CN1408002A - 具有缓慢吸水率的超吸收剂聚合物 - Google Patents
具有缓慢吸水率的超吸收剂聚合物 Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明公开了具有低吸收率的超吸收剂聚合物以及它们的制备方法。这种具有低吸收率的超吸收剂聚合物和共价交联剂以及多价金属盐的金属离子交联，它具有有至少5分钟的吸收速率指数。该聚合物通过将基质水溶胀性、水不溶性和多价金属盐溶液相接触制得，接触条件为使聚合物具有至少5分钟的吸收速率指数。
Description
本发明涉及超吸收剂聚合物(SAP)组合物和这种组合物的制备方法。
超吸收剂聚合物是公知的材料，其常规用于个人护理用品如尿布。这些聚合物可以吸收几倍于其自身重量的水、盐水溶液、尿、血液和浆液状体液。
薄型尿布的不断发展要求尿布具有高密度的吸收剂芯层，这种芯层在超吸收剂聚合物/纤维素绒毛混合物中具有更大的超吸收剂聚合物成分。因此，为了充分利用高膨胀聚合物的储存液体能力，使液体在吸收剂芯层中均匀分布就很重要。然而，吸收剂芯层中纤维绒毛量的减少对液体分布产生负面影响。因此，对液体处理是对这类高膨胀，储存液体的聚合物的附加要求。储存液体的聚合物必须允许或者支持液体在超级吸收剂聚合物/绒毛混合物的分布，甚至当超吸收剂聚合物/绒毛混合物中高膨胀聚合物的比例很高时。
当尿布中超吸收剂聚合物/绒毛比例高时，低的绒毛含量会导致更差的液体分布，因为这种绒毛的液体分布能力不足以抵消常规吸收聚合物的高吸收率和吸收能力。因此，大量流进个人卫生用品的体液应该在液体进入处即被吸收剂聚合物吸收。
常规吸收聚合物的膨胀效应在水性液体一加入时就发生，高的吸收速率可立即被观察到。几分钟之后，在自由膨胀的条件下，基于交联、部分中和聚丙烯酸盐的高膨胀性聚合物达到了其吸收容量的大约95％。这种特性是交联的聚丙烯盐超吸收剂聚合物的典型性质。
围绕体液进入吸收剂芯材处聚合物颗粒的迅速膨胀会造成在SAP-绒毛基质中空隙空间和孔的封闭。由于扩散通过溶胀水凝胶进行的液体传送要比通过空隙空间的速度慢，密封作用发生在流体进入的区域。这种作用通常被称之为“凝胶阻塞”。其余的液体不能再穿透吸收剂芯材而不受控制地穿过已经表面饱和的区域流向边缘，从而导致吸收剂芯材不希望发生的泄漏。
此外，由于靠近表面的颗粒发生凝胶阻塞，吸收剂芯材的贮存能力下降，其余的体流不再能够到达深含于吸收剂芯材之中的高溶胀性聚合物中，因此，也就不能增加总的贮存能力。
对凝胶阻塞的一种可行的处理方法是改变吸收聚合物的吸收速率特性。例如，美国专利4,548,847描述了一种通过至少一个二价金属阳离子如Ca+2或Ba+2进行可逆交联的水凝胶。该专利教导我们，通过采用所谓的“阳离子脱除剂”可实现溶胀延迟。这些试剂的优选实例为水溶性化合物，如Na2HPO4、六偏磷酸钠和乙二胺四乙酸的二钠盐。这些物质的作用是通过阳离子脱除剂破坏了由至少二价金属阳离子形成可逆交联位点。通过减少交联浓度，产品可更为溶胀。该专利也描述了包含具有延迟溶胀特性的吸收剂聚合物的吸收制品。例如，描述了在各层中(缠绕)聚集的吸收制品，其中，每一层包含本发明的聚合物。
GB 2,280,115 A描述了一种吸收制品，其在体液释放的区域中包含涂敷的超吸收剂颗粒。超吸收剂颗粒的涂层防止溶胀，直至涂层溶解于试验流体或体液中或通过其渗透。这些超吸收剂颗粒显示出直至开始溶胀的活化时间，该时间会随涂层材料与厚度的不同而变化。所采用的某些涂层材料为非活性的多糖，如明胶、微晶纤维素和纤维素衍生物。开始溶胀的活化时间应至少为5分钟，优选15分钟，更优选60分钟。
涂敷过的超吸收剂聚合物的缺点是，即使开始有少量的润湿，并不必需导致高溶胀性聚合物的溶胀，但会导致通过溶解、脱离、溶胀或分解的表面处理的破坏。一旦围绕聚合物的涂层溶解，则超吸收剂聚合物就会表现为未进行表面处理的常规材料的高溶胀速率。因此，丧失了吸收剂材料所期望的改善液体控制的效果。
EP 0 631 768 A1描述了一种吸收制品，该制品采用具有不同吸收速度的超吸收剂聚合物。在所采用的各种超吸收剂聚合物间吸收速度的差异是由于粒径分布不同(类型1：600-850μm，类型2：＜250μmm)引起的，并且所述差异相对较小。
美国专利5,115,011提到的凝胶阻塞问题通过以下方法解决：用两种水溶性盐的水溶液和一种吸水聚合物相接触，第一种盐是铝、钙或镁的卤化物、硫酸盐、醋酸盐或者硝酸盐，第二种盐至少一种选自亚硫酸和硫代硫酸的含氧酸的单价金属盐或铵盐。在这个专利的对比例3中制备了0.6g硫酸钙和30g聚合物的干混合物，其具有70％的阻塞效应或者说超过5分钟。
美国专利4,090,013公开了从水溶性阴离子聚电解质和多价金属阳离子制得的物质。然而在产品美国专利5,578,318中显示具有凝胶阻塞效应。
美国专利5,578,318公开了“亲水性涂敷颗粒”的超级吸收剂的制备：将非交联的聚丙烯酸盐和多价离子干燥混合，然后任选地加入乙醇、某种润湿剂和聚硅氧烷衍生物。这种润湿的物质在使用之前要干燥。这项专利的实施例XXIII公开了2.61wt％AQUALON A-250、0.21wt％醋酸铝和97.18wt％水的混合物。干燥后，这个实施例获得的物质显示了作为超级吸收剂相对比较差的性能。
美国专利4,693,713公开了一种吸收血和水样体液的吸收剂，这种吸收剂包含某些聚合物和某些化合物的物理混合物。这种化合物被描述为水溶性，环境温度下以易流动粉末形式存在，对身体无害。这项专利教导我们，这种化合物可以溶解在单体溶液中加入聚合物，或者在任何时间以干燥或者溶解形式加入聚合物的制备过程中。聚合物和化合物的干燥混合物在这项专利的实施例中制备。
多层吸收制品中的凝胶阻塞问题需要特别注意。解决该问题的一种方式就是在制品中掺入慢速聚合物。已提出了生产这些制品的几种方法。但是，这些方法中还没有一种能够生产出整体上令人满意的慢速聚合物。
期望获得一种制备具有缓慢吸收速度的超吸收剂的聚合物的方法，这种方法无需使用阳离子脱除脱除剂或用于聚合物的涂层。这样一种方法很明显的一个优点是，由于取消使用外来材料，从而与之相关的成本可以降低。
本发明包括一种制备具有缓慢吸收速度的超吸收剂的聚合物的改进方法，以及由该方法制备的聚合物。更具体地说，本发明的方法是一种具有缓慢水吸收速度的水溶胀性、水不溶性聚合物颗粒的制备方法，该方法包括将水溶胀性、水不溶性聚合物颗粒和多价金属盐溶液接触，条件为使形成的聚合物具有至少5分钟的吸收速率指数。本发明的聚合物是具有低吸收速率的水溶胀性、水不溶性聚合物，该聚合物和共价交联剂，多价金属盐的金属交联，吸收速率指数至少为5分钟。另一方面，本发明包括含低吸收速率超吸收剂聚合物的吸收制品。
本发明的一个优选的制备改良的水溶胀性、水不溶性聚合物的方法包括用多价金属盐溶液和共价交联的超吸收剂聚合物相接触，制得的聚合物具有至少5分钟的吸收率指数。
“吸收速率指数”(ARI)指的是用以下描述的ARI检验方法测定的吸收速率指数。
本发明使用足够量的多价金属盐生产具有至少5分钟的吸收速率指数的聚合物。这种多价金属盐优选是水溶性的。优选的金属阳离子包括Al、Fe、Zr、Mg和Zn。优选的金属阳离子具有至少+3的共价态，最优选的是铝。多价金属盐中优选的阴离子包括卤化物、氯化氢、硫酸盐、柠檬酸盐、硝酸盐和醋酸盐，优选氯化物、硫酸盐、柠檬酸盐、氯化氢和醋酸盐，更优选柠檬酸盐、氯化氢和硫酸盐，最优选柠檬酸盐。铝的高水溶性盐是优选的。柠檬酸铝是最优选的多价金属盐并且市场有售。也可以用多价金属盐混合物。优选地，使用的多价金属盐每摩尔羧基含至少0.003摩尔金属离子。更优选地，使用的多价金属盐每摩尔羧基含至少0.016摩尔离子，最优选地，使用的多价金属盐每摩尔羧基含至少0.03摩尔金属离子。优选地，以聚合物重量为基础，使用的多价金属盐每摩尔羧基含不超过0.1摩尔金属离子。更优选地，使用的多价金属盐每摩尔羧基含不超过0.086摩尔金属离子，最优选地，使用的多价金属盐每摩尔羧基含不超过0.07摩尔的金属离子。优选地，使用的多价金属盐每摩尔羧基含金属离子的量为0.003到0.1摩尔。更优选地，使用的多价金属盐每摩尔羧基组中金属离子的量从0.016到0.086摩尔，最优选地，使用的多价金属盐每摩尔羧基组中金属离子的量从0.03到0.07摩尔。
适合本发明使用的水溶胀性、水不溶性、亲水性聚合物可以是任何能够吸收大量流体的亲水性聚合物。这些聚合物在本领域是已知的并且商业中普遍有售。具体地，本发明使用的吸水聚合物含羧基部分。优选地，每100克吸水树脂含至少0.01当量的羧基。优选的含羧基的水吸收剂聚合物为淀粉-丙烯腈接枝共聚物的水解产物、淀粉-丙烯酸或聚乙烯醇接枝共聚物的部分中和产物、乙酸乙烯酯丙烯酸酯共聚物的皂化产物、异丁烯和马来酸酐共聚物的衍生物、丙烯腈共聚物的水解产物、丙烯腈共聚物的水解产物的交联产物、交联羧甲基纤维素、丙烯酰胺共聚物的聚门冬氨酸酯水解产物、丙烯酰胺共聚物水解产物的交联产物、聚丙烯酸的部分中和产物和部分中和的聚丙烯酸的交联产物。适合本发明的基础聚合物基具有从20g/g到50g/g的吸收能力，尽管吸收能力超出此范围的其它聚合物也能使用。
某些适宜的水溶胀性、水不溶性聚合物和其制备方法包括凝胶聚合法的实例公开于下述文献中：美国专利3,997,484；3,926,891；3,935,099；4,090,013；4,093,776；4,340,706；4,446,261；4,683,274；4,459,396；4,708,997；4,076,663；4,190,562；4,286,082；4,857,610；4,985,518和5,145,906。此外，参见Buchholz，F.L.和Graham，A.T.，“现代超吸收剂聚合物技术”(Modem Superabsorbent Polymer Technology)，”John Wiley & Sons(1998)。这种亲水聚合物是由水溶性的α，β-烯属不饱和单体如一元羧酸、多元羧酸、丙烯酰胺和其衍生物制备的。
采用合适的方法将基础聚合物和多价金属盐溶液接触。接触条件要使产生的聚合物具有至少5分钟的ARI。本发明的优选方法包括用多价金属盐溶液浸泡超吸收剂聚合物。浸泡时间使多价金属盐能扩散进入聚合物中，合适时间范围从少于1小时到接近72小时或更多时间。优选的时间长度要求至少1小时。浸泡步骤也可进行超过2小时，超过3小时，超过4小时，超过5小时，超过6小时，或者时间更长。铝盐扩散进入聚合物的过程中胶体维持的适宜温度从10℃到150℃。每1份基础聚合物所需水的比例从1份到10份。优选地，聚合物和多价金属盐在至少一种选自亚硫酸和硫代硫酸的含氧酸的单价金属盐或氨盐基本上不存在条件下相接触。在一个优选实施方案，接触是在二价金属盐基本上不存在条件下进行的，另一个优选实施方案是在乙醇不存在条件下进行的。优选地，接触是在纤维素和美国专利4,548,847的“阳离子去除剂”不存在条件下进行的。
本发明的优选方法中，聚合物和多价金属盐溶液接触后干燥。优选地，湿颗粒在至少100℃的温度中干燥，更优选120℃。适宜的干燥装置包括流化床干燥器、旋转干燥器、迫风炉和循环带式干燥器。在某些情形下，干燥过程分成两步或多步进行，即多段干燥。在完全干燥后，进一步调整聚合物的大小以形成具有平均粒径小于2mm，更优选小于1mm的颗粒。优选地，最终的聚合物产品的平均粒径至少为160μm。
任选地将干燥得到的聚合物热处理，热处理的方法并非关键。例如，迫风炉、流化床加热器、受热螺旋转送带均可成功使用。如果需要的话，加热后的聚合物可再次润湿以易于进行处理。
另一个任选的过程是表面交联，它可以提高聚合物颗粒的吸收性能。表面交联工艺在本领域是已知的，并且被描述于，例如，U.S.4,734,478和U.S.4,666,983。这些工艺能增加聚合物颗粒的吸收指数。
本发明的组合物可任选地包括其它添加剂，例如，防结块剂。防结块剂是已知的。硅土是优选的防结块剂。
本发明的组合物具有低的吸收速率。优选地，组合物具有至少5分钟的吸收速率指数，更优选的组合物至少10分钟，更优选的至少20分钟，最优选的至少30分钟。优选地，本发明聚合物能发生可逆的阳离子交联。优选地，本发明聚合物能使多价金属盐的金属在整个聚合物中均匀分布。优选地，本发明的聚合物不被涂层。
本发明的超吸收剂聚合物用于生产含水的吸收制品，如一次性尿布、卫生巾、失禁服装和绷带。本发明的超吸收剂组合物特别适用于生产薄型和超薄型一次性尿布，其具有优异的吸水能力、流体分布性能并减少了泄漏。例如，本发明的超吸收剂聚合物可用于生产在下述文献中所述的吸收制品：美国专利3,669,103；3,670,731；4,654,039；4,430,086；4,973,325；4,892,598；4,798,603；4,500,315；4,596,567；4,676,784；4,938,756；4,537,590；4,673,402；5,061,259；5,147,343和5,149,335。尿布和其它吸收制品的构造是公知的，用作在吸收制品中绒毛材料也是公知的。本发明中，术语“绒毛”是指现有技术中普通技术人员理解的含义。绒毛的实例包括棉纤维、弯曲纤维、木材纸浆纤维、合成纤维或其组合，它们形成了衬垫并主要通过毛细管吸引机理吸收。例如，参见美国专利4,610,678。
在用本发明的组合物制备吸收制品时，超吸收剂组合物可与纤维多孔基质混合、粘附于其上、层压于其中或分散于其中。这种基质是用亲水性纤维制备的，如木浆或绒毛、棉毛，以及合成纤维或纤维与木头绒毛的混合物。纤维可以松动或无纺形式连接。合成纤维的实例包括采用聚乙烯、聚丙烯、聚酯和聚醚与聚酰胺的共聚物制成的合成纤维。合成纤维可为熔喷纤维或经处理具有亲水性的纤维。
本发明的超吸收剂聚合物可更为有利地用于吸收剂结构中，其将具有缓慢吸收速度的超吸收剂聚合物单独或串联地掺入具有不同吸收速度的超吸收剂聚合物进入多划分或多层的结构中。这些结构的实例如下述文献所述：美国专利4,338,371；4,935,022；5,364,382；5,429,629；5,486,166；5,520,673；5,531,728；5,562,646和5,728,082。
本发明的超吸收剂聚合物也可有利地用于那些与含水流体接触是过程固有的生产方法中。在这些过程中，缓慢吸收速度有助于防止过量超吸收剂溶胀，这种溶胀导致大量水脱除，在干燥时大量的体积发生变化。这些方法的实例是湿复合法，以及制备泡沫吸收剂结构的方法。湿复合法的实例在以下文献中有述：美国专利4,354,901；4,986,882；5,300,192；5,308,896；5,538,783；5,543,215；5,795,439和5,651,862。泡沫吸收剂结构的实例如下述文献所述：美国专利4,990,541和5,011,864。
吸收制品，如一次性尿布，通常是用不渗透液体的背材、可渗透液体的面对身体一侧的面材和夹在背材与面材间的吸收液体的复合材料。不渗透液体的背材可由商购的聚烯烃膜制造，可渗透液体的面材可用商购的无纺材料制造，如可润湿并能透过尿液的纺粘或捆扎的纤维网。
本发明的吸收制品可包含5-95wt％的本发明的超吸收剂聚合物。在典型的吸收制品中，本发明的超吸收剂聚合物可分散于纤维基质中。这样，在该制品中，超吸收剂用量优选为30-70wt％，以制品的重量计，纤维基质的用量为70-30wt％，以制品的重量计。在另一种形式的吸收制品中，超吸收剂存在于容纳结构中，其中，超吸收剂聚合物的用量为30-95wt％。分散的超吸收剂聚合物与包含的超吸收剂聚合物的组合是公知的。
下述实施例和比较例用于说明本发明，但它们并非对本发明保护范围的限制。所有份数和百分数均指重量，除非另有说明。
吸收能力(AC)按照下述文献所述方法测量：Buchholz，F.L.和Graham，A.T.，“现代超吸收剂聚合物技术(Modern SuperabsorbentPolymer Technology)”，John Wiley & Sons(1998)，153页。
在超吸收剂聚合物中，本发明金属盐的金属的均匀分布按照电子微探针分析法进行测量，如下述文献所述：Buchholz，F.L.和Graham，A.T.，同前述文献，57-58页。ARI检测法：测量吸收速率指数的方法
在100mL带刻度的量筒中加入100mL的0.9wt％盐水溶液。采用规格为ASTME-11的筛子将超吸收剂聚合物样品筛分至-30/+50目，得到粒度为300-600微米的样品。将1.00g筛分后的聚合物倾倒入带刻度的量筒中。当样品一到达刻度量筒的底部时打开精确到秒的记时器。测量在以下时刻凝胶层的体积：0.5、1、2、3、4、5、6、8、10、15、30、60、90、180、330和480分钟。将数据绘图，通过内推法测量在8小时时达到其值60％凝胶体积时所需的时间。该时间记录为t60时间，在本发明中用作“吸收速率指数。”实施例1
通过美国专利5,629,277实施例36的方法制备100g超吸收剂聚合物样品，除了使用2,200份HE-TMPTA和8,000份PEG200。该聚合物具有1小时44g/g的AC。将该聚合物浸入10g水合硫酸铝(Al2(SO4)3·14H2O)溶解在250g水中形成的溶液中。将所得胶体被覆盖，在室温中静置23个小时。然后通过在175℃下使空气穿过胶体干燥胶体35分钟。干燥产品在球磨机中研磨并过筛，获得最大粒度小于1,000微米的颗粒。所得产品具有1小时27g/g的AC。使用ARI检测法测定研磨聚合物的ARI。ARI超过10分钟。实施例2一柠檬酶铝溶液的应用
将实施例1中使用的同种原料超吸收剂聚合物(100份)分散在一溶液中，该溶液包含2.88份柠檬酸、7.12份硫酸铝(Al2(SO4)3·18H2O)和300份水。获得的胶体在室温中静置。胶体间隔取样，并且样品在加压对流炉中在165℃下加热干燥2小时。干燥样品在球磨机中研磨并过筛得到最大颗粒粒度小于约1,000微米的颗粒。下表列出不同浸泡时间的ARI值。
作为对照，测量具有类似AC(DRYTECH2035牌超吸收剂聚合物，由Dow Chemical Company获得)的常规聚合物的溶胀率，并作为样品#1在下表中列出。
| 样品 | 浸泡时间(hr) | ARI(min) |
| 1* | 0(DRYTECH2035) | ＜4 |
| 2* | 0(基础聚合物) | 4.5 |
| 3 | 0.25 | 7.4 |
| 4 | 1.0 | 8.2 |
| 5 | 4 | 10 |
| 6 | 8 | 14 |
Claims (20)
1.制备水溶胀性、水不溶性的低吸水速率的聚合物颗粒的方法，该方法包括将多价金属盐溶液和水溶胀性、水不溶性聚合物颗粒相接触，接触条件为使形成的聚合物具有至少5分钟的吸收速率指数。
2.如权利要求1的方法，其中吸收速率指数为至少10分钟。
3.如权利要求1的方法，其中吸收速率指数为至少20分钟。
4.如权利要求1的方法，其中吸收速率指数为至少30分钟。
5.如权利要求1的方法，其中聚合物主要选自：淀粉-丙烯腈接技共聚物的水解产物、淀粉-丙烯酸或淀粉-聚乙烯醇接技共聚物的部分中和产物、乙酸乙烯酯丙烯酸酯共聚物的皂化产物、异丁烯和马来酸酐共聚物的衍生物、丙烯腈羧甲基纤维素的水解产物、丙烯酰胺共聚物的水解产物和聚丙烯酸的部分中和产物。
6.如权利要求1的方法，其中聚合物是聚丙烯酸的部分中和产物。
7.如权利要求1的方法，其中多价金属盐的金属阳离子的价态至少为+3价。
8.如权利要求1的方法，其中的多价金属盐的金属阳离子是铝离子。
9.如权利要求1的方法，其中的多价金属盐的阴离子是柠檬酸根离子、硫酸根离子或它们的混合物。
10.如权利要求1的方法，其中形成的聚合物具有可逆的阳离子交联，并且金属离子基本上均匀地分布在聚合物颗粒中。
11.如权利要求1的方法，其中该盐的阴离子是硫酸根离子。
12.如权利要求1的方法，其中聚合物至少部分从含部分中和的羧酸的单体组合物形成。
13.如权利要求1的方法，其中该盐是柠檬酸铝。
14.如权利要求1的方法，其中阴离子包括柠檬酸根离子和硫酸根离子。
15.如权利要求1的方法，还包括在至少120℃下干燥湿的聚合物颗粒的步骤。
16.如权利要求1的方法，其中的金属盐的金属离子在聚合物中的均匀地分布，该聚合物具有至少5分钟的ARI。
17.一种吸收制品，包含通过权利要求1的方法制备的聚合物。
18.如权利要求17的吸收制品，其是尿布或尿布的一部分，其中水溶胀性、水不溶性聚合物对绒毛的重量比至少为0.3。
19.一种水溶胀性、水不溶性聚合物，其具有至少5分钟的吸收速率指数，该聚合物通过权利要求1的方法制备。
20.一种水溶胀性、水不溶性聚合物，其具有低吸收率，该聚合物与共价交联剂和多价金属盐的金属离子交联，使得聚合物的吸收速率指数至少为5分钟。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/455,927 | 1999-12-07 | ||
| US09/455,927 US6433058B1 (en) | 1999-12-07 | 1999-12-07 | Superabsorbent polymers having a slow rate of absorption |
Publications (2)
| Publication Number | Publication Date |
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| CN1408002A true CN1408002A (zh) | 2003-04-02 |
| CN1178976C CN1178976C (zh) | 2004-12-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB008167168A Expired - Fee Related CN1178976C (zh) | 1999-12-07 | 2000-11-16 | 具有缓慢吸水率的超吸收剂聚合物 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6433058B1 (zh) |
| EP (1) | EP1244729B1 (zh) |
| JP (1) | JP2003516445A (zh) |
| KR (1) | KR20020062654A (zh) |
| CN (1) | CN1178976C (zh) |
| DE (1) | DE60032941T2 (zh) |
| WO (1) | WO2001042339A1 (zh) |
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-
1999
- 1999-12-07 US US09/455,927 patent/US6433058B1/en not_active Expired - Fee Related
-
2000
- 2000-11-16 DE DE60032941T patent/DE60032941T2/de not_active Expired - Fee Related
- 2000-11-16 EP EP00980432A patent/EP1244729B1/en not_active Expired - Lifetime
- 2000-11-16 WO PCT/US2000/031489 patent/WO2001042339A1/en active IP Right Grant
- 2000-11-16 KR KR1020027007298A patent/KR20020062654A/ko not_active Application Discontinuation
- 2000-11-16 CN CNB008167168A patent/CN1178976C/zh not_active Expired - Fee Related
- 2000-11-16 JP JP2001543632A patent/JP2003516445A/ja active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101827616A (zh) * | 2007-10-15 | 2010-09-08 | 金伯利-克拉克环球有限公司 | 具有改进的流体芯吸效应和织物整体性的吸收性复合材料 |
| CN101827616B (zh) * | 2007-10-15 | 2014-04-30 | 金伯利-克拉克环球有限公司 | 吸收性制品 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60032941D1 (de) | 2007-02-22 |
| EP1244729B1 (en) | 2007-01-10 |
| EP1244729A1 (en) | 2002-10-02 |
| US6433058B1 (en) | 2002-08-13 |
| CN1178976C (zh) | 2004-12-08 |
| JP2003516445A (ja) | 2003-05-13 |
| WO2001042339A1 (en) | 2001-06-14 |
| KR20020062654A (ko) | 2002-07-26 |
| DE60032941T2 (de) | 2007-10-31 |
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