CN100594944C - 软表面涂层组合物、修饰软表面的方法和包含载金属纳米颗粒的吸收制品 - Google Patents
软表面涂层组合物、修饰软表面的方法和包含载金属纳米颗粒的吸收制品 Download PDFInfo
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Abstract
本发明涉及一种软表面涂层组合物、采用该组合物修饰软表面的方法、和包含载金属纳米颗粒的吸收制品。所述组合物包含:1)含有(a)具有表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料,其中,所述金属负载在所述纳米颗粒的表面上;2)载体介质;3)表面活性剂;和4)一种或多种辅助成分。
Description
相关申请的交叉引用
本申请要求2003年10月30日提交的美国临时申请S/N 60/515,758的优先权。
发明领域
本发明涉及包含功能化纳米颗粒、尤其是载金属纳米粘土复合材料的软表面涂层和吸收制品。
发明背景
几百年来,已知金属银是能够杀死许多不同微生物的试剂。在现代抗生素出现以前,通常用它来纯化饮用溶液或给患者施用。即使在发现青霉素及其后续产物之后,胶体银溶液也常常用于耐受抗生素的顽固细菌的情况。
今天,胶体银溶液可以商品形式获得。但是,它们常常不稳定且货架期短。这是因为银颗粒倾向于聚集并形成聚簇,大到它们不再能够悬浮在溶液中。由于这个原因,需要将不需要的胶凝剂加入到溶液中,通过防止颗粒聚集而保证银颗粒悬浮。市售溶液的另一个问题是,银通常大多以银离子形式存在。这对于医疗应用产生大问题,银离子可结合普遍存在的氯离子,形成不溶性白色沉淀。
已知纳米颗粒可用作填充剂,如美国专利6,492,453所述;用作涂层,如美国专利US 2003/0185964所述;用作起泡成分,如美国专利6,518,324所述。
US2002/0150678中公开了可用于组合物中的纳米颗粒系统,该系统还可用在修饰软和硬表面的方法中。具体地说,该申请公开了一种制品(如织物和衣服)的软表面涂层。
无机颗粒,例如粘土、硅酸盐和氧化铝已广泛与辅助的去污和清洁化合物联合使用,以赋予一些形式的抗静电控制和/或织物软化优点。
本发明涉及包含载金属剥脱纳米颗粒的复合材料。这种功能化纳米颗粒可掺入软表面涂层中,以提高或调节其整体物理特征和性能特征。该软表面涂层又可用于制备具有改进特性的吸收制品。将该涂层加入到(例如)一次性吸收制品的吸收芯中有助于控制恶臭形成并增加吸收性。
在一个实施方式中,金属是银,纳米颗粒是纳米粘土。银离子被还原为中性金属状态(Ag0),并负载到纳米粘土上。载银纳米粘土尤其具有优良的抗微生物特性,是代替胶体银溶液使用的较廉价选择。本发明制备的纳米颗粒稳定,使用较少金属银,就可形成与固体银颗粒相同的表面,使其性价比更高。
发明概述
本发明涉及一种软表面涂层,该涂层包含:1)含有(a)具有一表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料,其中,金属负载在纳米颗粒的表面上;2)载体介质;3)表面活性剂;以及4)一种或多种辅助成分。
本发明还涉及一种吸收制品,该制品包含含有(a)具有一表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料,其中,金属负载在纳米颗粒的表面上。
本发明还涉及一种修饰软表面的方法,该方法包括对其施加一种软表面涂层,该涂层包含:1)含有(a)具有一表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料,其中,金属负载在纳米颗粒的表面上;2)载体介质;3)表面活性剂;以及4)一种或多种辅助成分。
附图简要说明
图1是本发明吸收制品的立体图。
发明详述
本说明书中的所有界限包括所有下限或上限,就如清楚地写明这些下限或上限那样。本说明书中的所有范围包括所有落在该较宽范围内的较窄范围,就如清楚地写明这些较窄范围那样。
根据本发明,可制备包含含有(a)具有一表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料的吸收制品,其中,金属负载在纳米颗粒的表面上。该复合材料可以软表面涂层的形式应用于吸收制品,例如制品的一层上,如下详细所述。
本文所用纳米颗粒指颗粒(包括但不限于杆形颗粒、盘形颗粒、血小板形颗粒、四面体形颗粒)、纤维、纳米管、或具有纳米级尺寸的任何其它材料。在一个实施方式中,纳米颗粒的平均粒径约为1-1000纳米,优选约2-750纳米。即,细米颗粒的最大尺寸(例如直径或长度)约为1-1000纳米。纳米管可包括长达1厘米的结构,或者粒径约为2-50纳米。纳米颗粒具有非常高的表面-体积比。纳米颗粒可以是结晶或无定形。可使用单一类型的纳米颗粒,或使用不同类型纳米颗粒的混合物。使用纳米颗粒混合物时,它们可均匀或不均匀分散在复合材料或含复合材料的系统或组合物中。
纳米颗粒合适的粒径分布的非限制性例子约为2-750纳米,或约为2-200纳米,或约为2-150纳米。应理解某种粒径分布可能有利于提供特定优点,而其它粒径分布范围可能有利于提供其它优点(例如,色彩增强需要不同于其它特性的粒径范围)。一批纳米颗粒的平均粒径可不同于这些纳米颗粒的粒径分布。例如,层合的合成硅酸盐的平均粒径约为25纳米,而其粒径分布通常约为10-40纳米。应理解本文所述粒径分布是就分散在水性介质中时的纳米颗粒而言的,且平均粒径是基于粒径分布的平均值。
根据本发明,纳米颗粒是剥脱的。具体地说,原料剥脱或剥落而形成纳米颗粒。原料的平均大小至多约为50微米(50,000纳米)。在另一个实施方式中,纳米颗粒增加到所需的平均粒径。纳米颗粒可包含(例如)天然或合成纳米粘土(包括那些从无定形或结构粘土制备的纳米粘土)、无机金属氧化物或纳米乳胶。
在一个实施方式中,剥脱的纳米颗粒是纳米粘土。在另一个实施方式中,纳米颗粒是可溶胀纳米粘土或其加合物。可溶胀纳米粘土在层间位置具有弱结合离子,这些离子可水合或吸收有机溶剂。这些可溶胀纳米粘土通常具有低的阳离子电荷或阴离子电荷,即每晶胞小于约0.9单位电荷。
如本文所用,“加合物”指油可溶胀纳米粘土,即可在有机、非水溶剂,如极性和非极性溶剂中溶胀的纳米粘土。通过使水可溶胀纳米粘土与结合可溶胀纳米粘土的有机材料反应,制备上述纳米粘土。这种结合有机材料的例子包括但不限于具有以下结构的季铵化合物:
R1R2R3R4N+X-
其中,
R1、R2、R3和R4各自独立地选自H、C1-C22烷基、C1-C22烯基和C1-C22芳烷基,前提是至少一个R基团是烷基、烯基或芳烷基;和
X是水可溶胀纳米粘土。
可溶胀纳米粘土可以是无定形或结构化的,即包括片或层,这些层的组合称为晶格结构。具有晶格结构的合适的纳米粘土的例子包括叶蜡石(二八面体)型、滑石(三八面体)型或其混合物。合适的结构化可溶胀纳米粘土的类型包括但不限于,蒙脱石纳米粘土、海泡石纳米粘土、沸石纳米粘土、坡缕石纳米粘土或其混合物。
无定形可溶胀纳米粘土的例子包括水铝英石和伊毛缟石。
在一个实施方式中,纳米颗粒由(例如)粒径为10-18微米(10000-18000纳米)的Nanomer 1.34TCN(得自Nanocor)制备。在另一个实施方式中,纳米颗粒由粒径为20-25微米的PGV(也得自Nanocor)制备。在另一个实施方式中,使用粒径范围为1-3纳米、剥脱的PGV。在其它实施方式中,使用粒径范围为1-9纳米的Nanomer 1.34TCN和Nanomer 1.30E。
软水铝石矾土的平均粒径分布为2-750纳米。
层状粘土矿物可用作剥脱纳米颗粒的原料。适用于本发明的层状粘土矿物包括地质学分类的蒙脱石、高岭土、伊利石、绿泥石、绿坡缕石和混合层粘土。属于这些类型的具体粘土的典型例子有蒙脱石、高岭土、伊利石、绿泥石、绿坡缕石和混合层粘土。例如,蒙脱石包括蒙脱土、膨润土、叶蜡石、锂蒙脱石、皂石、锌皂石、绿脱石、滑石、贝得石、铬高岭石、硅镁石和蛭石。在一个实施方式中,优选蒙脱土纳米粘土。见美国专利5,869,033,其内容被纳入本文作为参考。高岭土包括高岭石、地开石、珍珠陶土、叶蛇纹石、蠕陶土、埃洛石、indellite和纤维蛇纹石。伊利石包括漂云母、白云母、钠云母、金云母和黑云母。绿泥石包括绿泥间蛭石、叶绿泥石、片硅铝石、铝绿泥石、叶绿泥石和斜绿泥石。绿坡缕石包括海泡石和坡缕石。混合层粘土包括钠板石和蛭石、黑云母。这些层状粘土矿物的变异和同晶型取代物提供独特的应用。
层状粘土矿物可以是天然来源或合成的。例如,天然或合成的锂蒙脱石、蒙脱土和膨润土可用作纳米颗粒的原料。
天然粘二矿物典型地以层状硅酸盐矿物形式存在,较少以无定形矿物形式存在。层状硅酸盐矿物具有排列成二维网络结构的SiO4四面体片。2∶1型层状硅酸盐矿物是几个到几十个硅酸盐片的层压结构,具有三层结构,其中镁八面体片或铝八面体片夹在两片硅石四面体片之间。
一片可膨胀的硅酸盐层具有负电荷,碱金属阳离子和/或碱土金属阳离子的存在可中和负电荷。蒙脱石或可膨胀云母可分散在水中,形成具有触变特性的溶胶。而且,通过与各种阳离子有机或无机化合物反应,可形成蒙脱石型粘土的络合变体。作为这种有机络合物的一个例子,通过阳离子交换,引入亲有机溶媒粘土中的二甲基双十八烷基铵离子(一种季铵离子)。这可工业生产,并用作涂层胶凝剂。
本发明可采用合成纳米粘土。通过适当过程控制,合成纳米粘土的生产过程的确产生纳米级的初级颗粒。然而,这些颗粒通常不是以离散颗粒的形式存在,而是由于初级颗粒的固结,主要以聚集体形式存在。这些聚集体的直径可达到几千纳米,使得不能达到与纳米级性质有关的所需特征。通过诸如EP-A 637,616所述的研磨,或通过分散在合适的载体介质如水或水/醇及其混合物中,这些颗粒可解聚。
制备合适的纳米粘土的合成材料包括层状含水硅酸盐、层状含水硅酸铝、氟代硅酸盐、云母-蒙脱土、碳酸镁铝、硅酸镁锂和氟代硅酸镁锂。硅酸镁锂的适当变体的例子是羟基部分地被氟取代。锂和镁也可部分地被铝取代。硅酸镁锂可被任何选自镁、铝、锂、铁、铬、锌或其组合的元素同晶型取代。
例如Southern Clay Products,Inc.以商品名LAPONITETM市售的合成锂蒙脱石,可用作纳米颗粒的原料。市售LAPONITETM有许多级别或变体和同晶型替代物。市售锂蒙脱石的例子有LAPONITE BTM、LAPONITE STM、LAPONITE XLSTM、LAPONITE RDTM、LAPONITE XLGTM和LAPONITERDSTM.
合成锂蒙脱石不含有任何氟。氟取代羟基的同晶型取代物可产生称为氟代硅酸锂镁钠的合成粘土,它也其可用作原料。这些氟代硅酸锂镁钠以LAPONITETM和LAPONITE STM市售,可含有多达约10重量%的氟离子。本文所述组合物中有用的氟离子含量高达约10%或更高。LAPONITE BTM,一种氟代硅酸锂镁钠为平面、圆形、板形,取决于氟离子含量,平均粒径约为25-100纳米。例如,在一个非限制性实施方式中,可使用直径约为25-40纳米,厚度约为1纳米的LAPONITE BTM。在另一个实施方式中,所述LAPONITE STM含有约6%的焦磷酸四钠作为添加剂。
在一个实施方式中,采用Laponite XLSTM作为纳米颗粒的原料,银负载其上作为金属。Laponite XLS是通过八面体镁和锂羟基桥连接的四面体硅酸盐层。这种结构允许通过金属插层或吸附于纳米粘土表面进行剥脱和修饰。在插层的情况下,金属插入纳米粘土的层之间。在表面吸附的情况下,金属结合于纳米粘土的表面。优选Laponite XLS,因为其合成连续且纯净,不用费什么力即可剥脱而形成纳米颗粒。纳米颗粒的表面覆盖有钠离子,以平衡许多硅酸根的负电荷。
在一些情况下,剥脱纳米颗粒的长厚比与形成含具有所需特征的复合材料的薄膜有关。分散体的长厚比可充分地被TEM(透射电镜)表征。
在一个实施方式中,纳米颗粒的长厚比为100-250。在另一个实施方式中,纳米颗粒的长厚比为200-350。
例如,各个LAPONITE BTM颗粒的平均长厚比约为20-40,各个LAPONITE RDTM颗粒的平均长厚比约为10-15。分散体中LAPONITE BTM基本上为单一粘土颗粒或两个粘土颗粒的块。LAPONITE RDTM基本上是两个或多个单一粘土颗粒的块。
在一些实施方式中,形成薄膜需要高的长厚比。分散在适当载体介质如水中的剥脱纳米颗粒,其长厚比也是有关系的。当几个颗粒聚集时,分散介质中纳米颗粒的长厚比较小。
在某些实施方式中,可需要至少一些单个(非聚集的)血小板形和盘形纳米颗粒,以使至少一个维度大于或等于约0.5纳米,长厚比大于或等于约15。血小板形和盘形纳米颗粒比杆形纳米颗粒更需要较大的长厚比。
杆形纳米颗粒的长厚比可以小于盘形或血小板形纳米颗粒的长厚比,同时维持足够的薄膜形成特性。在某些非限制性实施方式中,可能需要至少一些单个杆形纳米颗粒,以使至少一个维度大于或等于约0.5纳米,长厚比大于或等于约3。
球形纳米颗粒的长厚比通常小于或等于约5。本发明实施方式中优选的纳米颗粒具有长厚比小于或等于约250。在其它非限制性实施方式中,优选纳米颗粒的长厚比约为10。
根据本发明,使用一种或多种金属官能化纳米颗粒。具体地说,通过包括插层、吸附或离子交换等多种方法中的一种,将金属负载在剥脱的纳米颗粒上。优选地,在纳米颗粒上时,金属保留其特性,例如银的抗微生物特性。本文所用术语“负载”包括完全覆盖纳米颗粒的表面,或可选地,仅覆盖一部分。
在一个实施方式中,金属选自元素周期表的第3-12族、铝和镁。优选地,金属选自银、铜、锌、锰、铂、钯、金、钙、钡、铝、铁及其组合。在一个尤其优选的实施方式中,金属是银。
可根据通过使用复合材料所需达到的作用选择金属。例如,可基于银已知的抗微生物特性选择银。
金属可通过插层作用负载在纳米颗粒上。例如,尤其是银离子可插入层状纳米粘土各层之间,通过定位于“洞”中,尽可能扩大正电荷银离子和硅酸盐结构中各种氧之间有益的相互作用。银离子显示具有抗微生物特性,含插层离子银的Laponite保留这种特性。其它金属离子,如铜、锌、锰等也可插层。
金属可通过离子交换负载在纳米颗粒上。例如,Laponite血小板形颗粒的表面主要由钠离子组成,钠离子的存在可平衡下层硅酸盐结构中提供的负电荷氧原子。当将正电荷金属离子加入到剥脱的Laponite溶液中时,一部分表面钠离子被加入的金属离子取代。
金属可通过吸附负载在纳米颗粒上。例如,某些官能化基团如胺基、铵离子和羧基是Laponite血小板形颗粒的面或边的有力的结合基团。可通过加入这些配基修饰金属离子,使其能够强效结合于Laponite表面。一个例子的反应顺序如下所示:
2AgNO3+2NaOH→Ag2O+2NaNO3+H2O
Ag2O+4NH3+H2O→2Ag(NH3)2OH
最终产物Ag(NH3)2OH与Laponite接触,从而使Ag(NH3)2OH结合于Laponite的表面。
在本发明的一个实施方式中,在原料的存在下,金属离子还原为金属(0),其中原料剥脱形成纳米颗粒。还原和剥脱可相继发生(任一步骤先发生)或通过使金属与原料/剥脱的纳米颗粒接触而同时发生。因此,金属负载到剥脱的纳米颗粒的表面上。
在本发明的一个实施方式中,金属是银,用托伦试剂通过插层作用将银负载到纳米颗粒的表面上。托伦试剂是已知可于醛或酮发生还原反应而形成银金属(0)的试剂:
+Ag(NH3)2OH+葡萄糖→Ag0
该复合材料可掺入软表面涂层组合物中。该组合物可以是溶液或干燥物质,可对该组合物进行涂覆、施加、挤压、喷雾,如下进一步所述。这种组合物可在生产、商业、工业、个人或家庭应用中具有最终用途。使用这种含复合材料的涂层可带来某种所需的优点,例如改善流体吸收性、润湿性、透印性、舒适性、恶臭控制、润滑性、抗炎特性、抗微生物特性、抗真菌特性、表面摩擦修饰、柔韧性、透明性、模量、抗拉强度、彩色增强、粘性、平滑性或凝胶强度。
在某些实施方式中,组合物中复合材料的存在不影响组合物的所需特性,例如透明性。例如,与不含复合材料的原始液体材料相比,在液体组合物中加入复合材料不会改变所得组合物的透明性或色彩。而且,由于纳米颗粒具有大的表面积,复合材料也将允许整个制剂(例如)在治疗感染中负载更高浓度的金属。
如本文所用,术语“涂层”包括完全覆盖表面的涂层(例如连续涂层,包括在表面上形成薄膜),以及仅部分覆盖表面的涂层,例如干燥后形成的涂层,该涂层的表面覆盖具有间隔(例如不连续涂层)。后一种涂层包括但不限于复合材料在一个表面上的覆盖和不覆盖部分及分布形成的网,该复合材料之间具有间隙。在一些实施方式中,优选涂层在已涂覆表面上形成至少一层复合材料,且基本上是均质的。然而,当将本发明涂层用于表面时,应理解该涂层不需要应用于,或覆盖整个表面。例如,当将该涂层应用于表面时,甚至可仅应用于表面的一部分。
本发明软表面涂层组合物可包含复合材料和适合该组合物应用的任何其它成分。一些本发明组合物可包含:(a)复合材料,可以是有效量的复合材料;(b)合适的载体介质;和(c)任选一种或多种辅助成分。辅助成分可以是(例如)表面活性剂或带电功能化分子(显示以下与至少部分复合材料相关的特性:亲水性、疏水性、或同时显示亲水和疏水性),或加入表面活性剂和带电功能分子。
或者,组合物中可包含本文所述有效量的复合材料,用于涂覆多种需要治疗的软表面。如本文所述,有效量的复合材料指,赋予软表面所需优点必需的复合材料的量。本领域技术人员可容易地确定该有效量,取决于多种因素:例如所用的特定复合材料,软表面的性质,需要液体还是干燥(例如颗粒、粉末)组合物等。
可通过冲洗、喷雾、浸渍、涂刷、擦拭或其它方法施用组合物,以提供覆盖至少约0.5%的表面,或任何更大表面,包括但不限于:至少约5%、至少约10%、至少约30%、至少约50%、至少约80%、至少约100%的表面的涂层、特别是透明涂层。因此,涂层可以是连续或不连续的。
当将涂层组合物喷到表面上时,涂层组合物的粘度应能够通过喷雾装置的喷嘴。该粘度已知,且被纳入本文作为参考。组合物可发生剪切稀化以喷射出。
包含复合材料的组合物的合适载体介质包括液体、固体和气体。一种合适的载体介质是水,可以是蒸馏水、去离子水或自来水。水由于其成本低、易获得、安全和相容而有价值。可通过加入酸或碱调节液体、尤其是水的pH。水性载体介质也可容易地施涂于底物,然后干燥。虽然水性载体介质比无水、非水性介质更常见,组合物可以干燥粉末、颗粒或片剂或包封的络合物形式存在。
任选地,除水以外或代替水,载体介质可包含低分子量有机溶剂。优选地,溶剂水溶性高,例如乙醇、甲醇、丙醇、异丙醇、乙二醇、丙酮等,及其混合物。溶剂可以任何合适的水平应用。一些非限制性的例子包括占总组合物重量的水平多达约50%,或以上;约0.1%-25%;约2%-15%,约5%-10%。组合物中使用高含量溶剂时要考虑的因素有纳米颗粒的气味、易燃性、分散性以及环境影响。
载体介质还可包含薄膜形成剂,它干燥时可形成连续薄膜。薄膜形成剂的例子有:聚乙烯醇、聚氧化乙烯、聚氧化丙烯、丙烯酸乳剂、羟丙基甲基纤维素。
含复合材料的组合物中可使用的辅助成分包括聚合物和共聚物,它们具有至少一个包含用于使复合材料锚定于底物的官能团的区段或基团。这些聚合物也可包含至少一个用于给聚合物提供附加特征,如亲水性或疏水性的区段或基团。
锚定区段或基团的例子包括:聚胺、季铵化聚胺、氨基、季铵化氨基和相应的氧化胺;两性离子聚合物;聚羧酸酯;聚醚;多羟基聚合物;聚膦酸酯和聚磷酸酯;以及聚合螯合物。
亲水性区段或基团的例子包括:乙氧基化或烷氧基化聚胺;聚胺;聚羧酸聚胺;水溶性聚醚;水溶性多羟基化基团或聚合物,包括糖和多糖;水溶性羧酸酯和聚羧酸酯;水溶性阴离子基团如羧酸根、磺酸根、硫酸根、磷酸根、膦酸根及其聚合物;水溶性胺、季铵、氧化胺及其聚合物;水溶性两性离子基团及其聚合物;水溶性酰胺和聚酰胺;以及乙烯基咪唑和乙烯基吡咯烷酮的水溶性聚合物和共聚物。
疏水性区段或基团的例子包括:烷基、烯基和芳基,以及聚合脂族或芳族烃;碳氟化合物和含碳氟化合物的聚合物;硅酮;疏水性聚醚如聚(氧化苯乙烯)、聚(环氧丙烷)、聚(环氧丁烷)、聚(四氢呋喃)和聚(十二烷基缩水甘油醚);以及疏水聚酯如聚己酸内酯和聚(3-羟基羧酸)。
可掺入本发明组合物中的亲水表面聚合物的例子包括但不限于:乙氧基化或烷氧基化聚胺;聚羧酸聚胺;聚羧酸酯,包括但不限于聚丙烯酸酯;聚醚;多羟基物质;缩聚磷酸盐和膦酸酯。
可掺入本发明组合物中的疏水表面聚合物的例子包括烷基化聚胺,包括但不限于:脂肪烷化剂如十二烷基溴化物、十八烷基溴化物、油基氯化物、十二烷基缩水甘油醚和苄基氯化物或其混合物烷基化的聚乙烯亚胺;和脂肪酰化剂,如十二烷酸甲酯和油酰氯化物酰化的聚乙烯亚胺;硅酮,包括但不限于:具有侧链氨基丙基或氨基乙基氨基丙基的聚二甲基硅氧烷,以及氟化聚合物,包括但不限于:包含全氟化或高氟化烷基的(甲基)丙烯酸酯单体的聚合物。
可用作辅助成分的非聚合表面修饰材料包括脂肪胺和季铵化胺,包括:氯化二牛脂二甲基铵;溴化十八烷基三甲基铵;二油胺;和氯化苄基四癸基二甲基铵。组合物中也可包含硅酮基表面活性剂,脂肪两性离子表面活性剂和氧化脂肪胺。
表面活性剂也是任选的辅助成分。组合物中表面活性剂特别用作润湿剂以促进分散。
合适的表面活性剂选自:阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两亲表面活性剂、两性表面活性剂、两性离子表面活性剂及其混合物。合适的非离子、阴离子、阳离子、两性、两性离子和半极性非离子表面活性剂见美国专利5,707,950和5,576,282所述。非离子表面活性剂的特征是:HLB(亲水-亲脂平衡值)为5-20,或是6-15。
阴离子和非离子表面活性剂的混合物尤其有用。其它常规有用的表面活性剂在标准文本中列出。
另一类有用的辅助成分是硅酮表面活性剂和/或硅酮。它们可单独使用和/或可选地与其它上述表面活性剂联合使用。硅酮表面活性剂的非限制性例子有氧化聚烯烃聚硅氧烷,具有二甲基聚硅氧烷疏水部分和一条或多条亲水聚烯烃侧链。
使用时,表面活性剂应与组合物中存在的复合材料、载体介质和其它辅助成分相容。
组合物可包含其它辅助成分,包括但不限于:碱源、抗氧化剂、抗静电剂、螯合剂、氨基羧酸盐螯合剂、金属盐、光活化无机金属氧化物、气味控制物质、芳香剂、光活化剂、聚合物、防腐剂、加工助剂、颜料、pH控制剂、增溶剂、沸石以及它们的混合物。可包含任何所需水平的这些任选成分。
包含复合材料的涂层组合物可用于所有类型的软表面上,包括但不限于,机织纤维、无纺纤维、皮革、塑料(例如,牙刷柄、合成膜、纤丝、牙刷毛)及其混合物。这里所感兴趣的软表面可包括任何已知类型的软表面,包括但不限于与一次性吸收制品有关的软表面,包括但不限于覆盖物和顶层、吸收芯、转移层、吸收嵌入物和背衬层,包括由透气和不透气膜构成的外层。
在某些实施方式中,软表面可包括一根或多根纤维。一根纤维定义为植物、矿物或合成来源的细毛发样结构。市售纤维的直径从不到约0.001毫米(约0.00004英寸)到约0.2毫米(约0.008英寸)以上,它们具有几种不同的形式:短纤维(称为化学短纤维)、连续单纤维(纤丝或单纤丝)、连续纤丝的无捻束(麻)、连续纤丝的扭曲束(纱)。根据其来源、化学结构或两者,可将纤维分类。它们可编成绳和绳索,制成毡(也称为无纺布或无纺织物),机织或针织成纺织品,对于高强度纤维,在复合物中(即两种或多种不同材料构成的产品)可用作增强成分。
软表面可包括天然纤维(自然纤维)、人工纤维(合成或人造纤维)或它们的组合。天然纤维的例子包括但不限于:动物纤维如羊毛、丝、毛皮和毛发;植物纤维如纤维素、棉花、亚麻、亚麻布和麻;和某些天然来源的矿物纤维。合成纤维可来源于天然纤维或非天然纤维。来自天然纤维的合成纤维的例子包括但不限于人造丝和莱赛尔(lyocell),两者都来源于纤维素,一种天然多糖纤维。来源于非天然纤维的合成纤维可来源于其它天然来源或来源于矿物来源。来源于天然来源的合成纤维的例子包括但不限于多糖如淀粉。来源于矿物来源的纤维的例子包括但不限于聚烯烃纤维(如来源于石油的聚丙烯和聚乙烯纤维)和硅酸盐纤维(如玻璃和石棉)。可能的话,合成纤维一般通过流体处理过程(例如,挤压、拔拉或旋压流体如树脂或溶液)形成。合成纤维也可通过固体处理粉碎过程(例如,机械截断或切割较大的物体如整料、薄膜或织物)形成。
一次性吸收制品,如内裤衬垫、卫生巾、阴唇间用品、成人失禁制品、胸垫、鞋垫、绷带和尿布通常由吸收性无纺材料(包括纤维)构成,且是本领域熟知的。这些制品通常具有流体可渗透的面向身体侧和流体不可渗透的面向衣服侧。此外,这些制品可包括吸收芯,用以保留其间的流体。在产品,如一次性吸收制品的吸收芯中加入复合材料,有助于控制恶臭的形成和增加吸收性。
图1显示了本发明吸收制品。虽然不是必需的,该吸收制品1可包括覆盖吸收芯30的覆盖层10。覆盖层的外表面形成该吸收制品面向身体的表面。如本领域技术人员已知的那样,覆盖层可由对使用者的皮肤通常适应、感觉柔软、非刺激性的任何流体渗透性材料构成,使流体渗透入吸收芯以容留流体。覆盖层通常用于将流体从配戴者转移入吸收制品。这样,流体和水汽不再接触配戴者,从而使配戴者感觉干燥和舒适。除转移流体外,覆盖层也可吸收和/或容留流体。
覆盖层可由常用作该用途的任何材料构成。可用作覆盖层的合适的材料的非限制性例子包括由纤维素、聚酯、聚丙烯、尼龙和/或人造丝纤维形成的织物和无纺织物,或者覆盖层可以是具孔热塑膜和成形膜。制备覆盖层时使用的其它材料包括纱网或具有合适的身体接触表面的任何已知多孔材料,包括但不限于,无纺网、塑料网等。覆盖层也可由双组分纤维和短纤浆的纤维性无纺复合物构成。
双组分纤维是本领域已知的,它由两种熔点不同的聚合物构成。各个双组分纤维外表面的至少一部分为熔点较低的聚合物可以这样。排列两种聚合物,从纤维的截面看时两种聚合物是并排的。或者,可以所谓鞘/芯的排列形式设置聚合物,其中熔点较高的聚合物被熔点较低的聚合物包围。一种有用的双组分纤维是由聚酯芯和高密度聚乙烯鞘构成的3.0旦尼尔、1.5″长人造纤维。类似的纤维(聚乙烯鞘和聚丙烯芯)可以Danaklon ES-C或ES Bico(Danaklon A/S,Varde Denmark)获得。纸浆纤维可以是得自International Paper Company(Memphis,Tennessee)的IP′″SUPERSOFT″ELM、′″RAYFLOC″XJ-HM E-型纤维素短纤浆(ITT Rayonier)或KorsnasVigorfluf-EN White(KorsncAs,Gavle,Finland)。
可任选用表面活性剂处理覆盖层,操纵其亲水/亲脂性以利于较佳的流体转移特性。接触体液时,构成覆盖层的纤维或其它材料不应崩塌或丧失其回弹性。纤维可通过梳理过程定向,并通过压花热粘结。纤维或细丝可以是单旦尼尔或多旦尼尔。
覆盖层的厚度约为0.025-5毫米,取决于所选材料。面向身体层材料的重量应约为每平方米5-150克(gsm)。
通常,任选的覆盖层是单层材料,其宽度足以形成吸收制品面向身体的表面。该覆盖层可比吸收芯更长更宽。
可在给定区域内给覆盖层压花。例如,将一系列或一定量的图像如圆形、三角形、正方形、线形、蜂窝形、钻石形、花形等,压花到覆盖层外表面的整个长度和宽度上。各个压花图像具有延伸通过其中的主轴和次轴,主轴长度大于或等于次轴长度。压花图像可以是重复图案。
在一个实施方式中,覆盖层包括射流喷网无纺布。具体地说,射流喷网材料可由约0-100%的人造丝和约0-100%的聚酯形成。射流喷网材料也可使用约10-65%的人造丝和约35-90%的聚酯。任选地,用作面向身体层的材料可包含粘合剂,例如热塑粘合剂纤维素和乳胶粘合剂。
任选地,本发明吸收制品包括转移或分配层(未示出)。转移或分配层如果存在,通常位于覆盖层10下方,且转移层通常直接接触吸收芯。如果包括的话,转移层可由吸收流体、然后将流体分配和释放至相邻吸收层储存的任何已知材料构成。转移层具有相对开放式结构,允许流体在该层中流动。适用于转移层的材料包括纤维网、弹性泡沫等。
转移层从流体渗透覆盖层接受体液并保留体液直到吸收芯有机会吸收该体液。优选地,转移层比覆盖层更致密,比覆盖层具有更大比例的较小孔。这有利于允许转移层包含体液并保留其远离覆盖层10的外面,从而防止再次润湿覆盖层及其外表面。然而,转移层也不能太致密,以免阻止流体通过转移层并进入下方的吸收芯。
转移层可包括多种材料,例如包括纤维网、弹性泡沫等。转移层可包括(例如)木纸浆的纤维素纤维、纤维或其他形式中包含热塑材料(例如,聚酯、聚丙烯、聚乙烯等)的单组分或双组分纤维、人造丝、有机粘合剂(例如可涂覆到热塑纤维上或引入转移层的乙烯共聚物、丙烯酸和/或其它单体)、以及其它本领域已知的材料。例如,转移层的基本重量约为40-120gsm,厚度约为0.5-4毫米,密度约为0.03-0.15g/cc。
构成转移层的材质可以是吸收性的,虽然材料本身不是吸收性的。因此,由疏水、非吸收性纤维构成的转移层能够接受大量流体进入纤维内空隙,而纤维本身不吸收任何显著量的流体。类似地,由非吸收性材料构成的开孔泡沫结构也可吸收流体进入泡沫腔中。然而,腔壁不吸收任何流体。转移层内累积的空间,即泡沫转移层中纤维性转移层或开放腔中的纤维内空隙,更多地用作容纳流体的容器。
一般地,转移层纤维网由弹性、非吸收性材料构成,以提供空隙容积并使流体通过结构自由流动。大部分由吸收性纤维网构成的转移层在流体进入该结构时吸收流体,不能像含非吸收性材料的网那样有效地将流体分布到该结构的其余部分。
大部分由吸收性纤维网构成的转移层在流体进入该结构时吸收流体,不能像含非吸收性材料的网那样有效地将流体分布到该结构的其余部分。优选转移层纤维网包含非吸收性材料,以提供空隙容积并使流体通过结构自由流动。这种材料的例子包括聚丙烯、聚乙烯、聚酯、双组分材料、尼龙以及它们的混合物或组合物。转移层不一定非得是具孔膜;它可以是任何其它无纺材料,例如泡沫或网状物,以转移体液,并与覆盖层一起为吸收芯提供掩蔽。然而,在一个实施方式中,转移层是由聚乙烯构成的25gsm的具孔膜。覆盖纤维,也覆盖覆盖层、转移层、吸收芯。
吸收芯30可由任何已知吸收材料构成,包括但不限于吸收纤维,如纤维素纤维,包括但不限于木纸浆、再生性纤维素纤维、棉花纤维、人造丝纤维等;超吸收粉末(SAP)如Sumitomo SA-70或纤维(SAF),其它天然来源的吸收材料,如泥炭藓;以及其它合成的吸收材料,如泡沫等。吸收芯30还可保护一种或多种以下成分:粘合剂(如热塑和乳胶粘合剂)、恶臭控制化合物(如香料)、EDTA(乙二胺四乙酸盐)、抗微生物剂、润湿剂、湿度指示物质、给予或递送药物的物质(如包封的药物)、以及保持皮肤水份的物质(如包封的保湿剂)。
例如,吸收芯可由(例如)从具有较高吸收容量的较松无纺纤维网切割形成的绒毛棉絮材料构成。虽然吸收芯可具有任何形状或轮廓,但它通常为不对称构型。吸收芯30也可由整体致密层纤维棉絮材料构成。在这种情况下,如果需要背衬层,吸收芯位于吸收制品的背衬层上,使得致密层毗邻背衬层。致密层比上述棉絮的其余部分具有较高的润湿性和液体保留性,通常通过稍稍润湿棉絮的一个表面、然后压制润湿表面而形成。吸收芯30也可为多层,各层具有不同的密度,使得最上层(最贴近身体)不如外层(最贴近衣服)致密。
此外,吸收芯可由来自离线形成、均匀混合的气流成网层、卷曲良好的层压层或任何其它离线形成的吸收复合物的吸收材料形成。
本发明吸收材料可由多种方法制备,包括但不限于,气流成网、纺粘结、粘结和梳理、熔吹和共同成形。在一个实施方式中,吸收芯是吸收芯气流成网纸浆。
气流成网方法是公知的。由Buckeye Foley FluffsTM(Memphis,TN)纸浆、Trevira或KoSa T255(Houston,TX)双组分纤维构成的纤维无纺复合物可通过分离带入气流的短纤维束而形成。在抽真空的帮助下,这些纤维沉积到成形筛,一般是水平式或旋转式圆筒上。可存在多个成形段(成形封头)。可通过热气活化乳胶粘结粘合剂、热粘结纤维或其组合,使无定向纤维网粘结到一起,如美国专利4,640,810和5,885,516所述。
粘合剂可以是纤维、液体或颗粒形式。粘合剂有助于防止材料湿崩塌。可用于本发明的合适的纤维粘合剂包括以标号T-255和T-256得自KoSa Inc.(Houston,TX)的鞘芯偶联纤维,它们都具有聚烯烃鞘;或是具有低熔点共聚酯鞘的T-254。其它纤维粘合剂是本领域技术人员已知的,可从许多生产商如Chisso和Fibervisions LLC,Wilmington,Del获得。合适的液体粘合剂是得自Hercules,Inc.,Wilmington,Del的557LX。其它合适的液体粘合剂包括National Starch和Chemical Company(Bridgewater,N.J.)以商品名DUR-O-SET系列(包括33和22)销售的乙烯醋酸乙烯酯乳剂聚合物。其它合适的粘合剂有Air Products Polymers andChemicals以商品名销售的粘合剂。
一些粘合剂需要催化、升高温度和/或酸性条件以促进交联。由可聚合酰胺与醛反应得到的单体通常用作该目的。粘合剂可以多种添加水平应用于层的顶部、底部或顶部和底部。不同类型的乳胶粘合剂,例如高Tg约为+10到+35℃,或低Tg约为-3到-30℃,那些Tg在高和低之间的粘合剂具有不同程度的刚度和柔韧性,根据所得结果的所需性质,可单独或联合应用。例如参见美国专利4,449,978和5,143,954。如美国专利5,415,926所述的其它粘合剂是自交联的,该专利的全部内容被纳入本文作为参考。在这些聚合物系统中,反应性官能团使聚合物自身交联,并化学键合底物如纸浆或薄纱。可通过使用酸催化剂加速自交联反应。一种自交联粘合剂包括“X-LINK 25-033A”,它是具有高玻璃态转化温度的自交联乙烯基丙烯酸共聚物乳剂,得自National Starch and Chemical Company(Bridgewater,NJ)。
吸收材料也可沉积于载体底物如薄纱(未示出)或其它气体可渗透组合物上,以形成吸收结构。在该构型中,一般用粘合剂喷射层以稳定所得吸收结构。可进一步对该结构进行压花以获得美观效果和/或功能性,例如芯吸、致密化等。所得结构可用作吸收产品如卫生巾或内裤衬垫中的吸收结构。
在一个实施方式中,吸收结构包括由吸收材料构成的吸收芯和薄纱层。在一个实施方式中,薄纱层位于吸收材料和屏障层50之间。薄纱层可由软材和/或硬木纤维构成,可绉折、湿压或通过气流干燥。
吸收芯中可包含其它添加剂,例如表面活性剂、SAP和SAF。这些添加剂提供附加的优点,如提高的流体渗透性和增加的流体吸收性。例如,在一个实施方式中,吸收层是纸浆层构成的吸收材料。在另一个实施方式中,将SAP与纸浆混合,以形成吸收复合物。可浓缩该复合物,以形成致密薄层。该材料的一个例子是得自Rayonier,Jesup,GA的
SAP是一种颗粒,它在0.5psi的压力下,能够吸收其自身重量许多倍,至少10倍,更优选15,还要更优选超过15倍的渗出物。应理解,在本发明的内容中,并不限定超吸收颗粒实际上是微粒状态。该表达包括超吸收纤维和其它超吸收材料,无论它们是什么形式和形状。这些超吸收颗粒通常分为三类,分别是淀粉接枝共聚物、交联羧甲基纤维素衍生物和改性的亲水性聚丙烯酸酯。这种吸收聚合物的例子包括水解淀粉-丙烯腈共聚物接枝共聚物、中性淀粉-丙烯酸接枝共聚物、皂化丙烯酸酯-醋酸乙烯酯共聚物、水解丙烯腈共聚物或丙烯酰胺共聚物、改性交联聚乙烯醇、中性自交联聚丙烯酸、交联聚丙烯酸盐、羧基纤维素、中性交联异丁烯-马来酸酐共聚物。在本发明的一个实施方式中,超吸收颗粒是交联聚丙烯酸盐。
将超吸收颗粒以不到约60%(w/w)的量加入到吸收芯中。优选地,加入的量约为0-25%(w/w)。更优选地,加入的量约为5-20%(w/w)。例如,在本发明中,7%的超吸收颗粒“w/w”表示每1克吸收芯的所有组分中平均含有0.07克超吸收颗粒。
本发明吸收层或吸收芯可由常规技术制造,例如使木纸浆纤维和超吸收材料气流成网。所有这些常规技术在本发明的范围内。在一个实施方式中,吸收层如美国专利5,866,242所述,其内容被纳入本文作为参考。
SAP与木纸浆的比率可在较宽的范围内变化。如果需要,一层或多层干燥成网型材料可用作吸收材料来形成吸收芯。吸收材料可以是具有所需密度的本领域所用类型的SAP和木纸浆纤维。
本领域已知的任何薄纱可用于产生本发明吸收结构,例如气流成网薄纱和湿成网薄纱。
屏障层,也称为背衬层50,其位置紧邻吸收芯30和覆盖层10。本发明屏障层50是体液不可渗透材料,至少基本不可渗透体液。其外表面形成吸收制品面向衣服的表面。背衬层50可以是任何薄层、弹性、体液不可渗透材料,包括但不限于:聚合物膜如聚乙烯、聚丙烯或玻璃纸;或已经处理成不具渗透性的普通流体可渗透材料,如浸渍防流体纸或无纺材料,包括无纺织物材料;或弹性泡沫,如聚氨基甲酸酯或交联聚乙烯。
任选地,背衬层50透气,即允许蒸汽透过。为实现该目的的已知材料包括无纺材料、整体和微孔膜,其中,微孔是由拉伸定向膜等方法形成的。提供弯曲通道和/或具有防止液体渗透的液体表面的单层或多层渗透膜、织物、熔吹材料及其组合,也可用作透气背衬层。
吸收制品的层可以,但不是必需与相邻的层粘结,例如胶粘或粘合。例如,覆盖层10底面可与吸收芯30的顶面粘合。吸收芯30的底面可与屏障层50的顶面粘合。可使用任何本领域已知的方法,例如融合粘结、粘合附着或通过任何其它固定方法,将各层固定在一起,以形成最终的吸收制品。这些方法包括共压花、热粘结、化学键合等。融合粘结包括热粘结、超声粘结等。
粘合剂一般用于将层粘贴到单个吸收制品中。例如,在一个实施方式中,用得自H.B Fuller and Company(St.Paul,MN)的粘合剂HL 1491将面向身体的覆盖层10与屏障层50粘住。可以任何方式施加粘合剂。
粘合剂可包括以条带状、涡旋状或破浪状等施加的压敏型粘合剂。如本文所用,术语压敏型粘合剂指任何可揭粘合剂或可揭粘合工具。合适的粘合剂组合物包括,例如水基压敏型粘合剂,如丙烯酸酯粘合剂。或者,粘合剂组合物可包括基于以下物质的粘合剂:天然或合成聚异戊二烯、苯乙烯-丁二烯、聚丙烯酸酯、醋酸乙烯酯共聚物及其组合的乳剂或溶剂型粘合剂;基于合适的嵌段聚合物的热熔粘合剂,用于本发明的合适的嵌段聚合物包括具有通式(A-B)x的线性或放射状共聚物结构,其中,嵌段A是聚乙烯芳烃嵌段,嵌段B是聚(单烯基)嵌段,x表示聚合臂的数目,x是大于或等于1的整数。合适的嵌段A聚乙烯芳烃包括但不限于聚苯乙烯、聚α-甲基苯乙烯、聚乙烯甲苯及其组合。合适的嵌段B聚(单烯基)嵌段包括但不限于,共轭二烯弹性体如聚丁二烯或聚异戊二烯,或氢化弹性体如乙烯丁烯或乙烯丙烯,或聚异丁烯、或是它们的组合。这种嵌段共聚物的市售例子包括Shell Chemical Company的KratonTM弹性体、Dexco的VectorTM弹性体、Enichem Elastomers的SolpreneTM以及Firestone Tire & Rubber Co.的StereonTM;基于烯烃聚合物和共聚物的热熔粘合剂,其中,烯烃聚合物是乙烯和共聚单体如醋酸乙烯酯、丙烯酸、甲基丙烯酸、乙基丙烯酸酯、甲基丙烯酸酯、正丁基丙烯酸酯乙烯基甲硅烷或马来酸酐的三聚物。这种聚合物的市售例子包括Ateva(来自AT Plastics的聚合物)、Nucrel(来自DuPont的聚合物)、Escor(来自Exxon Chemical)。
通过将面向衣服的表面置于裤裆内表面,本发明吸收制品可应用于裤裆。可使用各种方法贴附吸收制品。例如,技术人员可使用的多种方式包括化学方式如粘合剂,机械附着方式如夹住、系带、绑带,以及连锁装置如按钮、纽扣、VELCRO(Velcro USA,Inc.,Manchester,NH)、拉链等。
可将粘合剂施加于吸收制品面向衣服的一侧。该定位粘合剂可以是本领域已知的任何粘合剂。作为非限制性的例子,可施加条带状、涡旋状或破浪状压敏型粘合剂,以帮助吸收制品保持在适当位置。如本文所用,术语压敏型粘合剂指任何可揭粘合剂或可揭粘合工具。合适的粘合剂组合物包括:水基压敏型粘合剂如丙烯酸酯粘合剂。或者,粘合剂组合物可包含快速凝固热塑“热熔”粘合剂、橡胶粘合剂、两面粘合胶带等。
当将定位粘合剂应用于屏障层50面向衣服一侧时,在吸收制品贴附到裤裆之前,采用可揭带来保护吸收制品上的粘合剂。可揭带可由以足够的粘性与粘合剂粘连的任何合适的片样材料构成,使用前保持在原位,而在使用吸收制品时,可揭带可容易地除去。任选地,可揭带上可施加涂层,以提高可揭带从粘合剂上除去的容易性。可使用任何能够达到这种作用的涂层,例如硅酮。
护翼,也称为翼或垂片等,也可作为本发明吸收制品的一部分。护翼及其在卫生防护用品中的应用参见Van Tilburg的美国专利4,687,478;VanTilburg的美国专利4,589,876;McCoy的美国专利4,900,320,Mattingly的美国专利4,608,047。这些专利的内容被纳入本文作为参考。
如上所述,一般来说,护翼柔韧,且被构造成折叠在内裤边缘上方,以使护翼位于内裤的边之间。
覆盖层、吸收层、转移层、背衬层和粘合层中的任一层或所有的层都可以是透明的或有色的。这种颜色包括但不限于白色、黑色、红色、黄色、蓝色、橙色、绿色、紫色或它们的组合。根据本发明,可通过染色、着色和印刷来形成颜色。根据本发明,所用着色剂包括染料以及无机和有机颜料。所述染料包括但不限于蒽醌染料(Solvent红111,Disperse紫罗兰1,Solvent蓝56和Solvent绿3)、呫吨染料(Solvent绿4,酸性红52,基本红1和Solvent橙63)、吖嗪染料(深黑)等。
无机颜料包括但不限于二氧化钛(白色)、炭黑(黑色)、氧化铁(红、黄和褐色)、氧化铬(绿色)、铁铵亚铁氰化物(蓝色)等等。
有机颜料包括但不限于二芳基黄AAOA(颜料黄12)、二芳基黄AAOT(颜料黄14)、酞菁蓝(颜料蓝15)、立索红(颜料红49:1)、红色淀C(颜料红)等等。
在一个实施方式中,吸收制品具有覆盖层和背衬层,它们通过粘合层结合在一起。粘合层包含纳米颗粒,纳米颗粒吸收体液。在另一个实施方式中,吸收制品具有覆盖层、背衬层、包含纳米颗粒的吸收部分,并且垂悬性小于2001年12月19日提交的美国专利2003114822描述的XX。
在另一个实施方式中,吸收制品是透明的,如美国专利6,497,690和6,482,192所述。在该实施方式中,制品的吸收部分包含纳米颗粒,以使所得制品保持透明性。
吸收制品可被包装成纸箱、盒子或袋子内打开的吸收制品。消费者在需要时,取出来即可使用。吸收制品也可独立包装(每个吸收制品都被包装在一个外包装内)。
这里还包括具有平行纵向边缘、狗骨形或花生形、圆形、椭圆形等的吸收制品。
本发明吸收制品可用于传统内裤,或使其形状适合带形衣服。如本文所用,术语带形包括但不限于,带形内裤、带形游泳底裤、G-带、Rio式内裤、Rio式游泳底裤、Brazilian式内裤、Brazilian式游泳底裤以及任何其它暴露臀部、具有由腰带、腰索、带或衣服本身支撑的穿过大腿间的织物或索窄带的衣服。吸收制品可包括其它已知材料、层和添加剂,如泡沫、网状材料、香料、药物或药剂、润湿剂、气味控制剂等。吸收制品可任选经过压花形成装饰。
在本文所述方法的实施方式中,需要以合适的方式进行制备软表面的步骤,以提高表面接受涂层组合物的能力。
疏水或临界亲水软表面包括但不限于以下材料:由疏水或临界亲水结构组分构成的编织、机织和无纺材料。该编织、机织或无纺材料的结构组分可包括纱、索、纤维、线或其它结构组分。一些或所有结构组分可疏水、临界亲水或其组合。疏水结构组分的表面上全部由疏水材料构成,或部分地由疏水材料构成(例如具有部分或全部被疏水鞘围绕的一种或多种材料芯的多组分纤维)。
类似地,临界亲水结构成分完全由临界亲水材料构成,或部分地由临界亲水材料构成。当结构组分表面上包含疏水材料和临界亲水材料时,认为它是疏水的。疏水材料常常是合成聚合物、共聚物、掺合物或其组合。例子包括但不限于:聚烯烃如聚丙烯和聚乙烯,某些聚酯如聚对苯二甲酸乙二酯(PET)以及一些聚酰胺。临界亲水材料一般也是合成聚合物、共聚物、掺合物或其组合。例子包括但不限于:显示临界亲水性的聚酰胺和聚酯。具有临界亲水性的聚酯包括最近称为亲水性聚酯的一类聚酯。一个例子是PET/分支聚乙二醇(分支PEG)共聚物如Wellman,Inc.,Charlotte,N.C.,USA.出品的T870、T289和T801级。另一个例子是PET的一些或全部芳族重复单元被脂族重复单元代替的聚酯。Cargill Dow Polymers,LLC,BlairNebr.出品的聚丙交酯(聚乳酸或PLA)聚合物包含脂族重复单元。
可以许多不同的方式提高施加涂层组合物的表面接受涂层组合物的能力。
如本文所述,一种提高材料表面接受涂层组合物能力的方法是使用表面活性剂。表面活性剂可降低水基纳米颗粒分散体的表面张力,从而改进软表面的润湿性。润湿软表面非常重要,因为它可使分散体携带纳米颗粒横跨更大的表面区域,从而增加覆盖率。
虽然在一些上述疏水或临界亲水材料中,表面活性剂非常适合于多种应用,但涂布过程中残留表面活性剂的存在对该材料使用时的再润湿尤其有害,例如在转运流体的制品中,包括但不限于吸收制品和一次性吸收制品如尿布和其它失禁及月经产品如妇女护垫中,使用时经受一重或多重液体涌出(例如尿液、月经、汗液或其它身体排泄物)。
使用时,液体涌出物将残留的表面活性剂从软表面冲洗到液相中。液相中即使低水平的残留表面活性剂也可降低液体的表面张力。液相中表面张力的降低使得沿纤维的芯吸张力降低(表面张力X接触角的余弦)。较低的芯吸张力降低了芯吸速率,进而降低了通过或沿多孔织物的芯吸通量(单位时间内、单位截面积上流体的量)。芯吸通量的降低导致最终使用者的流体处理性能较低。
液相中表面张力的降低也可增加其润湿本来疏水的纤维表面的能力。一旦原来疏水的纤维被润湿,它开始显示亲水行为。通过芯吸张力、重力、压力梯度力或其它的力,流体可通过排斥流体(如水)的疏水表面。
降低流体表面张力以改进纳米颗粒分散体润湿软表面程度的另一种方法是增加软表面的表面能。因此,在一些实施方式中,可通过对材料进行某种高能表面处理以形成处理表面,来增加表面的表面能。高能表面处理包括但不限于:电晕放电处理、等离子处理、UV辐射处理、离子束处理、电子束处理、某些激光处理如脉冲激光器处理和其它辐射技术处理,只要能够增加某些纤维当中的一部分的表面能。要小心,以避免对待处理材料产生不良影响。在一些情况下,希望在软表面的两面上都进行这种处理。此外,考虑该任选步骤是与对软表面施加涂层组合物相独立的预处理步骤,也可以联合这两种步骤。
增加表面能的高能表面处理是有用的,因为其与纳米颗粒联用可提供具有持久亲水性质的表面。同时,增加表面能可提高软表面的润湿性,而无需在分散体中使用表面活性剂以实现润湿。避免使用表面活性剂是因为上述原因。在非限制性实施例中,电晕处理使纤维热塑表面上形成短暂电荷。如前所述,部分或全部电荷随时间消散,维持纤维热塑表面上部分或全部电荷是一个普遍的限制。然而,已发现电晕处理可与纳米颗粒联用,以在材料上产生持久电荷,随时间增加材料继续吸引水。纳米颗粒与高能表面处理结合使用可将该处理的短暂性质转化为更持久的性质。在一个非限制性例子中,对13克/平方米疏水SMS聚丙烯无纺材料进行电晕处理,再用纳米颗粒分散体处理并干燥后,它显示经多次侵袭后始终能快速透水。不希望受理论限制,电晕处理可增加纤维的表面能。电荷消散之前,不含表面活性剂的纳米颗粒分散体与纤维表面接触。较高的表面能使得分散体比不进行电晕处理更好地润湿纤维表面。在润湿的表面上,纳米颗粒与表面上部分或全部电荷结合,如果不结合,这些电荷是短暂的。结合是以范德华相互作用的形式或以一些其它相互作用或键合的形式实现的。纳米颗粒足够小,以使结合强度足以经受多次透水。纳米颗粒足够大,以抵抗旋转远离氧进入聚合物或,如上所述消散。纳米颗粒需要高能表面处理,无需表面活性剂而可润湿,一旦干燥,能均匀沉积;高能表面处理需要纳米颗粒产生持久的带电表面。
经受高能表面处理,并且其上沉积有复合材料的材料适用于许多用途,包括但不限于,用于转运制品,如包含疏水或临界亲水纤维的吸收制品以及部分一次性吸收制品中的液体。一次性吸收制品部分包括但不限于,顶层、获取层、分布层、芯吸层、储存层、吸收芯、吸收芯外包装和内容结构。
在另一些实施方式中,可使用其它方法提高材料表面接受涂层组合物的能力。这些方法包括但不限于:在材料上提供压力梯度(包括但不限于通过使用压力辊、印刷辊、展平辊、流体静压等);不使用表面活性剂而降低表面上涂层组合物的表面张力(例如,用乙醇代替表面活性剂);通过使用“可降解”或“可清除”的表面活性剂;以及,如下更详细介绍的,通过在材料上喷墨印刷组合物。
在这里,表面也可称为“底物”。不希望被任何具体理论或特征所束缚,在一些实施方式中,在这里提高表面接受涂层组合物的能力的处理物等,也可认为是表面的“底涂层”。在一些实施方式中,软表面涂层组合物可认为是含活性材料(复合材料)的水性分散体。当涂层干燥时,将分布在表面上的活性电荷材料留下来。并且,不希望被任何具体理论或特征所束缚,在一些实施方式中,底涂层和复合材料是相互独立的。在一些实施方式中,分布在表面上的复合材料可用于“锁定”底涂层的性质,以使这些性质不再短暂,并且底涂层能更有效地使纳米颗粒与表面结合。
存在许多将涂层组合物直接或间接施加于软表面的方法的实施方式。术语“直接施加”在这里指将涂层组合物直接施加于软表面的方法。直接施加包括但不限于,将涂层组合物直接喷射到软表面上。术语“间接施加”在这里指将涂层组合物施加于某种其它制品,该制品将涂层组合物施加于软表面。间接施加包括但不限于,将涂层组合物施加于辊,辊将涂层组合物施加于软表面上。
在一个非限制性实施方式中,将有效量的液体软表面涂层组合物可选地喷射到软表面和/或软表面制品上,软表面制品包括但不限于:吸收制品,包括那些具有合成和天然纤维等的吸收制品。当将涂层组合物喷射到软表面上时,有效量的涂层组合物可沉积于软表面上,软表面变得潮湿或完全被涂层组合物所饱和。通过喷射将涂层组合物施加于表面(如软表面)具有许多优点。如果需要,该涂层组合物可定向施加在要施加涂层组合物的制品的特定区域;仅施加于制品的一面(与浸没方法不同);并且更有效,因为更多的复合材料保留在表面上而不是在冲洗或漂洗过程中被冲走。
也可在浸没容器中通过浸渍或浸泡方法、再通过任选的干燥步骤,将涂层组合物施加于表面如软表面上。该施加过程可在工业应用中,或在消费者家里,在软表面和/或成品上大规模进行。
在另一个非限制性实施方式中,可通过将涂层组合物印刷到软表面上,而将涂层组合物应用于软表面。可使用任何合适的印刷技术,包括但不限于:传输印刷如旋转印刷、凹版印刷、橡皮版印刷和喷墨印刷。尤其感兴趣的是喷墨印刷,因为其小滴较高的惯性能够使涂层组合物沿底物表面分布,暂时提高涂料组合物润湿软表面的能力。液滴的低热质量使载体介质能快速蒸发,一般约为0-10秒,优选约为0.1-1秒或更短。冲击后液滴表面张力从铺展状态完全恢复之前,载体介质开始蒸发。若分散体在载体介质蒸发之前润湿表面,则复合材料保留。所述分散体的喷墨印刷对疏水表面、临界亲水表面以及前进结合角充分大于后退接触角的表面有益。
可以较低粘度的分散体形式制备涂层组合物(例如,如果需要,可小于约10厘泊,优选小于约5厘泊),使其可流过喷墨喷嘴并以比粘度较高时要小的流阻穿过表面。与常规分散体中常规大小的颗粒不同,纳米颗粒足够小而不会进入低粘介质中,也不会阻塞喷墨印刷机的喷嘴。可使用任何合适类型的喷墨印刷技术,包括但不限于,响应式液滴喷墨印刷机如具有振荡加热元件的液滴蒸发型和具有机械泵和振荡晶体的液滴喷射型。在一些实施方式中,可将软表面和其它制品移过或通过喷墨印刷喷嘴。在另一些实施方式中,例如在硬表面的情况下,喷墨印刷机被设计成相对于表面移动。
在一些实施方式中,希望复合材料的折光指数大于或等于约1.3。在一些实施方式中,希望复合材料的折光指数小于或等于5.5。可使用整块复合材料或整块材料薄膜,用椭圆计测定复合材料的折光指数。
在一些实施方式中,发现随着粒径的增加,通常软表面变暗。当然,所用颗粒也不应大到在软表面上肉眼可见。
在一些实施方式中,可以这样施加涂层组合物,待涂层组合物干燥后,复合材料覆盖大于或等于约0.5%的软表面的表面积。
本发明还涉及一种产品,该产品的包装中包含本发明软表面涂层组合物。涂层组合物可与如何使用涂层组合物的指导说明一起提供,该说明介绍了如何处理软表面以修饰软表面,得到至少一个所述希望的结果。
在一个非限制性实施方式中,产品的喷雾分散器中包含软表面涂层组合物,以及如何使用该涂层组合物来正确处理软表面的指导说明,例如喷射组合物的方式和/或量,施加涂层组合物的优选方法,如下详细所述。指导说明应尽可能简单明了,包括在需要时使用图片和/或图标。
可将软表面涂层组合物置于喷雾分散器中,以分布到软表面上。喷雾分散器可以是任何将涂层组合物施加到表面区域和/或多种底物上的手动激活型,以及方便地将涂层组合物施加于大的硬表面区域和/或多种底物上的非手动操作的电动型。喷雾分散器可包括但不限于以下任意一种:气溶胶喷雾分散器、自加压喷雾分散器、非气溶胶手动激活型、泵式喷雾分散器、手动激活触发-喷雾分散器、触发型喷雾器或指泵喷雾器、非手动操作的喷雾分散器,包括但不限于,电动喷雾器、吸气式喷雾器、吸液式喷雾器、静电喷雾器和雾化喷雾器。电动喷雾器包括但不限于,离心或正位移设计。其它类型的喷雾器包括但不限于:静电喷雾器,可降低泡沫并在多种条件下形成目测残留较少的合适的涂层。这使得涂层组合物中可使用多种表面活性剂。
本发明还涉及一种产品,该产品包含以可防止过量的涂层组合物释放入开放环境的方式来喷雾和/或雾化整个软表面或制品的软表面涂层组合物,与用于确保消费者施加至少有效量的涂层组合物的指导说明一起提供,以提供所需的软表面多用途优点。
本发明还考虑包括关于本发明软表面涂层组合物的使用的指导说明,包装上包括本发明涂层组合物或其它形式的关于该涂层组合物的销售和使用的广告。可以消费品生产商或供应商一般使用的任何方式提供指导说明。例子包括在装有涂层组合物的容器的标签上;在购买时的容器或附件所附清单上;或在关于涂层组合物的购买或使用的广告、说明和/或其它书面或口头指导说明中提供指导说明。
具体地说,指导说明可包括涂层组合物使用的描述,例如,用于涂覆表面或制品的推荐量;施加于表面的推荐量;采用喷雾、浸润或擦拭是否合适。
涂层组合物可包含在产品中。
除非另有说明,本文所用所有部分、百分比和比率是重量百分比。
虽然本发明组合物和方法集中在软表面的家用修饰上,本发明组合物的方法亦可月于软表面的工业修饰,例如纺织厂。
本文提及的所有专利、专利申请(其上公布的任何专利,以及相应的外国公开专利申请)和出版物的内容被纳入本文作为参考。然而,很清楚,参考包括在此的任何文献没有公开或描述本发明。
虽然描述了本发明的具体实施方式,本领域技术人员应明白,只要不背离本发明的精神和范围,可对本发明进行多种改变和改进。所附权利要求书旨在包括本发明范围内的所有这些改进。
列出的所有专利和专利申请的全部内容被纳入本文作为参考。
实施例
实施例1
为使金属银沉积到纳米粘土上,用托伦试剂在Laponite的存在下还原银离子,银离子可通过以下反应被醛或酮还原为银金属:
Ag(NH3)2OH+葡萄糖→Ag0
将两滴10%NaOH加入到5毫升5%AgNO3中形成灰棕色沉淀,制备托伦试剂。然后,通过滴加2%NH4OH溶解该沉淀,得到总的托伦试剂30毫升。
将600毫克Laponite加入到50毫升蒸馏水中,并用磁力搅拌器使其剥脱20分钟,制备载银Laponite溶液。将800毫克葡萄糖加入到该溶液中,继续搅拌10分钟,以确保葡萄糖完全溶解。将10毫升上述制备的托伦试剂加入到该溶液中。继续搅拌2小时后,溶液变成金黄色。继续反应得到暗琥珀棕色溶液。10倍稀释所制备的用于粒子大小测定和TEM测定的样品,以防止颗粒聚集。纳米颗粒的粒子大小决定了质子表面共振现象导致的溶液颜色。对于银颗粒,黄色表示粒径最小。
实施例2
图1所示吸收制品的制备如下。覆盖层是由75%聚酯和25%人造丝(3P075V25P75,购自Spuntech Industries Ltd.,Upper Tiberias,Israel)构成的75gsm射流喷网面向身体层。背衬层是30gsm微孔聚乙烯背衬层(01030A1-1-1-1-2,FullSafe,Manila,Philippines)。用本发明软表面涂层组合物处理。软表面涂层组合物包含实施例1制备的载银纳米粘土。此外,涂层组合物包含表面活性剂和水性载体材料。通过喷雾将涂层组合物施涂于吸收芯。
Claims (22)
1.一种软表面涂层组合物,所述组合物包含:1)含有(a)具有表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料,其中,所述金属负载在所述纳米颗粒的表面上;2)载体介质;3)表面活性剂;和4)一种或多种辅助成分。
2.如权利要求1所述的软表面涂层组合物,其特征在于,所述复合材料包括纳米粘土。
3.如权利要求1所述的软表面涂层组合物,其特征在于,所述复合材料含有选自银、铜、锌、锰、铂、钯、金、钙、钡、铝、铁及其混合物的金属。
4.如权利要求1所述的软表面涂层组合物,其特征在于,所述复合材料是载银纳米粘土。
5.如权利要求1所述的软表面涂层组合物,其特征在于,所述载体介质包括水性载体介质。
6.如权利要求5所述的软表面涂层组合物,其特征在于,所述辅助成分选自:带电功能化分子、成膜剂、碱源、抗氧化剂、抗静电剂、螯合剂、金属盐、光活化无机金属氧化物、气味控制物质、光活化剂、聚合物、防腐剂、加工助剂、颜料、pH控制剂、增溶剂、沸石以及它们的混合物。
7.如权利要求6所述的软表面涂层组合物,其中所述的螯合剂是氨基羧酸盐螯合剂。
8.如权利要求6所述的软表面涂层组合物,其中所述的气味控制物质是芳香剂。
9.一种吸收制品,所述吸收制品包含含有(a)具有表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料,其中,所述金属负载在所述纳米颗粒的表面上。
10.如权利要求9所述的吸收制品,其特征在于,所述复合材料包括纳米粘土。
11.如权利要求9所述的吸收制品,其特征在于,所述复合材料含有选自银、铜、锌、锰、铂、钯、金、钙、钡、铝、铁及其混合物的金属。
12.如权利要求9所述的吸收制品,其特征在于,所述复合材料是载银纳米粘土。
13.一种修饰软表面的方法,所述方法包括对软表面施加包含以下成分的软表面涂层组合物:1)含有(a)具有表面的剥脱纳米颗粒和(b)选自第3-12族、铝和镁的金属的复合材料,其中,所述金属负载在所述纳米颗粒的表面上;2)载体介质;3)表面活性剂;和4)一种或多种辅助成分。
14.如权利要求13所述的方法,还包括干燥软表面上的软表面涂层组合物。
15.如权利要求14所述的方法,还包括再次将软表面涂层组合物施加于软表面和再次干燥该软表面涂层。
16.如权利要求13所述的方法,其特征在于,所述复合材料包括纳米粘土。
17.如权利要求13所述的方法,其特征在于,所述复合材料含有选自银、铜、锌、锰、铂、钯、金、钙、钡、铝、铁及其混合物的金属。
18.如权利要求13所述的方法,其特征在于,所述复合材料是载银纳米粘土。
19.如权利要求13所述的方法,其特征在于,所述载体介质包括水性载体介质。
20.如权利要求13所述的方法,其特征在于,所述辅助成分选自:带电功能化分子、成膜剂、碱源、抗氧化剂、抗静电剂、螯合剂、金属盐、光活化无机金属氧化物、气味控制物质、光活化剂、聚合物、防腐剂、加工助剂、颜料、pH控制剂、增溶剂、沸石以及它们的混合物。
21.如权利要求20所述的方法,其特征在于,所述螯合剂是氨基羧酸盐螯合剂。
22.如权利要求20所述的方法,其特征在于,所述气味控制物质是芳香剂。
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CN2004800359771A Expired - Fee Related CN1925879B (zh) | 2003-10-30 | 2004-11-01 | 复合材料、其制备方法、以及含有该复合材料的化妆品和药物组合物 |
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EP (2) | EP1677843B1 (zh) |
JP (2) | JP2007519767A (zh) |
CN (2) | CN100594944C (zh) |
AT (2) | ATE405300T1 (zh) |
AU (2) | AU2004285578B2 (zh) |
BR (2) | BRPI0415633B1 (zh) |
CA (2) | CA2544119C (zh) |
DE (2) | DE602004015134D1 (zh) |
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- 2004-11-01 CN CN200480035982A patent/CN100594944C/zh not_active Expired - Fee Related
- 2004-11-01 DE DE602004015134T patent/DE602004015134D1/de active Active
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- 2004-11-01 BR BRPI0415633-1A patent/BRPI0415633B1/pt not_active IP Right Cessation
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AU2004285578B2 (en) | 2010-10-07 |
US7988779B2 (en) | 2011-08-02 |
CA2544119A1 (en) | 2005-05-12 |
WO2005042040A1 (en) | 2005-05-12 |
AU2004285578A1 (en) | 2005-05-12 |
EP1682193B1 (en) | 2008-07-16 |
DE602004015134D1 (de) | 2008-08-28 |
CN1925879A (zh) | 2007-03-07 |
CA2544109C (en) | 2012-05-29 |
CN1925880A (zh) | 2007-03-07 |
US20050175649A1 (en) | 2005-08-11 |
ES2311879T3 (es) | 2009-02-16 |
US20050115462A1 (en) | 2005-06-02 |
WO2005042041A1 (en) | 2005-05-12 |
US20130189334A1 (en) | 2013-07-25 |
ATE401100T1 (de) | 2008-08-15 |
EP1677843A1 (en) | 2006-07-12 |
JP2007519615A (ja) | 2007-07-19 |
CA2544109A1 (en) | 2005-05-12 |
CN1925879B (zh) | 2011-07-13 |
ATE405300T1 (de) | 2008-09-15 |
CA2544119C (en) | 2012-05-29 |
BRPI0416114A (pt) | 2007-01-02 |
JP2007519767A (ja) | 2007-07-19 |
DE602004016022D1 (de) | 2008-10-02 |
BRPI0415633B1 (pt) | 2014-03-04 |
AU2004285579A1 (en) | 2005-05-12 |
EP1677843B1 (en) | 2008-08-20 |
BRPI0415633A (pt) | 2006-12-12 |
EP1682193A1 (en) | 2006-07-26 |
AU2004285579B2 (en) | 2011-02-10 |
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