CN1122681C - 具有超吸收性材料的基材,其制备方法和用途 - Google Patents

具有超吸收性材料的基材,其制备方法和用途 Download PDF

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CN1122681C
CN1122681C CN96192140A CN96192140A CN1122681C CN 1122681 C CN1122681 C CN 1122681C CN 96192140 A CN96192140 A CN 96192140A CN 96192140 A CN96192140 A CN 96192140A CN 1122681 C CN1122681 C CN 1122681C
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A·P·克罗伊斯比根
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Abstract

本发明涉及提供了超吸收性材料的基材，该基材是通过如下获得的：在催化剂存在下将合适的单体进行聚合反应以获得聚合物溶液，往该聚合物溶液中添加交联剂来获得糊状组合物，随后将组合物施涂到基材上或施涂于基材中并将施涂的组合物干燥和交联，获得具有超吸收性材料的基材。糊状组合物进一步含有其它添加剂。本发明进一步涉及制造这一基材的方法。该基材能够用作电缆的保护材料，用于卫生产品如婴儿尿布、卫生擦脸纸和失禁用产品，用于或用作包装和包装材料以及用于农业基材。本发明还涉及这些产品。

Description

具有超吸收性材料的基材，其制备方法和用途
本发明涉及提供了超吸收性材料的基材，涉及其制备方法，制造超吸收性材料的方法，还涉及基材在不同产品中的应用。
用于各种应用中的超吸收性材料已经存在几十年。这类超吸收性材料能够结合相对于它们本身重量几倍的液体(尤其水)，有时候高达500倍之多。
这类材料的超吸收容量是以溶胀为基础的。该材料是含有大量COOH基的至少部分地交联的聚合物链。通过与水或含水液体接触，氢原子将分离并形成COO-基团。这些带负电荷的羧酸根相互排斥，从而使交联的聚合物形成三维网络，其中水分子被原样捕集。水分子由氢桥保持在超吸收性材料中。材料的(部分)交联对于其有效性来说是必要的，因为“单独的”聚合物链将简单地溶于液体中而不是吸收它。
超吸收性材料以粉末或纤维形式存在。粉末的优点是它们比纤维具有显著更高的吸收容量，归因于它们显著较大的表面积。超吸收性纤维尤为昂贵。
粉末通常被施涂于基材上，进而加工成最终产物。在特殊的情况下粉末也可以直接加工。但是粉末的较大缺点是它在制造用粉末涂敷的基材和在这些基材或疏松粉末物本身的加工中引起扬尘和粉尘污染。粉尘污染不仅非常令人讨厌，而且引起材料的损失和因此引起浪费，这对于与粉末打交道的那些人来说有害于健康。
所以，本发明的目的是提供一种不具有上述缺点的有超吸收性材料的基材。
这可由本发明制备基材来实现，该制备按照以下步骤进行：在催化剂存在下将合适的单体进行聚合反应以获得聚合物溶液，添加交联剂来获得糊状组合物，随后将组合物施涂到基材上或施涂于基材中并将施涂的组合物干燥和交联，获得具有超吸收性材料的基材。
在本发明的另一个实施例中，不是通过聚合反应，而是通过将早已制备的聚合物溶于水或含水溶剂中，然后仅添加交联剂也可以制备聚合物溶液。然后再将所获得的组合物施涂于合适的基材上。
本发明的超吸收性材料优选是发泡的。
制备超吸收性粉末的传统方法包括同时添加合适的单体和交联剂并使这些物质在催化剂存在下进行聚合反应。以这种方法获得的聚合物被胶凝和干燥，然后研磨成粉末。图1示出了根据现有技术制备超吸收粉末的制备步骤的流程图。
然而在根据本发明的方法中，交联步骤不是在聚合反应过程中进行而是在聚合反应之后进行。交联过程刚好在聚合物溶液和交联剂的混合物的施涂之前，过程中或之后发生。具有超吸收特性的材料随后通过干燥来制备。图2给出了示意形式的本发明方法，其中SA意指“超吸收性”。
本发明的方法序列的优点是在将超吸收性材料施涂到基材上或施涂于基材中的过程中或在基材本身的加工中不再存在粉尘污染。附加废物的产生也避免了。
如果需要，其它添加剂也可在添加交联剂之前，同时或之后引入到组合物。此种添加剂的目的是例如，改变组合物的粘度，从而有利于施涂，改进材料对基材的粘结作用，软化超吸收性材料，从而也可改进粘结作用，增加导电性能或在涂敷之后或涂敷过程中使组合物起泡沫。
改变组合物粘度的添加剂可从例如，丙烯酸盐，聚氨酯或其混合物中选择。改变粘度对于将组合物涂敷于基材的特定方法来说可能是必需的。在丝网印刷技术中，在特定情况下希望材料的施涂量不用完或只是慢慢地用完。铺展速度可通过提高粘度来影响。
改进超吸收性材料对基材粘结作用的添加剂是，例如，聚酰胺(PA)，聚乙烯(PE)，乙烯乙酸乙烯酯共聚物(EVA)或其结合物。这些材料可较好地粘结到通常使用的基材上。通过将它们包含到超吸收性材料中，可以改进其粘结性。这些粘结剂也可在涂敷糊状组合物之前作为涂层涂敷在基材上。粘结性也可通过添加增塑剂来提高。合适的增塑剂优选是与超吸收性材料共聚的增塑剂，使得它们不能从聚合物扩散到例如电缆隔层。增塑剂确保了所得到的超吸收性材料不会变得太硬，从而轻易地与基材分开。
为了改进材料或最终产品的导电性，例如可在其中混入炭黑(碳)或其它导电材料。
合适的发泡剂是例如Servo Amfolyt JA 140TM，NekanilTM或其结合物。以泡沫形式存在的吸收性材料的优点是表面被显著地增大。从而溶胀能力也因水分子更容易接近聚合物网络的羧基且这些羧基更快地水解而增大。
原则上，任何具有合适溶胀能力的聚合物都可以按照上述方式加工成可以涂敷到基材上的糊状组合物。然而特别推荐的是聚丙烯酸盐、聚酰胺和纤维素状聚合物或它们的混合物，优选聚丙烯酸的钠盐或铵盐以及钠-或铵中和的丙烯酰胺。合适的交联剂根据聚合物来添加。本领域内熟练人员使用其普通专业知识能够选择合适的交联剂。另外合适的交联剂优选含有两种官能基团，它们能够在热激发之后在短时间内与羧酸根或碳酸官能基团反应。
原则上，可以用任何需要的材料作基材，只要超吸收性材料粘结到上面是可能的。基材的例子是，例如，织物，无纺织物，纸，膜，例如塑料或金属的膜，带材，例如铝的带材，或石油膏状(petrojelly-like)填充化合物。除扁平基材外，也可以使用单纤维或纤维状基材。
本发明进一步涉及具有超吸收性材料涂层的基材的制备方法，它包括在催化剂存在的情况下将合适的单体进行聚合，将交联剂添加到其中以获得糊状组合物，随后将组合物涂敷于基材并将涂敷的组合物交联和干燥来获得具有超吸收性材料的基材。
另外，还可以在糊状组合物中加入发泡剂，随后将该组合物施涂于基材上并在组合物施涂过程中或之后使其发泡。
根据另一个实施方案，这里的聚合物溶液也可通过将聚合物链溶于水或含水溶剂中来制备，而不是通过聚合反应来制备。
将糊状组合物涂敷在基材上有不同的可能性。全表面涂敷将得到十分紧闭的层。一般情况，紧闭层具有较低的吸收能力。然而，对于具体的应用，这类产物是需要的。除了表面涂敷以外，糊状材料也可以通过刷涂、辊涂和类似方法来涂敷。
施涂的第三种方法是浸涂。通过将基材与糊状组合物一起通过双辊来进行浸涂。取决于基材的可润湿性，将得到紧闭层或组合物的局部集中。当使用疏水性基材时特别容易发生后一情况。
施涂糊状组合物的第三种可能性是通过丝网印刷技术。该材料通过模板施涂到基材上。模板中开孔的形式、分布和尺寸决定了基材上所得到的图案。
溶胀材料的性能取决于几个因素。因此，在温度(施涂和干燥过程中)和干燥时间之间的比以及组合物的粘度对于粘结于基材和溶胀能力都是重要的。交联剂通常在较高温度下和在含水环境中显示活性。在理想的情况下，交联应该在150-200℃，优选约175℃下，和在水还没有蒸发的压力下进行。但是，在实际中通常选择常压和约175℃的温度。根据本发明已经发现，在175℃下1-3分钟的干燥时间将获得具有良好性能的吸收性材料。然而，时间和温度将根据丙烯酸盐和交联剂的量之比和混合物的粘度来变化。
还发现在第一次干燥周期中必须尽可能地阻止交联剂的蒸发。这可通过最低可能的空气循环的操作来实现。
还有，超吸收性材料被涂敷的形式对于吸收性能也是重要的。对于粉末，在实际中已经发现直径在约100和200μ之间的颗粒具有最佳吸收性能。因此根据本发明，组合物优选以直径在约100和200μ之间的离散、基本上半球形小岛状物的形式进行涂敷。然而，取决于涂敷方法，小岛状物也可以具有更大或更小的直径，例如在10-1000μ之间，优选在50-500μ。
小岛状物在基材上的分布能够是无规的或符合所规定的图案。还有，可以在规定的位置于基材上设置许多具有不同直径的小岛状物，以局部提高吸收能力。这在例如该产物用于卫生产品如婴儿尿布和卫生擦脸纸时是重要的。熟练人员可通过简单的试验来确定何种图案对于具体应用最合适。
基材的吸收能力取决于所使用的超吸收性材料的量。在目前的情况下，30g/m2早已能够提供足够的吸收性。从这一给定的信息开始，能够计算每一个具有200μ的小岛状物必须使用多少材料，和在小岛状物之间的距离必须是多少，例如由下面计算：
-小岛状物的体积是：
2/3πr3＝2/3*3.14*(0.002)3＝1.7.10-8dm3
-比重设定在：
1kg/m3
-那么一个半球的重量是
1.7.10-5g
-30g/m3的重量则求得：
1.75.106个半球
-一个半球的直径表面积是：
3.14.10-8m2
-全部点的总表面积是：
0.0553m2
-点之间的距离为：
8.10-6-2.10-6＝600μ
所要使用的材料的量将由模板中开孔的形式和尺寸决定。在半球小岛状物的情况下，该材料优选以圆柱形状施涂，然后通过缓慢流出呈现理想的半球形形状。
现已发现，用CP30模板施涂的超吸收性材料在自来水中具有约1mm每10g/m2的溶胀能力。吸收性材料的全表面涂敷层例如具有约0.2mm每10g/m2的溶胀能力(在具有平均导电性的自来水中)。
具有本发明的超吸收性材料的基材原则上能够用于其中也可以使用超吸收性粉末和纤维及提供了超吸收性粉末和纤维的基材的任何领域。
特别有利的应用的一个例子是基材在电缆工业上用作保护材料。保护材料用于输电电缆和数据电缆并具有许多功能。它用来包裹电缆的导电部分并形成与环境隔离的阻隔层(所谓的埋藏功能)。还有，保护材料用于将电缆的各组件固定在一起(所谓的紧固作用)。此外，电缆的确定组件必须相互分离(分离作用)。保护材料也可用于这一目的。重要的第四个和最后的功能是所谓的阻水作用，它必须阻止水沿横向和纵向渗透到核心部分。本发明的保护材料特别适合于后一功能。以前的涂敷了超吸收性粉末的石油膏状化合物或基材已用于这一目的。石油膏的加工远不尽人意，并在电缆的制造和连接过程中引起石油膏显著地玷污、渗漏。粉末状超吸收性材料的缺点早已描述。本发明的基材特别适合在电缆中用作阻水材料。
超吸收性材料也大量用于卫生产品中，如婴儿尿布、卫生擦脸纸和失禁用产品。在这类产品的制造和使用过程中，通过使用本发明的基材避免了迄今使用粉末的缺点。
本发明基材的另一应用是农业领域，借助于该材料的超吸收性能，在农业基材中能够提供水分调节条件。
该材料也可以用于包装工业。在必须绝对无水贮存的产品中，通常还装入了硅胶袋。本发明得以使产品直接包装在提供有超吸收性材料的基材中。
在本申请中，使用下面的术语。其中“聚合物溶液”应该理解为在加入交联剂之前含有聚合物的液相。“组合物”应理解为在加入交联剂之后，在其施涂在基材上之前以及之后，任意性地在交联之后但仍在干燥之前的聚合物溶液。“吸收性材料”表示交联和干燥之后的组合物。
下面以实施例为基础来进一步说明本发明，它仅仅是为了说明给出的，不想以任何方式限定本发明。
实施例
根据本发明的超吸收性材料是从两组分制备的。组分1由预交联的聚(甲基)丙烯酸(能够部分地以盐形式存在)的水溶液组成。在这种情况下，反离子是钠，钾或铵。还有，该溶液任意性地含有作为共聚单体的丙烯酰胺。但是，含有羧基的单体((甲基)丙烯酸)总是过量存在。
第二种组分是实际上反应活性的交联剂，它优选含有两种官能基团，它们能够在热激发之后在短时间内与羧酸根或碳酸官能基团反应。
刚好在混合物涂敷在基材上之前，组分2以相对于组分1总量为0.1-5wt％，优选0.5-3wt％的量加入到组分1(95-99.9wt％)中并与其均匀混合。
由丝网印刷技术将混合物施涂于合适的基材上，其中丝网具有500-1000，优选745μ的网眼宽度，为的是获得直径为100-500，优选250μ的小岛状物的规则图案，其筛孔面积为5-20，优选13％。在印刷之后，有混合物在上面的基材被干燥，为的是引起交联反应。如此获得的产物在9g/m2(干燥)的施用率下具有1mm的溶胀能力。
本发明提供新型的基材，该基材上提供了超吸收性材料并在制造和加工过程中不显示涂敷了通常使用的超吸收性粉末的基材的缺点。还提供一种新方法来制造该基材。该基材能够采取不同形式并可用于许多应用。

Claims (29)

1、提供了超吸收性材料的基材，所述超吸收性材料呈许多直径为10-1000μ的离散、基本上为半球形小岛状物形式，所述基材可通过如下获得：在催化剂存在下将合适的单体进行聚合反应或将已形成的聚合物溶于水或水溶液中以获得聚合物溶液，向聚合物溶液中添加交联剂来获得糊状组合物，随后将该组合物通过丝网印刷技术施涂到基材上，并使施涂的组合物干燥和交联。
2、根据权利要求1所要求的基材，其特征在于小岛状物的直径为50-500μ。
3、根据权利要求1或2所要求的基材，可通过如下获得：在催化剂存在下将合适的单体进行聚合反应或将已形成的聚合物溶于水或水溶液中以获得聚合物溶液，向聚合物溶液中添加交联剂来获得糊状组合物，向糊状组合物中添加发泡剂，随后将该组合物通过丝网印刷技术施涂于基材上并在组合物施涂过程中或之后使其发泡，干燥和交联。
4、根据权利要求3所要求的基材，其特征在于该超吸收性材料是发泡的。
5、根据权利要求2所要求的基材，其特征在于小岛状物的直径为100-200μ。
6、根据权利要求1或4所要求的基材，其特征在于糊状组合物通过模板施涂。
7、根据权利要求6所要求的基材，其特征在于模板中的开孔决定了该超吸收性材料在基材上所得到的图案。
8、根据权利要求1或4所要求的基材，其特征在于糊状组合物进一步包含其它添加剂，所述添加剂选自：改变组合物粘度用的试剂，改进超吸收性材料对基材的粘结作用的试剂，使超吸收性材料软化的试剂，使组合物导电的试剂。
9、根据权利要求8所要求的基材，其特征在于改变组合物粘度用的试剂选自丙烯酸盐，聚氨酯或它们的混合物。
10、根据权利要求8所要求的基材，其特征在于改进超吸收性材料对基材的粘结作用的试剂选自聚酰胺(PA)，聚乙烯(PE)，乙烯乙酸乙烯酯共聚物(EVA)或它们的混合物。
11、根据权利要求8所要求的基材，其特征在于使超吸收性材料软化的试剂是与该超吸收性材料共聚合的增塑剂。
12、根据权利要求1或4所要求的基材，其特征在于交联剂含有两种官能基团，它们能够在热激发之后在短时间内与羧酸根或碳酸官能基团反应。
13、根据权利要求8所要求的基材，其特征在于组合物含有炭黑(碳)以使组合物导电。
14、根据权利要求1所要求的基材，其特征在于超吸收性材料是聚丙烯酸盐、聚酰胺、纤维素状聚合物或它们的混合物。
15、根据权利要求14所要求的基材，其特征在于聚丙烯酸盐为钠盐或铵盐。
16、根据权利要求1所要求的基材，其特征在于基材是织物，无纺织物，纸，膜，铝带，纤维或石油膏状填充化合物。
17、根据权利要求1或4所要求的基材，其特征在于糊状组合物包含0.1-5wt％的交联剂。
18、根据权利要求17所要求的基材，其特征在于糊状组合物包含0.5-3wt％的交联剂。
19、制造提供了超吸收性材料的基材的方法，其特征在于：在催化剂存在下将合适的单体进行聚合反应或将已形成的聚合物溶于水或含水溶剂中，往其中添加交联剂来获得糊状组合物，随后将该组合物施涂到基材上以形成直径为10-1000μ的离散、基本上为半球形小岛状物并将施涂的组合物干燥和交联。
20、根据权利要求19所要求的制造基材的方法，其特征在于：往糊状组合物中加入发泡剂，随后将该组合物施涂于基材上并在组合物施涂过程中或之后使其发泡。
21、根据权利要求19或20所要求的方法，其特征在于借助于丝网印刷技术将糊状组合物施涂在基材上。
22、根据权利要求21所要求的方法，其特征在于丝网印刷技术使用了具有一定形式、分布和尺寸的开孔的模板，以使组合物以离散的小岛状物施涂在基材上。
23、根据权利要求22所要求的方法，其特征在于模板开孔的形状经选择后使所得到的小岛状物基本上是半球形。
24、根据权利要求22或23所要求的方法，其特征在于半球形小岛状物的直径在10-1000μ之间。
25、根据权利要求1-18中任何一项所要求的基材用作电缆中的保护材料。
26、根据权利要求1-18中任何一项所要求的基材用于卫生产品。
27、根据权利要求26所要求的卫生产品为婴儿尿布、卫生擦脸纸和失禁用产品。
28、根据权利要求1-18中任何一项所要求的基材用于或用作包装和包装材料。
29、根据权利要求1-18中任何一项所要求的基材用于农业基材。
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US20030153228A1 (en) 2003-08-14
AU4678996A (en) 1996-08-14
CN1176650A (zh) 1998-03-18
BR9606835A (pt) 1997-12-30
DE69634723T2 (de) 2006-02-23
ES2242964T3 (es) 2005-11-16
HUP9801765A3 (en) 1999-05-28
FI973018A0 (fi) 1997-07-16
JPH10513123A (ja) 1998-12-15
FI973018A (fi) 1997-09-18
KR100423661B1 (ko) 2004-06-18
PL321462A1 (en) 1997-12-08
CA2211111A1 (en) 1996-08-01
PL185536B1 (pl) 2003-05-30
HUP9801765A2 (hu) 1998-11-30
JP3917178B2 (ja) 2007-05-23
KR19980701584A (ko) 1998-05-15
US6946189B2 (en) 2005-09-20
ATE295389T1 (de) 2005-05-15
EP0813566A1 (en) 1997-12-29
EP0813566B1 (en) 2005-05-11
MX9705500A (es) 1997-10-31
US5998312A (en) 1999-12-07

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