CN105246443A - 包含多孔聚烯烃膜的吸收性制品 - Google Patents
包含多孔聚烯烃膜的吸收性制品 Download PDFInfo
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- CN105246443A CN105246443A CN201480030835.XA CN201480030835A CN105246443A CN 105246443 A CN105246443 A CN 105246443A CN 201480030835 A CN201480030835 A CN 201480030835A CN 105246443 A CN105246443 A CN 105246443A
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- absorbing products
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- inclusion additive
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Abstract
本发明提供了包含聚烯烃膜的吸收性制品。所述聚烯烃膜由包含连续相的热塑性组合物形成,所述连续相包括聚烯烃基质聚合物和纳米包含物添加剂。纳米包含物添加剂作为离散的纳米级相区域分散在连续相内。当拉伸时,所述纳米级相区域能够以独特的方式与基质相互作用以产生纳米孔的网络。
Description
相关申请
本发明要求申请号为61/833,980的美国临时申请(于2013年6月12日提交)和申请号为61/907,572的美国临时申请(于2013年11月22日提交)的优先权,将其引入本文作为参考。
发明背景
吸收性制品,如尿布或女性护理制品,通常由设置在液体可渗透的顶片和通常液体不可渗透的底片之间的吸收性元件构成,所述顶片限定朝向身体设置的“朝向身体的”表面,所述底片限定远离身体设置的“朝向服装的”表面。聚烯烃膜通常用于吸收性制品的组件和/或层的构造中。例如,许多吸收性制品的底片包含微孔聚乙烯膜。然而,近年来,石油资源已变得更加昂贵,并且制造商和消费者也已变得更加意识到对于具有更小的碳足迹的吸收性制品的可持续性需求,这意味着在整个产品寿命周期过程中降低的碳排放。虽然已尝试将各种添加剂添加到聚烯烃膜以降低石油衍生的烯烃聚合物的含量,但这通常导致一些机械性能(例如,延展性或抗拉强度等)相应降低,这是很不希望的。因此,目前存在对可以具有降低的石油基聚合物的消耗,但仍然可以显示良好的性能的吸收性制品的膜的需求。
发明内容
根据本发明的一个实施方案,公开了包含设置在底片和顶片之间的吸收性元件的吸收性制品。所述吸收性制品包括由包含连续相的热塑性组合物形成的膜,所述连续相包括聚烯烃基质聚合物和以离散区域的形式分散在连续相内的纳米包含物添加剂。在组合物中限定了多孔网络,其包括多个平均横截面尺寸为约800纳米或更小的纳米孔。
本发明的其它特征和方面在下文更加详细地讨论。
附图的简要说明
针对本领域普通技术人员的本发明的完整且能够实现的公开内容,包括其最佳方式,在说明书的剩余部分更具体地阐述,并参照附图,其中:
图1是用于形成本发明的膜的方法的一个实施方案的示意图;
图2是本发明的吸收性制品的一个实施方案的透视图;
图3是在14,243X的放大倍率下拍摄的实施例4的膜的表面的SEM显微照片;和
图4是在5,382X的放大倍率下拍摄的实施例4的膜(在机器方向平面上切割)的SEM显微照片。
代表性实施方案的详细描述
现在将详细参照本发明的各种实施方案,其一个或多个实例在下文阐述。每个实例以解释本发明而不是限制本发明的方式提供。事实上,对本领域技术人员显而易见的是,在不背离本发明的范围或精神的情况下,可以在本发明中做出各种修改和变化。例如,作为一个实施方案的部分说明或描述的特征,可以用于另一个实施方案以产生又一个实施方案。因此,本发明旨在覆盖落入所附权利要求及其等同方案的范围内的这样的修改和变化。
一般来说,本发明涉及能够吸收水或其它流体的吸收性制品。一些吸收性制品的实例包括但不限于,个人护理吸收性制品,如尿布、训练裤、吸收性内裤、成人失禁制品、女性卫生产品(例如,卫生巾)、泳衣、婴儿揩巾、手套揩巾等;医疗吸收性制品,如服装、开窗术材料、垫料、绷带、吸收性帘和医用揩巾;食品服务揩巾;服装制品等等。不论预期应用如何,吸收性制品通常包含位于底片和顶片之间的吸收性元件(例如,芯层、浪涌层、传递延迟层等)。值得注意地,吸收性元件、底片和/或顶片以及吸收性制品的一个或多个其它组件(例如耳片、防护翼、侧片等)包含由热塑性组合物形成的膜。所述热塑性组合物包括含聚烯烃基质聚合物的连续相,还包括与所述聚烯烃基质聚合物至少部分地不相容的纳米包含物添加剂,使得所述纳米包含物添加剂成为分散在连续相中的离散的纳米级相区域。在拉伸过程中,当所述组合物经受变形和拉伸应变时,本发明人已发现的是,这些纳米级相区域能够以独特的方式相互作用以产生孔的网络。即,认为由于材料的不相容性引起的应力集中,拉伸应变可以在离散相区域附近产生加强的局部剪切区和/或应力强度区(例如,正应力)。这些剪切和/或应力强度区域导致在邻近区域的聚烯烃基质中的一些初始剥离。一旦初始孔形成,位于区域之间的基质可以塑性变形以产生局部变窄(或颈缩)并且应***化的内部拉伸区域。该过程使得通过在拉伸方向上增长的组合物的主体形成孔,从而当分子取向导致增强机械强度的应***化时,导致多孔网络的形成。
通过以上记载的技术,在聚烯烃膜中可以形成独特的多孔网络,使得在给定的单位体积的材料中,被孔占据的平均百分体积可以为每cm3材料约15%至约80%,在一些实施方案中为每立方厘米材料约20%至约70%,并且在一些实施方案中为每立方厘米材料约30%至约60%。通过这样的孔体积,所述组合物可以具有相对低的密度,例如约0.90克每立方厘米(“g/cm3”)或更小,在一些实施方案中为约0.85g/cm3或更小,在一些实施方案中为约0.80g/cm3或更小,在一些实施方案中为约0.10g/cm3至约0.75g/cm3,并且在一些实施方案中为约0.20g/cm3至约0.70g/cm3。在多孔网络中的大部分孔还是“纳米级”尺寸(“纳米孔”),如具有约800纳米或更小,在一些实施方案中为约5至约700纳米,并且在一些实施方案中为约10至约500纳米的平均横截面尺寸的那些。术语“横截面尺寸”通常是指孔的特性尺寸(例如宽度或直径),所述特性尺寸与孔的主轴(例如长度)基本正交,并且通常还与拉伸过程中所施加的应力的方向基本正交。所述纳米孔还可以具有为约100至约5000纳米,在一些实施方案中为约50至约2000纳米,并且在一些实施方案中为约100至约1000纳米的平均轴向尺寸。所述“轴向尺寸”为主轴(例如长度)方向的尺寸,所述主轴方向通常是拉伸的方向。这样的纳米孔例如可以占聚烯烃膜中总孔体积的约15vol.%或更多,在一些实施方案中为约20vol.%或更多,在一些实施方案中为约30vol.%至约100vol.%,以及在一些实施方案中为约40vol.%至约90vol.%。
除了降低的密度,纳米多孔结构还可以向产生的聚烯烃膜提供多种另外的不同益处。例如,这样的结构可以帮助限制流体通过膜的流动,并且一般是流体(例如,液态水)不可渗透的,从而允许膜隔离表面不被水渗透。在这方面,如根据ATTCC127-2008所测定的,聚烯烃膜可以具有约50厘米(“cm”)或更高,在一些实施方案中为约100cm或更高,在一些实施方案中为约150cm或更高,和在一些实施方案中约200cm至约1000cm的相对高的静水压值。还可以实现其它有益性能。例如,产生的聚烯烃膜可以一般是水蒸气可渗透的。膜对水蒸气的渗透性可以通过其相对高的水蒸气传递速率(“WVTR”)来表征,所述水蒸气传递速率是测量的是水蒸气渗透通过膜的速率,以克每平方米每24小时(g/m2/24hr)为单位。例如,如根据ASTME96/96M-12,程序B或INDA测试程序IST-70.4(01)所测定的,聚烯烃膜可以显示约300g/m2-24小时或更高,在一些实施方案中为约500g/m2-24小时或更高,在一些实施方案中为约1,000g/m2-24小时或更高,以及在一些实施方案中为约3,000至约15,000g/m2-24小时的WVTR。
现在将更详细地描述本发明的各种实施方案。
I.热塑性组合物
A.聚烯烃基质
聚烯烃通常占热塑性组合物的约60wt.%至约99wt.%,在一些实施方案中占约60wt.%至约98wt.%,和在一些实施方案中占约80wt.%至约95wt.%。聚烯烃可以具有约100℃至约220℃,在一些实施方案中为约120℃至约200℃,和在一些实施方案中为约140℃至约180℃的熔融温度。熔融温度可以根据ASTMD-3417应用差示扫描量热法("DSC")来测定。适合的聚烯烃可以例如包括乙烯聚合物(例如,低密度聚乙烯("LDPE")、高密度聚乙烯("HDPE")、线性低密度聚乙烯("LLDPE")等)、丙烯均聚物(例如,间同立构、无规立构、全同立构等)、丙烯共聚物等等。在一个具体的实施方案中,所述聚合物为丙烯聚合物,如均聚丙烯或者丙烯共聚物。丙烯聚合物例如可以由基本上全同立构的聚丙烯均聚物或者含有等于或低于约10wt.%的其它单体,即按重量计至少约90%的丙烯的共聚物形成。这样的均聚物可以具有约140℃至约170℃的熔点。
当然,其它聚烯烃也可以用于本发明的组合物中。在一个实施方案中,例如,聚烯烃可以是乙烯或丙烯与另一种α-烯烃,如C3-C20α-烯烃或者C3-C12α-烯烃的共聚物。适合的α-烯烃的具体实例包括1-丁烯;3-甲基-1-丁烯;3,3-二甲基-1-丁烯;1-戊烯;具有一个或多个甲基、乙基或丙基取代基的1-戊烯;具有一个或多个甲基、乙基或丙基取代基的1-己烯;具有一个或多个甲基、乙基或丙基取代基的1-庚烯;具有一个或多个甲基、乙基或丙基取代基的1-辛烯;具有一个或多个甲基、乙基或丙基取代基的1-壬烯;乙基、甲基或二甲基取代的1-癸烯;1-十二碳烯;以及苯乙烯。特别希望的α-烯烃共聚单体是1-丁烯、1-己烯和1-辛烯。这样的共聚物的乙烯或丙烯含量可以为约60摩尔%至约99摩尔%,在一些实施方案中为约80摩尔%至约98.5摩尔%,和在一些实施方案中为约87摩尔%至约97.5摩尔%。α-烯烃的含量同样可为约1摩尔%至约40摩尔%,在一些实施方案中为约1.5摩尔%至约15摩尔%,和在一些实施方案中为约2.5摩尔%至约13摩尔%。
用于本发明的示例性烯烃共聚物包括可以以名称EXACTTM获自Texas的Houston的ExxonMobilChemicalCompany的基于乙烯的共聚物。其它适合的乙烯共聚物可以以名称ENGAGETM、AFFINITYTM、DOWLEXTM(LLDPE)和ATTANETM(ULDPE)获自Michigan的Midland的DowChemicalCompany。其它适合的乙烯聚合物描述于Ewen等人的第4,937,299号美国专利;Tsutsui等人的第5,218,071号美国专利;Lai等人的第5,272,236号美国专利;和Lai等人的第5,278,272号美国专利。适合的丙烯共聚物也可以商购自Texas的Houston的ExxonMobilChemicalCo.,名称为VISTAMAXXTM;Belgium的Feluy的AtofinaChemicals,名称为FINATM(例如,8573);可得自MitsuiPetrochemicalIndustries的TAFMERTM;以及可得自Michigan的Midland的DowChemicalCo.的VERSIFYTM。适合的聚丙烯均聚物可包括ExxonMobil3155聚丙烯、ExxonMobilAchieveTM树脂,和TotalM3661PP树脂。适合的丙烯聚合物的其它实例描述于Datta等人的第6,500,563号美国专利;Yang等人的第5,539,056号美国专利;Resconi等人的第5,596,052号美国专利。
各种已知技术中的任一种通常都可以用于形成烯烃共聚物。例如,烯烃聚合物可以应用自由基或者配位催化剂(例如,Ziegler-Natta)形成。优选地,烯烃聚合物由单中心配位催化剂,如茂金属催化剂形成。这样的催化剂体系制备了这样的乙烯共聚物,其中共聚单体是在分子链内无规分布的并且在不同分子量的部分中都是均匀分布的。茂金属催化的聚烯烃描述于例如McAlpin等人的第5,571,619号美国专利;Davis等人的第5,322,728号美国专利;Obijeski等人的第5,472,775号美国专利;Lai等人的第5,272,236号美国专利;和Wheat等人的第6,090,325号美国专利。茂金属催化剂的实例包括双(正丁基环戊二烯基)二氯化钛、双(正丁基环戊二烯基)二氯化锆、双(环戊二烯基)氯化钪、双(茚基)二氯化锆、双(甲基环戊二烯基)二氯化钛、双(甲基环戊二烯基)二氯化锆、二茂钴、环戊二烯基三氯化钛、二茂铁、二氯二茂铪、异丙基(环戊二烯基-1-芴基(flourenyl))二氯化锆、二氯二茂钼、二茂镍、二氯二茂铌、二茂钌、二氯二茂钛、氢氯二茂锆、二氯二茂锆等。用茂金属催化剂制得的聚合物通常具有窄的分子量范围。例如,茂金属催化的聚合物可以具有4以下的多分散性数值(Mw/Mn)、受控的短链支化分布、以及受控的全同立构规整度。
B.纳米包含物添加剂
如本文所使用的,术语“纳米包含物添加剂”通常是指能够以纳米级尺寸的离散区域的形式分散在聚合物基质内的材料。例如,在拉伸之前,区域可以具有约1至约1000纳米,在一些实施方案中为约5至约800纳米,在一些实施方案中为约10至约500纳米,和在一些实施方案中为约20至约200纳米的平均横截面尺寸。区域可以具有多种不同的形状,如椭圆形、球形、圆柱形、板状、管状等。在一个实施方案中,例如,区域具有基本上椭圆的形状。基于连续相聚烯烃基质的重量,纳米包含物添加剂通常应用的量为热塑性组合物的约0.05wt.%至约20wt.%,在一些实施方案中为约0.1wt.%至约10wt.%,和在一些实施方案中为约0.5wt.%至约5wt.%。纳米包含物添加剂在整个热塑性组合物中的浓度同样地可以是热塑性组合物的约0.01wt.%至约15wt.%,在一些实施方案中为约0.05wt.%至约10wt.%,和在一些实施方案中为约0.3wt.%至约6wt.%。
纳米包含物添加剂可以基本上均匀地分布到聚烯烃基质中,但是以离散区域的形式,就这个意义而言,所述纳米包合物添加剂与所述聚烯烃部分地不相容。这样的部分不相容性可以通过各种方式实现。在某些实施方案中,例如,所述纳米包含物添加剂可以具有与聚烯烃基质相容并且允许其均匀分布在其中的非极性组分(例如烯烃)。然而,所述添加剂还可以包括与所述聚烯烃基质不相容的极性组分,从而允许其合并或分离成离散区域。这样的组分可以包括低或高分子量的极性分子链段或嵌段、离子基团、带电荷或不带电荷的极性区域和/或极性分子基团。供选择地,所述添加剂可以是性质完全非极性的,但是具有某些物理特性,从而仍然能够形成离散区域。例如,在某些实施方案中,所述纳米包含物添加剂在某个温度以上可以是与聚烯烃相容的或可混溶的,但是在低于临界共溶温度的温度下相分离。以这样的方式,所述纳米包含物添加剂可以与聚烯烃在熔融相中形成稳定的共混物,但是随着温度降低,所述连续相结晶并分离,从而所述纳米包含物添加剂可以相分离、合并并形成分离的纳米级区域。
只要可以形成期望的区域,则纳米包含物添加剂的具体状态或形式不是关键的。例如,在一些实施方案中,纳米包含物添加剂在室温(例如,25℃)下可以是液体或半固体形式。这样的液体可以容易地分散在基质中以形成亚稳态的分散体,然后通过降低共混物的温度急冷以保持区域尺寸。在40℃下测得的这样的液体或半固体材料的运动粘度通常为约0.7至约200厘沲(“cs”),在一些实施方案中为约1至约100cs,和在一些实施方案中为约1.5至约80cs。适合的液体或半固体可包括例如硅酮、硅酮-聚醚共聚物、脂肪族聚酯、芳香族聚酯、亚烷基二醇(例如乙二醇、二甘醇、三甘醇、四甘醇、丙二醇、聚乙二醇、聚丙二醇、聚丁二醇等)、烷二醇(例如,1,3-丙二醇、2,2-二甲基-1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2,4-三甲基-1,6-己二醇、1,3-环己烷二甲醇、1,4-环己烷二甲醇、2,2,4,4-四甲基-1,3-环丁二醇等)、胺氧化物(例如辛基二甲基氧化胺)、脂肪酸酯、脂肪酸酰胺(例如油酸酰胺、芥酸酰胺、硬脂酰胺、亚乙基双(十八酰胺)等)、矿物和植物油等。一种特别适合的液体或半固体是聚醚多元醇,例如可以从BASFCorp.以商标名WI商业购得。
在又一个实施方案中,纳米包含物添加剂是固体形式,其可以是无定形的、结晶或半结晶。例如,纳米包含物添加剂的性质可以是聚合的,并且具有相对高的分子量以帮助改进热塑性组合物的熔体强度和稳定性。如上所述的,纳米包含物添加剂与聚烯烃基质部分不相容。这样的添加剂的一个实例是微晶聚烯烃蜡,其通常源自乙烯和/或C3-C10-烷(alk)-1-烯,如源自丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯和1-癸烯。微晶蜡通常具有相对低的熔融温度,如约30℃至约150℃,在一些实施方案中为约50℃至约140℃,和在一些实施方案中为约80℃至约130℃。在这样低的熔融温度下,当在熔融相中时,蜡可以与聚烯烃形成易混溶的共混物,但当温度降低并且聚合物结晶或固化时,蜡将分离和合并,形成分开的纳米级区域。
聚合纳米包含物添加剂的另一个实例是包含极性和非极性组分的官能化的聚烯烃。极性组分可以例如由一个或多个官能团提供,并且非极性组分可以由烯烃提供。纳米包含物添加剂的烯烃组分可以一般由任意直链或支链α-烯烃单体、低聚物或源自烯烃单体的聚合物(包括共聚物)形成,如以上所述的。纳米包含物添加剂的官能团可以是任何基团、分子链段和/或嵌段,其向分子提供极性组分并且与聚烯烃基质聚合物是不相容的。与聚烯烃不相容的分子链段和/或嵌段的实例可以包括丙烯酸酯、苯乙烯、聚酯、聚酰胺等。官能团可以具有离子性质并包括带电的金属离子。特别适合的官能团是马来酸酐、马来酸、富马酸、马来酰亚胺、马来酰肼、马来酸酐和二胺的反应产物、甲基降冰片烯二酸酐、二氯马来酸酐、马来酸酰胺等。马来酸酐改性的聚烯烃特别适用于本发明。这样的改性的聚烯烃通常通过将马来酸酐接枝到聚合物主链材料上形成。这样的马来酸化的聚烯烃以名称得自E.I.duPontdeNemoursandCompany,如P系列(化学改性的聚丙烯)、E系列(化学改性的聚乙烯)、C系列(化学改性的乙烯醋酸乙烯酯)、A系列(化学改性的乙烯丙烯酸酯共聚物或三元共聚物)或N系列(化学改性的乙烯-丙烯、乙烯-丙烯二烯单体(“EPDM”)或乙烯-辛烯)。供选择地,马来酸化的聚烯烃也以名称得自ChemturaCorp.、以名称EastmanG系列得自EastmanChemicalCompany和以名称得自Arkema。
在某些实施方案中,聚合纳米包含物添加剂还可以是反应性的。这样的反应性纳米包含物添加剂的一个实例是聚环氧化物,其平均每个分子含有至少两个环氧乙烷环。不打算受理论限制,认为这样的聚环氧化物分子可以与组合物的某些组分进行反应(例如,链延伸、侧链支化、接枝、共聚物形成等),从而在不显著降低玻璃化转变温度的情况下改进其熔体强度。反应性添加剂还可以提供聚烯烃和其它更多种极性添加剂如微米包含物添加剂之间的相容性,并且可以改进分散均匀性并降低微米包含物添加剂的尺寸。例如,如以下将更加详细地描述的,本发明的某些实施方案可以应用聚酯作为微米包含物添加剂。在这样的实施方案中,反应性纳米包含物添加剂可以通过聚酯的羧基末端基团实现亲核开环反应(酯化)或通过羟基实现亲核开环反应(醚化)。可以同样发生噁唑啉副反应以形成酯酰胺部分。通过这样的反应,聚酯微米包含物添加剂的分子量可以增加以抵消在熔融过程中通常观察到的降解。本发明人已发现太多反应可以导致聚合物主链之间的交联。如果允许这样的交联进行到显著的程度,所产生的聚合物共混物可以变脆并难以加工成具有期望的强度和伸长特性的材料。
在这方面,本发明人已经发现具有相对低环氧官能度的聚环氧化物可以是特别有效的,其可以通过其“环氧当量”定量。环氧当量反映含有一分子环氧基团的树脂的量,并且其可以通过将改性剂的数均分子量除以分子中环氧基团的数量来计算。本发明的聚环氧化物通常具有每摩尔约7,500至约250,000克,在一些实施方案中为每摩尔约15,000至约150,000克,和在一些实施方案中为每摩尔约20,000至100,000克的数均分子量,多分散指数通常为2.5至7。聚环氧化物可以含有小于50个,在一些实施方案中为5至45个,和在一些实施方案中为15至40个环氧基团。反过来,环氧当量可以小于每摩尔约15,000克,在一些实施方案中为每摩尔约200至约10,000克,和在一些实施方案中为每摩尔约500至约7,000克。
聚环氧化物可以是直链或支链的均聚物或共聚物(例如,无规、接枝、嵌段等),其包含末端环氧基团、骨架环氧乙烷单元和/或环氧侧基。用于形成这样的聚环氧化物的单体可以变化。在一个具体的实施方案中,例如,聚环氧化物含有至少一种环氧官能的(甲基)丙烯酸单体组分。如本文所使用的,术语“(甲基)丙烯酸”包括丙烯酸和甲基丙烯酸单体,以及其盐或酯,如丙烯酸酯和甲基丙烯酸酯单体。例如,适合的环氧官能的(甲基)丙烯酸单体可以包括但不限于含有1,2-环氧基团的那些,如丙烯酸缩水甘油酯和甲基丙烯酸缩水甘油酯。其它适合的环氧官能的单体包括烯丙基缩水甘油醚、乙基丙烯酸缩水甘油酯和衣康酸缩水甘油酯(glycidylitoconate)。
如上所指出的,聚环氧化物通常具有相对高的分子量,以使其不仅可以导致链延伸,还可以帮助实现期望的共混物形态。因此在2160克的负载和190℃的温度下测定的产生的聚合物的熔体流动速率通常为每10分钟约10至约200克,在一些实施方案中为每10分钟约40至约150克,和在一些实施方案中为每10分钟约60至约120克。
聚环氧化物通常还包括至少一种直链或支链的α-烯烃单体,如具有2至20个碳原子和优选为2至8个碳原子的那些。具体实例包括乙烯、丙烯、1-丁烯;3-甲基-1-丁烯;3,3-二甲基-1-丁烯;1-戊烯;具有一个或多个甲基、乙基或丙基取代基的1-戊烯;具有一个或多个甲基、乙基或丙基取代基的1-己烯;具有一个或多个甲基、乙基或丙基取代基的1-庚烯;具有一个或多个甲基、乙基或丙基取代基的1-辛烯;具有一个或多个甲基、乙基或丙基取代基的1-壬烯;乙基、甲基或二甲基取代的1-癸烯;1-十二烯;和苯乙烯。特别期望的α-烯烃共聚单体是乙烯和丙烯。另一种适合的单体可以包括非环氧官能的(甲基)丙烯酸单体。这样的(甲基)丙烯酸单体的实例可以包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁酯、丙烯酸仲丁酯、丙烯酸异丁酯、丙烯酸叔丁酯、丙烯酸正戊酯、丙烯酸异戊酯、丙烯酸异冰片酯、丙烯酸正己酯、丙烯酸-2-乙基丁酯、丙烯酸-2-乙基己酯,丙烯酸正辛酯、丙烯酸正癸酯、丙烯酸甲基环己酯、丙烯酸环戊酯、丙烯酸环己酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸正丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丙酯、甲基丙烯酸异丁酯、甲基丙烯酸正戊酯、甲基丙烯酸正己酯、甲基丙烯酸异戊酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸-2-乙基丁酯、甲基丙烯酸甲基环己酯、甲基丙烯酸肉桂酯、甲基丙烯酸巴豆酯、甲基丙烯酸环己酯、甲基丙烯酸环戊酯、甲基丙烯酸-2-乙氧基乙酯、甲基丙烯酸异冰片酯等,以及其组合。
在本发明的一个特别期望的实施方案中,所述聚环氧化物是由环氧官能的(甲基)丙烯酸单体组分、α-烯烃单体组分和非环氧官能的(甲基)丙烯酸单体组分形成的三元共聚物。例如,聚环氧化物可以是乙烯-甲基丙烯酸酯-甲基丙烯酸缩水甘油酯共聚物,其具有以下结构:
其中x、y和z为1或更大。
环氧官能的单体可以使用各种已知技术形成聚合物。例如,含有极性官能团的单体可以接枝到聚合物主链上以形成接枝共聚物。这样的接枝技术在本领域是熟知的并描述于例如第5,179,164号美国专利中。在其它实施方案中,可以使用已知的自由基聚合技术,如高压反应、齐格勒-纳塔催化剂反应体系、单位点催化剂(例如,金属茂)反应体系等使含有环氧官能团的单体与单体共聚以形成嵌段或无规共聚物。
可以选择单体组分(或多种单体组分)的相对比例以实现环氧反应性和熔体流动速率之间的平衡。更具体地,高环氧单体含量可以导致良好的反应性,但是太高的含量可以使熔体流动速率降低到这样的程度,使得聚环氧化物不利地影响聚合物共混物的熔体强度。因此,在大多数实施方案中,环氧官能的(甲基)丙烯酸单体(或多种环氧官能的(甲基)丙烯酸单体)占共聚物的约1wt.%至约25wt.%,在一些实施方案中占约2wt.%至约20wt.%,和在一些实施方案中约占4wt.%至约15wt.%。α-烯烃单体(或多种α-烯烃单体)可以同样地占共聚物的约55wt.%至约95wt.%,在一些实施方案中占约60wt.%至约90wt.%,和在一些实施方案中占约65wt.%至约85wt.%。当应用时,其它单体组分(例如,非环氧官能的(甲基)丙烯酸单体)可以占共聚物的约5wt.%至约35wt.%,在一些实施方案中占约8wt.%至约30wt.%,和在一些实施方案中占约10wt.%至约25wt.%。可以用于本发明的适合的聚环氧化物的一个具体实例以名称AX8950或AX8900商购自Arkema。例如,AX8950具有70至100g/10min的熔体流动速率且具有7wt.%至11wt.%的甲基丙烯酸缩水甘油酯单体含量、13wt.%至17wt.%的丙烯酸甲酯单体含量和72wt.%至80wt.%的乙烯单体含量。另一种适合的聚环氧化物以名称PTW商购自DuPont,其为乙烯、丙烯酸丁酯和甲基丙烯酸缩水甘油酯的三元共聚物,并且具有12g/10min的熔体流动速率。
除了控制用于形成聚环氧化物的单体的类型和相对含量以外,还可以控制总重量百分比以实现期望的益处。例如,如果改性水平太低,可能不能实现熔体强度和机械特性的期望的升高。然而,本发明人还已发现,如果改性水平太高,可能由于强的分子相互作用(例如,交联)和由环氧官能团引起的物理网络形成而使加工受限。因此,基于组合物中应用的聚烯烃的重量,聚环氧化物通常应用的量为约0.05wt.%至约10wt.%,在一些实施方案中为约0.1wt.%至约8wt.%,在一些实施方案中为约0.5wt.%至约5wt.%,和在一些实施方案中为约1wt.%至约3wt.%。基于组合物的总重量,聚环氧化物还可以占约0.05wt.%至约10wt.%,在一些实施方案中为约0.05wt.%至约8wt.%,在一些实施方案中为约0.1wt.%至约5wt.%,和在一些实施方案中为约0.5wt.%至约3wt.%。
其它反应性纳米包含物添加剂也可以用于本发明,如噁唑啉官能化的聚合物、氰化物官能化的聚合物等。当应用时,这样的反应性纳米包含物添加剂可以在上述针对聚环氧化物的浓度内应用。在一个具体实施方案中,可以应用噁唑啉接枝的聚烯烃,其为用含噁唑啉环的单体接枝的聚烯烃。噁唑啉可以包括2-噁唑啉,如2-乙烯基-2-噁唑啉(例如,2-异丙烯基-2-噁唑啉)、2-脂肪烷基-2-噁唑啉(例如,可获得自油酸、亚油酸、棕榈油酸、顺二十碳9-烯酸、芥酸和/或花生四烯酸的乙醇酰胺)及其组合。在另一个实施方案中,例如,噁唑啉可以选自蓖麻油酸噁唑啉马来酸酯、十一烷基-2-噁唑啉、大豆-2-噁唑啉、蓖麻-2-噁唑啉及其组合。在又一个实施方案中,噁唑啉选自2-异丙烯基-2-噁唑啉、2-异丙烯基-4,4-二甲基-2-噁唑啉及其组合。
在本发明的某些实施方案中,多种纳米包含物添加剂可以组合使用。例如,第一纳米包含物添加剂(例如,聚环氧化物)可以以平均横截面尺寸为约50至约500纳米,在一些实施方案中为约60至约400纳米,和在一些实施方案中为约80至约300纳米的区域的形式分散。第二纳米包含物添加剂还可以以比第一纳米包含物添加剂更小的区域,如平均横截面尺寸为约1至约50纳米,在一些实施方案中为约2至约45纳米,和在一些实施方案中为约5至约40纳米的区域的形式分散。当应用时,基于连续相(基质聚合物(或多种基质聚合物))的重量,第一和/或第二纳米包含物添加剂通常占热塑性组合物的约0.05wt.%至约20wt.%,在一些实施方案中为约0.1wt.%至约10wt.%,和在一些实施方案中为约0.5wt.%至约5wt.%。第一和/或第二纳米包含物添加剂在整个热塑性组合物中的浓度可以同样地为热塑性组合物的约0.01wt.%至约15wt.%,在一些实施方案中为约0.05wt.%至约10wt.%,和在一些实施方案中为约0.1wt.%至约8wt.%。
可以任选地将纳米填料用于第二纳米包含物添加剂,其实例可以包括碳黑、碳纳米管、碳纳米纤维、纳米粘土、金属纳米颗粒、纳米二氧化硅、纳米氧化铝等。纳米粘土是特别适合的。术语“纳米粘土”一般是指粘土材料的纳米颗粒(天然存在的矿物质、有机改性的矿物质或合成纳米材料),其通常具有薄片结构。纳米粘土的实例包括,例如,蒙脱石(2:1层状蒙皂石粘土结构)、膨润土(主要由蒙脱石形成的层状硅酸铝)、高岭土(具有板状结构和经验式Al2Si2O5(OH)4的1:1铝硅酸盐)、埃洛石(具有管状结构和经验式Al2Si2O5(OH)4的1:1铝硅酸盐)等。适合的纳米粘土的实例是其为蒙脱石纳米粘土并可商购自SouthernClayProducts,Inc。合成纳米粘土的其它实例包括但不限于混合金属氢氧化物纳米粘土、层状双氢氧化物纳米粘土(例如,海泡石(sepiocite))、锂皂石、水辉石、皂石、indonite等。
如果期望,纳米粘土可以包含表面处理以帮助改善与基质聚合物(例如,聚酯)的相容性。表面处理可以是有机或无机的。在一个实施方案中,应用通过有机阳离子与粘土的反应获得的有机表面处理。适合的有机阳离子可以包括,例如,能够与粘土交换阳离子的有机季铵化合物,如二甲基双[氢化牛脂]氯化铵(2M2HT)、甲基苄基双[氢化牛脂]氯化铵(MB2HT)、甲基三[氢化牛脂烷基]氯化物(M3HT)等。市售有机纳米粘土的实例可以包括,例如,43B(Italy的Livorno的LaviosaChimica),其为用二甲基苄基氢化牛脂铵盐改性的蒙脱石粘土。其它实例包括25A和30B(SouthernClayProducts)和Nanofil919(Chemie)。如果期望,纳米填料可以与载体树脂共混以形成色母粒,其提高添加剂与组合物中的其它聚合物的相容性。特别适合的载体树脂包括,例如,聚酯(例如,聚乳酸、聚对苯二甲酸乙二醇酯等);聚烯烃(例如,乙烯聚合物、丙烯聚合物等);等等,如以上更详细地描述的。
不论使用哪种材料,所述纳米包含物添加剂通常被选择成具有特定的粘度(或熔体流动速率)来确保离散区域和所产生的孔可被足够地维持。例如,如果纳米包含物添加剂的粘度过低(或熔体流动速率过高),则其倾向于不可控地流动并分散通过连续相。这导致难以维持并还可能过早断裂的薄片状、板状区域或共连续相结构。相反地,如果粘度过高(或熔体流动速率过低),则其倾向于聚集在一起并形成非常大的椭圆形区域,其在共混期间是难以分散的。这可能导致纳米包含物添加剂在整个连续相中的不均匀分布。例如,聚烯烃的熔体流动速率与聚合物纳米包含物添加剂的熔体流动速率之比例如可以为约0.2至约8,在一些实施方案中为约0.5至约6,和在一些实施方案中为约1至约5。根据ASTMD1238,在2160克的负载下和在高于熔融温度(例如190℃)至少约40℃的温度下测定时,纳米包含物添加剂可以例如具有每10分钟约0.1至约100克,在一些实施方案中为每10分钟约0.5至约50克,和在一些实施方案中为每10分钟约5至约15克的熔体流动速率(以干基计)。同样地,根据ASTMD1238,在2160克的负载下和在至少高于熔融温度(例如230℃)约40℃的温度下测定时,聚烯烃可以具有每10分钟约0.5至约80克,在一些实施方案中为每10分钟约1至约40克,和在一些实施方案中为每10分钟约5至约20克的熔体流动速率(以干基计)。
C.微米包含物添加剂
虽然不需要,但本发明的组合物还可以应用微米包含物添加剂。如本文所使用的,术语“微米包含物添加剂”通常指能够以微米级尺寸的离散区域形式分散在所述聚合物基质内的任何材料。例如,在拉伸前,所述区域可具有约0.1μm至约25μm、在一些实施方案中为约0.5μm至约20μm,和在一些实施方案中为约1μm至约10μm的平均横截面尺寸。当应用时,本发明人已发现当经历变形和伸长应变(例如,拉伸)时,微米级和纳米级相区域能够以独特的方式相互作用以产生孔的网络。也就是说,认为由于材料的不相容性引起的应力集中,伸长应变可以在微米级离散相区域附近引发加强的局部剪切区和/或应力强度区(例如,正应力)。这些剪切和/或应力强度区导致在邻近微米级区域的聚合物基质中的一些初始剥离。然而,值得注意地,在纳米级离散相区域附近产生的局部剪切和/或应力强度区可以与微米级区重叠,导致在聚合物基质中发生甚至进一步的剥离,从而产生大量的邻近纳米级区域和/或微米级区域的纳米孔。
微米包含物添加剂的具体性质不是关键的,并且可以包括液体、半固体或固体(例如,无定形的、结晶或半结晶)。在某些实施方案中,微米包含物添加剂在性质上是聚合的并具有相对高的分子量,以帮助改善热塑性组合物的熔体强度和稳定性。通常,微米包含物添加剂聚合物一般可与基质聚合物不相容。以这种方式,添加剂可以作为离散的相区域更好地分散在基质聚合物的连续相内。离散区域能够吸收由外力产生的能量,这增加了所得到的材料的整体韧度和强度。所述区域可具有各种不同形状,如椭圆形、球形、圆柱形、板状、管形等。在一个实施方案中,例如,所述区域具有大致椭圆形的形状。单个区域的物理尺寸通常足够小以使当施加外部应力时穿过聚合物材料的裂纹传播最小化,但是足够大以引发微观塑性变形并且允许在颗粒包含物处和周围出现剪切区。
微米包含物添加剂可以具有某种熔体流动速率(或者粘度)来确保离散区域和所产生的孔可被足够地维持。例如,如果添加剂的熔体流动速率过高,则其倾向于不可控地流动并分散通过连续相。这导致难以维持并还可能过早断裂的薄片状、板状区域或共连续相结构。相反地,如果添加剂的熔体流动速率过低,则其倾向于聚集在一起并形成非常大的椭圆形区域,其在共混期间是难以分散的。这可能导致添加剂在整个连续相中的不均匀分布。在这方面,本发明人已经发现,微米包含物添加剂的熔体流动速率与基质聚合物的熔体流动速率之比通常为约0.5至约10,在一些实施方案中为约1至约8,和在一些实施方案中为约2至约6。在2160克的负载下和在其熔融温度(例如,210℃)以上至少约40℃的温度下测定时,微米包含物添加剂可以例如具有每10分钟约5至约200克,在一些实施方案中为每10分钟约20至约150克,和在一些实施方案中每10分钟约40至约100克的熔体流动速率。
除了以上所述的性能以外,也可选择微米包含物添加剂的机械特性,以实现所期望的多孔网络。例如,当施加外力时,可以在离散相区域处和周围产生应力集中(例如包括正应力或剪切应力)和剪切和/或塑性屈服区,这是因为由添加剂和基质聚合物的弹性模量的差异所引起的应力集中。较大的应力集中促进了在区域处更加加强的局部塑性流动,这使得所述区域当被赋予应力时变得明显伸长。这些伸长的区域能够使所述组合物呈现出更加柔韧和柔软的行为。为了增强所述应力集中,可将微米包含物添加剂选成具有与聚烯烃基质比较相对高的杨氏弹性模量。例如,添加剂的弹性模量与聚烯烃基质的弹性模量之比通常为约1至约250,在一些实施方案中为约2至约100,和在一些实施方案中为约2至约50。微米包含物添加剂的弹性模量可以例如为约200至约3,500兆帕(MPa),在一些实施方案中为约300至约2,000MPa,和在一些实施方案中为约400至约1,500MPa。相反地,聚烯烃的弹性模量可以例如为约100至约1,500MPa,和在一些实施方案中为约200至约1000MPa。供选择地,微米包含物添加剂的弹性模量可以低于聚烯烃基质的弹性模量。弹性模量可以例如为约10MPa至约100MPa,以及任选为约20MPA至约80MPa。
虽然可以应用具有以上所示性能的多种微米包含物添加剂,但是这样的添加剂的特别适合的实例可以包括:苯乙烯共聚物(例如,苯乙烯-丁二烯-苯乙烯、苯乙烯-异戊二烯-苯乙烯、苯乙烯-乙烯-丙烯-苯乙烯、苯乙烯-乙烯-丁二烯-苯乙烯等);含氟聚合物,如聚氯乙烯(PVC)、聚四氟乙烯(PTFE)、聚三氟氯乙烯(PCTFE)等;聚乙烯醇;聚醋酸乙烯酯;聚酯,如脂肪族聚酯,如聚己内酯、聚酰胺酯、聚乳酸(PLA)及其共聚物、聚乙醇酸、聚碳酸亚烷基酯(例如,聚碳酸亚乙酯)、聚-3-羟基丁酸酯(PHB)、聚-3-羟基戊酸酯(PHV)、3-羟基丁酸酯与4-羟基丁酸酯的共聚物、3-羟基丁酸酯与3-羟基戊酸酯的共聚物(PHBV)、3-羟基丁酸酯与3-羟基己酸酯的共聚物、3-羟基丁酸酯与3-羟基辛酸酯的共聚物、3-羟基丁酸酯与3-羟基癸酸酯的共聚物、3-羟基丁酸酯与3-羟基十八烷酸酯的共聚物和基于琥珀酸酯的脂族聚合物(例如,聚琥珀酸丁二醇酯、聚琥珀酸己二酸丁二醇酯、聚琥珀酸乙二醇酯等),脂族-芳香族共聚酯(例如,聚己二酸对苯二甲酸丁二醇酯、聚己二酸对苯二甲酸乙二醇酯、聚己二酸间苯二甲酸乙二醇酯、聚己二酸间苯二甲酸丁二醇酯等),芳香族聚酯(例如,聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等)等等。
特别适合的是这样的微米包含物添加剂,其性质上通常为刚性并且到达其具有相对高的玻璃化转变温度的程度。例如,玻璃化转变温度("Tg")可为约0℃或更高,在一些实施方案中为约5℃至约100℃,在一些实施方案中为约30℃至约80℃,在一些实施方案中为约50℃至约75℃。玻璃化转变温度可以根据ASTME1640-09通过动态机械分析来测定。
一种特别适合的刚性聚酯是聚乳酸,其通常可源自乳酸的任意异构体的单体单元,如左旋乳酸(“L-乳酸”)、右旋乳酸(“D-乳酸”)、内消旋乳酸(meso-lacticacid)或其混合物。单体单元也可以由乳酸的任意异构体的酸酐形成,包括左旋丙交酯、右旋丙交酯、内消旋丙交酯(meso-lactide)或其混合物。这样的乳酸和/或丙交酯的环状二聚体也可以被应用。任意已知的聚合方法,如缩聚或开环聚合,均可以用来聚合乳酸。少量的扩链剂(例如,二异氰酸酯化合物、环氧化合物或者酸酐)也可以被应用。聚乳酸可以是均聚物或者共聚物,如含有源自L-乳酸的单体单元和源自D-乳酸的单体单元的。虽然不要求,源自L-乳酸的单体单元和源自D-乳酸的单体单元中之一的含量比率优选为约85摩尔%或者更高,在一些实施方案中为约90摩尔%或者更高,和在一些实施方案中为约95摩尔%或者更高。多种聚乳酸可以以任意百分比共混,其中每种均具有不同的源自L-乳酸的单体单元与源自D-乳酸的单体单元之比。当然,聚乳酸也可以与其它类型的聚合物(例如,聚烯烃、聚酯等)共混。
在一个具体的实施方案中,聚乳酸具有以下通式结构:
本发明中可使用的适合的聚乳酸聚合物的一个具体实例可商购自德国Krailling的Biomer,Inc.,名称为BIOMERTML9000。其它适合的聚乳酸聚合物可商购自Minnesota的Minnetonka的NatureworksLLC或者MitsuiChemical(LACEATM)。还有其它适合的聚乳酸被描述于第4,797,468号、第5,470,944号、第5,770,682号、第5,821,327号、第5,880,254号和第6,326,458号美国专利中,出于所有目的将其全部内容引入本文作为参考。
聚乳酸通常具有约40,000至约180,000克每摩尔,在一些实施方案中为约50,000至约160,000克每摩尔,和在一些实施方案中为约80,000至约120,000克每摩尔的数均分子量("Mn")。同样,所述聚合物还通常具有约80,000至约250,000克每摩尔,在一些实施方案中为约100,000至约200,000克每摩尔,和在一些实施方案中为约110,000至约160,000克每摩尔的重均分子量("Mw")。重均分子量与数均分子量之比("Mw/Mn"),即"多分散性指数"也是相对低的。例如,多分散性指数通常为约1.0至约3.0,在一些实施方案中为约1.1至约2.0,和在一些实施方案中为约1.2至约1.8。重均和数均分子量可以通过本领域技术人员已知的方法测定。
一些类型的净聚酯(例如,聚乳酸)可以从周围环境中吸收水,以至于其具有基于起始聚乳酸的干重约百万分之500至600("ppm"),或者甚至更高的水分含量。水分含量可以用本领域已知的各种方式测定,如根据ASTMD7191-05,例如下面所描述的。因为在熔融加工期间水的存在可以水解降解聚酯并降低其分子量,所以有时候在共混之前希望干燥聚酯。在大多数的实施方案中,例如,希望可再生的聚酯在与微米包含物添加剂共混之前具有约百万分之300("ppm")或更低,在一些实施方案中为约200ppm或者更低,在一些实施方案中为约1至约100ppm的水分含量。聚酯的干燥可以例如在约50℃至约100℃,和在一些实施方案中为约70℃至约80℃的温度下发生。
无论应用何种材料,选择热塑性组合物中的微米包含物添加剂的相对百分率,以获得所期望的性能,而没有显著影响所产生的组合物。例如,基于组合物中应用的聚烯烃基质的重量,微米包含物添加剂通常的用量为热塑性组合物的约1wt.%至约30wt.%,在一些实施方案中为约2wt.%至约25wt.%,和在一些实施方案中为约5wt.%至约20wt.%。微米包含物添加剂在整个热塑性组合物中的浓度可以同样地占约0.1wt.%至约30wt.%,在一些实施方案中占约0.5wt.%至约25wt.%,和在一些实施方案中占约1wt.%至约20wt.%。
D.其它组分
出于各种不同原因,可在组合物中应用多种成分。例如,在一个具体实施方案中,可在热塑性组合物中应用界面改性剂以帮助降低纳米包含物和/或微米包含物添加剂与聚烯烃基质之间的摩擦和连通性程度,并因此增强剥离的程度和均匀性。以这种方式,所述孔可以以更加均匀的方式分散在整个组合物中。改性剂可以在室温(例如25℃)下为液体或半固体形式,以使得该改性剂具有相对低的粘度,以允许其更容易被结合到该热塑性组合物中并容易转移至该聚合物表面。认为通过降低在聚烯烃基质和添加剂间的界面处的物理力,该改性剂的低粘度疏水性质可帮助促进剥离。如在本文中所用的,术语“疏水的”通常是指具有约40°或更大,且在一些情况下为约60°或更大的空气中水的接触角的材料。相反地,术语“亲水的”通常是指具有小于约40°的空气中水的接触角的材料。用于测量接触角的一种适合的测试是ASTMD5725-99(2008)。
虽然不要求,但界面改性剂可以特别适用于其中应用微米包含物添加剂和其中纳米包含物添加剂为固体(例如,聚合物材料)的实施方案中。适合的疏水性、低粘度界面改性剂可以包括例如,上述的液体和/或半固体。一种特别适合的界面改性剂是聚醚多元醇,其例如可以从BASFCorp.以商标名WI商业购得。另一种适合的改性剂是部分可再生酯,其例如可以从Hallstar以商标名IM商业购得。
当应用时,基于连续相聚烯烃基质的重量,界面改性剂可占热塑性组合物的约0.1wt.%至约20wt.%,在一些实施方案中为约0.5wt.%至约15wt.%,以及在一些实施方案中为约1wt.%至约10wt.%。同样地,界面改性剂在整个热塑性组合物中的浓度可以占约0.05wt.%至约20wt.%,在一些实施方案中为约0.1wt.%至约15wt.%,以及在一些实施方案中为约0.5wt.%至约10wt.%。当按照上述量时,该界面改性剂具有这样的特性,即该特性能够使其容易转移至聚合物的界面表面并且在不干扰热塑性组合物的整体熔融性能的情况下促进剥离。例如,热塑性组合物的熔体流动速率还可以与聚烯烃基质的熔体流动速率相似。例如,根据ASTMD1238,在2160克的负载和190℃下测定时,组合物的熔体流动速率(以干基计)可以为每10分钟约0.1至约250克,在一些实施方案中为每10分钟约0.5至约200克,以及在一些实施方案中为每10分钟约5至约150克。
也可应用增容剂以改善区域与基质之间的界面粘附并降低区域与基质之间的界面张力,从而允许在混合过程中形成较小的区域。适合的增容剂的实例可以包括例如用环氧基或马来酸酐化学部分官能化的共聚物。马来酸酐增容剂的一个实例是聚丙烯接枝的马来酸酐,其可从Arkema以商品名OrevacTM18750和OrevacTMCA100商业购得。当被应用时,基于连续相聚烯烃基质的重量,增容剂可占热塑性组合物的约0.05wt.%至约10wt.%,在一些实施方案中占约0.1wt.%至约8wt.%,以及在一些实施方案中占0.5wt.%至约5wt.%。
也可在热塑性组合物中使用其它适合的材料,如添加以增强热塑性组合物的加工性能和机械性能的催化剂、抗氧化剂、稳定剂、表面活性剂、蜡、固体溶剂、成核剂、微粒、纳米填料和其它材料。然而,本发明的一个有益方面是可在不需要各种传统添加剂如发泡剂(例如氯氟烃、氢氯氟烃、烃、二氧化碳、超临界二氧化碳、氮气等)和引发孔的无机氧化物填料(例如碳酸钙)的情况下提供良好的性能。事实上,热塑性组合物通常可以不含形成微孔膜通常需要的发泡剂和/或引发孔的无机氧化物填料。这可以提供多种益处,包括成本和制造复杂度的潜在降低。事实上,热塑性组合物和/或膜的一层或多层(例如,基层)可以一般地不含这样的发泡剂和/或填料(例如,碳酸钙),其存在的量可以为不多于热塑性组合物的约1wt.%,在一些实施方案中为不多于约0.5wt.%,以及在一些实施方案中为约0.001wt.%至约0.2wt.%。然而,在某些实施方案中,如果期望,更高量的发泡剂和/或填料可以用于热塑性组合物中。此外,由于所产生的组合物的如在以下更详细描述的应力发白性能,所述所产生的组合物可以在无需传统颜料如二氧化钛的情况下获得不透明颜色(例如白色)。例如,在某些实施方案中,颜料可以以不多于热塑性组合物的约1wt.%,在一些实施方案中不多于约0.5wt.%,以及在一些实施方案中为约0.001wt.%至约0.2wt.%的量存在。
II.共混
为了形成热塑性组合物,通常使用各种已知技术中的任意一种将组分共混在一起。例如,在一个实施方案中,组分可以被单独提供或组合提供。例如,所述组分可首先被干混在一起以形成基本均匀的干燥混合物,并且它们同样也可被同时或陆续供应至分散共混所述材料的熔融加工装置内。可应用分批的和/或连续的熔融加工技术。例如,可利用混合机/捏合机、班布里混合机(Banburymixer)、法劳连续混合机(Farrelcontinuousmixer)、单螺杆挤出机、双螺杆挤出机、滚碎机等来共混和熔融加工这些材料。特别适合的熔融加工装置可以是同向双螺杆挤出机(例如可从新泽西州拉姆齐城的Werner&Pfleiderer公司获得的ZSK-30挤出机或从英国Stone的ThermoElectron公司获得的ThermoPrismTMUSALAB16挤出机)。这样的挤出机可包括进料口和通风口并提供高强度分布和分散的混合。例如,组分可被进料至双螺杆挤出机的相同或不同的进料口并熔融共混以形成基本均匀的熔融混合物。如果需要,其它添加剂也可被注入到聚合物熔体中和/或在沿挤出机长度的不同位置处被分别进料至挤出机中。
无论选用何种具体加工技术,所产生的熔融共混组合物通常包含纳米包含物添加剂的纳米级区域和任选的微米包含物添加剂的微米级区域。可控制剪切/压力程度和热来确保充分分散,但不会高到不利地降低区域尺寸以使得它们不能实现期望性能的程度。例如,共混通常在约180℃至约300℃,在一些实施方案中为约185℃至约250℃,在一些实施方案中为约190℃至约240℃的温度下进行。同样,在熔融加工过程中的表观剪切速率可以为约10秒-1至约3000秒-1,在一些实施方案中为50秒-1至约2000秒-1,以及在一些实施方案中为100秒-1至约1200秒-1。表观剪切速率可以等于4Q/πR3,其中,Q是聚合物熔体的体积流动速率(“m3/s”),且R为熔融聚合物流动经过的毛细管(例如挤出机模头)的半径(“m”)。当然,也可控制其它变量,如与生产速率成反比的在熔融加工过程中的停留时间,以获得期望程度的均质性。
为了获得期望的剪切条件(例如速率、停留时间、剪切速率、熔融加工温度等),挤出机螺杆(或多个挤出机螺杆)的速率可在一定范围内选择。通常,随着螺杆速率的增加,由于额外的机械能输入***中,可观察到产品温度的升高。例如,螺杆速率可以为每分钟约50至约600转(“rpm”),在一些实施方案中为约70至约500rpm,以及在一些实施方案中为约100至约300rpm。这可在不负面影响所产生区域的尺寸的情况下产生用于分散纳米包含物添加剂的足够高的温度。熔体剪切速率,以及还有添加剂被分散的程度也可通过在挤出机的混合部中应用一个或多个分布式和/或分散式混合元件来增加。用于单螺杆挤出机的适合的分布式混合机可包括例如Saxon混合机、Dulmage混合机、CavityTransfer混合机等。同样,适合的分散式混合机可包括Blisterring混合机、Leroy/Maddock混合机、CRD混合机等。如在本领域内熟知的那样,可通过在圆筒中使用导致聚合物熔体折叠和再取向的销钉来进一步改善所述混合,例如在BussKneader挤出机、CavityTransfer混合机和VortexIntermeshingPin(VIP)混合机中所使用的那些。
III.膜构建
任何已知的技术可以用于由组合物形成膜,包括吹塑、流延、平模挤出等。在一个具体的实施方案中,膜可以通过吹塑工艺形成,其中使用气体(例如空气)使通过环形模头挤出的聚合物共混物的气泡膨胀。然后气泡塌陷并以平坦膜的形式收集。用于制备吹塑膜的方法描述于例如,Raley的第3,354,506号、Schippers的第3,650,649号和Schrenk等人的第3,801,429号美国专利,以及McCormack等人的第2005/0245162号、Boggs等人的第2003/0068951号美国公开专利申请中。然而,在又一个实施方案中,使用流延技术形成膜。
参照图1,例如,显示了用于形成流延膜的方法的一个实施方案。在该实施方案中,原料(未显示)从料斗40供应至挤出机80,随后铸塑到铸轧辊90上以形成单层前体膜10a。如果要制备多层膜,则将多层一起共挤出到铸轧辊90上。铸轧辊90可以任选地设有压花元件以向膜赋予图案。通常地,在当片材10a形成时铸轧辊90保持在足以固化并骤冷片材10a的温度下,如约10℃至60℃。如果希望,可以将真空箱设置在邻近铸轧辊90处以帮助保持前体膜10a靠近辊90的表面。另外,气刀或静电扣针(electrostaticpinner)可以帮助迫使前体膜10a在围绕纺丝辊移动时靠在铸轧辊90的表面上。气刀是本领域已知的装置,其以非常高的流动速率集中空气流以压住膜的边缘。
一旦形成,然后膜10a就可以任选地在一个或多个方向上取向以进一步改善膜均匀性。膜可以立即被重新加热到这样的温度,所述温度在膜中的一种或多种聚合物的熔点以下,但足够高以使组合物能够被拉伸或伸展。在连续取向的情况下,“软化的”膜通过以不同的转动速度转动的辊拉伸,以使片材在纵向(机器方向)上被拉伸至希望的拉伸比。该“单轴”取向的膜可以随后任选地被层压到纤维纤网。此外,单轴取向的膜还可以在机器横向上取向以形成“双轴取向的”膜。例如,膜可以在其侧面边缘被链夹夹持并传送到张布架炉(tenteroven)中。在张布架炉中,膜可以被重新加热并在机器横向上被偏离其向前行进的链夹拉伸至希望的拉伸比。
再次参照图1,例如,显示了用于形成单轴取向的膜的一种方法。如所说明的,前体膜10a对准膜取向单元100或机器方向定向器(“MDO”),如商购自RhodeIsland的Providence的MarshallandWillams,Co.的机器方向定向器。MDO具有多个拉伸辊(如5至8个),其渐进地在机器方向上拉伸膜并使膜变薄,所述机器方向是膜通过图1所示的方法行进的方向。虽然使用八根辊举例说明MDO100,但应懂得的是,根据希望的拉伸水平和每根辊之间的拉伸程度,辊的数量可以更多或更少。膜可以在单个或多个分开的拉伸操作中被拉伸。应注意MDO设备中的一些辊可以不在逐渐更高的速度下运行。如果希望,MDO100的一些辊可以充当预热辊。如果存在,这些前几个辊加热膜10a至室温以上(例如,至125°F)。MDO中的邻近辊的逐渐更快的速度起到拉伸膜10a的作用。拉伸辊转动的速率决定了膜中的拉伸量和最终的膜重量。
产生的膜10b可以随后缠绕并储存在收线辊60上。虽然此处未显示,但本领域已知的各种另外的可能的加工和/或精加工步骤,如切割、处理、打孔、印刷图像或将膜与其它层(例如,非织造纤网材料)层压,可以在不脱离本发明的精神和范围的情况下进行。
本发明的膜可以是单层或多层(例如,2至20层,在一些实施方案中为3至10层)。例如,多层膜可以包含至少一个设置在邻近至少一个外层处的芯层。在一个实施方案中,例如,可以希望应用夹着芯层的第一和第二外层。芯层(或多个芯层)通常占膜的大部分重量,如膜的约50wt.%至约99wt.%,在一些实施方案中为约55wt.%至约90wt.%,和在一些实施方案中为约60wt.%至约85wt.%。外层(或多个外层)可以同样地占膜的约1wt.%至约50wt.%,在一些实施方案中为约10wt.%至约45wt.%,和在一些实施方案中为约15wt.%至约40wt.%。每个外层还可以具有约0.1至约10微米,在一些实施方案中为约0.5至约5微米,和在一些实施方案中为约1至约2.5微米的厚度。同样地,芯层可以具有约1至约40微米,在一些实施方案中为约2至约25微米,和在一些实施方案中为约5至约20微米的厚度。
本发明的热塑性组合物可以用于膜的任何层中,包括芯层和/或外层。在一个实施方案中,例如,所述芯层由本发明的组合物形成,外层(或多个外层)由组合物或由另外的聚合物材料形成。同样地,在其它可能的实施方案中,一个或多个外层由本发明的组合物形成,芯层由另外的聚合物材料形成。当应用时,另外的材料可以包括任意类型的聚合物,如聚烯烃(例如,聚乙烯、聚丙烯等)、聚酯、聚酰胺、苯乙烯共聚物、聚氨酯、聚醋酸乙烯酯、聚乙烯醇等。
如果希望,膜还可以层压到一个或多个非织造纤网饰面以降低摩擦系数并提高复合材料表面的布样感觉。用于形成非织造纤网饰面的示例性聚合物可以包括,例如,聚烯烃,例如,聚乙烯、聚丙烯、聚丁烯等;聚四氟乙烯;聚酯,例如,聚对苯二甲酸乙二醇酯等;聚醋酸乙烯酯;聚氯乙烯-醋酸酯;聚乙烯醇缩丁醛;丙烯酸树脂,例如,聚丙烯酸酯、聚丙烯酸甲酯、聚甲基丙烯酸甲酯等;聚酰胺,例如,尼龙;聚氯乙烯;聚偏二氯乙烯;聚苯乙烯;聚乙烯醇;聚氨酯;聚乳酸;其共聚物;等等。如果希望,还可以应用可再生聚合物,如上述的那些。还可以使用合成或天然纤维素聚合物,包括但不限于,纤维素酯;纤维素醚;硝酸纤维素;醋酸纤维素;醋酸丁酸纤维素;乙基纤维素;再生纤维素,如粘胶纤维、人造丝等。应注意聚合物(或多种聚合物)还可以包含其它添加剂,例如赋予纤维希望的性能的加工助剂或处理组合物、残留量的溶剂、颜料或着色剂等等。
单组分和/或多组分纤维可以用于形成非织造纤网饰面。单组分纤维通常由从单一挤出机挤出的聚合物或聚合物的共混物形成。多组分纤维通常由从不同的挤出机挤出的两种或更多种聚合物形成(例如,双组分纤维)。聚合物可以跨纤维的横截面排列在基本上恒定设置的不同区域中。组分可以以任何希望的构型排列,如皮芯构型、并行构型、饼式构型、海中岛构型、三岛构型、牛眼构型或本领域已知的各种其它排列。还可以形成具有各种不规则形状的多组分纤维。
可以应用具有任意期望长度的纤维,如短纤维、连续纤维等。在一个具体实施方案中,例如,可以使用纤维长度为约1至约150毫米,在一些实施方案中约5至约50毫米,在一些实施方案中为约10至约40毫米和在一些实施方案中为约10至约25毫米的短纤维。虽然不需要,但是如本领域所熟知的,梳理技术可以用于形成具有短纤维的纤维层。例如,可以通过将纤维捆放置在分离纤维的清棉机中使纤维形成梳理纤网。接下来,将纤维输送通过精梳或梳理单元,所述精梳或梳理单元进一步分开纤维并使纤维排列在机器方向上,以便于形成机器方向取向的纤维非织造纤网。随后可以使用已知的技术粘合梳理纤网以形成粘合梳理非织造纤网。
如果希望,用于形成非织造复合材料的非织造纤网饰面可以具有多层结构。适合的多层材料可以包括例如,纺粘/熔喷/纺粘(SMS)层压材料和纺粘/熔喷(SM)层压材料。多层结构的另一个实例是在多个纺纱组机器(spinbankmachine)上制备的纺粘纤网,其中纺纱组使纤维沉积在由前一个纺纱组沉积的一层纤维上方。这样的单个纺粘非织造纤网也可以被认为是多层结构。在该情况下,非织造纤网中的沉积的纤维的多个层可以是相同的,或其可以在基重和/或在组成、类型、尺寸、皱褶水平和/或制备的纤维的形状方面不同。作为另一个实例,单个非织造纤网可以作为两个或更多个单独制备的纺粘纤网、梳理纤网等的层提供,所述层已被粘合在一起以形成非织造纤网。如以上讨论的,这些单独制备的层在制备方法、基重、组成和纤维方面可以不同。非织造纤网饰面还可以包含另外的纤维组分以使其被认为是复合材料。例如,可以使用本领域已知的多种缠结技术中的任意一种(例如,水力、空气、机械等)使非织造纤网与另一种纤维组分缠结。在一个实施方案中,使用水力缠结将非织造纤网与纤维素纤维整体缠结。典型的水力缠结方法利用高压水射流缠结纤维,以形成高度缠结的加固纤维结构,例如非织造纤网。复合材料的纤维组分可以包含任意希望量的所产生的基材。
无论膜形成的具体方式如何,所述膜均可以被拉伸以形成希望的多孔网络。如果希望,膜可以在形成时在线拉伸。供选择地,膜可以在形成后,在层压到任何任选的饰面材料之前和/或之后,在其固体状态下被拉伸。“固体状态”拉伸通常是指将组合物保持在聚烯烃基质聚合物的熔融温度以下的温度下。这尤其有助于确保聚合物链不改变至多孔网络变得不稳定的程度。例如,膜可以在约-50℃至约150℃,在一些实施方案中为约-40℃至约140℃,在一些实施方案中为约-20℃至约100℃,和在一些实施方案中为约0℃至约50℃的温度下拉伸。在某些情况下,拉伸温度可以任选地为在具有最高玻璃化转变温度的组分(例如,微米包含物添加剂)的玻璃化转变温度以下至少约10℃,在一些实施方案中为至少约20℃,和在一些实施方案中为至少约30℃。在这样的实施方案中,膜可以在约0℃至约50℃,在一些实施方案中为约15℃至约40℃,和在一些实施方案中为约20℃至约30℃的温度下拉伸。
拉伸可以发生在一个或多个阶段,并使用任意各种不同的技术。在一个实施方案中,例如,膜可以使用机器方向定向器(“MDO”),例如使用如图1所示的单元100拉伸。为了以上述方式拉伸膜,通常希望MDO的辊是未加热的。然而,如果希望,一个或多个辊可以被加热至轻微的程度以促进拉伸过程,只要组合物的温度保持在上述范围以下。膜通常被拉伸(例如在机器方向上)至约1.1至约3.5,在一些实施方案中为约1.2至约3.0,和在一些实施方案中为约1.3至约2.5的拉伸比。拉伸比可以通过将拉伸膜的长度除以其拉伸前的长度来测定。拉伸率也可以不同以帮助实现希望的性能,如每分钟约5%至约1500%变形,在一些实施方案中为每分钟约20%至约1000%变形,和在一些实施方案中为每分钟约25%至约850%变形。虽然膜通常在不施加外部热(例如,加热的辊)的情况下拉伸,但是可以任选地应用这样的热以改进可加工性,降低拉伸力,提高拉伸率以及改善均匀性。
以上述方式拉伸可以导致具有“纳米级”横截面尺寸,如约800纳米或更低,在一些实施方案中为约5至约700纳米,和在一些实施方案中为约10至约500纳米的孔的形成(“纳米孔”)。纳米孔还可以具有约100至约5000纳米,在一些实施方案中为约50至约2000纳米,和在一些实施方案中为约100至约1000纳米的平均轴向尺寸(例如,长度)。还可以在拉伸过程中形成微米孔,其具有约0.2微米或更大,在一些实施方案中为约0.5微米或更大,和在一些实施方案中为约0.5微米至约5微米的平均横截面尺寸。在某些情况下,微米孔和/或纳米孔的轴向尺寸可以大于横截面尺寸以使长宽比(轴向尺寸与横截面尺寸之比)为约1至约30,在一些实施方案中为约1.1至约15,和在一些实施方案中为约1.2至约5。例如,微米孔的轴向尺寸可以为1微米或更大,在一些实施方案中为约1.5微米或更大,和在一些实施方案中为约2至约30微米。
无论其具体尺寸如何,本发明人已发现孔(例如,纳米孔、微米孔或两者)可以以基本均匀的方式分布在整个材料中。例如,所述孔可以分布成列,所述列在与施加应力的方向大致垂直的方向上取向。这些列可以跨所述材料的宽度大致彼此平行。在不打算被理论限制的情况下,认为这样的均匀分布的多孔网络的存在可导致高热阻以及良好的机械性能(例如在负载和冲击强度下的能量耗散)。这与涉及使用发泡剂成孔的、趋于导致不受控的孔分布和差的机械性能的产生孔的传统技术完全相反。
除了形成多孔网络之外,拉伸还可明显增加某些离散区域的轴向尺寸,以使得它们具有大致线性的伸长形状。例如,所述伸长的微米级区域可具有比在拉伸前所述区域的轴向尺寸大约10%或更多,在一些实施方案中为约20%至约500%,以及在一些实施方案中为约50%至约250%的平均轴向尺寸。在拉伸后的轴向尺寸(例如长度)可以例如为约1μm至约400μm,在一些实施方案中为约5μm至约200μm,和在一些实施方案中为约10μm至约150μm。微米级区域还可以相对薄并从而具有小的横截面尺寸,如约0.02至约20微米,在一些实施方案中为约0.1至约10微米,和在一些实施方案中为0.4至约5微米。这可以导致区域的长宽比(轴向尺寸与正交于轴向尺寸的尺寸之比)为约2至约150,在一些实施方案中为约3至约100,和在一些实施方案中为约4至约50。由于其小的尺寸,纳米级区域通常不以与微米级区域相同的方式伸长。因此,纳米级区域可以保持约1至约1000纳米,在一些实施方案中为约5至约800纳米,在一些实施方案中为约10至约500纳米,和在一些实施方案中为约20至约200纳米的平均轴向尺寸(例如长度)。
即使在本发明所实现的非常低的密度下,产生的膜也不是脆的,并且可以是相对可延展的。表示良好延展性的一个参数是膜在机器方向(“MD”)和/或机器横向(“CD”)上的峰值伸长率。例如,膜通常显示在机器方向上约50%或更高,在一些实施方案中为约60%或更高,在一些实施方案中为约70%或更高,和在一些实施方案中为约80%至约200%的峰值伸长率。膜可以同样地显示在机器横向上约750%或更高,在一些实施方案中为约800%或更高,在一些实施方案中为约800%或更高,和在一些实施方案中为约850%至约2500%的峰值伸长率。除了具有这样良好的延展性以外,本发明的膜还能够保持良好的机械强度。例如,本发明的膜可以显示在机器方向和/或机器横向上约20至约150兆帕(MPa),在一些实施方案中为约25至约120MPa,和在一些实施方案中为约30至约100MPa的最终抗拉强度。膜的杨氏弹性模量也可以是良好的,其等于拉伸应力与拉伸应变之比,并且由应力-应变曲线的斜率确定。例如,膜通常显示在机器方向和/或机器横向上约250至约10,00MPa,在一些实施方案中为约500至约8,000MPa,和在一些实施方案中为约1,000至约5,000MPa的杨氏模量。令人惊讶地,即使膜具有非常低的厚度,也可以实现良好的延展性和其它机械性能。例如,在拉伸后,膜的厚度通常为约150微米或更低,在一些实施方案中为约1至约120微米,在一些实施方案中为约2至约100微米,和在一些实施方案中为约5至约40微米。
IV.制品
由于其独特并且有益的性能,本发明的膜特别好地适合在吸收性制品的层和/或组件中使用。吸收性制品,例如,通常包括位于底片和顶片之间的吸收性元件(例如,芯层、浪涌层、传递延迟层、包裹片、透气层等)。吸收性制品还可以包括本领域已知的其它组件,例如侧片、防护翼、耳片、腰带或腿带等。一般而言,本发明的膜可以用于吸收性制品的任何层或组件,例如顶片、底片和/或吸收性元件。当在某些层或组件(如底片)中使用时,可能期望的是如以上所描述的将本发明的膜层压到非织造纤网。
在这方面,将描述所述吸收性制品的各种示例性实施方案。参照图1,例如,以尿布的形式示出了吸收性制品201的一个具体的实施方案。然而,如以上所述,本发明可以体现在其它类型的吸收性制品,例如失禁制品、卫生棉、尿布裤、女性纸巾、训练裤等。在所述示例说明性实施方案中,吸收性制品201显示为具有解开构型的沙漏形。然而,当然可以使用其它的形状。例如普通的矩形、T形或I形。如示出的,吸收性制品201包括由各种组件形成的基底(chassis)202,所述基底202包括底片217和顶片205和吸收性元件,所述吸收性元件包括吸收性芯层203和浪涌层207。然而,应理解的是,在本发明中也可以使用其它层。同样地,图1中提及的一种或多种层也可能在本发明的某些实施方案中删除。
如以上指出的,底片217可以包含本发明的膜,所述膜可以任选地层压到非织造纤网。如果需要,所述膜或非织造纤网可以被设置成限定吸收性制品201朝向服装的表面333。所述吸收性制品201还包括顶片205。所述顶片205一般被设计成接触使用者的身体并且是液体可渗透的。例如,顶片205可以限定朝向身体的表面218,其典型地为顺从的、感觉柔软的并且对穿戴者的皮肤没有刺激。如果需要,所述顶片205可以包含本发明的膜。例如,如果需要,所述膜可以被设置成其限定朝向身体的表面218。所述顶片可以包围吸收性芯层203,使得它完全地包封所述吸收性制品。供选择地,所述顶片205和底片217可以延伸超过所述吸收性元件,并且使用已知的技术,例如粘合剂粘合、超声粘合等整体地或部分地沿周边结合在一起。如以上所指出的,顶片205可以包括本发明的膜。其它包含非织造纤网的示例性的顶片结构在第5,192,606号;第5,702,377号;第5,931,823号;第6,060,638号和第6,150,002号美国专利以及第2004/0102750号、第2005/0054255号和第2005/0059941号美国公开专利申请中有描述。顶片205还可以包含穿过其中形成的多个孔,以允许体液更容易地通过进入吸收性芯层203。所述孔可以随机或均匀排列遍及顶片205,或者它们可以仅位于沿着吸收性制品的纵轴排列的狭窄的纵向带或条中。所述孔允许体液向下快速渗透进入吸收性元件。所述孔的尺寸、形状、直径和数目可以是变化的以适合个体的具体需求。
所述吸收性制品还可以包括位于顶片和底片之间的吸收性元件。所述吸收性元件还可以由单一吸收性层或包含独立的和不同的吸收性层的复合材料形成。然而,可以理解的是,在本发明中可以使用任何数目的吸收性层。在图1中,例如吸收性元件包含吸收性芯层203和浪涌层207,所述浪涌层207帮助快速引入到吸收性芯层203的液体的浪涌或喷涌减速并且扩散。期望地,在将液体释放到吸收性芯层203的储存或保留部分之前,所述浪涌层207快速接受并暂时保留所述液体。在示例说明性的实施方案中,例如浪涌层207***到顶片205的朝向内部的表面216和吸收性芯层203之间。供选择地,浪涌层207可以位于顶片205的朝向外部的表面218上。浪涌层207通常由高度液体可渗透的材料制造。适合的材料可以包括多孔纺织材料、多孔非织造材料和有孔膜。在一个实施方案中,浪涌层207可以包含本发明的膜。适合的浪涌层的其它实例描述于Ellis等人的第5,486,166号和Ellis等人的第5,490,846号美国专利中。
如果需要,所述吸收性元件还可以包含垂直地位于浪涌层下方的传递延迟层。所述传递延迟层可以包含亲水性小于其它的吸收性层的材料,并且可以一般表征为是基本上疏水的。例如,所述传递延迟层可以包含非织造纤网(例如,粘纺纤网)或它可以包含本发明的膜。纤维的横截面形状可以是圆形的、三叶形的或多叶形的,并且其结构可以为中空或实心的。所述纤网通常超过纤网区域的约3%至约30%是粘合的,例如通过热粘合。可以用于传递延迟层的适合的材料的其它实例描述于Meyer等人的第4,798,603号和Serbiak等人的第5,248,309号美国专利中。为了调节本发明的性能,所述传递延迟层还可以使用选择量的表面活性剂处理以增加其最初的润湿性。
所述传递延迟层一般可以具有任何尺寸,例如约150mm至约300mm的长度。典型地,传递延迟层的长度约等于吸收性制品的长度。所述传递延迟层还可以在宽度上等于浪涌层,但是通常会更宽。例如,所述传递延迟层的宽度可以为约50mm至约75mm,并且更具体地为约48mm。所述传递延迟层通常具有小于其它吸收性元件的基重。例如,所以传递延迟层的基重通常小于每平方米约150克(gsm),并且在一些实施方案中为约10gsm至约100gsm。如果需要,所述传递延迟层可以包含本发明的膜。
所述吸收性元件还可以包括复合材料吸收性层,例如共成形材料。在此情况下,流体可以从传递延迟层芯吸进入到复合材料吸收性元件。所述复合材料吸收性层可以与浪涌层和/或传递延迟层分开形成,或者可以与其同时形成。在一个实施方案中,例如,所述复合材料吸收性层可以在传递延迟层或浪涌层上形成,所述传递延迟层或浪涌层在以上描述的共成形加工过程中作为载体。
除了以上提到的组件,吸收性制品201还可以包含各种本领域中已知的其它的组件。例如,吸收性制品201还可以包含基本上亲水的包裹片(未示出)以帮助维持吸收性芯层203的纤维结构的完整性。所述包裹片通常围绕吸收性芯层203在其至少两个主要朝向的表面之上放置,并且由吸收性纤维素材料,例如皱纹填塞物或高湿强度薄纸组成。包裹片可以被构造成提供芯吸层来帮助将液体快速地分散到吸收性芯层203的吸收性纤维团上。可以将在吸收性纤维团一侧的包裹片材料粘合到位于纤维团的相对侧的包裹片以有效地包封吸收性芯层203。进一步地,吸收性制品201还可以包括位于吸收性芯层203和底片217之间的透气层(未示出)。当使用时,所述透气层可以帮助底片217与吸收性芯层203隔离,从而减小底片217中的湿度。这样的透气层的实例可以包括层压到透气膜的非织造纤网,例如在Blaney等人的第6,663,611号美国专利中所描述的。如果需要,所述包裹片和/或透气层可以包含本发明的膜。
在一些实施方案中,吸收性制品201还可以包括从吸收性制品201的侧边232延伸到腰部区域之一的一对耳片(未示出)。所述耳片可以与选择的尿布组件整体地形成。例如,所述耳片可以与底片217,或者由使用用于提供顶部表面的材料整体地形成,如果需要,所述耳片可以包含本发明的膜。在供选择的构造中,所述耳片可以通过连接并组装到底片217、顶部表面、底片217和顶部表面之间或者各种其它的构造中的元件提供。如以上指出的,如果需要,所述耳片可以包含本发明的膜。
如图1中代表性地示出的,吸收性制品201还可以包括一对防护翼212,所述防护翼被构造成提供屏障并且包含身体渗出液的测流。所述防护翼212可以沿着顶片205的侧面相对的侧边232位于邻近吸收性芯层203的侧边处。防护翼212可以沿着吸收性芯层203的全长纵向延伸,或者可以仅部分地沿着吸收性芯层203的长度延伸。当防护翼212比吸收性芯层203的长度短时,它们可以被选择性地设置到裆部区域210中沿着吸收性制品201的侧边232的任何地方。在一个实施方案中,防护翼212沿着吸收性芯层203的全长延伸以更好的包含身体渗出液。这样的防护翼212一般是本领域技术人员已知的。例如,对于防护翼212的适合的结构和设置描述于Enloe.的第4,704,116号美国专利中。如果需要,所述防护翼可以包含本发明的膜。
吸收性制品201可以包括各种弹性或可伸缩的材料,例如附着到侧边232的一对腿部弹性元件206,以进一步地阻止身体渗出液渗漏并支撑吸收性芯层203。此外,一对腰部弹性元件208可以纵向相对地附着到吸收性制品201的腰部边缘215。腿部弹性元件206和腰部弹性元件208一般适合围绕使用中穿戴者的腿部和腰部紧密地固定,以用于维持与穿戴者之间的正面的接触关系并且有效地减小或消除身体渗出液从吸收性制品201渗漏。吸收性制品201还可以包括一个或多个紧固件230。例如,图1中示出了在腰部区域的相对侧边的两个弹性紧固件130,以产生围绕穿戴者的腰部开口和一对腿部开口。紧固件230的形状一般可以变化,但是可以包括例如,一般的矩形、正方形、圆形、三角形、椭圆形、线形等。所述紧固件可以包括例如钩材料。在一个具体的实施方案中,每个紧固件230包括附着到弹性衬垫的内部表面的一片单独的钩材料。如果需要,所述弹性元件(例如腿部、腰部等)和/或紧固件可以包含本发明的膜。
吸收性制品201的各个区域和/或组件可以使用任何已知的连接机制组装到一起,例如粘合剂粘合,超声粘合、热粘合等。适合的粘合剂可以包括例如,热熔胶粘合剂、压敏粘合剂等。当使用时,可以将所述粘合剂作为均匀层、图案层、喷雾形式、或任何分离的线、漩涡或点施加。在所述举例说明的实施方案中,例如,使用粘合剂将底片217和顶片205相互组装并组装到吸收性芯层203。供选择地,可以使用常规的紧固件例如纽扣、钩和环型紧固件、粘合带紧固件等等将吸收性芯层203连接到底片217。类似地,也可以使用任何连接机制,将其它的尿布组件,例如腿部弹性元件206、腰部弹性元件208和紧固件230组装到吸收性制品201中。
尽管以上描述了尿布的各种构造,但是应该理解的是,在本发明的范围中也包括其它的尿布和吸收性制品构造。此外,本发明并没有限制为尿布。实际上,可以根据本发明形成任何其它的吸收性制品,包括但不限于,其它的个人护理吸收性制品,例如训练裤、吸收性内裤、成人失禁产品、女性卫生产品(如卫生巾)、游泳衣、婴儿揩巾等等;医用吸收性制品,如外衣、开窗术材料、衬垫、绷带、吸收性帘和医用揩巾;食品服务揩巾;服装制品等等。
参照以下实施例可以更好地理解本发明。
测试方法
熔体流动速率:
熔体流动速率("MFR")是指,当通常在190℃、210℃或230℃下经受10分钟的2160克的负载时,聚合物被迫使通过挤出流变仪孔口(直径为0.0825-英寸)的重量(以克计)。除非另有说明,熔体流动速率是用TiniusOlsen挤压式塑性计根据ASTM测试方法D1238测量的。
热性能:
玻璃化转变温度(Tg)可以根据ASTME1640-09通过动态力学分析(DMA)测定。可以使用得自TAInstruments的Q800仪器。实验运行可以在3℃/min的加热速率下用-120℃至150℃的温度扫描模式以拉力/拉力几何图形来实施。应变幅度频率在测试期间可以保持恒定(2Hz)。可以测试三(3)个独立的样品,以获得用tanδ曲线的峰值来定义的平均玻璃化转变温度,其中tanδ被定义为损耗模量与储能模量之比(tanδ=E”/E')。
熔融温度可以通过差示扫描量热法(DSC)来测定。差示扫描量热仪可以是DSCQ100差示扫描量热仪,其配备有液氮冷却附件和UNIVERSALANALYSIS2000(4.6.6版)分析软件程序,二者均可以获得自Delaware的NewCastle的T.A.InstrumentsInc.。为了避免直接操作样品,使用镊子或者其它工具。将样品放入铝盘并在分析天平上称重至0.01毫克的精确度。在材料样品上方,将盖子卷到所述盘上。通常地,树脂颗粒是直接放置在称重盘上的。
如在差示扫描量热仪的操作手册中所述的,差示扫描量热仪使用铟金属标准品来校准,并且进行基线校正。将材料样品放入差示扫描量热仪的测试室中来测试,并且使用空盘作为对照。所有测试均在测试室中在每分钟55立方厘米的氮气(工业级)吹扫(purge)下运行。对于树脂颗粒样品而言,加热和冷却程序为2-循环测试,该测试首先是平衡所述室至-30℃,随后是以每分钟10℃的加热速率加热到200℃的温度的第一加热段,随后将样品在200℃下平衡3分钟,随后是以每分钟10℃的冷却速率冷却到-30℃的温度的第一冷却段,随后将样品在-30℃下平衡3分钟,并且随后是以每分钟10℃的加热速率加热到200℃的温度的第二加热段。所有测试均在测试室中在55立方厘米每分钟的氮气(工业级)吹扫下运行。
利用UNIVERSALANALYSIS2000分析软件程序来评价结果,该软件程序识别并量化拐点(inflection)的玻璃化转变温度(Tg)、吸热峰和放热峰,以及DSC图上的峰下面积。玻璃化转变温度被确定为图线上斜率发生明显变化的区域,而熔融温度是使用自动拐点计算来确定的。
膜拉伸性能:
可以在MTSSynergie200拉伸架上测试膜的拉伸性能(峰值应力、模量、断裂应变和单位体积断裂能)。测试可以根据ASTMD638-10(在约23℃下)进行。膜样品可以切割成狗骨形,在测试前中心宽度为3.0mm。狗骨膜样品可以使用标距长度为18.0mm的MTSSynergie200装置上的夹具固定就位。膜样品可以在5.0英寸/分钟的十字头速度下拉伸,直到发生断裂。在机器方向(MD)和机器横向(CD)上均针对每种膜测试五个样品。计算机程序(例如,TestWorks4)可以用于在测试过程中收集数据并生成应力-应变曲线,许多性能可以从所述曲线中测定,包括模量、峰值应力、伸长率和断裂能。
密度和空隙体积百分率:
为测定密度和空隙体积百分率,在拉伸前,可初始测量试样的宽度(Wi)和厚度(Ti)。拉伸前的长度(Li)也可以通过测量试样表面上的两个标记之间的距离来测定。然后,可将试样拉伸,以引发孔形成。然后,可利用DigimaticCaliper(MitutoyoCorporation)测量试样的宽度(Wf)、厚度(Tf)和长度(Lf),精确至0.01mm。拉伸前的体积(Vi)可通过WixTixLi=Vi计算。拉伸后的体积(Vf)也可通过WfxTfxLf=Vf计算。密度(Pf)可以计算如下:Pf=Pi/Φ,其中Pi为前体材料的密度;以及空隙体积百分率(%Vv)计算如下:%VV=(1-1/Φ)x100。
静水压测试(“静水压”):
所述静水压测试是材料在静压力下抵抗液态水渗透的量度的测试并且该测试根据AATCC测试方法127-2008进行。可对各试样的结果进行平均并以厘米(cm)记录。较高的值代表较大的抗水渗透性。
水蒸气透过率(“WVTR”):
该测试用于确定可基于材料性质变化的材料的WVTR。一种用于测量WVTR值的技术是ASTME96/96M-12,程序B。另一种方法涉及使用INDA测试程序IST-70.4(01)。所述INDA测试程序被总结如下。用永久防护膜和待测试的样品材料将干燥室与已知温度和湿度的潮湿室分开。防护膜的用途是限定一个明确的空气隙,并在表征该空气隙的同时使该空气隙中的空气不动或静止。干燥室、防护膜和潮湿室构成了该测试膜密封在其中的扩散单元。样品夹持器是Minnesota的Minneapolis的Mocon/ModemControls,Inc.制造的Permatran-WModel100K。第一个测试是由在产生100%相对湿度的蒸发器组件之间的防护膜和空气隙的WVTR组成。水蒸气扩散通过空气隙和防护膜,然后与正比于水蒸气浓度的干燥气流相混合。将电信号传输至计算机用于处理。计算机计算出空气隙和防护膜的透过率,并存储该值以备进一步使用。
防护膜和空气隙的透过率作为CalC存储于计算机中。然后将样品材料密封于测试单元中。再次地,水蒸气扩散通过空气隙至防护膜和测试材料,然后与吹扫测试材料的干燥气流相混合。同样,再次将该混合物携带至蒸气传感器。随后,计算机计算出空气隙、防护膜和测试材料的组合的透过率。随后,使用该信息根据以下方程来计算水分透过测试材料的透过率:
TR-1 测试材料=TR-1 测试材料、防护膜、空气隙-TR-1 防护膜、空气隙
然后,水蒸气透过率("WVTR")是如下计算的:
其中,
F=水蒸气流量,以cm3/分钟计;
ρsat(T)=温度T下饱和空气中水的密度;
RH=所述单元中特定位置处的相对湿度;
A=所述单元的横截面积;和
Psat(T)=温度T下的水蒸气的饱和蒸气压
实施例1
形成了材料的共混物,其包含91.5wt.%的聚丙烯(TotalPetrochemicalsM-3661)、7.5wt.%的聚乳酸(NatureworksIngeo6251D)和1.0wt.%的聚环氧化物改性剂(ArkemaLotaderAX8900)。该混合物随后通过双螺杆挤出机在220℃下熔融共混以形成均质的聚合物共混物。熔融的聚合物共混物通过多纤丝模头挤出,通过水骤冷,并通过水下制粒***如可得自Virginia的EagleRock的GalaIndustries的那些切割成颗粒。然后将配混的颗粒大批进料到具有流延膜模头的单螺杆挤出机(长度与直径比为24:1)。在220℃的温度下熔融材料并通过膜模头挤出到在25℃的温度下的铸轧辊上。将熔体拉伸力施加到熔融的膜上以将厚度降低至约177至203微米。
实施例2
如实施例1中所述形成膜,不同之处在于厚度为254至279微米。
实施例3
在拉伸架(例如,可得自MTSsystems的Sintech1/S架)中以50毫米每分钟的速率固态拉伸实施例1的膜至300%的应变。拉伸后,测得膜的长度在机器方向上增加了5.2倍,膜的宽度降低了20%。
实施例4
在拉伸架(例如,可得自MTSsystems的Sintech1/S架)中以50毫米每分钟的速率固态拉伸实施例2的膜至300%的应变。拉伸后,测得膜的长度在机器方向上增加了5.6倍,膜的宽度降低了20%。膜的SEM显微照片显示在图3-4中。
测试了实施例3和4的拉伸的膜的各种机械性能。结果显示在下表中。
实施例5
如实施例1中所述形成膜,不同之处在于厚度为48至55微米。
实施例6
形成了材料的共混物,其包含78wt.%的聚丙烯(TotalPetrochemicalsM-3661)、15wt.%的聚乳酸(NatureworksIngeo6251D)和7.0wt.%的聚环氧化物改性剂(ArkemaLotaderAX8900)。该混合物随后通过双螺杆挤出机在220℃下熔融共混以形成均质的聚合物共混物。熔融的聚合物共混物通过多纤丝模头挤出,通过水骤冷,并通过水下制粒***如可得自Virginia的EagleRock的GalaIndustries的那些切割成颗粒。然后将配混的颗粒大批进料到具有流延膜模头的单螺杆挤出机(长度与直径比为24:1)。在220℃的温度下熔融材料并通过膜模头挤出到在25℃的温度下的铸轧辊上。将熔体拉伸力施加到熔融的膜上以将厚度降低至约48至55微米。
实施例7
如实施例6中所述形成膜,不同之处在于厚度为70至80微米。
实施例8
如实施例6中所述形成膜,不同之处在于厚度为120至132微米。
虽然本发明已经就其具体实施方案得以详述,但是将领会的是,本领域技术人员一旦获得对前述内容的理解,就可以容易地设想这些实施方案的替代、变型和等同物。因此,本发明的范围应被评估为所附权利要求和其任意等同物的范围。
Claims (40)
1.一种吸收性制品,其包含设置在底片和顶片之间的吸收性元件,其中所述吸收性制品包括由包含连续相的热塑性组合物形成的膜,所述连续相包含聚烯烃基质聚合物和以离散区域的形式分散在所述连续相内的纳米包含物添加剂,其中在所述组合物中限定多孔网络,其包括多个平均横截面尺寸为约800纳米或更小的纳米孔。
2.权利要求1所述的吸收性制品,其中所述纳米孔的平均横截面尺寸为约5至约700纳米,优选为约10至约500纳米。
3.权利要求1或2所述的吸收性制品,其中所述纳米孔的平均轴向尺寸为约100至约5000纳米,优选为约50至约2000纳米,和更优选为约100至约1000纳米。
4.前述权利要求任一项所述的吸收性制品,其中根据ASTMD1238在2160克的负载下以及在230℃下测定时,所述聚烯烃基质聚合物具有每10分钟约0.5至约80克,在一些实施方案中为每10分钟约1至约40克,和在一些实施方案中为每10分钟约5至约20克的熔体流动速率。
5.前述权利要求任一项所述的吸收性制品,其中所述聚烯烃基质聚合物是丙烯均聚物、丙烯/α-烯烃共聚物、乙烯/α-烯烃共聚物或其组合。
6.前述权利要求任一项所述的吸收性制品,其中所述聚烯烃基质聚合物是包含按重量计至少约90%的丙烯的基本上全同立构的聚丙烯均聚物或共聚物。
7.前述权利要求任一项所述的吸收性制品,其中所述连续相占所述热塑性组合物的约60wt.%至约99wt.%。
8.前述权利要求任一项所述的吸收性制品,其中所述纳米包含物添加剂在室温下为液体或半固体。
9.前述权利要求任一项所述的吸收性制品,其中所述纳米包含物添加剂为具有非极性组分的聚合物。
10.权利要求9所述的吸收性制品,其中所述聚合物为微晶聚烯烃蜡。
11.权利要求9所述的吸收性制品,其中所述聚合物还包含极性组分。
12.权利要求11所述的吸收性制品,其中所述聚合物为官能化的聚烯烃。
13.权利要求12所述的吸收性制品,其中所述官能化的聚烯烃为聚环氧化物。
14.前述权利要求任一项所述的吸收性制品,其中根据ASTMD1238在2160克的负载下以及在高于熔融温度至少约40℃的温度下测定时,所述纳米包含物添加剂具有每10分钟约0.1至约100克,优选为每10分钟约0.5至约50克,和更优选为每10分钟约5至约15克的熔体流动速率。
15.前述权利要求任一项所述的吸收性制品,其中所述聚烯烃基质聚合物的熔体流动速率与纳米包含物添加剂的熔体流动速率的比率为约0.2至约8,优选为约0.5至约6,和更优选为约1至约5。
16.前述权利要求任一项所述的吸收性制品,其中所述纳米包含物添加剂为纳米级区域的形式,其中所述纳米级区域的平均横截面尺寸为约1纳米至约1000纳米。
17.前述权利要求任一项所述的吸收性制品,其中基于所述连续相的重量,所述纳米包含物添加剂占所述组合物的约0.05wt.%至约20wt.%。
18.前述权利要求任一项所述的吸收性制品,其中所述组合物还包含以离散区域的形式分散在所述连续相内的微米包含物添加剂。
19.权利要求18所述的吸收性制品,其中所述微米包含物添加剂为聚合物。
20.权利要求19所述的吸收性制品,其中所述微米包含物添加剂的聚合物为苯乙烯共聚物、含氟聚合物、聚乙烯醇、聚醋酸乙烯酯或聚酯。
21.权利要求19所述的吸收性制品,其中所述微米包含物添加剂的聚合物是聚乳酸。
22.权利要求19所述的吸收性制品,其中所述微米包含物添加剂的聚合物具有约0℃或更高,优选为约5℃至约100℃,更优选为约30℃至约80℃,和甚至更优选为约50℃至约75℃的玻璃化转变温度。
23.权利要求19的吸收性制品,其中在2160克的负载下以及在210℃的温度下测定时,所述微米包含物添加剂具有每10分钟约5至约200克,优选为每10分钟约20至约150克,和更优选为每10分钟约40至约100克的熔体流动速率。
24.权利要求19所述的吸收性制品,其中所述微米包含物添加剂的熔体流动速率与聚烯烃基质聚合物的熔体流动速率的比率为约0.5至约10,优选为约1至约8,和更优选为约2至约6。
25.权利要求18所述的吸收性制品,其中所述聚烯烃基质聚合物的杨氏弹性模量与所述微米包含物添加剂的杨氏弹性模量的比率为约1至约250,优选为约2至约100,和更优选为约2至约50。
26.权利要求18所述的吸收性制品,其中所述微米包含物添加剂为平均轴向尺寸为约1微米至约400微米的微米级区域的形式。
27.权利要求18所述的吸收性制品,其中基于所述连续相的重量,所述微米包含物添加剂占所述组合物的约1wt.%至约30wt.%。
28.前述权利要求任一项所述的吸收性制品,其中所述热塑性组合物还包含界面改性剂。
29.前述权利要求任一项所述的吸收性制品,其中所述多孔网络还包括微米孔。
30.前述权利要求任一项所述的吸收性制品,其中所述多孔网络以基本上均匀的方式分布在整个组合物中。
31.前述权利要求任一项所述的吸收性制品,其中所述纳米孔分布在大体上平行的列中。
32.前述权利要求任一项所述的吸收性制品,其中所述组合物的总的孔体积为每立方厘米约15%至约80%。
33.前述权利要求任一项所述的吸收性制品,其中所述纳米孔占所述组合物的总的孔体积的约20vol.%或更多。
34.前述权利要求任一项所述的吸收性制品,其中所述热塑性组合物的密度为约0.90g/cm3或更低,优选为约0.85g/cm3或更低,更优选为0.80g/cm3或更低,更优选为约0.10g/cm3至约0.75g/cm3,和甚至更优选为约0.20g/cm3至约0.70g/cm3。
35.前述权利要求任一项所述的吸收性制品,其中所述膜具有约300g/m2/24小时或更高,优选为约500g/m2-24小时或更高,更优选为约1,000g/m2-24小时或更高,和甚至更优选为约3,000至约15,000g/m2-24小时的水蒸气透过率。
36.前述权利要求任一项所述的吸收性制品,其中所述膜为包含芯层和至少一个外层的多层膜,其中所述芯层、外层或两者包含所述热塑性组合物。
37.前述权利要求任一项所述的吸收性制品,其中所述热塑性组合物通常不含碳酸钙填料。
38.前述权利要求任一项所述的吸收性制品,其中所述底片包含所述膜。
39.前述权利要求任一项所述的吸收性制品,其中所述顶片包含所述膜。
40.前述权利要求任一项所述的吸收性制品,其中所述制品包含包括所述膜的另外的组件,所述另外的组件包括耳片、防护翼、侧片、弹性元件、紧固件或其组合。
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