合深度为0.023英寸(0.584mm)。最终形成的花纹在初始时具有约29.5%的粘合面积。另一种典型的点粘合花纹是所谓展开的Hansen Pennings或“EHP”粘合花纹,它在初始时产生约15%的粘合面积,方形针点的边长为0.037英寸(0.94mm)而针点间距为0.097英寸(2.464mm),深度为0.039英寸(0.99mm)另一种标号为“714”的点粘合图案具有这样的方形针点粘合区,其中各针点的边长为0.023英寸而针点间距为0.062英寸(1.575mm),粘合深度为0.033英寸(0.838mm)。这样形成的花纹在初始时具有约15%的粘合面积。单侧花形粘合花纹包括分隔开的菱形重复花纹,这是现有粘结花纹的另一个例子。还有另一种普遍的花纹是C-星形花纹,它在初始时具有约16.9%的粘合面积。这种C-星形花纹具有为流星中断的横向条或“灯芯绒”式的设计。其他共用的花纹包括钻石式的花纹,这种钻石的花纹重复着并相互错开,具有约16%的粘合面积;还有一种类似窗屏花纹的丝织花纹,具有约15%的粘合面积。通常,这种百分粘合面积对于织物层压件可从约5%至约35%之间变化,而粘合点密度为约40-约400点/英寸2。正如本技术中周知的,点粘合能将层压件的各层保持到一起,通过各层中的纱和/或纤维相粘合而成为整体。
这里所用的词“血阻挡件”是指较为不易为血透过的织物,亦即能通过ASTM试验F1670-97中所述血透过试验。除能阻止血渗透外,还可以要求本发明的膜和/或层压件起到对细菌、病毒或其他类似生物体的阻挡件的作用。
这里所用的词“病原体阻挡件”是指较不易为病原体透过的织物,即能通ASTM试验F-1670-97a所述血载病原体试验的织物。
这里所用的词“液位差”是指按以下所述的由毫巴(mbar)测量织物的液体阻挡性质的测量结果。本发明的微孔膜可以具有超过50mbar的液位差,同时,取决于特殊应用的需要,此液位差值可以大于约80mbar、150mbar或甚至于200mbar。
这里所用的词“可透气的”是指材料所能透过的水蒸汽气具有的最低WVTR至少约300g/m2/24hr。织物的WVTR是水蒸汽透过率,它从一个方面是织物穿用时舒适感的指示。WVTR的单位是克/米2/日(g/m2/day),其可以按下述方式测量。
这里所用的词“基重”是指膜或其他材料每单位面积的质量,例如每平方米的克数(g/m2)。
这里所用的词“衣着”是指任何类型的非医用的可以穿用的衣服。这包括工业工作服装和衣裤相连的工作服、内衣、裤子、衬衣、茄克衫、手套、短袜、等等。
这里所用的词“感染控制产品”是指医用品种如外科用外罩和服装、面罩、头罩如膨松帽、外科帽与护罩、鞋袜之类如护袜、靴盖与拖鞋、创伤衣服、绷带、杀菌包裹件、揩布、衣着如试验时外套、背带式工作裤、围裾与短外衣、病人床上用品、担架与婴儿摇篮单,等等。
这里所用的词“个人贴身产品”是指尿布、训练婴儿小便用裤、吸湿性内裤、成人失禁产品、妇女卫生产品等。
这里所用的词“防护罩”是指交通工具如轿车、卡车、船舶、飞机、摩托车、自行车、高尔夫球器械装运小车等用的防水布或罩;常置于户外如门和窗栅等设备、庭院和公园设备(除草机、旋转碎土机等)与草坪设备的外罩,以及地板盖面、桌布和野餐区的地面罩。
这里所用的词“户外织物”是指虽非专门而主要是用于户外的织物。户外织物包括用于防护罩的织物、帐蓬/车拖活动房屋织物、防雨布、凉篷、天棚、帐棚、农业用织物与户外衣服如头罩、工业用工作服和背带裤、裤子、衬衣、茄克衫、手套、短袜、护袜,等等。
本发明的描述
参看图1,其中所示的本发明的拉伸充填膜/非织造织物层压件10包括第一膜层12和第一非织造织物支承层14。此层压件还可以包含另外的膜和/或支承层,例如可以有纺粘/膜层压件、纺粘/膜/纺粘层压件、纺粘/膜/膜/纺粘、熔喷/膜/纺粘层压件等。
膜层12可以由任何至少能沿一个方向拉伸从而能减少膜厚的任何热塑性膜制成。适用的膜料包括至少三种组份:热塑性聚烯烃聚合物、填料以及单官能受阻酚稳定剂。这些(和其他)组份能混合到一起,加热然后挤压成单层或多层膜。这种膜可以由本技术中周知的种种成膜方法之一制成,例如采用铸膜或吹膜设备制成。所述膜最好是平铸膜或冷铸膜。制造拉伸充填膜的方法描述于下述美国专利中,No.4777073(Sheth)、No.5695868(McCormack)、申请系列No.08/929562、申请系列NO.08/854460(Stopper等)以及欧洲专利申请公开Wo96/19346中,这些参考文件中的整个内容已综合于此供参考。
用来制造本发明的膜的热塑性聚合物包括但不限于聚烯烃类的均聚物、共聚物以及它们的混合物。举例来说,“聚烯烃基”膜也适用于本发明,在用于本发明时,一种膜被看作是“聚烯烃基”的时,是当它的不含任何填料的聚合物部分所含的聚烯烃重量至少是此膜中的聚合物总重的50%。可单独或可结合其他聚合物用作本发明另外的成膜聚合物包括乙烯乙酸乙烯酯(EVA)、乙烯丙烯酸乙酯(EEA)、乙烯丙烯酸(EAA)、乙烯甲基丙烯酸酯(EMA)、乙烯正丁基丙烯酸酯(EnBA)、聚酯(PET)、尼龙、乙烯基乙烯醇(EVOH)、聚苯乙烯(PS)、聚氨酯(PU)、聚丁烯(PB)与聚对苯二甲酸丁二酯(PBT)。但最好主要是线性聚合物如乙烯、丙烯、1-丁烯、4-甲基戊烯、1-己烯、1-辛烯等的聚合物以及它们的共聚物和混合物。此外,适用的聚合物还可包括烯属聚合物,它们是多步反应剂产物,其中无定形的乙烯丙烯无规聚合物以分子形式分散于主要是半结晶高聚丙烯单体/低乙烯单体连续基质中。在最佳实施例中,是把乙烯和/或丙烯的聚合物用于这种薄膜中;例子包括但不限于线性低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)、聚烯烃塑料和乙烯-丙烯弹性体混合物。
除热塑性聚合物外,这种薄膜还包括填料以在薄膜拉伸时赋予其可透气性。这里所用的“填料”包括这样的粒料和其他形式的材料,它们能添加到这种膜的聚合物挤压混合物中而对挤压成的膜无化学干扰或不利影响,此外还能均匀地分散到整个薄膜内。一般,这种填料为粒状形式,平均粒度为约0.1-10微米,最好约1-约4微米。这里所用的词“粒度”描述的是填料粒的最大直径或最大长度。有机和无机填料都是可以用于本发明中的,只需它们不干扰成形过程和/或接续的层压过程。填料的例子包括碳酸钙(CaCO3)、各种粘土、二氧化硅(SiO2)、氧化铝、硫酸钡、碳酸钠、滑石、硫酸镁、二氧化钛、沸石、硫酸铝、纤维类型粉末、硅藻土、石膏、硫酸镁、碳酸镁、碳酸钡、高岭土、云母、碳、氧化钙、氧化镁、氢氧化镁、木浆粉、木材粉、纤维素衍生物、聚合物粒料、甲壳质与甲壳质衍生物。在一实施例中,这种填料粒可以是磨碎的碳酸钙。这种填料粒可以以脂肪酸涂层,例如用山嵛酸或硬脂酸,它们有助于粒料(松散的)自由流动和易于使它们分散到聚合物内。这种膜通常含有按膜层总重计至少为30%而更好是约40-70%的填料。
通过在挤压前可给基础聚合物添加单官能的受阻酚,可以获得改进了特性和拉伸性质的膜。在这一方面,意外地惊奇发现单官能受阻酚稳定剂显著地改进了充填膜的伸展特性,例如能改进充填膜在拉伸到“变白”时对缺陷的容许能力。这里所谓的膜的“变白”是指膜的这种不透光性,其中从半透明开始,当由于填料粒的取向和薄膜中形成的微孔使光衍射而成为均匀的不透光。“变白”点一般是在延伸到破裂时的50-约90%的范围实现的。
受阻酚是指塑料工业中用作抗氧化剂的一类稳定剂。在本发明中,最好采用具有伸展的碳链的色满衍生物,例如生育酚(维生素E),包括α生育酚或2,5,7,8-四甲基-2-(4′,8′,12′-三甲基十三基)-6-色满。适用的生育酚填加剂可购自Ciba Specialty Chemicals ofTerrytown,N.Y.商品名IRGANOX E 17(以前可购自Hoffmon-LaRoche,Inc.of Paramus,N.J.,商品名RONOTEC Dry 17)以及IRGANOX E217 DF。其他适用的受阻酚包括IRGANOX 1076,可购自Ciba Specialty Chemicalsof Terrytown。N.Y.IRGANOX 1076,是十八烷基3,5-二叔丁基-4-羟基氢化肉桂醛。在挤压之前最好在基础聚合物中添加约100-1000ppm(相对于膜总重的每百万部分)而尤为最好是约100-约600 PPM的单官能受阻酚。
可以于膜的挤出物中添加粘合剂如增粘剂。有关的粘合剂和/或增粘树脂已描述于授予Kieffer等的美国专利No.4789699中,其整个内容已综合于此供参考。本发明的粘合剂是用来将膜和非织造层在低温下粘合。粘合剂的例子包括氢化烃树脂例如REGALREZ系列增粘剂,可购自Hercules,Inc.of Wilmington,Delaware.REGALREZ增粘剂是高度稳定的低分子量的非极性树脂。REGALREZ 3102、1094是适用于本发明的粘合剂的具体例子。其他的适当粘合剂的例子包括以下所述、ARKON P系列树脂,其是合成的增粘树脂,由Arakawa Chemical(U.S.A.)Inc.ofChicago Illinois根据石油烃树脂制成;ZONATAC树脂,其属增粘剂,它包括软化点约为105℃的萜烯烃,由Arizona Chemical Company ofPanama City,Florida制造,EASTMAN 1023PL树脂,其是无定形聚丙烯增粘剂,可购自Eastman Chemical Company Longview,Texes;无定形聚α烯烃例如REXTAC,其可购自Huntsman Corporation of Salt lakeCity.UT,又例如VESTOPLAST,其可购自德国的Hüls AG of Marl。
至于粘合剂的其他例子,一般地包括有但不限于聚酰亚胺,乙烯共聚物如乙烯乙酸乙烯酯(EVA)、乙烯丙烯酸乙酯(EEA)、乙烯丙烯酸(EAA)、乙烯甲基丙烯酸酯(EMA)与乙烯正丁基丙烯酸酯(EnBA)、木松香及其衍生物、烃树脂、多萜烯树脂、无规聚丙烯和无定形聚丙烯。还包括主要是无定形乙烯丙烯共聚物,周知有乙烯-丙烯橡胶(EPR)和一类称之为韧化聚丙烯(TPP)以及烯烃类聚合物。这里的EPR用机械方法或以分子形式,通过反应器内多级聚合而分散聚丙烯或聚丙烯/聚乙烯混合物中。
应知上面列出的粘合或增粘剂只是用于说明目的而无限制本发明之意。一般,这种粘合剂将占膜总重约2-约20%。虽然在上述范围之外的重量百分比也可使用,但当此百分比较高时,膜的透气性就会受到影响而这对于个人贴身制品的衣着一般是不希望的。
此外,与膜的成形过程、拉伸和任何继后的层压步骤相匹配的其他添加剂,也可用于本发明。例如为使所述的膜具备所需的特性可以添加其他一些添加剂,如熔体稳定剂、处理稳定剂、热稳定剂、光稳定剂、热陈化稳定剂以及本技术中周知的其他添加剂。一般地说,亚磷酸酯稳定剂(例如IRGAFOS,可购自Ciba Specialty Chemicals of Terrytown,N.Y;DOVERPHOS,可购自Dover Chemical Corp.of Dover Ohio)是典型的熔体稳定剂,而受阻胺稳定剂(例如CHIMASSORB,可购自Ciba SpecialtyChemicals of Terrytown,N.Y.)是有代表性的热与光稳定剂。
如上所述,这种膜可以用内行人士周知的方法形成。将热塑性聚合物、填料、单官能受阻酚与其他有选择的添加剂按前述适当的比例混合;加热然后挤压成膜。一般地说,这种膜一旦形成后最好使所具有的基重小于约每平方米100克(100g/m2)。然后将此膜沿至少一个方向拉伸,如本技术中周知的例如用机器方向定向器(MDO)。MDO单元可以购自Marshalland William Company of Providence,Rhode Island和其他公司。MDO单元有多个拉伸辊,它们沿机器方向逐渐地拉伸和减薄此膜。此外,这种膜可以在单一连续区或在多个不同的区拉伸。经拉伸和减薄后,拉伸充填的膜的基重最好小于约50g/m2而尤为更好是约10-35g/m2。
作为拉伸与减薄处理的结果,这种膜的不透光性发生了变化。通常,在形成时,此膜是较为透明的,但经拉伸后便成为均匀地不透光。如已指出的。此膜于拉伸过程成为定向膜。为使拉伸的膜具有所需的可透气性,此膜沿一个方向至少应拉伸到其原有长度的2倍。通常,未拉伸的膜应拉伸到其原有长度的2-约7倍,以达到变白点并赋予其所需的透气性水平。但是,为赋予所需透气性而需要的拉伸程度将随聚合物组成、膜的初始厚度以及填料的类型和数量而变化。此外,这种膜也可以沿横切机器方向拉伸或取双轴向拉伸。
本发明的拉伸减薄的微孔膜可供多方面的应用,包括用于衣着、感染控制产品,个人贴身产品、户外用织物、防护罩和其他制品或是具有阻挡性质的织物。此外,本发明的拉伸减薄微孔膜能够提供优越的阻挡性质,例如这种微孔膜能够具有超过80mbar的液位差以及能用作血阻挡层和/或病原体的阻挡层。通常,这种可透气膜将叠层到一个或多个支承层例如非织造织物、纱布、织造织物、泡沫塑料和其他可透气材料上。理想的支承层可以包括粘合/粗梳短纤维、纺粘纤维、熔喷纤维的可透气非织造品以及采用它们的多层层压件。这种膜与支承层可以用本技术中周知的方法进行层压,这包括但不限于热粘合、超声粘合和粘合剂粘合。理想上,热粘合是用热点粘合实现,这时的粘合花纹总的粘合面积小于织物表面积的约35%,更为理想的是,这种粘合面积为约5-25%。此外,正如本技术中周知的,粘合剂可以用非连续的方式或花纹涂布到膜和/或支承层上。用来形成这种透气膜/支承层层压件的适当方法公开于美国专利No.5695868和共同转让的美国专利申请No.08/777365(1996年12月27日提交)和08/359986(1994年12月20日提交),它们的整个内容已综合于此供参考。
这样,业已证明,本发明的充填式膜与其他的充填式膜相比具有相当多的工艺方面的优点和特点。例如,这种挤压物简化了挤压机口模的安装工作同时形成了聚合物分布较好的膜(即具有更均匀的CD膜厚)。拉伸充填膜通常包含有不均匀性例如聚合物凝胶、粒状污染物、填料聚集体以及不均匀的聚合物分布。但是,对于这种膜的许多应用来说,上述不均匀性关系甚微,然而当膜的厚度减小时,这种不均匀性造成的潜在问题就会加大。当拉伸时,膜厚的差别和/或膜内的其他不均匀性一般会造成撕破形状的区域或“尾部”,它们沿MD而形成于这种不均匀性的任一侧的周围。这种尾部随着拉伸的程度成比例地加剧,常常在膜料中造成极薄的弱区或缺口。在此方面已然发现,本发明的膜则较能容许(拉伸前)在其中存在的不均匀性,因而能在较大的程度上避免膜中的弱区和/或缺口。此外,由于从模具中改进了拉伸或流动特性,这种拉伸减薄膜还可以有更均匀的厚度。再有,本发明的挤出物改进了熔体流率的稳定性,减少了整体的不均匀性和降低了因温度引起的不均匀性,从而能允许较高的熔体温度从而能取得较大的产量。另外,这种拉伸减薄膜的性质具有较高的峰值载荷和延伸负荷,这就是说一般地获得了“较韧性的”膜。这样,与现有的拉伸充填膜相比,本发明的膜及其制造方法给出了更多的优点。
试验
基重:可以根据联邦试验法NO.191A/5041测定各种材料的基重。试样材料的试样尺寸为15.24cm×15.24cm,对每个材料至少求出三个值再平均。
WVTR:试样材料的水蒸汽透过率(WVTR)可以根据下述的改进的试验ASTM标准E96-80计算。从各个试样材料上裁切出直径为3英寸的圆形试样,对比材料则是一片CELGARDTM2500膜,它购自Hoechst CelaneseCorporation of Sommerville,New Jersey。CELGARDTM2500膜是微孔聚丙烯膜。对各种材料都准备了三个试样。试验皿为NO.60-1挥发度计盘,购自Thwing-Albert Instrument Company ofPhiladelphia,Pennsylvania。在各挥发度计盘中注入100ml的水,然后将试验材料和对比材料的各个试样跨置于各个盘的敞开的顶部上。紧固拧入式凸缘沿盘的边缘形成密封,让相关的试验材料或对比材料在6.5cm直径的具有约33.17cm2暴露面积的圆内与环境温度接触。将此盘放入100°F(32℃)的强制通风炉约1小时至平衡。这种炉是恒温炉,有外部空气循环通过其中以防水蒸汽集聚于其内。适用的强制通风炉例如有Blue MPower-O-Matic 60炉,可购自Blue M.Electric Company of BlueIsland,Illinois。在达到上述平衡结果后将此盘从炉中取出,称重后立即退回到炉内。经24小时后,再次从炉中将盘取出并称重。用下述公式(1)计算初步试验的水蒸汽透过率值:(I)试验的WVTR=(重量损耗的克数24小时以上)×315.5克/米2/24小时 (1)
炉内的相对温度未作特别控制.在预设的100°F(32℃)和环境相对湿度的状态下,CELGARDTM2500对比材料的WVTR已确定为5000克/米2/24小时。因此,此对比试样用于各次试验中,而用下述公式:
(II)将初步试验值校正到设定条件:
(II)WVTR=(试验WVTR/对比WVTR)×(5000克/米2/24小时)
上述试验适用于测定高达约3000克/米2/日的织物的WVTR。为了测定超过3000克/米2/24小时(g/m2/24hr)的WVTR。最好采用其他试验系统,例如PERMATRAN-W 100K水蒸汽渗透分析系统,可购自ModernControls,Inc.(MOCON) of Minneapolis,MN。
液位差:测度织物的液体阻挡性质的一种方法是液位差试验。液位差试验测定织物在液体通过之前所能支承水位的高度或水压值(mbar)。具有较高水位差读数的织物即表明它与具有较低液位差的织物相比,对于液体的渗透有更大的阻挡力。液位差试验可以根据联邦试验标准191A,方法5514进行。液位差的数据也可以用类似于上述联邦试验标准方法作下述修正后取得。这种液位差也可以用购自Marl Enterpreses,Inc.ofConcord,NC的静压头测试议进行测定。试样承受标准化的水压,以恒定的速率增加,直至在三个不同的区域于织物的表面上出现了第一次漏泄迹象(与夹具相邻的边缘处漏泄忽略不计)。对薄的织物和/或材料例如薄膜则加以支承以防试样的渗透破坏。
峰值负荷:峰值负荷测量织物的峰值或破裂负荷,此种负荷以克为单位测量。在峰值负荷试验中,用两个各有一对爪而每个爪有一个与试样接触的面的夹具将材料保持于同一平面内,通常是沿垂向分开3英寸并按规定的延伸率移离开。为求得峰值负荷值,所用试样的尺寸为3英寸×6英寸,爪面尺寸为1英寸高×3英寸宽,取300mm/min的恒定延伸率。这项试验中可采用:Sintech 2试验机,其可购自SintechCorporation,1001 Sheldon Dr.,Cary,NC 27513;the Instron Model,TM,可购自Instron Corporation,2500 Washington St.,Canton,MA 02021;或是Thwing-Albert Model INTELLECT,II;可购自Thwing-AlbertInstrument CO.,10960 Dutton Rd.,Philadelphia;PA 19154.所报导的结果是作为三个试样的平均值,可以由沿横向(CD)或机器方向(MCD)的试样来进行。
例子
采用的60g/m2的母体膜按重量计包括;60%的FILMLINK 2029 CaCO3,购自English China Clays;23.5%的Union Carbide不稳定的6D82(7MFR丙烯/乙烯共聚物,含有约5.5%乙烯);12.5%Montell不稳定的X11395-49-1(5 MFR Catallog共聚物)和4.0%Montell不稳定的X11395-49-2(10 MFR Catalloy共聚物)。对于上述母体混合物添加了下述表1中给出的不同量的各种主与副稳定剂。所含的主稳定剂为Ciba-Geigy工RGANOX 1076或Ciba-Gergy IRGANOX E17。所含副稳定剂为Ciba-GeigyIRGAFOS 168,DOVERPHOS S-9228以及/或者受阻的胺光稳定剂CHIMASSOORB 119。所有包括稳定剂的混合物组份都是在薄膜制造步骤前混合好的。
这种复合物具3.32MFR(230℃)和1.49g/cm3的密度。这种膜是在吹制膜生产线上按13磅/英寸/小时(lb/inch/hr)的速率于414°F的熔化温度生产,产品厚1.5mil。将这样形成的已充填膜在未拉伸下卷绕,输送给离机的机器方向取向器(MDO)。此膜于该MDO中分几个阶段于加热到185°F的辊之间拉伸,然后于210°F下退火。最终的拉伸比是其原有长度的3.4倍而最终厚度约为0.5mil。此MDO的输出速度设定为600英尺/分钟。拉伸减薄膜这时已是均匀不透光的,再通过按MDO出口速度80%运行的热点粘合机,粘合机中有刻花辊和隆起的光滑砧辊的辊隙,形成具有17g/m2热点粘合聚丙烯纺粘织物的整体式层压件。最终所得的层压件包括许多均匀分开的凹坑,它们是由此刻花辊的隆起花纹于进行热粘合之处形成的。这种粘合花纹是“C-星形”花纹,它们产生约15%的粘合面积。
表1
试验号 | IRGANOXE-17 | IRGANOX1076 | CHIMASSORB119 | IRGAFOS168 | DOVERPHOSS-9228 | MD峰值负荷(Ibs) | 缺陷英寸/100码2 | 基重的标准偏差(g) |
93K | 1000ppm | 1000ppm | 17.0 | 0.02467 | 0.0598g | |||
93L | 1000ppm | 100oppm | 16.2 | 0 | 0.0095g | |||
93J | 1000ppm | 1000ppm | 1000ppm | 13.5 | 0.006 | 0.0328g | ||
93M | 1000ppm | 1000ppm | 1000ppm | 15.7 | 0 | 0.0325g | ||
93I | 1000ppm | 1000ppm | 15.4 | 0 | 0.030g | |||
93G | 1000ppm | 1000ppm | 15.5 | 0 | 0.0760g | |||
93H | 1000ppm | 1000ppm | 1000ppm | 15.9 | 0.004 | 0.0380g |
对上述例子来说,“缺陷”是指面积等于或大于0.0027英寸的孔。缺陷的等级可以通过比较拉伸膜的每100码2的开口面积(孔)的英寸2来确定,并且可以由目测观察或自动摄影系统计算。为了帮助目测计算,可在分析膜时于其后设置光源。在采用了IRGANOX E 17稳定剂后显著地减少了拉伸充填膜中的缺陷。IRGANOX 1076同样能降低缺陷等级,但与包含IRGANOX E 17的拉伸充填膜相比则有较多的缺陷。这两种单官能的受阻酚稳定剂比未作稳定控制的有着显著低的缺陷。此外,由单官能受阻酚制成的拉伸充填微孔膜同样还提高了韧性,例如有较高的峰值负荷以及较均匀的膜厚和/或基重。在这个方面,基重在整个膜上的变化(g/m2)如上所示已有改进,膜的各段的基重相对于膜的平均基重的标准偏差降低了。
虽然在此作为参考综合了种种专利与其他参考文献,但这里所写的说明书控制到使综合的材料与此所写说明书中的材料不存在有任何的一致性。此外,这里虽然给出了各种范围,但这种范围意味着包括其中的各个和每一个子范围。例如范围100-1000这样也就包括了101-1000,101-999,101-998,等等。此外,虽然本发明业已相对于其具体实施例作了详细的描述,特别是通过其中的例子作了详细的说明,但内行的人士在不脱离本发明的精神与范围的前提下是可以作出种种变型、改进与其他变更的。为此,应将所有这类改进、变型与其他变更视作为它含在这里的权利要求书之内。
Claims (20)
1.一种拉伸减薄膜,它包括:约30-70%重量的热塑性聚合物;约30-70%重量的平均粒度小于约10微米的填料;和约100-1500ppm的单官能受阻酚;其中此拉伸充填膜是可透气的阻挡膜。
2.如权利要求1所述的拉伸减薄膜,其中,所述单官能受阻酚包括生育酚。
3.如权利要求1所述的拉伸减薄膜,其中,所述单官能受阻酚包括2,5,7,8-四甲基-2-(4′,8′,12′-三甲基十三基)-6-色满。
4.如权利要求2所述的拉伸减薄膜,其中,所述生育酚存在于所述膜中的量为约100-1000ppm。
5.如权利要求4所述的拉伸减薄膜,其中,所述生育酚存在于所述膜中的量为约100-600ppm。
6.如权利要求4所述的拉伸减薄膜,其中,所述热塑性聚合物包括聚烯烃及其混合物以及共聚物。
7.如权利要求4所述的拉伸减薄膜,其中,所述热塑性聚合物包括选自聚乙烯和聚丙烯两者的混合物或共聚物。
8.如权利要求7所述的拉伸减薄膜,其中,所述填料包括碳酸钙粒料且其中所述膜具有基重小于约35g/m2、峰值负荷大于15磅、WVTR大于约300g/m2/24小时。
9.如权利要求6所述的拉伸减薄膜,其中,所述膜具有的基重小于约35g/m2和WVTR大于约300g/m2/24小时。
10.一种可透气阻挡层织物的制造方法,此方法包括:形成膜的挤出物,它包括约30-70%重量的热塑性聚合物;约30-70%重量的平均粒度小于约10微米的填料;以及约100-1000ppm的单官能受阻酚;加热所述膜,且沿至少一个方向拉伸所述膜,形成WVTR超过300g/m2/24小时的微孔膜。
11.如权利要求10所述的方法,其中,所述填料膜是沿单一方向拉伸到破裂时延伸率为约50-约90%。
12.如权利要求10所述的方法,其中,所述填料膜是沿机器方向单轴向地拉伸到其原有长度至少2.5倍,且其中此拉伸充填膜具有的WVTR至少为1500g/m2/24小时。
13.如权利要求10所述的方法,其中,所述单官能受阻酚包括生育酚。
14.如权利要求10所述的方法,其中,所述单官能受阻酚包括2,5,7,8-四甲基-2-(4′,8′,12′-三甲基十三基)-6-色满。
15.如权利要求13所述的方法,其中,所述生育酚存在于所述膜挤出物中的量为约100-600ppm。
16.如权利要求13所述的方法,其中,所述热塑性聚合物包括聚烯烃及其混合物以及共聚物。
17.如权利要求13所述的方法,其中,所述热塑性聚合物包括选自聚乙烯和聚丙烯两者的混合物或共聚物。
18.如权利要求17所述的方法,其中,所述填料包括粒状碳酸钙。
19.如权利要求17所述的方法,其中,所述填料膜经充分拉伸,其中此拉伸填料膜具有小于约35g/m2的基重和超过1500g/m2/24小时的WVTR。
20.如权利要求19所述的方法,其中,所述方法还包括将所述膜层压到非织造织物上的步骤。
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US09/037,345 US6156421A (en) | 1997-04-02 | 1998-03-10 | Stretched-filled microporous films and methods of making the same |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003086256A1 (fr) * | 2002-04-05 | 2003-10-23 | Guanhong Liu | Tampon de papier absorbeur de lait |
CN108274862A (zh) * | 2018-01-03 | 2018-07-13 | 新乐华宝医疗用品有限公司 | 一种高强度、高耐风等级的拒水复合材料及其制备方法 |
Families Citing this family (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999061521A1 (en) | 1998-05-22 | 1999-12-02 | Ecc International Ltd. | Particulate carbonates and their preparation and use in thermoplastic film compositions |
US6488198B1 (en) * | 1999-07-01 | 2002-12-03 | International Business Machines Corporation | Wire bonding method and apparatus |
US6472445B1 (en) * | 1999-12-27 | 2002-10-29 | Tokuyama Corporation | Polypropylene base porous film and production process for the same |
EP1278596A2 (en) * | 2000-05-05 | 2003-01-29 | Imerys Pigments, Inc. | Particulate carbonates and their preparation and use in breathable film |
US20020119300A1 (en) * | 2000-12-22 | 2002-08-29 | Taylor Jack D. | Breathable and elastic polyurethane films and laminates containing same |
KR100411835B1 (ko) * | 2001-01-19 | 2003-12-18 | 유피씨(주) | 통기성 합지 제조시스템, 제조 방법 및 그 통기성 합지 |
US6808795B2 (en) | 2001-03-27 | 2004-10-26 | The Procter & Gamble Company | Polyhydroxyalkanoate copolymer and polylactic acid polymer compositions for laminates and films |
JP2002293973A (ja) * | 2001-03-30 | 2002-10-09 | Tokuyama Corp | ポリプロピレン系多孔質フィルム及びその製造方法 |
US6638636B2 (en) | 2001-08-28 | 2003-10-28 | Kimberly-Clark Worldwide, Inc. | Breathable multilayer films with breakable skin layers |
US20030092344A1 (en) * | 2001-10-05 | 2003-05-15 | Polymer Group, Inc. | Outdoor fabric with improved barrier performance |
US20030114825A1 (en) * | 2001-12-19 | 2003-06-19 | Morman Michael Tod | Method for making an absorbent article with elastic cuff areas and necked substrates |
US6884310B2 (en) * | 2001-12-19 | 2005-04-26 | Kimberly-Clark Worldwide, Inc. | Method for making an absorbent article with elastic cuff areas and expandable substrates |
US6827806B2 (en) * | 2001-12-19 | 2004-12-07 | Kimberly-Clark Worldwide, Inc. | Method for making an absorbent article with printed elastomers |
US6869494B2 (en) * | 2001-12-19 | 2005-03-22 | Kimberly-Clark Worldwide, Inc. | Method for making a disposable garment having softer waist and leg cuffs |
US7083839B2 (en) | 2001-12-20 | 2006-08-01 | Kimberly-Clark Worldwide, Inc. | Laminate structures containing activatable materials |
US7510758B2 (en) * | 2002-11-12 | 2009-03-31 | Kimberly-Clark Worldwide, Inc. | Breathable elastic multilayer film laminate and method of making a breathable elastic multilayer film laminate |
US7312167B2 (en) * | 2002-12-23 | 2007-12-25 | Kimberly-Clark Worldwide, Inc. | Breathable multilayer films for use in absorbent articles |
US7098292B2 (en) | 2003-05-08 | 2006-08-29 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer |
US6706942B1 (en) | 2003-05-08 | 2004-03-16 | The Procter & Gamble Company | Molded or extruded articles comprising polyhydroxyalkanoate copolymer compositions having short annealing cycle times |
US7932196B2 (en) * | 2003-08-22 | 2011-04-26 | Kimberly-Clark Worldwide, Inc. | Microporous stretch thinned film/nonwoven laminates and limited use or disposable product applications |
US7220478B2 (en) | 2003-08-22 | 2007-05-22 | Kimberly-Clark Worldwide, Inc. | Microporous breathable elastic films, methods of making same, and limited use or disposable product applications |
US7270723B2 (en) * | 2003-11-07 | 2007-09-18 | Kimberly-Clark Worldwide, Inc. | Microporous breathable elastic film laminates, methods of making same, and limited use or disposable product applications |
US20050124256A1 (en) | 2003-12-09 | 2005-06-09 | Vanessa Mason | Synthetic insulation with microporous membrane |
US20050164584A1 (en) * | 2003-12-31 | 2005-07-28 | Baratian Stephen A. | Retractable nonwoven layers having minimal application of coalesced elastomers |
KR100531042B1 (ko) * | 2004-01-26 | 2005-11-25 | 주식회사 효성 | 의료용 폴리프로필렌 수지 조성물 |
US20050245687A1 (en) * | 2004-04-30 | 2005-11-03 | Appel Marvin R | Multimodal polyethylene extrusion |
US7476047B2 (en) * | 2004-04-30 | 2009-01-13 | Kimberly-Clark Worldwide, Inc. | Activatable cleaning products |
DE102004024042A1 (de) * | 2004-05-07 | 2005-11-24 | Paul Hartmann Ag | Vlies-/Folienlaminat |
US7604623B2 (en) | 2005-08-30 | 2009-10-20 | Kimberly-Clark Worldwide, Inc. | Fluid applicator with a press activated pouch |
US7565987B2 (en) | 2005-08-31 | 2009-07-28 | Kimberly-Clark Worldwide, Inc. | Pull tab activated sealed packet |
US7575384B2 (en) | 2005-08-31 | 2009-08-18 | Kimberly-Clark Worldwide, Inc. | Fluid applicator with a pull tab activated pouch |
US7812214B2 (en) * | 2006-02-28 | 2010-10-12 | Kimberly-Clark Worldwide, Inc. | Absorbent article featuring a laminated material with a low Poisson's Ratio |
AU2006347731B2 (en) | 2006-08-31 | 2012-09-13 | Kimberly-Clark Worldwide, Inc. | Highly breathable biodegradable films |
DE102007004511A1 (de) | 2007-01-19 | 2008-07-31 | Forschungsinstitut für Leder und Kunststoffbahnen gGmbH | Offenporige mikroporöse Folie, Verfahren zu deren Herstellung und Verwendung |
US8227658B2 (en) * | 2007-12-14 | 2012-07-24 | Kimberly-Clark Worldwide, Inc | Film formed from a blend of biodegradable aliphatic-aromatic copolyesters |
WO2012178011A2 (en) * | 2011-06-24 | 2012-12-27 | Fiberweb, Inc. | Vapor-permeable, substantially water-impermeable multilayer article |
CA2808848A1 (en) * | 2013-03-07 | 2014-09-07 | Airboss-Defense | Low burden protective glove |
US9492332B2 (en) | 2014-05-13 | 2016-11-15 | Clopay Plastic Products Company, Inc. | Breathable and microporous thin thermoplastic film |
US10487199B2 (en) * | 2014-06-26 | 2019-11-26 | The Procter & Gamble Company | Activated films having low sound pressure levels |
PE20180807A1 (es) | 2015-07-10 | 2018-05-09 | Berry Plastics Corp | Pelicula transpirable microporosa y metodo para fabricar la pelicula transpirable microporosa |
JP6784759B2 (ja) | 2015-11-05 | 2020-11-11 | ベリー グローバル インコーポレイテッド | 高分子フィルムおよび高分子フィルムの形成方法 |
US11472085B2 (en) | 2016-02-17 | 2022-10-18 | Berry Plastics Corporation | Gas-permeable barrier film and method of making the gas-permeable barrier film |
US12098015B2 (en) | 2016-10-12 | 2024-09-24 | Boveda Inc. | Device for controlling headspace humidity and methods for making the same |
JP6884431B2 (ja) * | 2017-07-13 | 2021-06-09 | エンズパイア インダストリー カンパニー リミテッド | 活動性細孔を有する滅菌可能な医療用包装 |
BE1025398B1 (nl) | 2017-12-29 | 2019-02-06 | Plastic Science By Design Besloten Vennootschap Met Beperkte Aansprakelijkheid | Zeoliethoudend additief geschikt voor polymeervormgeving |
US11584111B2 (en) | 2018-11-05 | 2023-02-21 | Windmoeller & Hoelscher Kg | Breathable thermoplastic film with reduced shrinkage |
JP2022507577A (ja) * | 2018-11-16 | 2022-01-18 | ザ プロクター アンド ギャンブル カンパニー | 選択的不透明度コントラストを有するフィルム |
WO2022055834A1 (en) * | 2020-09-11 | 2022-03-17 | Dow Global Technologies Llc | Breathable films having uniform micro-voids |
Family Cites Families (58)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE577252A (zh) * | 1958-04-04 | Hercules Powder Co Ltd | ||
US3338992A (en) * | 1959-12-15 | 1967-08-29 | Du Pont | Process for forming non-woven filamentary structures from fiber-forming synthetic organic polymers |
US3502763A (en) * | 1962-02-03 | 1970-03-24 | Freudenberg Carl Kg | Process of producing non-woven fabric fleece |
US3418045A (en) * | 1966-08-24 | 1968-12-24 | Edward J. Rovsek | Intermittently operated movie film projector for projecting still pictures |
US3341394A (en) * | 1966-12-21 | 1967-09-12 | Du Pont | Sheets of randomly distributed continuous filaments |
US3542615A (en) * | 1967-06-16 | 1970-11-24 | Monsanto Co | Process for producing a nylon non-woven fabric |
US3849241A (en) * | 1968-12-23 | 1974-11-19 | Exxon Research Engineering Co | Non-woven mats by melt blowing |
DE2048006B2 (de) * | 1969-10-01 | 1980-10-30 | Asahi Kasei Kogyo K.K., Osaka (Japan) | Verfahren und Vorrichtung zur Herstellung einer breiten Vliesbahn |
DE1950669C3 (de) * | 1969-10-08 | 1982-05-13 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Vliesherstellung |
CA948388A (en) * | 1970-02-27 | 1974-06-04 | Paul B. Hansen | Pattern bonded continuous filament web |
GB1453447A (en) * | 1972-09-06 | 1976-10-20 | Kimberly Clark Co | Nonwoven thermoplastic fabric |
US3947473A (en) * | 1972-12-22 | 1976-03-30 | Hoffman-La Roche Inc. | Antioxidant chroman compounds |
GB1565745A (en) * | 1977-02-07 | 1980-04-23 | Ici Ltd | Stabilisation of propylene polymers containing inorganic additives |
JPS54114551A (en) * | 1978-02-28 | 1979-09-06 | Nisshin Flour Milling Co Ltd | Material for packaging |
JPS555337A (en) * | 1978-06-22 | 1980-01-16 | Toyo Seikan Kaisha Ltd | Laminate sack for packing food |
JPS6036173B2 (ja) * | 1980-02-26 | 1985-08-19 | 王子油化合成紙株式会社 | 色相の改良された樹脂組成物 |
DE3010505A1 (de) * | 1980-03-19 | 1981-10-01 | Basf Ag, 6700 Ludwigshafen | Chromanderivate, verfahren zu ihrer herstellung, ihre verwendung als stabilisatoren von organischen materialien sowie diese stabilisatoren enthaltende organische materialien |
US4340563A (en) * | 1980-05-05 | 1982-07-20 | Kimberly-Clark Corporation | Method for forming nonwoven webs |
DE3103707A1 (de) * | 1981-02-04 | 1982-08-19 | Basf Ag, 6700 Ludwigshafen | Chromanderivate |
DE3103740A1 (de) * | 1981-02-04 | 1982-08-19 | Basf Ag, 6700 Ludwigshafen | Chromanderivate |
US4374888A (en) * | 1981-09-25 | 1983-02-22 | Kimberly-Clark Corporation | Nonwoven laminate for recreation fabric |
DE3504981A1 (de) * | 1985-02-14 | 1986-08-14 | Basf Ag, 6700 Ludwigshafen | Stabilisatoren |
DE3634531A1 (de) * | 1986-10-10 | 1988-04-14 | Basf Ag | Stabilisatorgemische fuer kunststoffe |
US4789699A (en) * | 1986-10-15 | 1988-12-06 | Kimberly-Clark Corporation | Ambient temperature bondable elastomeric nonwoven web |
US4777073A (en) * | 1987-03-11 | 1988-10-11 | Exxon Chemical Patents Inc. | Breathable films prepared from melt embossed polyolefin/filler precursor films |
DE68925581T2 (de) * | 1989-01-27 | 1996-10-02 | Asahi Chemical Ind | Stabilisiertes polyphenylenätherharz |
US5234750A (en) * | 1989-02-23 | 1993-08-10 | Fuji Photo Film Co., Ltd. | Packaging material for photosensitive materials |
DE69031395T2 (de) * | 1989-02-23 | 1998-01-15 | Fuji Photo Film Co Ltd | Harzzusammensetzung und Verpackungsmaterial für lichtempfindliches Material |
CA2019884A1 (en) * | 1989-07-07 | 1991-01-07 | Yoshiharu Fukui | Food container |
DE69014028T2 (de) * | 1989-08-28 | 1995-05-04 | Chisso Corp | Kristalline Polyolefinmischung. |
US5188885A (en) * | 1989-09-08 | 1993-02-23 | Kimberly-Clark Corporation | Nonwoven fabric laminates |
US5169706A (en) * | 1990-01-10 | 1992-12-08 | Kimberly-Clark Corporation | Low stress relaxation composite elastic material |
JPH0474515A (ja) * | 1990-07-13 | 1992-03-09 | Toray Ind Inc | 酸素吸収体 |
US5149576A (en) * | 1990-11-26 | 1992-09-22 | Kimberly-Clark Corporation | Multilayer nonwoven laminiferous structure |
US5145727A (en) * | 1990-11-26 | 1992-09-08 | Kimberly-Clark Corporation | Multilayer nonwoven composite structure |
US5200443A (en) * | 1991-03-29 | 1993-04-06 | Kimberly-Clark Corporation | Radiation stabilized fabric having improved odor characteristics containing an hindered amine compound |
TW209224B (zh) * | 1991-05-27 | 1993-07-11 | Yoshitomi Pharmaceutical | |
GB2257146B (en) * | 1991-07-03 | 1994-12-14 | Sandoz Ltd | Flameproofing polymeric material |
US5169712A (en) * | 1991-08-23 | 1992-12-08 | Amoco Corporation | Porous film composites |
US5236963A (en) * | 1991-08-23 | 1993-08-17 | Amoco Corporation | Oriented polymeric microporous films |
US5308549A (en) * | 1991-11-12 | 1994-05-03 | Hoffmann-La Roche Inc. | Stabilizers for thermo plastic materials |
US5270430A (en) * | 1991-11-13 | 1993-12-14 | The Dow Chemical Company | Polymers stabilized with 6-chromanol derivatives |
US5218008A (en) * | 1991-11-13 | 1993-06-08 | The Dow Chemical Company | Polyethers stabilized with 6-chromanol derivatives |
US5200433A (en) * | 1992-04-20 | 1993-04-06 | Shell Oil Company | Process for preparing low density porous crosslinked polymeric materials |
DE4214027A1 (de) * | 1992-04-29 | 1993-11-04 | Basf Ag | Aminoverbindungen als verarbeitungsstabilisatoren fuer thermoplastische kunststoffe |
US5258422A (en) * | 1992-05-05 | 1993-11-02 | Tredegar Industries, Inc. | Compostable thermoplastic compositions |
US5382400A (en) * | 1992-08-21 | 1995-01-17 | Kimberly-Clark Corporation | Nonwoven multicomponent polymeric fabric and method for making same |
DE4312992A1 (de) * | 1993-04-21 | 1994-10-27 | Rhein Chemie Rheinau Gmbh | alpha-Tocopherol-Zubereitung |
US5393831A (en) * | 1993-05-05 | 1995-02-28 | Kimberly-Clark Corporation | Shelf stable nonwoven fabrics and films |
JP3500635B2 (ja) * | 1993-12-10 | 2004-02-23 | ソニー株式会社 | 情報再生装置 |
CA2116081C (en) * | 1993-12-17 | 2005-07-26 | Ann Louise Mccormack | Breathable, cloth-like film/nonwoven composite |
AU684911B2 (en) * | 1994-01-14 | 1998-01-08 | Exxon Chemical Patents Inc. | Gas fade resistant ultraviolet additive formulations for polyethylene |
CA2148392A1 (en) * | 1994-06-06 | 1995-12-07 | Ann Louise Mccormack | Stretch-thinned film and nonwoven laminate |
ZA9510604B (en) * | 1994-12-20 | 1996-07-03 | Kimberly Clark Co | Low gauge films and film/nonwoven laminates |
ZA9510307B (en) * | 1994-12-20 | 1996-06-11 | Kimberly Clark Co | Mechanically compatibilized film/non-woven laminates |
US5914184A (en) * | 1996-12-30 | 1999-06-22 | Kimberly-Clark Worldwide, Inc. | Breathable laminate including filled film and continuous film |
US6045900A (en) * | 1997-09-15 | 2000-04-04 | Kimberly-Clark Worldwide, Inc. | Breathable filled film laminate |
US6072005A (en) * | 1997-10-31 | 2000-06-06 | Kimberly-Clark Worldwide, Inc. | Breathable films and process for producing them |
-
1998
- 1998-03-10 US US09/037,345 patent/US6156421A/en not_active Expired - Fee Related
- 1998-03-27 EP EP98913256A patent/EP0973824B1/en not_active Expired - Lifetime
- 1998-03-27 WO PCT/US1998/006173 patent/WO1998044025A1/en active IP Right Grant
- 1998-03-27 KR KR1019997008973A patent/KR100580982B1/ko not_active IP Right Cessation
- 1998-03-27 CA CA 2284596 patent/CA2284596C/en not_active Expired - Fee Related
- 1998-03-27 DE DE1998625881 patent/DE69825881T2/de not_active Expired - Fee Related
- 1998-03-27 AU AU67850/98A patent/AU734378B2/en not_active Ceased
- 1998-03-27 CN CN98805723A patent/CN1108336C/zh not_active Expired - Fee Related
- 1998-03-27 BR BR9808123A patent/BR9808123A/pt not_active IP Right Cessation
- 1998-04-02 AR ARP980101515 patent/AR012316A1/es active IP Right Grant
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003086256A1 (fr) * | 2002-04-05 | 2003-10-23 | Guanhong Liu | Tampon de papier absorbeur de lait |
CN108274862A (zh) * | 2018-01-03 | 2018-07-13 | 新乐华宝医疗用品有限公司 | 一种高强度、高耐风等级的拒水复合材料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP0973824A1 (en) | 2000-01-26 |
AR012316A1 (es) | 2000-10-18 |
CN1108336C (zh) | 2003-05-14 |
AU6785098A (en) | 1998-10-22 |
BR9808123A (pt) | 2000-03-08 |
CA2284596A1 (en) | 1998-10-08 |
KR20010005896A (ko) | 2001-01-15 |
KR100580982B1 (ko) | 2006-05-17 |
DE69825881T2 (de) | 2005-01-20 |
CA2284596C (en) | 2007-06-12 |
DE69825881D1 (de) | 2004-09-30 |
US6156421A (en) | 2000-12-05 |
AU734378B2 (en) | 2001-06-14 |
EP0973824B1 (en) | 2004-08-25 |
WO1998044025A1 (en) | 1998-10-08 |
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