CN1054858C - 用于吸收含水体液的湿前呈薄状的吸收泡沫材料及其制备方法 - Google Patents

用于吸收含水体液的湿前呈薄状的吸收泡沫材料及其制备方法 Download PDF

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Publication number
CN1054858C
CN1054858C CN93121142A CN93121142A CN1054858C CN 1054858 C CN1054858 C CN 1054858C CN 93121142 A CN93121142 A CN 93121142A CN 93121142 A CN93121142 A CN 93121142A CN 1054858 C CN1054858 C CN 1054858C
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foam
water
oil phase
monomer
foamy
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CN93121142A
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CN1090863A (zh
Inventor
J·C·戴耶
T·A·迪斯马莱斯
G·D·拉冯
K·J·史东
G·W·泰勒
G·A·杨格
P·赛登
S·A·戈德曼
H·L·列施
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Procter and Gamble Co
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Procter and Gamble Co
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Abstract

公开了较薄的密实的即未膨胀的聚合泡沫材料,当它与含水体液接触时,膨胀并吸收这些体液。还公开了通过聚合专门类型的油包水乳液,通称为高内相的乳液或“HIPE”来一致地制备这些较薄的密实聚合泡沫材料的方法。

Description

用于吸收含水体液的湿前呈薄状的吸收泡沫材料及其制备方法
本发明涉及有柔性的微多孔的开孔结构的聚合泡沫材料,它具有吸收和滞留流体的特性,这使得它特别适用于吸收含水的体液例如尿。本发明特别涉及在被这些流体润湿前是较薄的吸收泡沫材料。
可用作一次性尿布、成人失禁垫和三角裤及月经用品如卫生巾的高吸收性吸收物品的开发是有相当高的商业意义的主题。这些产品最希望的特征是薄。例如,尿布越薄穿着时肿涨感越小,在服装中越合体,且更不易被查觉。在包装中它们还更紧密,使得尿布的消费者更便于携带和保存。在包装中紧密性还为生产者和销售者降低了运输成本,包括在储存中没单位尿布要求较小的货架空间。
提供较薄的吸收物品的能力是受开发较薄的吸收芯或结构的能力所限制的,该吸收芯或结构能够获得并储有大量的排泄体液,特别是尿。在这方面,利用的某些微粒状吸收剂聚合物常常被称为“水凝胶”,“超吸收剂”或“水胶体”的材料特别重要。参见例如U.S.专利3699103(Harper等),1972年6月13日授权.和U.S.专利3770731(Harmon),1972年6月20日授权,上述文献公开了在吸收物品中使用这些微粒状的吸收剂聚合物。的确,较薄的尿布的开发是较薄吸收芯的直接结果,当与纤维基材组合使用时,这些特殊的吸收聚合物对排泄的含水的体液通常都能大量地吸收,它们的这种能力使吸收芯具有明显的优点。例如,参见U.S.专利4673402(Weisman等),1987年6月16日授权和U.S.专利4935022(Lash等),1990年6月19日授权,它们公开了双--层芯结构,包括纤维基材和微粒状吸收剂聚合物,用于样式薄、紧密无膨胀感的尿布中。
这些微粒状吸收剂聚合物在保留大量的体液如尿的能力方面是卓绝的。这些微粒状吸收剂聚合物的代表性实例是轻度交联的聚丙烯酸酯。与许多其它的吸收剂聚合物相似,这些轻度交联的吸收剂聚丙烯酸酯包括联接到聚合物骨架上的多重的阴离子(带电的)羧基。由于渗透力的原因,正是这些带电的羧基使聚合物能够吸收含水的体液。
除渗透力之外,在包括尿布的许多吸收物品中,毛细管力的吸收作用也很重要。毛吸管力在各种日常现象中可观察到,例如用纸巾吸收溅出的液体。毛细管吸收物品在流体获得和吸收速率方面可提供优良的性能,即将含水的体液移动到远离初始接触点的能力。的确,上述的双--层芯吸收剂结构,使用纤维基材作为毛细管转移的主要工具,将初始获得的含水体液移动通过吸收芯,使得设置在层中或芯区的微粒状吸收聚合物将体液吸收和保留。
能够潜在地提供毛细管流体转移的另一种吸收材料将是开孔结构的聚合物泡沫。如果制造得适当的话,开孔结构的聚合物泡沫就能够提供吸收物品例如尿布的高性能吸收芯中使用所要求的毛细管流体捕获、输送和储存特性。含这些泡沫的吸收物品可具有所希望的浸湿完整性,在该物品穿着的整个期间可提供适体的感觉,并可避免在使用期间物品的形状破裂。此外,含这些泡沫结构的吸收物品能够容易以商业规模生产。例如,尿布的吸收芯可简单地从连续的泡沫片中冲压出来,而且可设计得具有更高的完整性和均匀性,而含微粒状吸收聚合物的空气成网(air-laid)的纤维吸收芯则不能。这些泡沫结构还能够模压成任何希望的形状,或甚至成形为完整一体化的尿布。
文献和商业活动中有各种类型聚合物泡沫的描述,这些聚合物泡沫在各种各样的用途中吸收不同的流体。诚然,用作尿布和月经产品之类的吸收物品的元件的某些类型的聚合物泡沫材料以前曾建议过。例如,参见U.S.专利4029100(Karami),1977年6月14日授权,该文献描述一可保持形状的尿布,在其吸收垫组件的分叉区域采用一泡沫元件,以便提供好的湿的回弹性。某些类型的聚合物泡沫材料也已经提出用于吸收物品中,以便吸收、吸入和/或保留含水的体液。例如,参见U.S.专利3563243(Lindquist),1971年2月6日授权(尿布等用的吸收垫,其中主要的吸收材料是一种亲水的聚氨基甲酸酯泡沫片):U.S.专利4554297(Dabi),1985年11月19日授权(吸收体液的泡沫状聚合物,可以用于尿布和月经产品):U.S.专利4740528(Garvey等),1988年4月26日授权(吸收剂复合结构例如尿布、妇女保健产品等,都包含有某些类型的超毛细作用的交联的聚氨基甲酸酯泡沫制造的海绵状的吸收材料)。
虽然已经提议将各种聚合物泡沫材料用于吸收物品中,但是对具有最隹组合特征和特性的吸收泡沫材料仍然需要,这些综合特征(性)将使这些泡沫材料在商业上出售的吸收产品如尿布中特别有用。就所希望的吸收特性而言,包括毛细管流体转移能力,已经确定有最佳吸收性,开孔结构的聚合物泡沫应有如下特征:(a)与吸收物品中的其它成分相比,对吸收体液有更大的亲合力,因此泡沫材料可以从这些其它成分中抽吸(分布)体液,并将其储存在泡沫结构内。(b)有更好的毛细作用和流体分布特性,以便用泡沫来转移吸收的尿和其它体液,使其脱离初始的接收区,并进入泡沫结构未使用的平衡区,这样使得有能力接受随后流出的流体;和(c)在受力即在加压力的情况下,要有较高的储存容量和较高的流体容量。
如前所述,较薄的吸收芯通常是制备较薄的吸收物品所要求的,例如尿布。但是,所提供的吸收聚合物泡沫材料在被含水的体液浸湿前保持较薄形状是不容易的。在被浸湿前在通常的储存和使用期间,吸收泡沫材料需要保持较薄的形状。如果较薄的聚合物泡沫材料是用于高性能的吸收芯中的话,那么它还必须附加有上述所需的吸收特征。制成足够软和有柔性的较薄的聚合物泡沫使穿戴者感觉舒适也不是一个简单的任务。
因此,人们所希望能够制造一种开孔结构的吸收聚合物泡沫材料是:(1)有足够的或更优异的吸收特征,这包括毛细管流体转移能力,以便将有所希望的高性能的吸收芯用于吸收物品中,这些吸收物品如尿布、成人失禁垫或三角裤、卫生巾等;(2)直到被体液浸湿前,在一般的储存和使用期间较薄:(3)有足够的弹性和柔软性,以便吸收物品的穿戴者有高度的舒适感;和(4)以较合理的或低的成本可以商业规模地生产。
本发明涉及较薄的密实的(即未膨胀的)聚合物泡沫材料,当与含水体液接触时,膨胀并吸收这些体液。这些吸收聚合物泡沫材料包括亲水的、有弹性的相互连接的开孔的非离子的聚合物泡沫结构,每单位泡沫体积的比表面积为至少约0.025M2/cc。该泡沫结构至少加入约0.1%(wt)毒性上可接受的吸水的水合盐。在其密实状态下,泡沫结构的膨胀压约30000帕斯卡或低于此值。在它的膨胀状态下,泡沫结构当用表面张力为(65±5)×10-3牛顿/米的合成尿在88°F(31.1℃)饱和到它的自由吸收容量时,其密度约为它在密实状态下的干基密度的约10%至约50%。
根据本发明的聚合物泡沫结构保持在密实状态即未膨胀状态的能力是取决于在密实的泡沫结构内产生的毛细管压力,该压力至少等于压缩的聚合物通过弹性恢复倾向(即膨胀压力)产生的力。令人惊奇地是,在正常装运、储存和使用条件下,这些密实的聚合物泡沫材料保持较薄的状态,直到最终它们被含水体液浸湿并开始膨胀前都是如此。由于它们的优良吸收特性,这包括毛细管流体转移能力,这些密实的聚合物泡沫材料在用于尿布、成人失禁垫或三角裤、卫生巾等的吸收物品的高性能的吸收芯中都是极其有用的。这些密实的聚合物泡沫材料还有足够的挠性和柔软性,能够提供吸收物品的穿戴者高度的舒适感。
本发明进一步涉及用于一致性地制备这些较薄的密实的聚合物泡沫材料的方法,该方法是通过将特定类型的油包水乳液聚合,而该乳液由较小量的油相和较大量的水相组成,在本领域内统称为高内相乳液或“HIPE”。这HIPE乳液的油相包括约67%-约98%(wt)的单体成分是:(a)约5%-约40%(wt)基本上不溶于水的单功能的玻璃状的单体;(b)约30%-约80%(wt)的基本上不溶于水的单功能的橡胶状共聚单体;(c)约10%-约40%(wt)的基本上不溶于水的多功能的交联剂成分。油相还包括约2%-约33%(wt)的乳化剂成分,它溶于油相,并将为聚合过程提供稳定的乳液。这HIPE乳液的水相或“内”相包括约0.2-约20%(wt)的水溶性电解质的水溶液。在这HIPE乳液中水相与油相的重量比为约12∶1-约100∶1。聚合的泡沫随后脱水后(有或没有前置洗涤/处理步骤)就得到了密实的泡沫材料。
本发明的方法的一个重要方面是以减少在HIPE乳液中形成较小水滴的聚结的方式进行乳液形成和聚合步骤。这就使在生成的聚合物泡沫材料中的平均孔径值为约50微米或小于此值。据信这种降低HIPE乳液中形成较小水滴聚结和在聚合物泡沫材料中生成较小平均孔径的孔是一致性地形成较薄的密实的本发明的聚合物泡沫材料的主要机理,而且特别是使密实的泡沫材料具有良好的吸收性和流体的转移特性。聚结的这种降低作用通过使用某些乳化剂体系通过在聚合(固化)期间利用较低的温度或两种手段同时使用可以一致地实现,这将如下文所述。再有,这些较薄的密实的吸收聚合泡沫材料按照本发明的方法,以潜在地商业规模和潜在地合理的或低的成本可以一致性地生产。
图1是本发明的在密实状态下的一代表性的吸收集合物泡沫的剖视的侧视图的显微照片(放大1500倍)。
图2是本发明的在膨胀状态下的一代表性的吸收聚合泡沫的剖视图的显微照片。
图3a-3d是在不同温度下通过聚合/固化某一HIPE乳液而制备的吸收聚合物泡沫的剖视图的显微照片(放大500倍)。
图4是从含优选的助乳化剂体系的HIPE乳液制备的本发明的吸收聚合物泡沫的剖视图的显微照片(放大1000倍)。
图5是一次性的尿布的切开图,该尿布是利用本发明的吸收聚合泡沫在一双层构型的吸收尿布芯中作为水漏一型流体储存/分散成分。
图6是表示一贴身物品的切开的视图,该物品例如是一次性的训练裤产品,它采用了本发明的吸收聚合物泡沫作为吸收芯。
图7表示双层芯构型的尿布结构的各个组成部分排开的视图,该双层芯构型具有水漏-型流体捕获层,它复盖呈改进的水漏型的吸收泡沫流体储存/分散层。
本文所称的类型的聚合物泡沫其特征为这样生成的结构,就是当将相对不含单体的液体呈小滴或“小泡”样分散在含可聚合的单体的液体中,随后在含单体的围绕小滴的液体中各单体进行聚合。生成的聚合分散物可以为多孔的固化的结构形状,它是一些孔穴的聚集体,该孔穴的边缘或孔壁含固态的聚合材料。孔本身包含相对不含单体的液体,在聚合前,它在液体中分散形成小滴。
如下文更详细描述的,用作本发明的吸收剂的密实的聚合物泡沫材料通常通过使特定类型的油包水乳液聚合来制备。这种乳液是由较少量的含可聚合的单体的油相和较大量的相对不含单体的水相生成。相对不含单体的、不连续的“内部”水相构成被连续的含单体的油相围绕的分散的小滴。在连续的油相中单体随后的聚合就生成了多孔状的泡沫结构。聚合后滞留在泡沫结构中的水溶液可以通过加压、加热干燥和/或真空脱水来除去。
聚合物泡沫,包括从油包水乳液制备的泡沫其特征可以为相对封闭的孔结构或是相对的开孔结构,这取决于孔壁或周边即孔口,是被聚合材料充满或是空的,和/或被聚合材料填充的程度。用于本发明的吸收物品中和结构中的聚合泡沫材料是相对开孔结构的材料,在材料中泡沫的各个孔的大部分不被孔壁的聚合材料完全隔离。这样在这些基本上是开孔结构的泡沫结构的孔有相互连接的多孔状的开孔或“窗户”,它们大到足以允许流体容量从泡沫结构的一个孔转移到另一个孔内。
在本文中有用类型的基本上是开孔结构的结构中,该泡沫一般都有网状特征,由许多相互连接的三维的支化纤维网构成各个孔。构成开孔泡沫结构支化纤维网的聚合材料纤维丝可以称为“柱架”。有典型的柱架型结构的开孔结构泡沫以实例的方式示于图2的显微照片中。对本发明的任何来说,如果泡沫结构中至少80%的孔(至少为1微米孔径)与至少一个相邻的孔进行液体相通的话,那么该泡沫材料就是“开孔结构”。此外,如果泡沫材料测量的孔体积是理论上可利用孔体积的至少80%的话(理论体孔体积例如通过生成泡沫材料的HIPE乳液的油包水重量比确定),那么该泡沫材料可以为基本上是开孔结构。
除了是开孔结构外,本发明的密实的聚合泡沫材料为亲水性。本文中的泡沫必须是充分亲水的,以允许泡沫按下文说明的量吸收含水的体液。如下文讨论的,就优选的泡沫类型,和泡沫的制备方法而言,由于残余的亲水剂在聚合反应后留在泡沫结构中或由于选择的聚合反应后的泡沫处理步骤(该步骤可以被用来改变生成泡沫结构的材料的表面能)可以使泡沫结构的内表面得到亲水性。
本发明的聚合泡沫结构的亲水性程度可以定量表示,其方法是通过参考这些泡沫与可吸收试验液体相接触时所显示出的“粘合张力”来度量。粘合张力由下式计算:
AT=γCOSQ其中AT是粘合张力,单位为10-3牛顿/米;
γ是被泡沫材料所吸收的试验液体的表面张力,单位为10-3牛顿/米;
Q是聚合物泡沫表面与矢量之间的接触角,单位为度,该矢量是与表面相接触的点的试验液体的切线的矢量。
对任意给定的亲水泡沫材料,泡沫表现的粘合张力利用一种方法可以实验地测定,该方法是测量已知尺寸和毛细管吸入的比表面积(capillary suction specifie surface area)的泡沫样品吸收试验液体例如合成尿的重量。这种方法在下文的试验方法部分作了更详细地描述。在本发明中用作吸收剂泡沫的材料一般是亲水性达这种程度的那些,在该程度下,它们显示的粘合张力为(约15-约65)×10-3牛顿/米,更优选(约20-约65)×10-3牛顿/米,通过毛细管吸入表面张力为(65±5)×10-3牛顿/米的合成尿的量来确定。
除了“开孔结构”和“亲水性”外,在本发明中有用的聚合泡沫材料具有特殊的结构和机械性质、特征和/或特性。应当理解这些泡沫材料在泡沫与被吸收的体液之间接触前,在不同的时间可具有不同的性质、特征和/或特性。例如,在它们制造、运输、储存等期间,泡沫的密度和/或孔径值均在下文陈述的这些参数的范围之外。但是,如果它们后来经受物理的或流变学的改变,因此在它们与被吸收的体液接触前的至少某一点和/或接触期间的至少某一点,具有了在下文说明的所要求的这些性质、特征和/或特性值的话,这些泡沫材料仍然是在本发明的范围内。
本发明的聚合泡沫材料的性质、特征和/或特性是有相互联系和相互依存的,但是可以基本归类如下:(I)和它的密实状态特别有关的那些;(II)和它的膨胀状态特别有关的那些;(III)和它的密实状态或者膨胀状态同样有关的那些;和(IV)当与体液接触时,和它的吸收性特别有关的那些。
I、密实状态
本发明的密实的聚合泡沫材料通常通过下文描述的HIPE型乳液的聚合来制备。这些都是油包水的乳液,有较小量的油相和较大量的水相。而且,聚合后,生成的泡沫含相当量的水。通过施加压力,这种水可以从泡沫中压出来,和/或通过加热脱水例如在窑中加热,或通过真空脱水来使其减少。在加压、和/或加热脱水/真空脱水后,聚合泡沫材料为密实的或未膨胀的状态。图1的显微照片示出了通过加压压出了水的有代表性的密实的HIPE泡沫的多孔结构。如图1所示,泡沫的多孔结构变了形,特别是在与图2所示的HIPE泡沫结构比较时。(图2所示的泡沫结构为它的膨胀状态)。还如图1所示,泡沫结构中的空隙或孔(黑色的区域)已经变平或伸长。与泡沫结构的相邻柱架没有接触或有最小的接触。
接着加压和/或加热脱水/真空脱水之后,密实的聚合泡沫材料可再膨胀,特别是在与含水体液接触时。(参看图2,它示出了膨胀状态的本发明的一典型的HIPE泡沫结构)。令人惊奇地是,本发明的聚合泡沫材料保持这种密实状态,或未膨松的状态可以相当长的时间期间,例如至少高达约一年。本发明的这些聚合泡沫材料保持这种密实的/未膨松状态的能力被认为是由于毛细管力,特别是泡沫结构中产生的毛细管压力。这里所用的“毛细管压力”是指由于泡沫中的孔的窄的范围内的弯液面的弯曲部分,在液/空气界面的压力差。[参见Chatterjee,“Absrbency,”Textile Science and TechnoIogy.Vo.7,1985,p.36.]对浸润液体来说,这基本上是与大气压相比较的压力降。
在加压、和/或加热脱水/真空脱水后,本发明的聚合泡沫材料还残存有水,这包括与掺入的吸湿性的水合盐结合的水合水(如下文所述),以及泡沫内所吸收的自由水。据信正是这种残存的水(由水合盐参与)对生成的密实的泡沫结构引起了毛细管压力。本发明的密实聚合泡沫材料可残存的水量至少为约4%,通常为约4%-30%,以泡沫的重量计(在室温(72°F(22℃))和50%的相对湿度下储存时)。优选的本发明的密实的约聚合物泡沫材料的残存水量按泡沫的重量计为约5%-约15%。
在它的密实状态下,泡沫结构中所产生的毛细管压力至少等于由加压的聚合物弹性恢复或模量引起的力。换言之,使密实的泡沫材料保持较薄所需的毛细管压力是通过由加压的聚合泡沫结构当它企图“弹回”时引起的抵消力来测定。聚合物泡沫弹性的恢复倾向可以从压力-应力试验来测定,这里膨胀的泡沫压缩到它原来体积的约25%,膨胀卡钳(厚度)然后保持在该加压状态下直到测量平衡或松弛的压力值。另外,对本发明的目的来说,还可以当密实状态的聚合物泡沫与含水流体例如水接触时,对聚合物泡沫进行测量而测定平衡的松驰压力值。这个任意选择的松驰压力值下文称为泡沫的“膨胀压力”。测定泡沫膨胀压力的方法的详细描述在下文的测试方法一节提出。
本发明的聚合物泡沫的膨胀压力为约30千帕斯卡(KPa)或小于此值,通常为约7-约20KPa,即膨胀压力是在一较窄的范围内。这就意味着本发明的典型的聚合物泡沫结构的弹性恢复倾向是比较稳定的。而且提供本发明的密实的未膨胀的聚合泡沫材料所需的毛细管压力也通常落入一个恒定的范围内。
直接测量本发明的密实的聚合物泡沫的泡沫结构内产生的毛细管力在理论上是可行的。例如,如果简单模型化为一个空芯圆筒,毛细管压力(P)由LapIace方程确定: P = 2 γ cos ( Q ) γc 其中γ是流体的表面张力,Q是接触角,和γc是毛细管的半径。但是,由于各种复杂因素,包括难以为聚合物泡沫指定γc值,本发明的泡沫结构内产生的毛细管压力不直接测量。取而代之,通过将上述的LapIace方程改写成如下更一般的形式,这种形式可应用到任何多孔结构(例如泡沫),泡沫结构内产生的毛细管压力就更容易估算:
P=Scp γcosQ其中Sc是泡沫结构的毛细管吸入的比表面积,p是泡沫密度,是泡沫的孔隙率,和γcosQ是流体和泡沫结构之间的粘合张力(AT)。假设该值接近于1(通常情况下当泡沫结构是膨胀状态时),泡沫结构内产生的毛细管压力是:(A)毛细管吸入比表面积的作用;(B)泡沫密度的作用;和(C)流体和泡沫结构间的粘合张力作用。
对特定的粘合张力值,人们发现每泡沫体积的比表面积对经验地确定本发明的泡沫结构非常有用,该泡沫结构将保持在密实状态。这里所使用的“每泡沫体积的比表面积”是指泡沫结构的毛细管吸入比表面积乘以泡沫的密度,即上述一般方程中的值Scp。这个每泡沫体积的比表面积值是当作“经验”的特征,它来自于(a)在干泡沫浸湿期间,测量的毛细管吸入的比表面积和(b)在浸湿到饱和后的膨胀的泡沫的密度,而不是通过干的密实的泡沫结构的直接测量。即使如此,人们发生每泡沫体积的最小的比表面积值与保持在密实状态的泡沫结构的能力相符合。本发明的聚合物泡沫结构的每泡沫体积的比表面积至小为约0.025m2/cc,优选至少为约0.05m2/cc,更优选为约0.07m2/cc,本发明具备该范围值的泡沫材料已经经验地发现保持在密实状态。
下文将充分地讨论毛细管吸入比表面积、泡沫密度和流体的粘合张力的表面张力成分,以及与毛细管压力和/或聚合物泡沫的膨胀压力有关的其它因素:A)毛细管吸入比表面积
一般来说,毛细管吸入比表面积是试验-流体-最易接近的聚合物网状结构的表面积的测量,该网状结构为每单位质量的泡沫材料(聚合物结构材料加上固体残有材料)形成的具体泡沫。毛细管吸入比表面积是通过泡沫中的多孔状单元的尺寸和聚合物的密度来测量。因此,毛细管吸入比表面积是由泡沫网状结构所提供固体表面的总量的程度的定量的一种方式,这种表面参预了吸收。
开孔的泡沫结构如这里的聚合物泡沫的毛细管吸入比表面积是影响由泡沫表现的毛细管作用(或毛细管吸入)的主要特征。较高的毛细管吸入比表面积和低密度的泡沫提供了高容量和高毛细管作用的非常希望的组合。高比表面积还是构成泡沫结构柱架精细的一个结果。人们发现,泡沫的毛细作用必须进行控制和选择,以便这里的泡沫材料有足够毛细作用提供可接受的流体保留和发生在泡沫结构内的流体吸收速率。因此毛细管吸入比表面积的调节,以及泡沫聚合物表面亲水性的控制是为本发明的吸收泡沫提供所要求程度的毛细作用的途径。
毛细管吸入比表面积与泡沫结构内是否产生适当的毛细管压力,以使它在被含水的体液浸湿前保持密实状态特别有关。利用上述的一般形式的LapIace方程,在泡沫结构内产生的毛细管压力与毛细管吸入的比表面积成正比。假设其它的因素如泡沫密度和流体的粘合张力恒定,这就是说,随毛细管吸入比表面积的增加(或减少),泡沫结构内的毛细管压力也成比例地增加(或减少)。
通过调节影响泡沫形成的组合物成分和工艺参数,本文泡沫的毛细管吸入比表面积可进行影响及控制。对HIPE乳液泡沫,组成成分参数包括HIPE乳液中的油与水的比率和在HIPE乳液中所利用的单体、乳化剂和电解质的类型及用量。影响毛细管吸入比表面积的工艺参数包括混合能量和温度。
对本发明的目的来说,通过测量发生于已知质量和大小的泡沫样品内的毛细作用吸收的低表面张力液体(例如乙醇)的量来测定毛细管吸入比表面积。在下文的试验方法一节将详细描述用毛细管吸入法测定泡沫比表面积的这一方法。用于测定毛细管吸入比表面积任何合理的可供选择的方法也可以利用。
用于本发明的密实的开孔结构的吸收聚合物泡沫是毛细管吸入比表面积至少为约0.3m2/g的那些。一般,毛细管吸入比表面积在约0.7-约8m2/g,优选的约1-7m2/g,最优选约1.5-约6m2/g。对于将在下文定义的孔体积,有这些毛细管吸入比表面积值的亲水性的泡沫对含水体液如尿一般将具有特别希望的平衡吸收容量、保持流体和吸入流体或分散流体的特性。再者,有这些毛细管吸入比表面积的泡沫可以产生足够的毛细管压力,以保持泡沫密实的未膨胀状态,直到它被这些含水体液浸湿为止。B)泡沫密度
本文中泡沫的密度是以干基的在空气中的每cm3泡沫体积的泡沫的克数表示的。因此吸收的含水液体如残留在泡沫中的盐和液体,例如在HIPE乳液聚合、洗涤和/或亲水化之后残留的,在计算和表示的泡沫的密度中是全然不计的。但是在此描述的泡沫密度的确包括其它的残存物料,例如在聚合泡沫中存在的乳化剂。实际上,这些残存的物料在泡沫物料的质量中可占有显著位置。
与毛细管吸入表面积一样,本文泡沫材料的密度可以影响泡沫吸收剂的许多性能和机械特性。这些包括对含水体液的吸收能力、在泡沫内流体的分散程度和速率及泡沫的挠性与压缩的折转特性。尤其重要的是,泡沫吸收结构的密度可以决定这些结构的费用的有效性。最重要的是,泡沫密度可以部分决定在何毛细管压力下足以使泡沫在被含水体液浸湿前的一个相当长的时间期限内保持密实的未膨胀状态。
提供测定每单位体积的泡沫结构的固体泡沫材料质量的任何适宜的重量分析方法都可以用来测量泡沫的密度。例如,在下文的试验方法一节中更详细描述的ASTM重量分析法是可以采用测定密度的一种方法。对于泡沫样品的制备方法(脱水、老化、预弯等)都可以偶然地改变所得到的密度的测量值的情况下,其它的密度测定试验方法也可以使用。例如,这些其它的方法可包括利用泡沫材料内所吸收的试验液体来进行重量分析密度测量。这种类型的密度测定方法可以用于低密度泡沫例如干密度大约为泡沫孔体积倒数的泡沫密度的测定。[参见Chatterjee,“Ab orbency,”Textile Sciene andTechnology,Vol.7,1985,p.41.]正如毛细管吸入比表面积那样,下文描述的泡沫密度的范围是总括的,即包括可通过任何适宜的实验测试方法测定的密度值。
本发明的密实的吸收聚合物泡沫的干基密度值为约0.05-约0.4g/cm3,优选为约0.07-约0.25g/cm3,而最优选为约0.1-约0.2g/cm3。泡沫材料的密度可以调节到前述的范围,这是通过控制,特别是控制HIPE乳液的水与油的比率实现的。C)流体的表面张力
如前所述,本发明的密实的聚合泡沫材料有一定数量残存的水。在不存在其它表面张力改良剂的情况下,在22℃时纯水的表面张力为约73×10-3牛顿/米。但是,这种残存水通常含其它物料,这将增加或降低它的表面张力。这些物料可以存在在HIPE乳液的水相中,从这种HIPE乳液通常都可以制备本发明聚合物泡沫材料。这些材料还可以包括由聚合后的步骤、例如使泡沫表面亲水步骤导致的残存水。
密实的聚合泡沫残存水中存在的这样一种材料是毒理学上可接受的吸湿的可水合的盐,优选CaCl2。除了防止在泡沫结构中保持的残存水蒸发外,这些可水合的盐还可提高水的表面张力。例如,包括1%(wt)的CaCl2能将22℃时水的表面张力增加到约75达因/cm。在泡沫结构中存在的这些可水合的盐的量至少为约泡沫的约0.1%(wt),通常在约0.1%-约8%的范围,优选约3%-约6%,以泡沫的重量计。
在密实的聚合物泡沫材料中存在的另一种物料是某些油溶性乳化剂。在本发明的泡沫结构中可以存在的有代表性的油溶性乳化剂包括月桂酸山梨糖醇酯(例如SPAN20)、月桂酸山梨糖醇酯与棕榈酸山梨糖醇酯(例如SPAN40)的混合物、月桂酸山梨糖醇酯与某些下文待述的聚甘油脂肪酸酯的混合物和油酸山梨糖醇酯(例如,SPAN80)。这些乳化剂一般都掺入,以便为泡沫结构提供亲水的表面。但是,在这些乳化剂中更易溶于水的成分也可以溶于残存在泡沫结构的水中,并可以影响水的表面张力,一般是降低表面张力。在泡沫结构中存在的这些油溶性乳化剂的量为至少约0.5%,以泡沫的重量计,而一般在约0.5%-约20%,优选约5%-约12%的范围,以泡沫的重量计。D)孔大小
限定本发明优选的密实的聚合物泡沫材料的另一有用特征是孔的尺寸。泡沫的孔,特别是通过围绕相对无单体的水相小滴的含单体油相的聚合生成的那些孔常常基本上为球形。因此这些基本上为球形孔的大小或“直径”一般来说仍然是表征泡沫特性和表征本发明的某些优选的吸收泡沫结构特性所通常利用的参数。由于在给定的聚合物泡沫的样品中孔不必须是大约相同的尺寸,因此一种平均尺寸即平均孔径将是常常所描述的。
与泡沫的密度、毛细管吸入比表面积一样,孔大小是泡沫的参数,它也对本发明的吸收泡沫材料的许多重要力学性能和特征有影响。由于孔大小构成毛细管吸入比表面积,后者与泡沫的亲水性一起决定了泡沫的毛细作用,孔尺寸是可以直接影响泡沫吸收材料的内部流体吸收性能的泡沫结构参数,同样也是直接影响泡沫结构内产生毛细管压力的泡沫结构参数。
为测定泡沫的平均孔尺寸,可以利用许多技术。这些技术包括本领域内众所周知的汞孔度计方法。但是,测定泡沫中孔尺寸最有用的技术包括基于泡沫样品的扫描电子显微照相的简单测量。例如图2示出了在膨胀状态下的本发明的一般的HIPE泡沫结构。附加在显微照片上的是表示20微米级尺寸。这一尺寸通过图象分析法可以用来测定平均尺寸。实际上,泡沫样品的显微照片的图象分析是通常采用的可用来测定泡沫结构的平均孔尺寸的分析工具。这一技术在U.S.专利4788225(Edwards等)中作了详细描述,该专利1988年11月29日授权,本文将其结合参考。
在此给出的孔尺寸的测量值是以膨胀状态的泡沫的平均孔尺寸值为基础,如图2所示。用作本发明的用于吸收含水体液的吸收材料的泡沫优选的平均孔尺寸值为约50微米或小于此值,通常在约5-约50微米范围。更优选的平均孔尺寸值为约5-约40微米,最优选约5-约35微米范围。
泡沫中孔的尺寸或孔直径通过改变相同类型泡沫的组成成分和影响毛细管吸入比表面积及泡沫密度的加工特征可以进行影响和控制。为制备优选的HIPE泡沫,这些包括决定聚合物泡沫结构的HIPE乳液前体中水相小滴的大小的主要的那些因素。因此,通过调节在混合期间输入的能量和为生成HIPE乳液所使用的乳化剂的类型的数量,可以改变孔的尺寸。E)增塑效果
在密实泡沫结构中存在的油溶性乳化剂可以影响聚合物自身的模量,例如象增塑剂那样。这些增塑的作用可能是在HIPE乳液形成期间引入乳化剂的结果,否则就可能是由于聚合后亲水性处理引起的掺杂的结果。由乳化剂引起的增塑作用常常倾向于降低聚合物的模量,因而泡沫结构的膨胀压力就较低。这就是说稳定密实的泡沫结构所要求的毛细管压力可以稍稍降低。但是增塑作用不可太大,以致于大到不希望的程度。例如,聚合物泡沫结构可以增塑到这样程度,在这种情况下泡沫变弱,并且没有如下说明的耐压缩的弯折特性。II.膨胀状态A)被合成尿饱和时的密度
本发明的在其膨胀状态下的吸收泡沫的特别重要的性质是被含水体液泡和时它们的密度(相对于它的密实状态下的吸收泡沫的干基密度)。当被含水体液饱和时,膨胀泡沫的密度与它的密实(压缩)状态下的它的干基密度的比较提供了在它的膨胀状态下泡沫的相对厚度的测量。这就提供了当泡沫膨胀和被含水体液饱和时,它有多薄的特别相关的测量。
对本发明的目的来说,在吸收泡沫在88°F(31.1℃)被表面张力为(65±5)×10-3牛顿/米的合成尿饱和到它的自由吸收容量时,才测量它在膨胀状态下的密度。当泡沫被合成尿饱和时在膨胀状态下它的密度通过在试验方法一节更详细描述的方法可以测量。因此,在泡沫膨胀、饱和状态下测量的密度是用相对于它在密实状态下的干基密度的百分数表示的。对本发明的目的来说,当泡沫被合成尿饱和到它的自由吸收容量时它的膨胀状态的密度可以为它在密实状态下的它的干基密度的约10%-约50%,优选约10%-约30%,最优选约15%-约25%。B)孔体积
孔体积是在单位质量的生成泡沫结构的固体材料(聚合物结构加上任何残存的固体)的多孔泡沫结构中的开口或孔的体积的测量。孔体积在影响吸收泡沫的许多性能和机械特征,特别是在其膨胀状态时很重要。这些性能和机械特征包括泡沫对含水体液的吸收容量,泡沫的挠性和泡沫压缩折转的特性。
孔体积通过任何适宜的实验方法来测定,这将给出结构实际孔体积的精确指示。这些实验方法通常涉及测量可以引入泡沫结构的试验液体的体积和/或质量,因此就代表了泡沫开孔结构所占的体积。因此之故泡沫的孔体积参数还可以称为“可利用的孔体积”。
实验测定可利用孔体积的一种一般的方法包括将低表面张力的非聚合物-溶胀的液体例如2-丙醇引入泡沫结构。利用2-丙醇测定可利用的孔体积的方法在试验方法一节中描述。十分清楚,其它的试验液体和方法也可以用来测定可利用的孔体积。
本文使用的吸收泡沫的孔体积通过调节许多泡沫的组成成分和加工特征可以影响和控制。例如,对于本文优选的HIPE乳液泡沫来说,影响这些孔体积的特征可包括HIPE乳液中水与油的比率、所使用的水相电解质的种类和用量、所使用的油相乳化剂的类型和用量、实现泡沫洗涤和/或增稠的聚合后步骤以及在这些步骤后聚合泡沫结构的回收率。
本发明的泡沫材料的孔体积通常为约12-约100ml/g,更优选约20-约70ml/g,而最优选约25-约50ml/g。孔体积的这些范围真针对的是本发明范围内的泡沫的理论孔体积的“总括性”定义。因此,如果预期到可给出接近理论孔体积的测量值的任何实验方法给出的值在上述范围内,那么通过任意的这种方法所测试的泡沫材料属于本发明的范围。C)抗加压挠曲性
本发明聚合物泡沫的一个重要机械特征是吸收泡沫的强度,在其膨胀状态下,通过它的抗压缩挠曲测定。泡沫显示的抗压缩挠曲性是聚合物弹性模;量和泡沫网状结构密度的函数。聚合物弹性模量又由下面几方面决定:a)聚合物组成;b)聚合物泡沫由在加工后留在泡沫结构中的残余物如乳化剂增塑的程度;和c)泡沫聚合的条件。
对被用作吸收物品如尿布中的吸收结构,本发明的吸收泡沫材料必须是当这些吸收材料在吸收和滞留流体时,有适度的耐受由遭遇到的力引起的变形或压力的性能。不具有足够泡沫强度即抗加压挠曲性的那些泡沫,在无负荷的情况下,能够获得和储存可接受量的体液,但是在含该泡沫的吸收物品的穿戴者由于运动和活动产生的压缩应力下,将非常容易地排出这些体液。
本发明的聚合物泡沫的抗加压挠曲性通过测定在某一限定压力下的指定的时间期间内由饱和的泡沫材料样品中所产生的变形量来定量。对本发明的目的来说,对标准尺寸(0.25cm厚和截面为圆形的面积为6.5cm2的圆柱体)的泡沫样品可以进行这些测量。这些样品用表面张力为(65±5)×10-3牛顿/米的合成尿饱和,然后在88°F(31.1℃)下经受5.1kpa的限压15分钟。在这样测试中产生的变形的量以该样品压缩的厚度占饱和并完全膨胀的样品的厚度的百分数表示。为计量抗加压挠曲性所进行的这种特殊类型试验的方法在试验方法一节中更详细地描述。
有用的吸收泡沫是显示出抗加压挠曲性如下的那些,即它们在5.1kpa的限压下产生的变形一般为泡沫结构压缩约2%-约80%,是在它被表面张力为(65±5)×10-3牛顿/米的合成尿饱和到它的自由吸收容量时测得的。在上述条件下产生的优选变形量为约5%-约40%,最优选约5%-约25%。对本发明的优选的HIPE泡沫,通过适当地选择但体、共聚用单体和交联剂的类型及浓度与适宜的乳化形成和乳化聚合条件及技术相结合,抗加压挠曲性可以调节到上述范围的变形值。这样,这些优选的泡沫从弹性模量大到足以提供充分抗加压挠曲性的材料生成,即使这些泡沫是低密度和具有很微小的柱架。D)加压挠曲的恢复性
加压挠曲的恢复性与一片泡沫材料在制造、储存或使用中遭遇到力引起变形或压缩后恢复到它原来尺寸的趋势或倾向有关。对本发明的目的来说,优选的吸收泡沫的加压挠曲的恢复性是在它的膨胀状态下和含吸收体液时测定。因此,是用被合成尿饱和的膨胀泡沫测量加压挠曲的恢复性。
测定加压挠曲恢复性的适宜方法在试验方法一节中描述。一般来说,这一方法包括对合成尿饱和到它的自由吸收容量的标准尺寸的泡沫样品的加压和释压。样品在压缩到50%的状态下维一给定时间期间,然后释压。在有自由流体存在下,在释压后一分钟期间样品恢复到它的厚度的程度确定为样品加压挠曲的恢复性(能恢复原来形状的能力)的测量置。
本发明优选的吸收泡沫浸湿时一分钟后一般显示出为膨胀测径器至少75%的恢复性。更优选的是,这些优选的泡沫材料浸湿时的加压挠曲恢复至少80%。III.密实或膨胀状态
A)揉曲性
本发明的吸收泡沫应当有足够的揉曲性,以便它们可以在与穿戴者的体形一致的吸收产生中利用。因此有揉曲性的吸收泡沫的特性的意思是这些泡沫可以变形或弯曲到这些吸收物品中要求使用的程度,而对它们的结构完整性没有明显的损伤或它们的吸收性质没有明显的损失。
本发明优选的吸收泡沫还应当是有足够揉曲性,以经受在制备、加工、包装、运输和储存合这些泡沫材料的吸收物品的过程中所遭遇到的压力或变形力。例如,一次性尿布通常在折叠的情况下包装和销售,其中尿布芯在纵向和横向都要折叠。一次性尿布一般都以折叠尿布的捆的形式销售,这些尿布通过围绕它们的包装材料包住和压紧。因此,在加工和销售期间泡沫吸收材料所经受的压力和变形力比在使用时施加到泡沫材料上的更大。
给定吸收泡沫可以遇到的处理的类型,本发明优选的吸收泡沫材料具有揉曲的特性,可以通过参考它们对经受弯曲而不对结构的完整性有明显损伤的能力来定量表示。在后文试验方法一节中所描述的是测量吸收泡沫揉曲性的一种方法,其中是通过将给定尺寸的泡沫样品在描述的速度下绕一圆形卷筒测定是否可以弯曲和弯曲多少次而不破裂。本发明优选的泡沫是具有足够揉曲性的那些,因此在用作吸收体液的它们的使用点,在88°F(31.1℃)饱和的泡沫材料可以经受住这种弯曲试验而不破裂,即显示的弯曲值至少为一个圈(cycle)。更优选,优选的泡沫当经受这种测试方法时,至少可以弯曲三次而不破裂。B)泡沫的完整性和柔软性
虽然对于合用的或有用的吸收结构的实现不是必需的,但是本发明的吸收泡沫优选具有在使用中的结构完整性和触摸有柔软性的(没有刺激)的附加机械性能。例如,在婴儿的尿布之类的吸收物品中所采用的泡沫材料将常常经受动压力和静压力,当穿戴者步行、跑、爬或跳时,这些力就出现。这些力不仅倾向压缩吸收泡沫和挤出其中的体液,而且这些力还倾向于撕裂或扯裂或使泡沫结构成碎片。对以这样的方式使用的泡沫结构有利的是必须有足够的结构完整性,以使在使用中撕裂泡沫或使泡沫成碎片的可能性减至最小。
本发明的吸收泡沫还可以应用于如下构形的吸收物品中,在下文将更详细地描述,其中泡沫材料表面非常接近或甚至与穿戴者皮肤实际接触。因此人们很希望吸收泡沫的表面具有可接受的柔软性且触摸无刺激感。IV.体液处理和吸收特性
具有如上述的适宜的聚合物成分和结构特性及机械特征的吸收泡沫一般都显示出特别希望和有用的体液处理和吸收特性。这些处理和吸收特性又是本文优选的泡沫材料的属性,它们使这些泡沫特别适宜用作设计获得和保持含水体液的吸收物品中的吸收结构。
与获得适宜的吸收泡沫最有关的流体的处理和吸收性能是:A)泡沫的自由吸收容量;B)通过泡沫结构的流体垂直芯吸速率;C)在具体芯吸高度时的吸收容量;和D)泡沫吸收结构从它的泡沫可以接触的对抗吸收结构中抽吸(分布)流体的能力。这些特性中的每一条详细描述如下:A)自由吸收容量
自由吸收容量是对于给定的泡沫样品在该样品单位质量固体材料的多孔结构中所吸收的试验流体(合成尿)的总量。对本发明的目的来说,这种自由吸收容量的测量值是在平衡时计算,即在经过生成被试验液体完全饱和的泡沫样品所需的任何的时间期间之后使泡沫样品获得和/或保留其能力范围内的全部流体之后进行计量。在吸收物品如尿布中特别可用作吸收结构的泡沫材料至少要满足最小自由吸收容量。
利用在试验方法一节中更详细描述的方法,对任何给定的泡沫样品,通过重量分析技术,都可以测定自由吸收容量。在这一技术中,按照说明的已知尺寸和重量的泡沫样品置入一试验流体的碟中(合成尿),使其吸收试验流体达到平衡。在从流体中移出饱和样品后,则可计算每克泡沫保留的流体量,即测得的自由吸收容量。对专门用于吸收尿的吸收物品,本发明的吸收泡沫应有的吸收容量至少为约12,优选至少为约20ml合成尿/克干泡沫材料。B)垂直芯吸性能
本文可应用的吸收泡沫的另一个流体处理的性能与通过它们的泡沫结构迅速地移动或“芯吸”可接受量的体液的能力有关。垂直芯吸即在与重力相反的方向上的流体芯吸是本文的吸收泡沫材料特别希望的性能。这是因为这些材料常常以这样的方式被利用在吸收物品中,也就是待吸收的流体必须是从物品内的一个较低的位置移动到物品的吸收芯内的一个较高的位置。
垂直芯吸性能与移动液体通过泡沫并将其保持在泡沫结构中的毛细管吸入推动力有关。与垂直芯吸性质有关的泡沫特性参数将为本文优选的泡沫作为吸收物品中的吸收结构的性能表现如何,提供一个指征。对本发明的泡沫吸收材料来说,流体的芯吸倾向性通参考垂直芯流速率试验和垂直芯吸容量试验来计量。
1)垂直芯流速率
当试验在37℃进行时,测量来自容器的带色的试验液体(例如合成尿)通过按照说明尺寸的泡沫的试验条状物垂直芯流5cm距离所用的时间来进行垂直芯流速率试验。这种垂直芯流速率试验在试验方法一节中更详细的描述。对用于吸收尿的专门用途的吸收物品来说,本发明的吸收泡沫对于芯吸合成尿((65±5)×10-3牛顿/米)的5cm的垂直芯流速率优选不超过30分钟。更优选的是,本发明的优选泡沫吸收材料当吸收合成尿时5cm的垂直芯流速率不超过约5分钟。
2)垂直芯吸容量
垂直芯吸容量试验与垂直芯流速率试验结合进行。垂直芯吸容量是对在垂直芯流速率试验中所使用的相同标准尺寸的泡沫样品的每一英寸(2.54cm)垂直段测量每克吸收泡沫所吸收的试验流体量。这一测定一般在已使样品垂直芯吸试验流体达到平衡(例如在约18小时后)后进行的。与垂直芯流速率试验一样,垂直芯流吸收容量试验在试验方法一节中将更详细地描述。
对专门用于吸收尿的吸收物品,本发明优选的吸收泡沫通常的垂直芯吸容量在垂直芯吸高度为11.4cm(4.5英寸)时,泡沫试验条至少芯吸约50%,更优选约75%的它的自由吸收容量。C)分布
本文的泡沫吸收结构在吸收物品中常常与其它类型的吸收结构一起使用,所述其它类型吸收结构也参与获得、分配和/或储存排泄的体液。关于这些泡沫结构在吸收物品中主要用作流体储存/再分配的部件的情况,希望这些泡沫具有将体液从吸收这些流体的其它吸收部件中拉入泡沫结构的顿向。从其它吸收物品部件中抽吸流体的倾向在本技术领域内称为“分布”。分布这一概念和测定分布性能得的某些方法在下述专利文献中作过描述例如U.S.专利4610678(Weisman等),1986年9月9日授权。利用相似于U.S.专利4610678中描述的方法测试分布性能时,本发明的吸收泡沫结构显示了特别希望的流体分布特性。V.密实聚合物泡沫材料的制备
如前述,通过具有水相与油相较高比率的某些油包水乳液的聚合可以制备本发明的密实的聚合物泡沫材料。具有这些较高水与油相比率的这种类型的乳液在本技术领域通称为高内相乳液(“HIPEs”或HIPE乳液)。从这些乳液聚合所生成的聚合物泡沫材料称为“HIPE泡沫”。
生成HIPE泡沫结构的聚合物材料的化学特性、组成和形态是由单体,共聚用单体和在HIPE乳液中所利用的交联剂的浓度和种类及由所采用的乳液形成和聚合条件这两方面决定。无论什么特殊的单体组成、聚合物材料的分子量和形态,生成的聚合物泡沫通常为粘塑性,即泡沫结构都具有发粘,即类似于流体的性质和塑性,即象弹簧性质。重要的是生成多孔状泡沫结构的聚合材料的物理学的、流变学的和形态学的属性为,在使用条件下,给予吸收泡沫材料适宜的揉曲性、抗加压挠曲性和尺寸稳定性。
用来生成HIPE乳液的水和油相的相对量与许多其它参数一起,对于决定生成的聚合物泡沫的结构、机械性能和性质方面是重要的。具体讲,在生成泡沫的乳液中的水与油的比率可以影响泡沫密度、孔尺寸和泡沫的毛细管吸入的比表面积及形成泡沫的柱架的大小。制备本发明的HIPE泡沫使用的乳液通常的水与油相比率为约12∶1-约100∶1,更优选约20∶1-约70∶1,最优选约25∶1-约50∶1。A.油相成分
HIPE乳液的连续油相包括聚合生成固体泡沫结构的一些单体。该单体成分包括一“玻璃状”单体、一“橡胶状”共聚用单体和交联剂。单功能的单体及共聚用单体和多功能交联剂的具体类型的选择对实现具有结构、机械性能和流体处理性质的所希望的组合,以给予适宜在本发明中利用的这些材料是重要的。
在HIPE乳液的油相中所利用的单体成分包括一种或多种单功能单体,它们给予生成的聚合物泡沫结构似玻璃的性质,这些单体称为“玻璃状”单体,对本发明目的来说,被定义为单体材料的是将产生高分子量(6000以上),玻璃化转变温度Tg在约40℃以上的均聚物。这些单功能玻璃状单体类型包括甲基丙烯酸酯单体类(例如甲基丙烯酸甲酯)和苯乙烯单体类(例如苯乙烯)。优选的单功能玻璃状单体类型是苯乙烯单体类,而最优选的是苯乙烯自身。取代的,例如一取代的苯乙烯如对-甲基苯乙烯也可以采用。单功能的玻璃状单体通常占单体成分的约5%-约40%(wt)’更优选约10%-约30%(wt)、更优选约15%-约25%(wt)、最优选约20%(wt)。
单体成分还包括一种或几种单功能共聚用单体,它使生成的聚合物泡沫结构有类似橡胶状的性质。这些共聚用单体称为“橡胶状”共聚用单体,对本发明的目的来说,被定义为单体材料将产生高分子量(10000以上)且玻璃化转变温度Tg在约40℃或更低的均聚物。这种类型的单功能橡胶状共聚用单体包括例如C4-C12烷基丙烯酸酯、C6-C14烷基甲基丙烯酸酯和这些共聚用单体的组合物。关于这些共聚用单体,最优选丙烯酸正-丁酯和丙烯酸2-乙已酯。单功能橡胶状的共聚用单体一般占单体成分的约30%-约80%(wt)、更优选约50%-约70%(wt)、最优选约55%-约65%(wt)。
由于从玻璃状单体和橡胶状共聚用单体生成的聚合物链是交联的,因此单体成分还包括多功能交联剂。与单功能单体和共聚用单体一样,交联剂的具体类型和用量的选择对最后实现结构、机械和流体处理性质的所希望的组合的优选的聚合物泡沫是很重要的。
根据所利用的单功能单体和共聚用单体的类型和用量,进一步根据生成的聚合物泡沫的所希望的特性,多功能的交联剂可以从广泛的多功能的,优选双功能的单体中选择。因此,交联剂可以是二乙烯基芳烃物质,例如二乙烯基苯、二乙烯基甲苯、邻苯二甲酸二烯丙酯。另外,还可以使用二乙烯基脂族交联剂例如多元醇的二丙烯酸或二甲基丙烯酸酯,例如1,6-已二醇和它的同系物的。发生适用于制备优选的HIPE乳液的交联剂是二乙烯基苯。交联剂无论是何类型,一般都是在生成泡沫的乳液的油相中采用,其用量为单体成分的约10%-约40%(wt),更优选约15%-约25%(wt),最优选约20%(wt)。
HIPE乳液油相的主要部分包括上述的单体、共聚用单体和交联剂。这些单体、共聚用单体和交取剂必须基本上是不溶于水的,因此它们主要在油相中溶解,而在水相中不溶解。使用这些基本上不溶于水的单体保证将使得到的HIPE乳液有适宜的特征和稳定性。
当然,所用单体,共聚用单体和交联剂的特别优选的类型是使生成的聚合物泡沫是适宜的无毒性的和有适当化学稳定性的。如果在聚合后泡沫加工和/或使用期间这些单体、共聚用单体和交联剂以很低的残留浓度存在的话,那么这些残留物质应优选低或没毒性。
油相内另一个主要成分是乳化剂,它允许生成稳定的HIPE乳液。这些乳化剂是在所用来生成乳液的油相中可溶解的那些。所使用的乳化剂通常为非离子型的,包括脱水山梨糖醇脂肪酸酯、聚乙二醇脂肪酸酯和它们的组合。优选的乳化剂包括月桂酸脱水山梨糖醇酯(例如SPAN20)、油酸脱水山梨糖醇酯(例如SPAN80)、月桂酸脱水山梨糖醇酯和棕榈酸脱水山梨糖醇酯(例如SPAN40)的重量比为约1∶1-约3∶1的组合物,特别是月桂酸脱水山梨糖醇酯与下文描述的某些聚乙二醇脂肪酸酯的组合物。
生成HIPE乳液所使用的油相一般包括约67%-约98%(wt)单体成分和约2%-约33%(wt)的乳化剂成分。优选油相包括约80%-约95%(wt)的单体成分和约5%-约20%(wt)的乳化剂成分。
除了单体和乳化剂成分外,油相可包含其它的任选成分。一种这样任选的油相成分是一种油相可溶的聚合引发剂,它将在下文描述其通用类型。油相另一可能的任选的成分是单体和乳化剂的基本上不溶于水的溶剂。当然这种类型的溶剂必须不能溶解生成的聚合物泡沫。这种溶剂的使用不是优选的,但是如果采用了这种溶剂,通常不超过油相的10%(wt).B.水相成分
HIPE乳液的不连续的内相片是一般含一种或几种溶解成分的水溶液的水相。水相中一种主要溶解成分是溶于水的电解质。在HIPE乳液的水相中溶解的电解质用作使主要为油溶性的单体和交联剂在水相中溶解的趋势减至最小。这又被认为在乳液聚合期间,对聚合物材料充满由水相小滴生成的油/水界面处孔窗口的程度减到最小。因此,电解质的存在和生成的水相的离子强度被认为决定了生成的优选聚合物泡沫是否是开孔结构和达到什么样的程度。
可使用任意的电解质提供离子种类,以提供水相的离子强度。优选的电解质是一价、二价和三价的无机盐,例如水溶性的卤化物如碱金属和碱土金属氯化物、硝酸盐和硫酸盐。实例包括NaCl、CaCl2、Na2so4和Mgso4。对在本发明中使用CaCl2是最优选的。通常,用在HIPE乳液水相中的电解质浓度为水相的约0.2%-20%(wt)。更优选,电解质占水相的约1%-约10%(wt)。
HIPE乳液还一般包含聚合引发剂。这种引发剂成分通常加入HIPE乳液的水相,它可以是任何通用的水溶性自由基引发剂。这种类型物质包括过氧化物如钠、钾和铵的过硫酸盐、H2O2、过乙酸钠、过碳酸钠等。通用的氧化还原引发剂体系也可以利用。这样的体系通过将前述的过氧化物与还原剂如NaHso3、L-抗坏血酸或亚铁盐相结合来生成。
引发剂物质可含达约5mol%(以油相中可聚合单体的总摩尔数计)。更优选引发剂含量为约0.001-0.5mol%(以油相中可聚合的单体总摩尔数计)。当在水相中使用时,这些引发剂的浓度通过将引发剂加入水相达水相的约0.02%-约0.4%(wt),更优选约0.1%-约0.2%(wt)来实现。C.亲水剂和可水化的盐
生成密实吸收泡沫结构的交联聚合物物质优选在其聚合结构中基本上没有极性官能团的。这样,在聚合步骤后,构成这些优选吸收泡沫的泡沫结构表面的聚合材料一般是较憎水的。因此,优选的刚聚合的泡沫可能需要进一步处理,以使泡沫结构表面较更亲水性,其结果是可以使用这些泡沫作为含水体液的吸收物品。如果需要,泡沫表面的亲水作用一般通过用亲水剂以下文详细描述的方式处理聚合的HIPE泡沫结构来实现。
亲水性可以是满足以下条件的任何材料,即它将提高与它们接触的聚合物表面的水湿润性,而且它们可以在表面上沉积。亲水剂是本技术领域内公知的,它包括表面活性剂物质,优选非离子型。亲水剂一般以液态使用,可以溶解或分散在亲水溶液中,并施加到HIPE泡沫表面。以这样的方式,亲水剂可以吸附在优选HIPE泡沫结构聚合物表面上,其量适宜给予这些表面基本上的亲水性,但不改变泡沫的所希望的挠曲性和加压弯转特性。在已用亲水剂处理过的优选泡沫中,亲水剂掺入泡沫结构,保留在泡沫结构中的亲水剂的残留量为泡沫的约0.5%-约20%,优选约5%-约12%(wt)。
一种类型的适宜亲水剂是非刺激性的油溶性表面活性剂。这些表面活性剂包括所有上述的用作HIPE乳液的油相的乳化剂的那些,例如月桂酸脱水山梨糖醇酯(例如SPAN20),以及月桂酸脱水山梨糖醇酯与下述的某些多元醇脂肪酸酯的组合物。在HIPE乳液形成和聚合期间,可将这些亲水的表面活性剂掺入泡沫中,或可以通过用溶于或分散在适宜载剂或溶剂中的表面活性剂的溶液或悬浮液处理聚合物泡沫。使所述表面活性剂掺入。
需要掺入HIPE泡沫结构另外的物质是可水合的、优选吸水的或吸湿的水溶性无机盐。这些盐包括例如毒理学上可接受的碱土金属盐。这种类型的物质和它们与油溶性表表面活性剂结合作为泡沫亲水剂的用途在U.S.专利申请号07/743951中有更详细地描述(1991年8月12日申请)、该专利中公开的内容本文引为参考。这种类型优选的盐包括钙的卤化物如CaCl2,如前述,它也采用作为HIPE乳液水相的电解质,该乳液使用制备聚合物泡沫。
可水合的无机盐通过用这些盐的水溶液处理泡沫可以容易地掺入聚合物泡沫,可水合无机盐的溶液通常利用来在从刚聚合泡沫除去残余水相的过程完成后处理泡沫或用所述盐溶液的处理作为除去残余水相过程的一部分。泡沫与这些溶液的接触优选利用来沉积可水合的无机盐,例如CaCl2,其残留量至少为泡沫的约0.1%(wt),通常为约0.1%-约8%,优选为约3%-约6%(wt)。
对聚合后相对为憎水的优选泡沫结构用亲水剂(含或不含可水合的盐)的处理一般都进行到必须和充分给予本发明的优选HIPE泡沫适宜亲水性的程度。但是,用优选类型的HIPE乳液制成的一些泡沫在制备成的状态即可有适宜的亲水性,而且可能已掺入足够量的可水合盐,因此不要求用亲水剂或可水合盐另外处理。尤其是,这些优选的HIPE泡沫可以是那些其中脱水山梨糖醇脂肪酸酯例如月桂酸脱水山梨糖醇酯(例如SPAN20),或月桂酸脱水山梨糖醇酯与后文叙述的聚乙二醇脂肪酸酯的组合物用作乳化剂加入油相、CaCl2用作HIPE乳液水相中的电解质的。在那种情况下,含残余-乳化剂的内部聚合泡沫表面将有适宜的亲水性,而残留水相液将包合或沉积足够量的CaCl2,即使在聚合物泡沫脱水之后。D.得到HIPE泡沫的工艺条件泡沫的制备一般包括如下步骤:
1)生成稳定的高内相的乳液(HIPE);2)在适宜生成固体泡沫结构下的条件下,使这种稳定乳液聚合/固化;3)洗涤该固体聚合泡沫结构,以从聚合泡沫结构中除去原来残留的水相和如果需要,用亲水剂和/或可水合的盐处理聚合泡沫结构,以沉积任何需要的亲水剂/可水合盐,和4)之后使这种聚合泡沫结构脱水(优选包括在Z方向上加压),脱水程度为得到可用作含水体液吸收剂的密实未膨胀的聚合泡沫材料。
为了稳定地得到较薄密实的本发明的聚合泡沫材料,发现特别重要的是实现乳液的形成和聚合步骤的方式为使HIPE乳液中水滴聚结降低或减至最小。HIPE乳液不总是稳定的特别是在经受较高温度以实现聚合和固化的情况下。由于HIPE乳液的不稳定性,其中存在的水滴可能会聚结在一起,聚结生成很大的水滴。的确,在乳液聚合和固化期间,在泡沫结构固化和水滴的聚结之间实际上有一种竞争。适度的平衡必须打破,这样水滴的聚结就会减少,另外,泡沫结构的聚合和固化可以在合理的时间内完成。(如果残余的水滴尺寸很小的话,则某种程度的聚结是可容许的,但在生成的泡沫中这些非均匀的孔尺寸对泡沫的流体转移性质,特别是泡沫的芯流速率会有不利的影响。)
HIPE乳液中水滴聚结的降低,会导致在聚合和固化步骤后,生成的泡沫结构中较小的平均孔尺寸。据信在聚合泡沫材料中这种生成的较小平均孔尺寸是一致生成本发明较薄的密实聚合泡沫材料的主要机理。(在生成的泡沫中均匀的小的孔尺寸还认为导致了良好吸收特性和特别是流体转移(例如芯吸)特性)。聚合泡沫材料的平均孔尺寸值为约50微米或小于此值,通常为约5-约50微米,优选约5-约40微米,最优选约5-约35微米。这些值的材料是在HIPE乳液中的水滴减少聚结的条件下制备的。一致地降低HIPE乳液中水滴聚结的技术将在制备密实聚合泡沫的乳液形成和聚合/固化步骤的下述描述中更详细地讨论:1.HIPE乳液的形成
通过将按前述的重量比率的油相成分与水相成分相结合来生成HIPE乳液。油相将含前述的主要成分如必要的单体、共聚用单体、交联剂和乳化剂,而且还可包含任选成分如溶剂和聚合引发剂。所使用的水相将含前述的电解质作为主要成分,而且还可以包含任选成分如水溶性乳化剂和/或聚合引发剂。
HIPE乳液通过将这些组合相进行剪切力的搅拌,可以从组合的油相和水相生成。剪切力搅拌一般施加到从组合油和水相生成稳定乳液所必须的程度和时间期间。这一过程可以间歇进行,或者连续进行,并且一般是在适宜生成一种水相小滴分散达到使生成的聚合物泡沫将有所要求的孔体积和其它的结构特性这样一程度的乳液。油和水相组合物的乳化常常包括使用混合或搅拌装置如针式高速搅拌机。
可以采用的生成HIPE乳液的一种优选方法包括使所要求的油和水相混合和乳化的一种连续方法。在这一方法中,以约0.08-约1.5ml/秒的流速生成和提供包括油相的液流。同时,也以约4-约50ml/秒的流速生成和提供包括水相的液流。在上述范围的流速下,在适宜的混合室或区中,将这两种液流以接近达到和保持前述的要求的水与油相比率的方式相结合。
在混合室或区中,相结合的物流一般都经受所提供的剪切力的搅拌,例如,用适当构型和尺寸的针式高速搅拌机。剪切力搅拌一般加到约1000-约2500秒-1的程度。在混合室内的停留时间通常为约5-约30秒。一旦生成液状的稳定的HIPE乳液,就可从混合室或区以约4-约52ml/秒的流速排出。经连续过程生成HIPE乳液的这种优选的方法在U.S.专利5149720(DesMa-rais等)有详细的描述,1992年9月22日授权,该专利本文结合参考。
在一致地减少HIPE乳液的水滴聚结中,特别优选某些类型的油相的乳化剂体系,特别是当HIPE乳液是在约50℃以上的温度下聚合或固化时。这些优选的乳化剂体系包括月桂酸脱水山梨糖醇酯(例如SPAN20)和某些聚乙二醇脂肪酸酯(PGEs.)的组合物作为助乳化剂。月桂酸脱水山梨糖醇酯与PGE的重量比常常在约10∶1-约1∶10的范围内,优选,该重量比在约4∶1-约1∶1的范围内。
与月桂酸脱水山梨糖醇酯一起特别用作助乳化剂的PGE常常从如下特征的聚乙二醇来制备,这些聚乙二醇的特征是:高含量的线型(即无环的)聚乙二醇、低含量的三或更高的聚乙二醇,和低含量的环状的双甘油。适宜的聚乙二醇反应物(以重量为基础)通常含线型聚乙二醇量至少为约60%(典型地范围为约60%-约90%)、三或更高的聚乙二醇含量不大于约40%(典型地范围为约10%-约40%),和环状的双甘油含量不大于约10%(通常的范围为0-约10%)。优选的是,这些聚乙二醇的线型的双甘油含量为约60%-约80%,三或更高的聚乙二醇含量为约20%-约40%,和环状的双甘油含量为不大于约10%。(测定聚乙二醇分布的方法在下文的PGE分析方法一节中给出)。
与月桂酸脱水山梨糖醇酯一起特别用作助乳化剂的也是PGEs从如下特征的脂肪酸反应剂来制备,这些特征是:脂肪酸的组成是:高含量的C12和C14饱和脂肪酸的组合物,和低含量的其它脂肪酸。适宜的脂肪酸反应物具有的脂肪酸的组成是C12和C14饱和脂肪酸的总含量至少为约40%(典型地为约40%-约85%),C16饱和脂肪酸的含量不大于约25%(典型地范围约5%-约25%),C18或更高饱和脂肪酸的总含量不大于约10%(典型地范围为约2%-约10%),C10或更低脂肪酸的总合量不大于约10%(典型地范围为约0.3%-约10%),平衡量的其它脂肪酸主要是C18单饱和脂肪酸。优选,这些脂肪酸反应物的脂肪酸组成是至少约65%的C12和C14饱和脂肪酸总量(典型范围为约65%-约75%),不大于15%的C16饱和脂肪酸(典型范围是约10%-约15%),不大于约4%的C18或更高的饱和脂肪酸总量(典型范围为约2%-约4%),和不大于约3%的C10或更低的脂肪酸(典型地范围是约0.3%-约3%)。(测定脂肪酸组成的方法将在下文PGE分析方法一节中给出)。
与单月桂酸脱水山梨糖醇酯一起用作助乳化剂的PGEs也常常具有提供最小的油/水界面张力(IFT)的特征,其中油相包含在HIPE乳液中所使用的单体,而水相含CaCl2。适宜的PGE助乳化剂通常提供的最小油/水IFT至少为约0.06×10-3牛顿/米,而一般为(约0.06-约1.0)×10-3牛顿/米。特别优选的PGEs提供的最小的油/水IFT至少为约0.09×10-3牛顿/米,而一般为(约0.09-约0.3)×10-3牛顿/米。(这些PGEs的IFT的测量方法在PGE分析方法一节中给出)。
与单月桂酸脱水山梨糖醇酯一起用作助乳化剂的PGEs可以用本领域内公知的方法来制备。例如,参见U.S.专利3637774(Babayan等),1972年2月25日授权,和(McIntre,“PolyglycerolEsters”J.Am.Oil Chem.Soc.,Vol.56,NO.11(1979),pp.835A-840A,该文献本文结合参考,而且该文献描述了制备聚乙二醇和将其转化成PGEs的方法。PGEs通常是由用脂肪酸酯化聚乙二醇来制备。聚乙二醇的适宜组合物可以通过混合从商业来源得到或利用已知方法合成的聚乙二醇来制备,例如这些已知方法是U.S.专利3637774中描述的那些。脂肪酸的适宜组合物可以通过将脂肪酸和/或从商业来源得到的脂肪酸混合物进行混合来制备。在制备用作助乳化剂的PGEs中,聚乙二醇与脂肪酸的重量比通常为约50∶50-约70∶30,优选约60∶40-约70∶30。
制备适宜的PGE助乳化剂的典型反应条件包括在0.1-0.2%NaOH作为酯化催化剂存在的条件下,用脂肪酸酯化聚乙二醇。该反应在大气压约210℃-220℃时在机械搅拌和N2喷雾下开始。由于反应的进行,自由脂肪酸减少,真空度逐渐提高到约8mmHg。当自由脂肪酸含量减少到小于约0.5%时,催化剂用H3PO4溶液中和,反应混合物迅速冷却到约60℃。这种粗的反应混合物然后进行沉降或其它的一般纯化步骤(例如,降低未反应的聚乙二醇的含量),就得到了所要求的PGEs。2.HIPE乳液的聚合/固化
通常是将生成的HIPE乳液收集或倒入一个适宜的反应装置、容器或地方进行聚合或固化。在一个实施例中,反应装置包括一个聚乙烯制的桶,最后聚合/固化的固体泡沫材料从这里容易移出,这在聚合/固化过程进行达所要求程度后,便于进一步加工固体泡沫材料。通常优选HIPE乳液倒入反应装置的温度与聚合/固化温度接近相同。
HIPE乳液进行聚合/固化的条件可以改变,这取决于单体和乳液的油相和水相的其它组成,特别是所使用的乳化剂体系和所利用的聚合引发剂的类型和用量。但是,通常的聚合/固化条件将包括维持HIPE乳液的温度在约30℃以上,更优选约在35℃以上,时间约4-约24小时,最优选约4-约18小时。
在减少HIPE乳液中水滴的聚结时,特别优选在低温度下进行聚合/固化过程,特别是在制备HIPE乳液时不使用月桂酸脱水山梨糖醇酯和PGE助乳化剂的优选组合物情况下。在这些情况下,适宜的较低的聚合/固化温度为约30℃-约35℃,优选约35℃-约45℃,而最优选约40℃。如果聚合/固化是在高于50℃很多的温度下进行,那么在乳液上的热应力可能使存在的水滴聚集和聚结,因此在生成的聚合泡沫中形成更大的孔,特别是如果月桂酸脱水山梨糖醇酯和PGE助乳化的优选组合物不用于制备HIPE乳液时。这就可能导致聚合泡沫在脱水后不能保持密实不膨胀的状态。
当在一反应装置如一个桶中进行HIPE乳液聚合/固化时,通常得到大块固体聚合泡沫。这种大块聚合的HIPE泡沫通常切成或片成像薄片一样的泡沫。在随后处理/洗涤和脱水步骤期间,片状的聚合HIPE泡沫易于加工,并制成在吸收物品中使用的HIPE泡沫。被切开/切成片的大块聚合的HIPE泡沫提供切成的尺寸为约0.08-约2.5cm。在随后脱水期间,这一般导致密实的HIPE泡沫的尺寸为约0.008-约1.25cm。3.处理/洗涤HIPE泡沫
制造的固体聚合的HIPE泡沫一般将是挠曲性的,开孔的多孔结构,它的孔被所使用来制备HIPE乳液的残留水相物质所充满。这些残留的水相物质一般包含电解质水溶液、残留乳化剂和聚合引发剂,在泡沫进一步加工和使用前,这时残留物至少应当部分除去。原来的水相物质的除去通常是对泡沫加压以挤压出残留的液体和/或用水或其它的含水洗涤溶液清洗泡沫来进行。通常用几个加压和洗涤步骤,例如使用2-4个循环。
在原始水相物质从泡沫结构中除去达所要求的程度后,如果需要,HIPE泡沫可以进行处理,例如用适宜的亲水剂和/或可水合盐连续洗涤。可以采用的亲水剂和可水合的盐在前面已经描述过,它包括月桂酸脱水山梨糖醇酯(如SPAN20)和CaCl2。如所述的,如果必须,用亲水剂/可水合盐溶液处理HIPE泡沫结构连续进行,直到掺入了希望量的亲水剂/可水合盐和直到泡沫对所选择的任何试验液体显示出所要求的粘合张力为止。4.泡沫脱水
在HIPE泡沫处理/洗涤到给予最后的干泡沫适宜的亲水性所必须的程度和任选掺入足够量可水合盐如CaCl2后,通常泡沫进行脱水处理。脱水处理可以按下述方式进行,即通过加压泡沫(优选在Z-方向)以挤压出残留水,通过使泡沫或其中的水经受高温,例如在约60℃-约200℃加热干燥,或微波处理,通过真空脱水或通过加热干燥/微波/真空脱水技术的组合来进行。HIPE泡沫处理的脱水步骤通常进行到HIPE泡沫准好使用和象实用的那么干为此。通常,这些加压脱水泡沫的水含量(湿含量)为约50%-约500%,更优选约50%-约200%以干基重量计。随后,加压过的泡沫进行加热脱水(例如通过加热)到湿含量为约5%-约40%,更优选约5%-15%,以干基重量计。生成的压缩过的/脱过水的泡沫将是密实而未膨胀的状态。VI.吸收物品
本发明的密实的聚合泡沫材料在各种各样吸收物品中至少可以用作吸收结构的一部分(如吸收芯)。所谓“吸收物品”的意思是指一种消费品,它能够吸收显著量的尿或其它流体(如液体),像含水的排泄物(半液体的肠排泄物)、由失禁穿戴者或物品使用者排泄的排泄物。这些吸收物品的实例包括可以一次性使用的尿布、大小便失禁的服装、月经用品如止血塞和卫生巾、一次性的训练裤、床垫等。该吸收泡沫结构特别适宜用于如尿布、大小便失禁垫或衣物、衣服的保护层等的物品中。
在吸收物品的最简单形状中,本发明的吸收物品仅需要包括下片,通常它是不渗透液体的,和一个或几个与该下片相联系的吸收泡沫结构。吸收泡沫结构和下片将以使吸收泡沫结构位于吸收物品的穿戴者的体液排泄区域和下片之间的位置这样方式相联接。液体不渗透的下片可以包括任何材料,例如聚乙烯或聚丙烯,厚度(caliper)为约1.5密耳(0.038mm),它帮助将流体保持在吸收物品内。
更一般地是,吸收物品还包括液体能渗透的上片件,它覆盖吸收物品与穿戴者的皮肤相接触的那一面。在这种构型中,吸收物品包括一吸收芯,该吸收芯包括本发明位于下片和上片间一个或几个吸收泡沫结构。液体能渗透的上片可以包含任何的材料,例如聚酯、聚烯烃、尼龙等,上片实质上是多孔的,并允许体液容易通过并进入在下面的吸收芯。上片材料将优选对存于上片和穿戴者皮肤间的接触区域内的含水体液没有亲合性的材料。
本发明的一些吸收物品的实施例的吸收芯可只由一个或几个泡沫结构组成。例如,吸收芯可以包括一片单一单元的成型泡沫,它的形状为最适合使用它的吸收物品的类型所希望或需要的。另外,吸收芯可包括可以粘合连接在一起的许多泡沫片或粒状物,或者通过一个包皮或利用吸收物品的上、下片简单地强制成未粘接的聚集物。
吸收物品的吸收芯除了一个或几个本发明的吸收泡沫结构外,还可以包括其它的,如通用的部件或材料。吸收物品可利用含一组合的吸收芯,例如,包括颗粒状或片状吸收泡沫结构,与通用的吸收材料的空气成网混合物,所述通用吸收材料如a)木浆粕或其它的纤维素纤维,和/或b)聚合胶凝剂的颗粒或纤维。
在一个包括吸收泡沫和其它吸收材料的实施例中,吸收物品可以采用多层吸收芯构型,其中包含本发明的一个或几个泡沫结构的芯层可以与包括通用吸收结构或材料的附加的独立的芯层组合使用。例如,这些通用的吸收结构或材料可包括木浆粕或其它纤维的空气法或湿法成网的纤维网。这些通用的结构还可以包括通用如大孔的吸收泡沫或均匀的海绵状物。与本发明吸收泡沫一起使用的通用吸收结构也可包含例如高达80%(wt)的通常在吸收物品中使用类型的聚合胶凝剂的颗粒或纤维。所述吸收物品是捕获和保留含水体液的。这种类型的聚合胶凝剂和它们在吸收物品中的使用在U.S,再授权专利NO.Re.32469(Brandt等)中作了十分详细的描述,1988年4月19日再授权,该专利本文引入参考。
一种优选类型的吸收物品是利用多层吸收芯、流体处理层设置在物品穿戴者的流体排泄区域的一种。这种流体处理层可以是高膨松状的非织造织物,但是优选呈流体捕获/分散层形态它包括一层改性的纤维素纤维,例如经硬化的卷曲的纤维素纤维,且任选含高达约10%(wt)的聚合胶凝剂的这种流体捕获/分散层。在这种优选的吸收物品的流体捕获/分散层中所使用的改性纤维素纤维优选木浆粕纤维,这种纤维已经硬化并用化学和/或热处理卷曲。这种改性的纤维素纤维是与在U.S.专利4935622(Lash等)中所描述的吸收物品中所采用的相同类型,1990年6月19日授权,该专利本文引入参考。
这些多层吸收芯也包括一第二即较低的流体储存/再分散层,它包括本发明的泡沫结构。对本发明的目的,多层吸收芯的“上部”层是较贴近穿戴者身体的那一层,例如该层最靠近物品的上片。术语“下部”层的意思则相反,是多层吸收芯较远离穿戴者身体的那一层,例如该层最靠近物品的下片。这种下部流体储存/再分散层通常设置在吸收芯内,以便在(上部)的流体处理层之下,而且使流体与其相通。在位于上部流体捕获/分散层该层包含硬化的固化的纤维素纤维的下面的下部流体储存/再分散层中可以利用本发明吸收泡沫结构的吸收物品,在U.S.专利5147345(Young等)中有更详细地描述,1992年9月15日授权,该专利在本文引入结合参考。
如上述表明,本文的特殊的吸收泡沫结构的流体处理和机械特性授予这种结构特别适宜在一次性尿布类的吸收物品中使用。包括本发明吸收泡沫结构的一次性尿布通过使用一般的尿布制造技术可以进行制造。但是要用一个或几个本发明的泡沫结构来代替或补充在一般尿布中通常使用的木浆粕纤维网(“空气毛毡”)或改性的纤维素吸收物。因此,本发明的泡沫结构可以一单层,或如上所述以各种各样的多层芯构型使用于尿布中。一次性尿布类的物品,更详细地描述在U.S.专利Re 26151中,(Duncan等),1967年1月31日授权;U.S.专利3,592,194(Duncan),1971年7月13日授权;U.S.专利3489148(Duncan等)1970年1月13日授权:U.S.专利3860003(Alemany等),1989年5月30日授权,上述所有专利,本文均引入结合参考。
本发明的优选的一次性尿布的实施例如图5所示。这样的尿布包括一吸收芯50,包括上部流体捕获层51,和一在下面的包括本发明的吸收泡沫结构的流体储存/分散层52。叠加的上片53,与芯的一个面覆合,叠加的流体不能渗透的下片54,与被上片覆盖的那面的芯的另一面覆合。最优选的下片的宽度比芯的宽度宽,由此下片的边界部分延伸超过芯。尿布优选呈滴漏构型。
可以利用本发明的吸收泡沫结构的吸收物品的另一优选类型包括贴身的产品如训练裤。这种贴身的物品一般包括一非织造的挠性基材,它按体形设计成紧身裤或短裤。本发明的吸收泡沫结构可附加在这种体形的分叉区域,以便用作吸收“芯”。这种吸收芯通常是用外包装的棉纸或其它液体能渗透的的非织造材料包好。这样芯的外包装用作贴身吸收物品的“上片”。
形成贴身物品的外形的挠性基材可以包括布或纸或其它种类的非织造基材或所生成的薄膜,且可以是弹性的或可拉伸的。这种训练裤的腿带或腰带可以如通用式样的弹性,以改进物品的适合性。这种基材通常相对来说是液体不能渗透性的,或至少使液体不易渗透,这可通过处理或涂覆它的一个表面,或通过用其它的液体相对不渗透的基材层合这种挠性基材,由此形成液体相对不渗透的总的外形。在这个例子中,外形本身用作贴身物品的“下片”。这种典型地训练裤产品详细描述在U.S.专利4619649(Roberts)中,1986年10月28日授权,该专利本文引入参考。
一次性训练裤产品类的典型的贴身物品如图6所示。这种产品包括通过粘合的方法,将一外层60附加到衬层61及它的周边区域。例如,里层61沿一条腿带周边区62和另一条腿带周边区63及腰带的周边区64可以附加到外层60上。附加到物品的分叉区域通常是包含本发明吸收泡沫结构的矩形吸收芯65。
                           试验方法
在本发明的描述中,提出了HIPE泡沫吸收结构的许多特性。文中指出,利用下述的试验和试验方法,这些特性可以测定。I)试验流体和泡沫样品的制备
A)试验流体--合成尿
在试验中描述的几种测量涉及到使用合成尿、乙醇或2-丙醇(异丙醇)之类的试验流体。在后文描述的许多试验中利用合成尿是由商业上可得的合成尿制备的,由Jayco Pharmaceuticals生产(Mechanicsburg,PA,17055)。这种Jayco合成尿是由包括kcl 0.2%;Na2so4 0.2%;NH4H2PO4 0.085%;(NH4)2HPO40.015%:CaCl*2 2H2O 0.025%;和Mgcl2*6H2O 0.05%。(都是重量百分数)的制品制备的。这些合成尿样品利用蒸馏水按标明的说明来制备。为了帮助溶解,Jayco盐混合物慢慢加入水中。如果必要,将该样品过滤除去任何粒状物。任何未使用的合成尿一周后丢弃。为改进流体的能视度,在每升合成尿溶液中加入5滴蓝食用色。所利用的Jayco合成尿的表面张力为(65±5)×10-3牛顿/米。
B)泡沫样品的制备
一些下述的试验涉及特定尺寸泡沫样品的制备和测试。除非另有说明,要求尺寸的泡沫样品是利用锋利的往复式刀锯床从大块泡沫上切成。利用这种或相同类型的泡沫切割装置基本上排除了样品边缘的缺陷,而这种缺陷对在下文提出的进行的几种试验方法中的某些测量会产生不利的影响。
样品尺寸的说明一般还包括样品测厚或厚度的尺寸。对本发明的目的来说,测厚或厚度的测量应当是泡沫样品在限定压力为0.05Psi(350Pa)下进行。所有泡沫密度和干的重量的测量通常是在如后述的泡沫样品水洗和干燥后进行。II)泡沫性质、特征和特性的测定
A.密实状态1)膨胀压力
这个试验直接测量密实状态下的储存能量。当用比密实泡沫的自由吸收容量大的水量充溢时,释出密实泡沫的储存能量。借助压力使完全润湿的泡沫保持在泡沫密实态的大小(厚度)时,测量膨胀压力。
为进行这种试验,使用一冲压机小心切出密实泡沫的直径为23.8mm的圆筒。这种切割的样品用一变形测定器进行测量(例如Ono-Sokki型EG-225)到最接近0.005mm。在进行压力松弛试验中,使用有一能保持液体的平行板组件的Pheometrics型RSAII。这种平行板组件包括一内径为29mm的圆筒形室的底杯板,和一顶板直径为25mm的环形件。
将切成的干样品置入底杯形板室内,在顶板环形件的正中。全部组件/样品在88°F(31.1℃)下平衡至少10分钟,调节顶板,对切成的样品施加约10克力。在88°F(31.1℃)在0.5%(在加压)变形时,对Rheometrics型RSAII制定程序进行压力一松驰试验。在测压力随时间的函数进行调整的同时,用一注射器迅速地向底杯形板的样品加入温度为88°F(31.1℃)的足够量的水,保证切出的样品(例如1秒钟内3ml)处于完全饱和状态。在加水后至少15分钟内,当切出的样品试图膨胀时,记录切出样品施加在板上的压力(即它的膨胀压),在记录在5分钟时的值.作为切出样品的膨胀压。2)毛细管吸入比表面积
泡沫毛细管吸入比表面积可以从吸收的已知低表面张力的试验液体的平衡重量来测定。在这个例子中,使用无水乙醇(闪点为10℃)。
为进行试验,适宜尺寸(例如≥35cm长×2cm宽×0.25厚)的配衡(taved)泡沫样品条在22±2℃下平衡,并垂直设置,利用一实验室起重器将条的一端浸入一乙醇容器中1-2mm。乙醇被泡沫条向上芯吸达小于样品长度的平衡高度。然后含乙醇的条称重测定所吸收的总乙醇的重量。在这个试验过程中,样品应当隔离,例如,用一个杯形的玻璃圆筒以阻止乙醇蒸发。然后使乙醇从泡沫样品中蒸发,用水洗涤、干燥和称重。
泡沫样品的比表面积可以从下式计算:
        Sc=MeGLn
            Mnγe其中Sc=毛细管吸入比表面积,cm2/gm;Me=吸收液体乙醇的质量,g;G=重力加速度980cm/秒2;Ln=湿样品的总长度,cm;Mn=干样品的质量,gm;和γe=乙醇的表面张力22.3×10-3牛顿/米。将所得值除以10000cm2/m2,就得毛细管吸入比表面积m2/g。3)泡沫密度
可以利用来测定泡沫密度的一种方法是在ASTM Method NO.D3574-86试验A中描述的,设计的这一方法主要是用来进行聚氨酯泡沫测试的,但是也可以利用来测量本发明的优选的HIPE一型泡沫体的密度。具体讲,按这种ASTM方法进行密度的测量是按那个试验所描述的某种方式对泡沫样品进行事先的准备后进行的。
通过测量给定泡沫样品(在水洗和干燥后)的干质量和在22±2℃时它的体积来测定密度。对大泡沫样品体积的测定是从在不限压下样品尺寸的测量计算的。利用一千分表,利用350Pa(0.05psi)的尺脚压力,可测量较小泡沫样品的尺寸。
密度以每单位体积质量计算。对本发明的目的,密度通常用g/cm3表示。
B.膨胀状态1)合成尿饱和时的密度
在这种测量中,泡沫样品在88°F(31.1℃)用Jayco合成尿饱和到它的自由吸收容量。在这种完全膨胀状态下测量体积,在水洗和干燥后,测置样品的干质量。这样可计算当用合成尿饱和时其密度,以每湿体积的干质量表示g/cm3。2)可利用的孔体积
测量可利用空体积的方法包括测量可以引入吸收泡沫样品的结构的2-丙醇(闪点12℃)量。在进行这种测量中所使用的设备和材料在22±2℃下恒温,测量也是在该温度下进行。
干泡沫样品切成1英寸2(6.5cm2)的圆形表面积×0.1英寸(0.25cm)厚的圆柱形或相似的形状。这种圆柱形样品可通过利用直径为1.13英寸(2.87cm)的锋利冲头在0.1英寸(0.25cm)厚的泡沫薄片冲割而制得。干泡沫样品(在水洗和干燥后)每个称重以测定干重量(DW)。这些样品中的三个称重测定平均干重量(DW)。
这些样品的自由吸收容量测量值(MFC)的测量通过下述步骤测定:
a)将泡沫样品浸入装有2-丙醇的结晶碟中,并使其饱和。在这时,可挤压样品数次,逐出空气。
b)取出每个样品而不从样品中挤压出2-丙醇。过剩的液体在约30秒内从平置的样品中滴下。然后每一样品湿着称重,测定其湿重量(ww)。
c)重复步骤a)和b)两次以上,计算平均湿重量(ww)。
自由吸收容量测量值(MFC,g/g),以每单位干泡沫的质量的饱和泡沫中的2-丙醇重量表示。MFC按下式计算: MFC = [ WW ( g ) - DW ( g ) ] DW ( g )
然后计算可利用的孔体积,其方法是吸收2-丙醇的泡沫的MFC除以2-丙醇的密度0.785g/ml。这就得出了可利用的泡沫的孔体积ml/g。3)抗加压挠曲性
对本发明的目的,抗加压挠曲性可以通过测量泡沫样品的变形量(厚度减少的%)来计量,该样品是用合成尿饱和并完全膨胀,这是在泡沫样品将0.74psi(5.1kpa)的限压压力施加在其上后进行测定的。
为进行测量所使用的泡沫样品、Jayco合成尿和设备都是在88°F(31.1℃)下恒温过的。测量也在该温度下。
在密实状态的泡沫样品片用Jayco合成尿饱和到它的自由吸收容量。在2分钟后,在已饱和、完全膨胀的片上冲出圆形表面积为1英寸2(6.5cm2)的圆筒。适用于进行厚度测量的刻度盘形千分表定位在样品上。任何配有圆形表面积至少为1英寸2(6.5cm2)的尺脚且能测量厚度尺寸到0.001英寸(0.025mm)的刻度尺都可以采用。这些计量表的实例为Ames型482(Ames Co.,Waltham,MA)或Ono-SoKKi型EG-225(Ono-SoKiCo.,Ltd.;Japan)。
然后将一力施加到千分尺尺脚上,因此,在屏蔽上的饱和泡沫样品经受一为0.74psi(5.1kpa)的限压15分钟。在这次加压结束后,使用千分表测量样品厚度发生的改变,这是由于施加限压的结果而产生。从初始和最终的厚度测量,对样品诱导的变形百分数可以算出。4)加压挠曲性的恢复
为测试加压挠曲的恢复,用与制备抗加压挠曲试验(参见上述II(B)(3))所使用的样品的相似方法来制备样品。
使用刻度型千分表,在88°F(31.1℃)用Jayco合成尿和到自由吸收容量的试验样品在10秒钟内压缩到50%的它的原来厚度并保持在该加压状态1分钟。然后释放压力,泡沫在1分钟内在有逐出液体存在下恢复厚度。恢复百分数根据未加压泡沫的原来高度计算。
C.密实的或膨胀状态1)揉曲性
泡沫的揉曲性可以通过参考一试验方法计量,该方法是对用于测定纤维素有机聚合泡沫产品的揉曲性的ASTM D3574-86,3.3的的改进。这一改进试验利用的是用Jayco合成尿在88°F(31.1℃)饱和到它的自由吸收容量时的尺寸为7×0.8×0.8cm的样品。重要的是所使用的切割方法是使这些样品并不在泡沫条中产生边缘缺陷。合成尿饱和的泡沫条以在5秒内一个搭接的均匀速率绕0.8cm直径的圆筒形芯轴弯曲,直到条的两端接触为止。在试验期间该泡沫如不被撕裂或破裂,即它能通过一个弯曲循环的试验那么它便认为是有揉曲性的。
D.流体处理特性的测定1)自由吸收容量
在这个试验中,泡沫样品在88°F(31.1℃)用Jayco合成尿饱和。利用在可利用孔体积的上述II(B)(2)中所述的相同方法来测量无负荷(自由)下的吸收容量。2)垂直芯流速率和垂直芯吸容量
垂直芯流速率和垂直芯吸容量是干泡沫对来自容器的流体的垂直芯吸能力的测量。测量前缘流体芯吸通过泡沫条的5cm垂直长度所要求的时间就得出了垂直芯流速率。在流体芯吸达它的平衡高度后,在一特定的垂直芯吸高度(如4.5英寸或11.4cm)测定被泡沫条保持的流体量就得到垂直芯吸容量。
Jayco合成尿用食用蓝着色,用于下述方法中,以测定垂直芯流速率和垂直芯吸容量。在这一试验方法中,物料在37℃恒温,且试验也在该温度下进行。
近70cm长×2cm宽×0.25cm厚的泡沫条垂直支撑,其一端浸入1-2cm于合成尿容器中。是液体沿泡沫条向上芯吸达它的平衡高度(如约18小时),该高度应小于样品长度。在这个方法进行期间,样品应当被屏蔽,如用一只加盖的杯形玻璃圆筒,以防止液体的蒸发。
芯吸5cm所需的时间用作垂直芯流速率的测量。记录平衡浸湿高度,并用来计算粘合张力,这如下所述。
迅速取出样品,并置于非吸收表面上,使用一锋利的足以不对泡沫样品产生压力的工具,将样品切成1英寸.(2.54cm)的片。每片都称重,用水洗,干燥然后再称重。对每片计算吸收容量。中心在4.5英寸(11.4cm)芯吸高度的1英寸片的吸收容量是最希望测定的参数。3)粘合张力
经毛细管吸入的吸收试验液体的亲水泡沫样品显示出的粘合张力是试验流体的表面张力γ乘以试验流体与泡沫样品的内表面接触的接触角Q的余弦的积。粘合张力通过利用两种不同试验液体,由两个相同泡沫的试验样品所显示出的通过毛细管吸入所吸收的平衡重量的测量来实验地测定。在这方法的第一阶段中,利用乙醇作为试验液体如上述II(A)(2)中描述的用于毛细管吸入比表面积的方法测定泡沫样品的比表面积。
以相同于乙醇方法重复进行毛细管吸入吸收法,只是有下述不同:(a)使用Jayco和合成尿作为试验流体;(b)试验在37℃下进行;和(c)所使用的泡沫样品条≥70cm长×2cm宽×0.25cm厚。合成尿的接触角从已知的比表面积和合成尿的吸收数据按如下式计算: CosQu = MuGLn MnγuSc 其中Qu=Jayco合成尿接触角,为度;Mu=吸收Jayco合成尿液体的质量,为g;G=重力加速度,为980cm/秒2;Mn=干泡沫样品的质量,为g;γu=Jayco合成尿表面张力,为约65达因/cm;Sc=泡沫样品的比表面积,为cm2/g,以乙醇吸收法测定;和Ln=湿泡沫样品的长度,为cm。
当存在表面活性剂时(在泡沫样品表面上和/或在前上试验液体中),前述液体的前缘是通过应用粘合张力(AT)的方程确定: AT = MTGLN MNSC 其中MT是泡沫样品吸收试验液体的质量,而G、LN、MN、和SC都如前所定义。[参见Hodgson and Berg.J.Coll.Sci.,121(1),1988年,PP.22-31]
在对任意给定试验液体测定粘合张力中,没有假定在时间的任一点的表面张力值,因此在芯吸过程中,在样品表面上和/或前进液体中表面活性剂的浓度可能改变是无关紧要的。在试验液体(如利用Jayco合成尿最大表面张力将是[65±5][coso°]=65±5(×10-3牛顿/米)的表面张力作为最大粘合张力的百分数评述时,粘合张力(rcosQ)的实验值特别有用。
                    DEG分析方法A.界面张力(IFT)法(纺丝原液滴)
IFT可以利用Kruss SITE 04纺丝原液滴张力计或任何在相同原理下操作的相似的纺丝原液滴张力计来测量。参见Cayias等,Absorption at Interfaces由Mittal出版,ACS SymposiumSeries 8(1975),PP.234-47和Aveyard等,J.Chem.Soc.Faraday Trans.,Vol.1(1981),pp.2155-68,对纺丝原液滴的IFT方法的一般描述。对每一IFT测量来说,含PGE(通常5ml)的油相的液滴喷射入含预平衡到50℃的水相的张力计的纺丝毛细管中。管的纺丝速率提高到足以使液滴拉成圆柱形,因此,它的长度直径比大于4∶1。拉长的液滴在50℃下恒温,直到达到平衡(即不再改变液滴的直径)为止,或直到经过约30分钟为止。优选,拉长液滴的直径是均匀的(半球形两端除外),并且它与水溶液的界面基本上没有沉积的物料和/或较小的液滴。如果不是这样的话,那么则选择拉长液滴的基本上没有沉积物的且长:径之比大于4∶1并具有最小的直径(如果不同直径的区域存在的话)的区域用于测量。界面张力(γ)是从半径(γ,1/2圆柱形直径)、角速度(  ;2n,其中n是管转动的频率),和油相与水相之间的密度差(Δp)的测量值利用下述方程来计算:
                 γ=0.25γ3Δp    2
这个体系的校正通过测量正-辛醇和水(8.5达因/cm,20℃)之间IFT周期性地检查。
在这些测量中所使用的油相通常是通过将10份的PGE加入含苯乙烯、二乙烯基苯(55%工业级)和丙烯酸2-乙基己酯其重量比为2∶2∶6的100份的单体混合物中来制备。该混合物机械地搅拌以实现PGE的溶解。使该油相混合物在室温下静置过夜,因此不溶的或析出溶液的物料(通常是自由的聚乙二醇)可以沉降。在离心分离后,使上清液与任何沉淀物相分离。上清液被以该状态利用,并用附加的单体混合物稀释(相继地,如果必要),产生较低浓度的乳液。在这一方式中,可以制备PGE名义浓度为约9%-0.01%或更低的溶液。对这种测量所使用的水相是0.90m的CaCl2的水溶液(pH约为6),是将CaCl2.2H20溶于蒸馏水中来制备。
一系列的IFT测量是通过改变油相中PGE的浓度达至少3%来进行测量。IFT作为油相中PGE浓度的函数的10g-10g图表绘制一光滑的曲线。最小的IFT值可以从该曲线估算出。B.聚乙二醇的分散
样品中聚乙二醇的分散可以用毛细管超临界流体色谱法来测定。参见Chester等,J.High Res.Chrom. & Chrom,Commun.Vol.9(1986),P.178等。在该方法中,样品中的聚乙二醇通过与双(三甲基甲硅烷基)-三氟乙酰胺反应转化成有相应的三甲基甲硅烷基酯。分离三甲基烷基酯,然后通过毛细管超临界流体色谱法用火焰离子检测来定量。三甲基甲硅烷基酯从聚二甲基硅氧烷的固定相上洗脱,以便提高分子量。峰的识别是通过超临界流体色谱仪与质谱计相匹配做出的。聚乙二醇有关的分布的计算是从色谱图的峰面积进行。重量百分数的计算是假设火焰离子检测对样品中所有的聚乙二醇都同等地响应。C.脂肪酸的组成(FAC)
自由脂肪酸或脂肪酸酯的样品的脂肪酸组成通过高分辨的毛细管气相色谱法来测定。参见D′Alonzo等,J.Am.Oil Chem.Soc.,Vol.58(1981)P.215等。在该方法中,样品中的脂肪酸首先转化成脂肪酸甲基酯,然后将其分离并通过高分辨的毛细管气相信色谱和火焰离子检测器定量。毛细管柱固定相(稳定的聚乙二醇)按照链长和未饱和度分离甲基酯。峰的识别是通过与已知脂肪酸的标准峰相比较来进行的。脂肪酸的有关分布是从色谱峰的面积来计算。重量百分数是假设火焰离子检测器对样品中的所有脂肪酸的响应都相同来计算的。
                           实施例
密实的HIPE吸收泡沫的制备,这种密实泡沫的特性和这些密实吸收泡沫在一次性尿布中的利用都在下面的实施例中说明。
                           实施例1
这个实施例说明落入本发明范围内的密实的HIPE泡沫的制备。乳液制备
将无水的CaCl2(36.32kg)和过硫酸钾(568g)溶于378升水中。这就为在连续过程中生成HIPE乳液提供了所使用的水相物流。
将月桂酸脱水山梨糖醇酯(960g,如SPAN20)加入含苯乙烯(1600g)、二乙烯基苯55%工业级(1600g)和丙烯酸2-乙基己酯(4800g)的单体组合物中。在混合后,将该组合物料静置过夜。上清液排出,用作在连续过程中生成HIPE乳液的油相。(丢弃粘性的残留物约75g)
在水相温度为48-50℃和油相温度为22℃时,将油相和水相的独立物流加入一动力混合设备中。通过使用针形高速搅拌机使组合物流在动力混合装置中实现彻底混合。在这种操作规模时,一种适宜的针形高速搅拌机包括一圆筒形轴,它长21.6cm,直径为1.9cm。该轴固定4排针,2排有17根针,另2排有16根针,每跟针的直径为0.5cm,从轴的中心线向外延伸达1.6cm长度。针形高速搅拌机安装在一圆筒形套管上,形成动态混合器,针距圆形套管壁的间隙为0.8mm。
螺旋形的静态混合器安装在动态混合器的下游,提供动态混合器中的反压,并提供改进掺入乳液的成分,最后生成乳液。这种静态混合器为14英寸(35,6cm)长,0.5英寸(1.3cm)外径。静态混合器为TAH工业型070-821,通过切出2.4英寸(6.1cm)后改制成。
建立的组合混合设备用油相和水相充满,其相比例是2份水相1份油相。动态混合装置通风以允许空气排出,而使设备完全充满,在充填期间的流动的速率为1.127g/秒油相和2.19cm3/秒水相。
一旦建立的设备充满后,动态混合器中开始搅拌,其高速搅拌机的转速为1800RPM。水相的流率在130秒的期间内稳定地增加到流率为35.56cm3/秒。在这时由动态和静态混合器所产生的反压为7.5PSI(51.75kpa)。高速搅拌机的速度在60秒内稳定地降低到速度为1200RPM。反压降到4.5PSI(31.05kpa)。在这时,高速搅拌机的速度立即提高到1800RPM。此后,系统的反压保持稳定在4.5PSI(31.05kpa)。乳液的聚合
在静态混合器中流出的生成的乳液流收集在Rubber-maidEconomy Cold Food Storage Boxes.型号3500中。这些盒子用食品级的聚乙烯制造,标定尺寸为18″×26″×9″(45.7cm×66cm×22.9cm)。这些盒子的真实的内部尺寸为15″×23″×9″(38.1cm×58.4cm×22.9cm)。这些盒子用含SPAN20在等重量的二甲苯和2-丙醇的溶剂混合物中的20%溶液的溶液膜预处理。蒸发溶剂混合物仅留下SPAN20。在每个盒子收集47升的乳液。
装在盒子内的乳液保存在65℃的室内约18小时使盒子中的乳液聚合生成聚合泡沫。泡沫的洗涤和脱水
在固化完成后,从固化盒子中取出湿的固化泡沫。这时的泡沫含是聚合物质重量约34-40倍(30-40x)的残留水相,其中含有溶解的乳化剂,电解质和引发剂。泡沫用锋利的往复的片锯切片,片的厚度为0.350英寸(0.89cm)。这些片在串联的3个轧辊之间加压,逐渐减少泡沫的残留水相含量达聚合材料重量的(6x)。此时,泡沫片用1%CaCl2溶液在60℃下再饱和,在轧辊中挤压到水相含量约10x,再用1%CaCl2溶液在60℃再饱和,在轧辊中再挤压到水相含量约10x。
含约10x主要是1%CaCl2溶液的泡沫片通过设置了真空槽的最后的轧辊。该轧辊将CaCl2溶液含量降至约5倍(5x)的聚合物重量。在最后轧辊后,泡沫保持压紧的状态其厚度为约0.080英寸(0.2cm)。然后泡沫在60℃的空气循环窑中干燥约3小时。这个干燥过程将水含量减到约5-7%(wt)的聚合物质的重量。此时泡沫片的厚度约0.075英寸(0.19cm),且是很好摺皱的。该泡沫还包含约11%(wt)的残留月桂酸脱水山梨糖醇酯乳化剂和约5%(wt)(无水计)的残留的水合CaCl2。在密实状态下,该泡沫的密度为约0.17g/cm3。用Jayco合成尿膨胀时,它的自由吸收容量为约30.2ml/g。膨胀泡沫的毛细管吸入比表面积为约2.24m2/g,孔体积为约31ml/g,平均孔尺寸值为约15μm,粘合张力为约35达因/cm和垂直芯容量为约26.7ml/g或约88%它的自由吸收容量。
                         实施例II
一次性尿布利用图7所示的放大并分解开的构型和部件来制备。这种尿布包括热结合的聚丙烯上片70、流体不能渗透的聚乙烯下片71,和设置在上、下片间的双层吸收芯。双层吸收芯包括改性的滴漏型的流体储存/再分散层72,它包含设置在改性的滴漏型的流体捕获层73之下的实施例1类型的密实的HIPE泡沫。上片包含两个基本上平行的有弹性的屏蔽腿的裤边条74。固定在尿布下片上的是二根矩形有弹性的腰带75。还固定在聚乙烯下片每边的用聚乙烯制成的两根腰带屏蔽件76。还固定到下片上的是两根平行腿的弹性条77。聚乙烯片78固定到下片的外边,作为Y型的两组件79的固定表面,该两组件79可用来将尿布围绕穿戴者固定。
尿布芯的捕获层包括92%/8%的硬化的、编织的、卷曲的纤维素纤维和一般非一硬化的纤维素纤维的湿法成网的混合物。该硬化的编织的卷曲的纤维素纤维是由南部软木牛皮纸浆(Foley绒毛)制造,该纸浆用戊二醛交联到以干纤维素纤维脱水葡糖基计为约2.5mol%的程度。纤维的交联是按U.S.专利4822453(Dean等),描述的“干交联方法”进行,该专利1989年4月18日授权。
这些硬化纤维与下表II中描述特性的纤维相似。
                        表II硬化的编织的卷曲纤维素的(STCC)纤维
类型:南部牛皮纸浆用戊二醛交联达1.41mol%(以干纤维
      素纤维脱水葡基计)的程度。
干编织数:            6.8结点/mm
湿编织数:            5.1结点/mm
2-丙醇滞留值:        24%
水滞留值:            37%
卷曲因子:0.63
与STCC纤维结合使用的一般非硬化纤维素纤维也是由Foley绒毛制造。这些非硬化的纤维素纤维匀浆到约200CSF(Canadian Standard Freeness)。
捕获层的平均干密度为约0.07g/cm3,用合成尿饱和时的平均密度为约0.08g/cm3(干基重量),平均干基重量为约0.03g/cm2(average basis weight of约0.03g/cm2)。在尿布芯中使用了约13克的流体捕获层。捕获层的表面积为约46.8英寸2(302cm2)。它得厚度为约0.44cm。
尿布芯的流体储存/再分散层包括改性的滴漏型的实施例1中描述的类型的密实HIPE泡沫片。大约13克HIPE泡沫用于生成这种储存/分散层,该层的表面积约52.5英寸2(339cm2)和厚度为约0.1英寸(0.25cm)。
有这种特殊芯构型的尿布对于利用该芯保留排泄的尿是特别希望而有效的,因此当以通常的方式穿戴时,得到了异常优越低的泄漏发生率。如果吸收芯的捕获层中空气成网的硬化纤维被湿结成网硬化纤维所替代,也可以得到相似的结果。
                        实施例III
本实施例说明利用较低的聚合/固化温度对一致地降低HIPE乳液中的水滴的聚结和对一致地得到本发明的密实的聚合泡沫的益处,特别是在制备HIPE乳液中仅使用SPAN20乳化剂时。在该实施例中,通过与实施I相似的方法,但是利用不同批号的SPAN20作为乳化剂来制备HIPE乳液。这种HIPE乳液收集在一些1品托的塑料盖瓶中。四个烘箱的温度分别设置在100°F(37.8℃)、115°F(46.1℃)、130°F(54.4℃)和150°F(65.6℃),而几个HIPE乳液瓶在每个烘箱内固化24小时。生成的固化的泡沫的一部分用水洗涤并干燥。干泡沫的显微照片放大50倍,500倍和1000倍。图3a-图3d是这些显微照片(500倍)的代表。具体说,图3a表示在100°F(37.8℃)下固化泡沫的剖面图。图3b表示115°F(46.1℃)固化泡沫的剖面图,图3c表示130°F(54.4℃)固化泡沫的剖面图和图3d表示150°F(65.6℃)固化泡沫的剖面图。
如图3a和3b所示,在较低温度下固化的HIPE乳液(即在约低于50℃)生成的泡沫结构有较均匀尺寸的较小的孔,即泡沫结构较均匀。这就暗示在HIPE乳液固化期间,有降低水滴聚结的作用。反之,如图3c和3d所示,在较高温度下固化的HIPE乳液(即在约50℃以上),生成的泡沫结构有许多大孔且有较不均匀的孔尺寸,即泡沫结构实质上是不均匀的。这就意味着在HIPE乳液固化期间,明显地增加了水滴的聚结。
以孔尺寸和聚结程度表示的这些固化泡沫的均匀度利用下述的标度由显微照片可以定性地分级:等  级                            说    明
1.                 大块的聚结,几乎辨认不出是泡沫
2.                 很坏的聚结,散开的空隙,涂污的柱架
3.                 坏的聚结,原的柱架
4.                 中度的聚结,一些柱架不规则(增厚)
5.                 小的聚结,没有不规则的柱架
6.                 最小的聚结,没有不规则柱架
7.                 良好分辨的均匀结构
对固化泡沫的每一种按上述标度进行了数次测定,然后平均得到每一固化泡沫的平均等级,如下表所示:固化温度                                     平均等级100°F(37.8℃)                                 6.5115°F(46.1℃)                                 5.5130°F(54.4℃)                                 3.3150°F(65.6℃)                                 2.5
在115°F(46.1℃)、130°F(54.4℃)和150°F(65.6℃)固化的上述泡沫泡沫样品的一部分也评价了它们在用盐溶液洗涤后、随后加压和干燥后保持薄的性能的能力。通过用1.0%CaCl2溶液洗涤,加压除去一些水分和然后在烘箱中干燥(即在约150°F,65.6℃)对固化泡沫进行处理。对每一种干燥泡沫评价,测定是否保持其密实状态,即保持10-30%它原来膨胀的厚度。在130°F(54.4℃)和150°F(65.6℃)固化的干泡沫样品并不保持薄的性能。反之,在115°F(46.1℃)固化的干泡沫样品保持薄的性能。
                        实施例IV
下述的实施例说明利用月桂酸脱水山梨糖醇酯(SPAN20)和聚乙二醇脂肪酸酯(PGE)或棕榈酸脱水山梨糖醇酯(SPAN40)助乳化剂体系制备HIPE泡沫:
                        实施例IV A
无水CaCl2(36.32kg)和过硫酸钾(568克)溶于378升水中。这就得到了用于生成HIPE乳液的水相物流。
将(960克,SPAN20)月桂酸脱水山梨糖醇酯加入包含(1600克)苯乙烯、(55%工业级1600克)二乙烯基苯和(4800克)丙烯酸2-乙基已酯的单体混合物中。将提供最小油/水IFF为0.09×10-3牛顿/米的(480克)PGE乳化剂加入相同单体混合物的另一半的批料中。在210℃机械搅拌,氮气喷雾和逐渐提高真空的条件下,使用NaOH做催化剂用脂肪酸酯化聚乙二醇(其重量比为64∶36)得到了这种PGE,随后H3PO4中和,冷却到约60℃,沉清减少未反应的聚乙二醇。在制备PGE中所使用的聚乙二醇和脂肪酸的组成如下表所示:
聚乙二醇                                      wt%
线性聚乙二醇                                  63.5
三乙二醇或更高                                36.0
环二乙二醇                                    0.4
脂肪酸                                        wt%
C8                                           -
C10                                          -
C12                                          31.7
C14                                          37.2
C16                                          11.5
C18:0                                       3.2
C18:1                                       13.8
C18:2                                       1.5
在混合后,每批油相沉清过夜。上清液从每批中排出,并以2份含SPAN20的油相与1份含PGE的油相的比率混合。(从每批物料中约丢弃粘性残余物约75克。)
在水相温度为43℃-45℃和油相温度为22℃下,油相和水相的独立物流加入针形高速搅拌机的动态混合器中。该针形高速搅拌机的圆筒形轴为约21.6cm长,直径为约1.9cm。轴上固定4排针,两排有17根针,而另两排有16根针,每根针的直径为0.5cm,从轴中心线向外延伸约1.6cm。针形高速搅拌机安装在圆筒形套管内,针距内壁的间隙为0.8mm。
螺旋静态混合器(14英寸长×1/2英寸外径,TAH工业型号070-821,通过切去2.4英寸改制而成)安装在动态混合器下游,以在动态混合器中提供反压,并使HIPE乳液保持均匀性。组合的动和静态混合装置用比率为2份水相与1份油相充满。该装置排气,以使空气排出,直到装置完全充满为止。在装填期间的流率为3.0g/秒油相和4.5cc/秒水相。
装置一旦充满,就开始搅拌,高速搅拌机的转速为1100RPM。在120秒的期间内水相流率均速升高达46.5cc/秒,而油相流率平均下降到1.77g/秒。此时动和静态混合器产生的反压为约4.9psi.在30秒钟内,高速搅拌机减慢到1000RPM。当反压降到近3psi,高速搅拌机立即升速到1800RPM。而反压增加到5.5psi。水相和油相的;流率分别调节到47.8cc/秒和1.66g/秒。
将HIPE乳液收集在模子中(Rubbermaid Economy冷藏食品储存盒,用食品级聚乙烯制造,型号3500),内部尺寸为15英寸×23英寸×9英寸深。模子用含20%SPAN20的二甲苯溶液膜预处理,该溶液是经静置过夜除去不溶物的溶液。将模子预热,加速二甲苯蒸发,过后仅留下SPAN20。在每个模子中收集47升HIPE乳液。充满的模子在65℃的室内放置18小时,进行固化。固化的泡沫用1%CaCl2溶液洗涤。在干燥前,含在泡沫中的残留溶液是泡沫重量的5倍。
图4是一显微照片(放大1000倍),示出了利用与该实施例相似的SPAN20/PGE助乳化剂体系从HIPE乳液制备的有代表性的聚合泡沫。图4中所示的泡沫结构是在膨胀状态下的。如能看见的,这种泡沫结构有较小的孔,且有较均匀的孔尺寸,即泡沫结构较均匀。这就暗示出在HIPE乳液固化期间,水滴减少聚结的证据。
                      实施例IV B
按照实施例IV A的方法制备含CaCl2/过硫酸钾的水相和含SPAN20的油相单体混合物。通过添加提供最小的油/水IFT为0.22×10-3牛顿/米的PGE乳化剂来制一半批料量的单体混合物。该PGE是由聚乙二醇用脂肪酸按重量比为约67∶33,利用的反应条件与实施例IVA中描述的相似条件来酯化而得到的。在制备PGE中所使用的聚乙二醇和脂肪酸的组成如下表所示:
聚乙二醇                                      wt%
线型二乙二醇                                  73.1
三乙二醇或更高                                24.5
环状二乙二醇                                  2.4
脂肪酸                                        wt%
C8                                           -
C10                                          -
C12                                          32
C14                                                37
C16                                                11
C18:0                                             3.2
C18:1                                             13
C18:2                                             1.5
混合后,每个油相批料沉清过夜,上清夜排出,如实施例IV A那样,以2份含SPAN20的油相与1份含PGE的油相的比率混合。水相和油相加入如实施例IV A那样组合的动和静态混合器装置中。组合装置用比率为2份水相与1份油相的比率充填的同时,排出装置中的空气,直到装置完全充满为此。在充填期间的流率为3.0g/秒油相,而水相为7.5cc/秒。
一旦装置充满后,就开始搅拌,高速搅拌机的转速为1200RPM。在60秒期间内,水相流率均匀升达45.0cc/秒,油相流率均匀降到1.66g/秒。然后高速搅拌机的转速在30秒内均匀降到1100RPM,而然后立即提高到1800RPM。然后调节水相流率为47.6cc/秒。反压为5.3psi。将生成的乳液收集在模子中,并在65℃的室内放置18小时,使其固化,如实施例IV A所描述的。用1%CaCl2溶液洗涤固化的泡沫。干燥前,泡沫中含的残留溶液为泡沫重量的5倍。
                         实施例IV C
按实施例IV A制备含CaCl2/过硫酸钾的水相和含SPAN20的油相单体混合物,通过加入提供最小的油/水IFT为0.08达因/cm的PGE乳化剂来制备一半批料量的单体混合物。该PGE是通过聚乙二醇用脂肪酸按重量比为67∶33,利用的反应条件与实施例IV A描述的相似条件来酯化而得到的。在制备PGE中所使用的聚乙二醇和脂肪酸的组成如下表所示:
聚乙二醇                                         wt%
线型二乙二醇                                     ~71
三乙二醇或更高                                   ~24
环型二乙二醇                                     ~5
脂肪酸                                           wt%
C8                                              -
C10                                             4.4
C12                                             43.6
C14                                             25.1
C16                                             12.1
C18:0                                          3.8
C18:1                                          9.2
C18:2                                          1.4
混合后,每一种油相批料沉清过夜,上清液排出,以2份含SPAN20的油相和1份含PGE的油相比例混合,像实施例IVA那样。然后将水相(45℃-47℃)和油相加到如实施例IV A那样组合的动和静态混合装置中。组合装置用以2份水相与1份油相的比率的油相和水相充填,同时装置排出空气,直到装置完全充满为止。在充填期间,油相流率为2.2g/秒,水相流率为4.7cc/秒。
装置一旦充满后,就开始搅拌,高速搅拌机转速1800RPM。然后在90秒的期间内水相流率均匀升达45.5cc/秒,油相流率均匀降到1.59g/秒。反压为5.4psi。将HIPE乳液收集在模子中,在65℃的室内放置18小时,使其固化,如实施例IVA所述。用1%CaCl2溶液洗涤固化泡沫。干燥前泡沫中含残留溶液量为泡沫重量的5倍。
                      实施例IV D
按实施例IV A制备含CaCl2/过硫酸钾的水相和含SPAN20的油相,还通过加入提供最小油/水IFT为0.013达因/cm的PGE乳化剂来制备一半批料量的单体混合物。该PGE是通过聚乙二醇用脂肪酸按重量比为61∶39,利用与在实施例IV A中描述的相似反应条件来酯化而得到的。在制备PGE中所使用的聚乙二醇和脂肪酸的组成如下表所示:
聚乙二醇                                     wt%
线型二乙二醇                                 约15
三乙二醇或更高                               约85
环状二乙二醇                                 -
脂肪酸                                       wt%
C6                                          6
C10                                         5
C12                                         55
C14                                         23
C16                                         6
C18:0                                      3
C18:1                                      1
C18:2                                      1
混合后,每种油相沉清过夜,上清液排出,以2份含SPAN20的油相和1份含PGE的油相比率混合,如实施例IV A中的那样。然后将水相(55℃-60℃)和油相加入如实施例IV A中组合的动和静态混合装置中。组合装置被以2份水相与1份油相的比率的油相和水相充填,同时从装置中排出空气,直到装置完全充满为止。在充填期间,油相流率为3.0g/秒,水相的流率为6.0cc/秒。
装置一旦充满后,就开始搅拌,高速搅拌机转速1800RPM。然后在120秒的期间内将水相流率均匀升达45.7cc/秒,油相流率均匀降到1.58g/秒。反压为5.4psi。将HIPE乳液收集在模子中,并在65℃的室内放置18小时使其固化,如实施例IV A所述。固化泡沫用1%CaCl2溶液洗涤。干燥前泡沫中的残留溶液量为泡沫重量的5倍。
                        实施例IV E
按实施例IV A制备含CaCl2/过硫酸钾的水相和含SPAN20的油相,还通过加入提供最小油/水IFT为0.042达因/cm的PGE乳化剂来制备一半批料量的单体混合物。该PGE是通过聚乙二醇用脂肪酸在重量比为67∶33,利用与在实施例IVA描述的条件的相似条件来酯化而得到的。在制备PGE中所使用的聚乙二醇和脂肪酸的组成如下表所示:
聚乙二醇                                        wt%
线型二乙二醇                                    70.6
三乙二醇或更高                                  24.1
环型二乙二醇                                    5.3
脂肪酸                                          wt%
C8                                             -
C10                                            -
C12                                            32.1
C14                                            38.6
C16                                            11
C18:0                                         3.2
C18:1                                         13.4
C18:2                                         1.4
混合后,每一油相批料沉清过夜,上清液排出,按2份含SPAN20的油相与1份含PGE的油相的比例如实施例IV A那样混合。水相和油相加入如实施例IV A的组合的动和静态混合装置中。组合装置用以2份水相与1份油相的比例的油相和水相充填,同时从装置中排出空气,直到装置完全充满为止。在充填期间,油相流率为1.7g/秒,水相流率为3.0cc/秒。
装置一旦充满后,就开始搅拌,高速搅拌的转速1100RPM。然后在90秒的期间内,将水相流率均匀升到48.4cc/秒,反压为5.0psi。然后高速搅拌机的转速立即提高到1800RPM。反压提高到5.8psi。将HIPE乳液收集在模子中,在65℃的室内放置18小时,使其固化,如实施例IV A那样。固化的泡沫用1%CaCl2溶液洗涤。干燥前泡沫中的残留溶液量为泡沫重量的5倍。
                            实施例IV F
按实施例IV A制备合CaCl2/过硫酸钾的水相和含SPAN20的油相单体混合物,将月桂酸脱水山梨糖醇酯(480g,如SPAN20)和月桂酸脱水山梨糖醇酯(240g)与棕榈酸脱水山梨糖醇酯(240g,如SPAN40)的混合物加入单体混合物中。混合后,油相沉清过夜,排出的上清夜在生成HIPE乳液中使用。
将供水相(48℃-50℃)和油相加入如实施例IV A中的组合的动和静态混合装置中。该组合装置用比例为2份水相与1份油相的水相和油相充填,同时从装置排出空气,直到装置完全充满为止。在充填期间,油相流率为3.0g/秒,水相流率为6cc/秒。
装置一旦充满后,就开始搅拌,高速搅拌机转速为1800RPM。然后,在60秒的期间内,将水相流率均匀升到42.3cc/秒,而油相流率均匀降到1.5g/秒。反压为4.5psi。将HIPE乳液收集在模子中,(带中心芯的圆形管)并在65℃的室内放置18小时,使其固化,如实施例IV A中那样。固化泡沫用1% CaCl2溶液洗涤。干燥前,泡沫中的残留溶液量为泡沫重量的5倍。

Claims (18)

1.一种密实的聚合泡沫材料,当它与含水体液接触时,它膨胀并吸收上述的体液,上述的聚合泡沫材料包括一亲水的挠曲的有相互连接的开孔的非离子的聚合泡沫结构,该泡沫结构有:
A)每泡沫体积的比表面积为至少0.025m2/cc;
B)掺入了至少0.1%(wt)毒理学上可接受的吸湿的水合盐;
C)在它的密实状态下,膨胀压力为30 kpa或小于此值;和
D)在它的膨胀状态下,在用表面张力为(65±5)×10-3牛顿/米的合成尿在31.1℃饱和到其自由吸收容量时,其密度为它的密实状态下的干基密度的10%-50%。
2.按权利要求1的泡沫材料,其中上述泡沫结构的每泡沫体积的比表面积至少为0.05m2/cc和在它的密实状态下残留的水量至少为4%(wt)。
3.按权利要求2的泡沫材料,其中上述的泡沫结构有:
A)毛细管吸入比表面积为0.7-8m2/g;
B)0.1-8%(wt)的CaCl2和0.5-20%(wt)的非离子的油溶性的乳化剂掺入其中,使泡沫结构的表面有亲水性;
C)在它的密实状态下:
(i)残留的水量为4%-30%(wt);
(ii)干基密度为0.05-0.4g/cm3
D)在它的膨胀状态下:
(i)孔体积为12-100ml/g;
(ii)抗加压揉曲性为2%-80%,这是在31.1℃用表面张力为(65±5)×10-3牛顿/米的合成尿饱和到它的自由吸收容量时的值;
(iii)平均孔尺寸为5-50微米。
4.按权利要求3的泡沫材料,其中上述泡沫结构有:
A)毛细管吸入比表面积为1.5-6m2/g;
B)3%-6%(wt)的CaCl2和5%-12%(wt)的月桂酸脱水山梨糖醇酯掺入其中;
C)在它的密实状态下:
(i)残留的水量为5%-15%(wt);
(ii)干基密度为0.1-0.2g/cm3
(iii)膨胀压力为7-20kpa;
D)在它的膨胀状态下:
(i)孔体积为25-50ml/g;
(ii)抗加压揉曲性为5%-40%;
(iii)平均孔尺寸值为5-35微米;
(iv)在用上述的合成尿饱和时,密度为它的密实状态下的它的干基密度的10%-30%。
5.通过油包水乳液聚合制备的权利要求1的泡沫材料,所述乳液具有:
1)一油相包括:
a)67%-98%(wt)的单体成分,包含:
i)5%-40%(wt)的基本上不溶于水的单功能的玻璃状单体;
ii)30%-80%(wt)的基本上不溶于水的单功能的橡胶状单体;
iii)10%-40%(wt)的基本上不溶于水的多功能的交联剂;和
b)2%-33%(wt)的溶于油相的乳化剂成分,它生成稳定的油包水乳液;和
2)水相包括0.2-20%(wt)的溶于水的电解质;
3)水相与油相的重量比为12∶1-100∶1。
6.权利要求5的泡沫材料,其中:
1)油相包括:
a)80%-95%(wt)的单体成分,包含:
i)10%-30%(wt)的选自由苯乙烯基单体和甲基丙烯酸酯基单体组成的组中的玻璃状单体;
ii)50%-70%(wt)的选自由丙烯酸正丁酯和丙烯酸2-乙基己酯组成的组中的橡胶状单体;
iii)15%-25%(wt)二乙烯基苯;
b)5%-20%(wt)的包括月桂酸脱水山梨糖醇酯的乳化剂成分;
2)水相包括1-10%(wt)的CaCl2
3)水相与油相的重量比为12∶1-70∶1。
7.按权利要求6的泡沫材料,其中上述单体包括:
i)15%-25%(wt)的苯乙烯;
ii)55%-65%(wt)的丙烯酸2-乙基己酯;
iii)15%-25%(wt)的二乙烯基苯。
8.制备权利要求1的密实的聚合泡沫材料的方法,该方法包括如下步骤:
A)从下面各成分生成油包水乳液:
I)油相包含:
a)67%-98%(wt)的单体成分包含:
i)5%-40%(wt)的基本上不溶于水的单功能的玻璃状单体;
ii)30%-80%(wt)的基本上不溶于水的单功能的橡胶状单体;
iii)10%-40%(wt)的基本上不溶于多功能的交联剂;和
b)2%-33%(wt)的溶于油相的乳化剂成分,它适宜于生成稳定的油包水乳液;和
2)水相包含0.2-20%(wt)的水溶性电解质的一种水溶液;
3)水相与油相的重量比为12∶1-100∶1。
B)聚合油包水乳液的油相中单体成分,生成聚合泡沫材料;和
C)使聚合泡沫材料脱水达生成密实聚合泡沫材料的程度,当它与含水体液接触时,将再膨胀,其改进之处包括以减少油包水乳液中生成的水滴聚结的这样的方式,实现上述乳液的形成和聚合步骤(A)及(B),结果是聚合泡沫材料的平均孔尺寸为50微米或小于此值。
9.按权利要求8的方法,其中水相还包括0.02%-0.4%(wt)的溶于水的自由基聚合引发剂,且其中的水相与油相的重量比为20∶1-70∶1。
10.按权利要求9的方法,其中:
1)油相包括:
a)80%-95%(wt)的单体成分包含:
i)10%-30%(wt)的选自由苯乙烯基单体和甲基丙烯酸酯基单体组成的组中的玻璃状单体;
ii)50%-70%(wt)的选自由丙烯酸正丁酯和丙烯酸2-乙基己酯组成的组中的橡胶状单体;
iii)15%-25%(wt)的选自由二乙烯基苯、二乙烯基甲苯和对苯二甲酸二烯丙酯组成的组中的多功能的交联剂;和
b)5%-20%(wt)的包括月桂酸脱水山梨糖醇酯的乳化剂;
2)水相包含1%-10%(wt)的CaCl2
3)水相与油相的重量比为25∶1-50∶1。
11.按权利要求10的方法,其中单体成分包括:
i)15%-25%(wt)苯乙烯;
ii)55%-65%(wt)丙烯酸2-乙基己酯;
iii)15%-25%(wt)二乙烯基苯。
12.按权利要求9的方法,其中聚合步骤(B)是在30℃-50℃下进行4-24小时。
13.按权利要求12的方法,其中聚合步骤(B)是在35℃-45℃下进行4-18小时。
14.按权利要求9的方法,其中乳化剂成分包含月桂酸脱水山梨糖醇酯和聚乙二醇脂肪酸酯,其重量比为10∶1-1∶10,聚乙二醇酯来自:(I)聚乙二醇,它具有线型双甘油含量至少为60%(wt),三或更高的聚乙二醇含量不大于4%(wt),和环型双甘油含量不大于10%(wt);(2)具有脂肪酸成分的脂肪酸反应物,其中C12和C14饱和脂肪酸的总量至少为40%,C16饱和脂肪酸的含量不大于25%,C18或更高饱和脂肪酸的总量不大于10%,和C10或更低的脂肪酸的总量不大于10%;(3)聚乙二醇(1)与脂肪酸反应物(2)的重量比为50∶50-70∶30。
15.按权利要求14的方法,其中月桂酸脱水山梨糖醇酯与聚乙二醇酯的重量比为4∶1-1∶1,且其中的聚乙二醇酯来自:(1)聚乙二醇,它具有线型双甘油含量为60%-80%(wt),而三或更高的聚乙二醇含量为20%-40%(wt);(2)具有脂肪酸成分的脂肪酸反应物,其中C12和C14饱和脂肪酸的总量至少为65%,C16饱和脂肪酸含量不大于15%,C18或更高的脂肪酸的总量不大于4%,和C10或更低的脂肪酸总含量不大于3%(3)聚乙二醇(1)与脂肪酸反应物(2)的重量比为60∶40-70∶30。
16.按权利要求14的方法,其中聚乙二醇酯提供的最小油/水界面张力在50℃时至少为0.06×10-3牛顿/米。
17.按权利要求16的方法,其中聚乙二醇酯提供的最小油/水界面张力在50℃时为(0.09-0.3)×10-3牛顿/米。
18.按权利要求14的方法,其中聚合步骤(B)是在50℃以上温度下进行。
CN93121142A 1992-12-11 1993-12-11 用于吸收含水体液的湿前呈薄状的吸收泡沫材料及其制备方法 Expired - Fee Related CN1054858C (zh)

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EP0673393B1 (en) 1999-01-27
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