CN104169483A - 可分散的无纺物 - Google Patents

可分散的无纺物 Download PDF

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CN104169483A
CN104169483A CN201380014453.3A CN201380014453A CN104169483A CN 104169483 A CN104169483 A CN 104169483A CN 201380014453 A CN201380014453 A CN 201380014453A CN 104169483 A CN104169483 A CN 104169483A
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woven fleece
emulsion polymer
aqueous medium
base material
weight
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P·奈德威克
M·B·嫩
K·S·赖斯
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Rohm and Haas Co
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Abstract

本发明提供了一种用来在水性介质中形成可分散的无纺物基材的方法，该方法包括：a)形成一种水性无纺物粘合剂，其包含选择的乳液聚合物，其中所述聚合物已经被含三取代的N-原子的化合物改性，所述化合物的pKb值为4-7；b)使无纺物基材与所述水性无纺物粘合剂接触；c)将所述经过接触的无纺物加热到120℃-220℃的温度；以及d)使所述经过接触和加热的无纺物浸泡在最终的pH值<5的水性介质中。本发明还提供了一种通过上述方法形成的在水性介质中的可分散无纺物基材，以及一种提供分散在水性介质中的无纺物的方法。

Description

可分散的无纺物
技术领域
本发明涉及可分散的无纺物基材的形成方法。更具体而言，本发明涉及在水性介质中形成可分散的无纺物基材的方法，所述方法包括：a)形成一种水性无纺物粘合剂，其包含乳液聚合物，所述乳液聚合物包含以下组分作为共聚单元：以所述乳液聚合物的重量为基准计，10-30重量％的单烯键式不饱和单酸单体；其中所述乳液聚合物的Tg为-20℃到30℃；其中所述聚合物已经被含三取代的N-原子的化合物改性，所述化合物具有4-7的pKb；b)使无纺物(nonwoven)基材与所述水性无纺物粘合剂接触；c)将所述经过接触的无纺物加热到120℃-220℃的温度；以及d)使所述经过接触和加热的无纺物浸泡在最终的pH值<5的水性介质中，以在水性介质中提供可分散的无纺物。本发明还提供了一种通过上述方法形成的在水性介质中的可分散无纺物基材，以及一种在水性介质中提供分散的无纺物的方法。
背景技术
美国专利第5,451,432号揭示了一种使用不含甲醛的水性(water-borne)组合物处理挠性多孔基材的方法，所述组合物包含某些共聚的烯键式不饱和二羧酸或其衍生物，其中粘合剂用固定碱(fixed base)部分地中和。人们希望改进经过处理的无纺物基材在实现分散性与在该经过处理的无纺物基材分散之前保持所需湿强度水平之间的平衡。我们发现本发明提供了所需的性质。
发明内容
在本发明的第一个方面，提供一种用来在水性介质中形成可分散的无纺物基材的方法，该方法包括：a)形成一种水性无纺物粘合剂，其包含乳液聚合物，所述乳液聚合物包含以下组分作为共聚单元：以所述乳液聚合物的重量为基准计，10-30重量％的单烯键式不饱和单酸单体；其中所述乳液聚合物的Tg为-20℃到30℃；其中所述聚合物已经被含三取代的N-原子的化合物改性，所述化合物具有4-7的pKb；b)使无纺物基材与所述水性无纺物粘合剂接触；c)将所述经过接触的无纺物加热到120℃-220℃的温度；以及d)使所述经过接触和加热的无纺物浸泡在最终的pH值<5的水性介质中，以在水性介质中提供可分散的无纺物。
在本发明的第二个方面，提供一种用来在水性介质中提供分散的无纺物的方法，该方法包括将权利要求1或2所述的可分散的无纺物浸泡在过量的pH值>6.5的水性介质中。
在本发明的第三个方面，提供了一种由本发明第一方面所述的方法形成的在水中介质中的可分散的无纺物。
在本发明的用于在水性介质中形成可分散的无纺物基材的方法中，术语"水性"表示其中连续相为水，或者主要包含水但是还包含水混溶性溶剂的混合物的组合物。在本文中，术语“可分散的”表示在合适的条件下，能够造成无纺物基材崩解形成以下情况中的至少一种：较小的碎片、纤维的聚集体、单独的纤维，及其混合物。
在本文中，术语"无纺物"表示一种织物状纤维组织形式，它不是织造或编织的材料，通常为片或网形式。无纺物基材包括：纸张；无纺织物；毡材和垫；或者纤维的其它组织形式。无纺物基材可包括：纤维素纤维，例如棉花、人造丝和木质纸浆；合成纤维，例如聚酯、玻璃和尼龙；双组分纤维；及其混合物。优选主要量的纤维能够参与氢键结合。更优选无纺物基材包含主要量的纤维素纤维。无纺物基材可通过本领域已知的方法形成，例如湿法成网法、气流成网法、纺粘成网法和水力缠结(hydroentangling)成网法。通常对纤维进行选择，使得它们的长度和组成对经过处理的无纺物基材的最终分散性没有不利影响。
在本发明的用于在水性介质中形成可分散的无纺物基材的方法中，形成水性无纺物粘合剂，所述粘合剂包含乳液聚合物，所述乳液聚合物包含以下组分作为共聚单元：以所述乳液聚合物的重量为基准计，10-30重量％的单烯键式不饱和单酸单体，其中所述乳液聚合物的Tg(由福克斯公式(Fox equation)计算得到的玻璃化转变温度)为-20℃到30℃；其中所述聚合物已经被含三取代的N-原子的化合物改性，该化合物的pKb为4-7。在本文中，术语"粘合剂"指包含聚合物的组合物。
所述水性无纺物粘合剂包含乳液聚合物；也即是说，通过烯键式不饱和单体在水性乳液聚合法中进行加聚反应制得的聚合物。所述乳液聚合物可以是可固化的，也就是说，其可能在施加能量(最通常是加热)的情况下发生一定程度的化学变化过程(例如形成共价键)。所述乳液聚合物包含以下组分作为共聚单元：以所述乳液聚合物的重量为基准计，10-30重量％、优选12-25重量％的单烯健式不饱和单酸单体。单酸单体包括例如羧酸单体，例如丙烯酸、甲基丙烯酸、巴豆酸、衣康酸单甲酯、富马酸单甲酯、富马酸单丁酯。优选丙烯酸。
以所述乳液聚合物的重量为基准计，所述乳液聚合物任选地包含以下组分作为共聚单元：0.01-0.75重量％、优选0.2-0.6重量％的单烯键式不饱和二羧酸单体，所述二羧酸单体是例如衣康酸、富马酸、马来酸，包括它们的酸酐、盐和混合物。优选的是衣康酸。
所述乳液聚合物除了包含共聚的单酸和任选的二羧酸单体以外，还包含至少一种其他共聚的烯键式不饱和单体，例如(甲基)丙烯酸酯单体，包括(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、脲基官能(甲基)丙烯酸酯和乙酰乙酸酯、(甲基)丙烯酸的乙酰胺或氰基乙酸酯；苯乙烯或取代的苯乙烯；乙烯基甲苯；丁二烯；乙酸乙烯酯或其它乙烯基酯；乙烯基单体，例如氯乙烯、偏二氯乙烯；和(甲基)丙烯腈。优选丙烯酸乙酯。在本文中，在另一个术语，例如(甲基)丙烯酸酯或(甲基)丙烯酰胺的前部使用术语"(甲基)"分别表示丙烯酸酯和甲基丙烯酸酯或丙烯酰胺和甲基丙烯酰胺。较佳的是，本发明不使用那些在聚合或者随后的工艺中会产生甲醛的单体，例如N-烷醇基(alkylol)(甲基)丙烯酰胺。选择所述至少一种其他共聚的烯键式不饱和单体，使得所述乳液聚合物的Tg在所需的范围内。
在某些实施方式中，以乳液聚合物的重量为基准计，所述乳液聚合物包含0-2重量％或0-0.1重量％的共聚的多烯键式不饱和单体，但是其含量必须加以选择，从而不会造成用包含该乳液聚合物的水性无纺物粘合剂处理过的无纺物基材的分散性明显下降。多烯键式不饱和单体包括例如(甲基)丙烯酸烯丙酯、邻苯二甲酸二烯丙酯、二(甲基)丙烯酸1,4-丁二醇酯、二(甲基)丙烯酸1,2-乙二醇酯、二(甲基)丙烯酸1,6-己二醇酯和二乙烯基苯。
还考虑可以使用具有不同组成的乳液聚合物的混合物。对于两种或更多种乳液聚合物的混合物,共聚的单酸和任选的二羧酸的含量和所述Tg应当由乳液聚合物的总组成决定，而不考虑其中乳液聚合物的数量或单独的组成。
用来制备乳液聚合物的乳液聚合技术是本领域众所周知的，例如参见美国专利第4,325,856号；第4,654,397号；以及第4,814,373号。可以使用常规的表面活性剂，例如阴离子和/或非离子乳化剂，如碱金属或铵的烷基硫酸盐、烷基磺酸、脂肪酸、可共聚表面活性剂，以及乙氧基化的烷基酚。优选的是阴离子乳化剂。以全部单体的重量计，表面活性剂的用量通常为0.1-6重量％。可以使用热引发法或氧化还原引发法。可以采用常规自由基引发剂，例如过氧化氢、叔丁基过氧化氢或叔戊基过氧化氢以及过硫酸铵和/或碱金属过硫酸盐，以全部单体的重量为基准计，所述自由基引发剂的含量通常为0.01-3.0重量％。使用相同引发剂和合适还原剂(例如甲醛合次硫酸氢钠、连二亚硫酸钠、异抗环血酸、硫酸羟胺和亚硫酸氢钠)的组合的氧化还原体系可以类似的含量使用，任选地与金属离子如铁和铜组合，任选地还包含金属的络合剂。可以使用硫醇之类的链转移剂，以降低聚合物的分子量。单体混合物可以以纯的形式加入，或者以水乳液的形式加入。所述单体混合物可以一次性加入或在反应过程中使用均匀或变化的组成多次加入或者连续加入。可以在任何阶段之前、之中或之后加入附加成分，例如自由基引发剂、氧化剂、还原剂、链转移剂、中和剂、表面活性剂和分散剂。例如，可使用如美国专利第4,384,056号和第4,539,361号所揭示的产生多峰粒度分布的方法。
在本发明的另一个实施方式中，所述乳液聚合物可以通过多段乳液聚合法制备，其中至少两个组成不同的段(stage)以顺次的方式聚合。该方法通常会导致形成至少两种互不相容的聚合物组合物，从而使得聚合物颗粒中形成至少两个相。该颗粒由具有各种几何结构的两个或更多个相组成，例如为芯/壳或芯/鞘颗粒，壳相不完全包封芯的芯/壳颗粒，具有多个芯的芯/壳颗粒，以及互穿网络颗粒。多段乳液聚合物的各段可以包含选自上文关于乳液聚合物所述的单体、表面活性剂、链转移剂等。对于多段乳液聚合物，应该根据乳液聚合物的总组成确定共聚的单酸和二羧酸的含量和Tg，而不考虑其中的段或相的数目。用来制备这种多级乳液聚合物的聚合技术是本领域众所周知的，例如参见美国专利第4,325,856号；第4,654,397号；以及第4,814,373号。
所述乳液聚合物的计算的玻璃化转变温度("Tg")为-20℃至30℃。聚合物的Tg可使用福克斯公式(T.G.Fox,Bull.Am.Physics Soc.,卷1(3),第123页(1956))计算。也即是说,例如，用下式计算单体M1和M2的共聚物的Tg,
1/Tg(计算)＝w(M1)/Tg(M1)+w(M2)/Tg(M2)，其中
Tg(计算)是计算的共聚物的玻璃化转变温度
w(M1)是共聚物中单体M1的重量分数
w(M2)是共聚物中单体M2的重量分数
Tg(M1)是M1的均聚物的玻璃化转变温度
Tg(M2)是M2的均聚物的玻璃化转变温度，
所有温度的单位都是°K。
均聚物的玻璃化转变温度可以在例如J.Brandrup和E.H.Immergut编辑的、Interscience Publishers(国际科学出版社)出版的《聚合物手册(PolymerHandbook)》中找到。在任何情况中，以下均聚物的Tg用于以下聚酸的福克斯公式计算：聚(甲基丙烯酸)Tg＝185℃；聚(丙烯酸)Tg＝106℃；聚(衣康酸)Tg＝154℃；和聚(马来酸酐)Tg＝154℃。
使用纽约霍尔兹维尔的布鲁克哈文仪器公司(Brookhaven InstrumentCorp.,Holtsville,NY)提供的布鲁克哈文BI-90型号的粒度计(Brookhaven ModelBI-90Particle Sizer)测定，所述乳液聚合物颗粒的平均粒径通常为30-500纳米，优选为200-400纳米。
本发明的水性无纺物粘合剂优选是无甲醛组合物。“无甲醛组合物”是指所述组合物基本不含甲醛，也不会因为干燥和/或固化而显著释放甲醛。为了使所述组合物的甲醛含量最小化，优选在制备本发明的乳液聚合物的时候，使用聚合助剂，例如引发剂、还原剂、链转移剂、杀生物剂、表面活性剂等,其本身不含甲醛,在聚合过程中不会产生甲醛,在处理基材的过程中不会产生或放出甲醛。当水性组合物中可以含有少量甲醛或者因为客观原因必须使用会产生或者放出甲醛的助剂的时候，也可使用这样的组成。
用含三取代的N-原子的化合物对乳液聚合物进行改性，所述化合物的pKb为4-7。该pKb值是在20℃通过常规方法测得的。也可考虑使用包含三取代的N-原子的聚合物材料，所述化合物的pKb为4-7。所述化合物包括，例如单乙醇胺、二乙醇胺和三乙醇胺、聚乙烯基吡咯烷酮、阿拉伯胶(acacia)、酰胺化果胶、壳聚糖、明胶、阿拉伯树胶(gum arabic)。优选的化合物是单乙醇胺、二乙醇胺和三乙醇胺。所述改性可以在后续的接触无纺物基材的步骤之前、过程中或之后实施，但应在对经过接触的无纺物进行加热的步骤之前实施。用含三取代的N-原子的化合物(该化合物的pKb为4-7)进行改性的程度通常在以下范围内：1-120％，优选25-110％，更优选75-105％，最优选95-105％，乳液聚合物中酸基团的中和以当量计。
除了乳液聚合物外，本发明的水性无纺物粘合剂还可以包含常规处理组分，例如乳化剂、颜料、填料或增量剂、抗迁移助剂、固化剂、聚结剂、表面活性剂、杀生物剂、增塑剂、有机硅烷、消泡剂、腐蚀抑制剂、着色剂、蜡、其它聚合物，以及抗氧化剂。
在本发明的用于在水性介质中形成可分散的无纺物基材的方法中，使所述无纺物基材与水性无纺物粘合剂接触。通常而言，无纺物粘合剂与经过接触的无纺物基材的无纺物粘合剂的比例(以干重计，记作百分数形式，也称作增重％)为1-25％，优选1-10％，这根据无纺物基材的强度以及所需的最终用途来选择。使用常规的施涂技术使无纺物基材与水性无纺物粘合剂接触，例如空气喷涂或无气喷涂、刮涂、饱和浸渍、辊涂、幕涂、凹版印刷等。无纺物基材可与水性无纺物粘合剂接触，从而在一个或两个表面上或附近提供粘合剂，或者使粘合剂均匀或不均匀地分布在整个结构上。当需要图案化分布时，还可以考虑将水性无纺物粘合剂以非均匀的方式施涂。
在本发明的用于在水性介质中形成可分散的无纺物基材的方法中，将所述经过水性无纺物粘合剂接触的无纺物基材加热至120-220℃，优选140-180℃的温度，加热最够的时间以实现可接受的干燥水平和/或固化水平。如果需要，所述干燥和固化可以在两个或更多个独立的步骤中进行。例如，所述组合物可以首先在一定的温度下加热一定的时间，所述温度和时间足以使得组合物基本干燥，但是不足以使所述组合物充分固化，然后在较高的温度加热第二时间和/或加热较长的时间，以实现固化。该过程被称为“B-分段法(B-staging)”，可用来提供例如成卷形式的经过粘合剂处理的无纺织物,其可以在之后的阶段固化,在进行固化过程的同时通过成形或模塑而形成特定的构型，或者不进行所述成形或模塑。
在本发明的用于在水性介质中形成可分散的无纺物基材的方法中，将所述经过接触和加热的无纺物基材浸泡在最终pH值<5，优选最终pH值为3.0-4.99的水性介质中，以在水性介质中提供分散的无纺物。在本文中，术语“最终pH值”表示所述经过接触和加热的无纺物所浸泡在其中的水性介质的pH值(在20℃测量)。如果所选择的无纺物和水性介质及它们的用量没有达到最终pH值<5的话，则在浸泡步骤之前、过程中或之后通过添加酸性材料(例如柠檬酸)将pH值调节至所需的范围。我们认为，所需的水性介质的pH值有利于经过加热和处理的无纺物达到有利的湿强度水平，并且还有利于某些组合物达到合适的pH值，所述组合物是例如擦拭溶液和乳液，在所述组合物中可能存储有经过加热和处理的无纺物。通常，所述水性介质的重量是所述经过接触和加热的无纺物基材的重量的0.1-10倍，优选0.5-5倍。
在本发明的用于在水性介质中提供分散的无纺物的方法中，将本发明的可分散的无纺物浸泡在过量的pH值>6.5、优选最终pH值>6.5、优选最终pH值为6.8-10.0的水性介质中。在本文中，术语“过量的水性介质”表示水性介质的重量大于所述经过接触和加热的无纺物的重量。在指定的pH值(在20℃下测定)下，所述经过加热和处理的无纺物的湿强度被充分降低，从而有利于崩解形成以下情况中的至少一种：较小的碎片、纤维的聚集体、单独的纤维，及其混合物。当然，可施加的任意机械力都将有助于这一分散过程，例如，如果将经过处理的无纺物沉积在过量的pH值>6.5的水中并施加剪切力(例如在洗手间冲洗作用下)。
本发明所述的分散在水性介质中的无纺物是通过本发明所述的用于可分散在水性介质中的无纺物的方法形成的。
所用的缩写
AA＝丙烯酸
EA＝丙烯酸乙酯
IA＝衣康酸
MMA＝甲基丙烯酸甲酯
Sty＝苯乙烯
DI水＝去离子水
测试方法：
使用的乳液聚合物：(以重量计的组合物)
乳液聚合物A＝p(84EA/1Sty/15AA)
乳液聚合物B＝p(84EA/1Sty/14.5AA/0.5IA)
乳液聚合物C＝p(59EA/1Sty/20MMA/19.5AA/0.5IA)
实施例1-6和比较例A-B。可分散的无纺物的形成和评估
制备以下水性无纺物粘合剂。加入的顺序为水、胺，对其进行混合直至溶解；在搅拌下加入乳液聚合物。
对于各样品，称量两份沃特曼(Whatman)4过滤纸。在35psi压力下、速度设定为5的条件下使用伯奇兄弟公司轧染机(Birch Brothers Padder)(伯奇兄弟南方公司(Birch Brothers Southern,Inc.))浸渍并填塞沃特曼4过滤纸；在150℃下加热3分钟。对经过处理的纸片重新称重，使用以下公式计算增重：
增重％＝(最终重量–起始重量)*100％/(最终重量)
表1.1：水性无纺物粘合剂的形成
可分散的无纺物的评估
将乳液聚合物A涂覆在沃特曼4过滤纸上。在浸泡在50克市售的水性乳液A以及单独的0.1重量％TRITONTMX-100(陶氏化学公司(The Dow ChemicalCompany)的产品)自来水(已用110ppm碳酸氢钠将其pH值调至等于7)中30分钟后，在9个1英寸×4英寸条状物CD上测量拉伸强度(9次测量的平均值)。
表1.2在不同pH值条件下无纺物的拉伸强度
与未改性的乳液聚合物(比较例A)相比，实施例1-3(本发明的可分散的无纺物基材)在pH值<5的条件下具有增强的拉伸强度，在pH值>6.5的条件下拉伸强度下降；而未改性的乳液聚合物(比较例A)在所述特定的pH范围内在拉伸强度方面没有明显的变化，这表明本发明的可分散的无纺物基材具有可分散性。
表1.3在不同pH值条件下无纺物的拉伸强度
与未改性的乳液聚合物(比较例B)相比，实施例4-6(本发明的可分散的无纺物基材)在pH值<5的条件下具有增强的拉伸强度，在pH值>6.5的条件下拉伸强度下降；而未改性的乳液聚合物(比较例B)在所述特定的pH范围内在拉伸强度方面没有明显的变化，这表明本发明的可分散的无纺物基材具有可分散性。

Claims (4)

1.一种用来在水性介质中形成可分散的无纺物基材的方法，该方法包括：
a)形成一种水性无纺物粘合剂，其包含乳液聚合物，所述乳液聚合物包含以下组分作为共聚单元：
以所述乳液聚合物的重量为基准计，10-30重量％的单烯键式不饱和单酸单体，其中所述乳液聚合物的Tg为-20℃到30℃；其中所述聚合物已经被含三取代的N-原子的化合物改性，所述化合物的pKb值为4-7；
b)使无纺物基材与所述水性无纺物粘合剂接触；
c)将所述经过接触的无纺物加热到120℃-220℃的温度；以及
d)使所述经过接触和加热的无纺物浸泡在最终的pH值<5的水性介质中，以在水性介质中提供可分散的无纺物。
2.如权利要求1所述的用来在水性介质中形成可分散的无纺物基材的方法，其特征在于，以所述乳液聚合物的重量为基准计，所述乳液聚合物还包含作为共聚单元的0.01-0.75重量％的单烯健式不饱和二羧酸单体。
3.一种用来在水性介质中提供分散的无纺物的方法，该方法包括将权利要求1或2所述的可分散的无纺物浸泡在过量的pH值>6.5的水性介质中。
4.一种由如权利要求1或2所述的方法形成的在水中介质中的可分散的无纺物。
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