CN112852040A - 透气且多微孔的热塑性薄膜 - Google Patents

透气且多微孔的热塑性薄膜 Download PDF

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Publication number
CN112852040A
CN112852040A CN202110025167.3A CN202110025167A CN112852040A CN 112852040 A CN112852040 A CN 112852040A CN 202110025167 A CN202110025167 A CN 202110025167A CN 112852040 A CN112852040 A CN 112852040A
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film
alternatively
grams
machine direction
degrees celsius
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L·V·坎斯欧
F·埃申巴赫
J·福特
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Clopay Plastic Products Co Inc
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Clopay Plastic Products Co Inc
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Abstract

本发明涉及透气且多微孔的热塑性薄膜。透气的热塑性膜、层压物、和制造膜的方法，该膜具有小于或等于15gsm的基重和至少大约500克水每24‑小时每平方米的水蒸气传输速率，其中所述膜具有大约小于10的MD断裂负载和CD断裂负载的比，以及至少大约5克的机器方向切口埃尔门多夫抗扯强度或者至少大约15克的机器方向切口梯形抗扯强度中的至少一个。

Description

透气且多微孔的热塑性薄膜
本申请为国际申请号为PCT/US2015/030463、国际申请日为2015年05月13日、发明名称为“透气且多微孔的热塑性薄膜”的PCT申请于2016年11月11日进入中国国家阶段后申请号为201580027028.7的中国国家阶段专利申请的分案申请。
相关申请
本申请要求于2014年5月13日提交的美国临时专利申请号61/992,438、于2014年9月22日提交的美国临时专利申请号62/053,385、以及于2014年12月16日提交的美国临时专利申请号62/092,351的优先权。
技术领域
热塑性膜广泛用于个人护理产品，例如，作为尿布或其它一次性个人卫生用品的外层。由于各种原因，包括成本、舒适度、节约资源和最小化浪费，有需要尽可能使膜越薄越好，同时维持所述膜的其它必要性能。
热塑性膜需要的特点包括液体不可透性、蒸汽可透性(例如透气的)、可粘合至个人护理产品的其它层、以及有足够的物理强度可被处理成成品。当将热塑性膜用于包装(例如，用作消费品的外包装)时，强度是重要的考量。具有足够强度和基重的透气膜作为需要释放生产过程中产生的气味的产品的包装会尤其实用。
热塑性膜可通过将熔化的聚合组合物挤出到激冷辊(chill roller)上而形成，该过程中熔化的聚合组合物瞬间冷却以形成固态膜。膜的处理包括多个步骤，包括加热、冷却、以及拉伸来产生最终的膜产品，该膜产品的厚度比原始厚度小72倍或更小。在机器方向(MD)上拉伸形成高度定向型的薄型膜，这被称为机器方向定向(MDO)。MDO可以是实用的，然而也可影响尤其是更薄的膜的质量，例如降低横向方向(CD)的抗张强度、冲击强度、抗扯强度、和耐慢穿刺性(slow puncture resistance)。
背景技术
现有用于制造薄型热塑性膜的方法包括在美国专利7,442,332(Cancio et al)中描述的方法。在这个过程中，网的拉伸的大部分(超过一半)发生在所述挤出机模和第一轧点之间(比如在“熔化幕”内)。在这种浇铸过程中，两个缺陷是被称为“牵伸共振”的现象和膜内孔的形成，其中“牵伸共振”造成不均匀的膜厚度。这些问题随着生产速度增加而增加，且可进一步地限制可被应用的聚合组合物的种类。克服这些问题需要减慢生产，这最终导致成本提高。
因此，对于具有有限的MDO和需要的性质(比如没有孔、良好的透气性、良好的抗张强度和抗扯强度性质)、并且可被经济且高效地在高速生产线上生产的热塑性薄膜存在需求。
发明内容
通过提供具有低基重、大体上没有孔、且具有基重高得多的膜的物理属性特征的透气热塑性膜，本发明满足了上述的要求。本发明的膜表现出优秀的抗张强度、抗扯强度、和透气性。然而，抗张强度与膜的厚度成正比，一般更厚的膜表现出更高的抗扯强度，通过本发明的过程制成的膜表现出比针对具有相似厚度的相当的膜所预计的更高的抗扯强度。换言之，所述膜显示出抗扯强度与厚度的改进比例。
本发明的热塑性膜，其本身被视作独特的、通过新颖的流程制成，其中所述膜在某一温度下在MD上被拉伸，其中所述温度足够高来防止有害的MD定向，但低于热塑性聚合物的熔点。与描述在美国专利7,442,332中所述过程相反，这个过程发生在激冷辊的下游。本发明的方法允许所述挤出过程以常规生产速度发生，且不需要附加设备来减少牵伸共振。作为额外的优势，膜的质量(比如不透明度)可通过另外的下游MD拉伸控制，这会减少或消除了添加不透明剂的需求。
下面描述本发明的一些非限制性实施例。在一个实施例中，透气的热塑性膜被提供，其具有少于或等于大约15gsm的基重以及至少大约500克水/24小时/平方米的水蒸气传输速率(WVTR)，且其中所述膜的MD断裂负载与CD断裂负载的比小于大约10，并且该膜具有至少大约5克的机器方向切口埃尔门多夫(Elmendorf)抗扯强度或者至少大约15克的机器方向切口梯形抗扯强度中的至少一个。
在另一个实施例中，层压物被提供，其包括第一层，其中第一层依次包括透气热塑性膜，该膜具有少于或等于15gsm的基重以及至少大约500克水/24小时/平方米的水蒸气传输速率，且其中所述膜的MD断裂负载与CD断裂负载的比小于大约10，并且该膜具有至少大约5克的机器方向切口埃尔门多夫抗扯强度或者至少大约15克的机器方向切口梯形抗扯强度中的至少一个，所述第一层具有表面；以及附接至所述膜的所述表面的基底。
在另一个实施例中，制造热塑性膜产品的方法被提供，其包括将含有热塑性聚合物的熔化网从挤出机挤出到第一激冷辊上，所述第一激冷辊以圆周速度V1并在温度T1下操作，该温度在所述热塑性聚合物的熔点以下且冷却所述网来形成膜，并且其中所述挤出机和激冷辊之间的空间形成第一缝隙；将所述膜推进至所述第一激冷辊下游的拉伸辊，该拉伸辊以大于V1的圆周速度V2并在温度T2下操作，并且进一步在机器方向上拉伸所述膜，来产生具有大体上均匀厚度和有限机器方向定向的膜，其中所述膜的MD断裂负载与CD断裂负载的比例小于大约10，并且该膜具有至少大约5克的机器方向切口埃尔门多夫抗扯强度或者至少大约15克的机器方向切口梯形抗扯强度中的至少一个。
在上述方法提供的另一个实施例中，其中所述的热塑性膜具有至少2.0牛/厘米的MD断裂负载以及至少0.7牛/厘米的CD断裂负载。
在上述方法提供的另一个实施例中，其中所述热塑性膜产品的厚度从大约5gsm到大约20gsm。
在上述方法提供的另一个实施例中，其中所述熔化网被浇铸、吹制、压光、单独挤出、共挤出、冷浇铸、压印(nip embossed)、或其组合。
在上述方法提供的另一个实施例中，进一步包括至少一个附加的激冷辊，其在温度T下并以圆周速度V操作。
在上述方法提供的另一个实施例中，进一步包括在横向方向上拉伸所述膜来产生透气热塑性膜产品的步骤，其中该热塑性膜产品具有至少大约500克水/24小时/平方米的水蒸气传输速率。
在上述方法提供的另一个实施例中，其中膜用交叉辊在横向上递增地拉伸。
在上述方法提供的另一个实施例中，其中膜被推进穿过第一机器方向定向工段，该工段包括至少一个加热辊和至少一个拉伸辊，该加热辊具有温度T3。
在上述方法提供的另一个实施例中，其中其中膜被推进穿过至少第二机器方向定向工段，该工段包括至少一个加热辊和至少一个拉伸辊。
在上述方法提供的另一个实施例中，其中第二机器方向定向工段位于横向交叉辊工段的下游。
在上述方法提供的另一个实施例中，其中所述第二机器方向定向工段位于横向交叉辊工段的上游。
在上述方法提供的另一个实施例中，其中T1是从大约80摄氏度到大约160摄氏度。
在上述方法提供的另一个实施例中，其中T2是从大约60摄氏度到大约100摄氏度。
在上述方法提供的另一个实施例中，其中T3是从大约80摄氏度到大约150摄氏度。
在上述方法提供的另一个实施例中，其中T与T1相同。
在上述方法提供的另一个实施例中，其中T与T1不同。
在上述方法提供的另一个实施例中，其中V与V1相同。
在上述方法提供的另一个实施例中，其中V与V1不同。
在上述方法提供的另一个实施例中，其中激冷辊和拉伸辊形成从大约7.5厘米到大约30厘米的第二缝隙。
在上述方法提供的另一个实施例中，其中V2与V1的比是从大约2到大约8。
在上述方法提供的另一个实施例中，其中膜是共挤出多层膜。
在上述方法提供的另一个实施例中，其中膜是单独挤出的膜。
在上述方法提供的另一个实施例中，其中膜是吹制的膜。
在上述方法提供的另一个实施例中，其中所述膜具有至少大约50％的不透明度。
在上述方法提供的另一个实施例中，其中所述膜包括烯烃嵌段共聚物，其是基于乙烯的、基于丙烯的、或其组合物。
在又一个实施例中，提供透气的热塑性膜，其中该膜以如下流程生产：其中将含有热塑性聚合物的熔化网从挤出机挤出到具有温度T1的第一激冷辊上来形成膜，并且将所述膜推进至所述第一激冷辊下游的、具有温度T2的拉伸辊，并且进一步将膜推进穿过第一机器方向定向工段，其中该工段包括具有温度T3的至少一个加热辊和至少一个拉伸辊，其中膜具有有限的机器方向定向，并且其中所述膜具有小于或者等于大约15gsm的基重、至少大约500克水/24小时/平方米的水蒸气传输速率，并且其中所述膜具有小于大约10的MD断裂负载与CD断裂负载的比。
在上述方法提供的另一个实施例中，其中该膜具有至少大约5克的机器方向切口埃尔门多夫抗扯强度。
在上述方法提供的另一个实施例中，其中该膜具有至少大约15克的机器方向切口梯形抗扯强度。
在上述方法提供的另一个实施例中，其中所述的热塑性膜具有至少2.0牛/厘米的MD断裂负载以及至少0.7牛/厘米的CD断裂负载。
在上述方法提供的另一个实施例中，其中所述熔化网被浇铸、吹制、压光、单独挤出、共挤出、冷浇铸、压印(nip embossed)、或其组合。
在上述方法提供的另一个实施例中，其中膜是共挤出多层膜。
在上述方法提供的另一个实施例中，其中膜是单层膜。
在上述方法提供的另一个实施例中，其中所述膜具有至少200psi的水头压。
在上述方法提供的另一个实施例中，其中膜用交叉辊在横向上递增地拉伸。
在上述方法提供的另一个实施例中，其中所述的膜具有至少大约50％的不透明度。
附图说明
图1描述了一个适合制造本发明膜的装置的非限制性实施例。
具体实施方式
如此处应用：
“活跃缺陷”、“活跃孔”、或“针孔”，意味着当膜经历成形、层压、激活、或其它制造或处理步骤时膜中的小孔或裂痕，这可进而导致减小抗扯强度、增大多孔性、增加渗漏或其它不期望的特点。
“Gsm”意味着克每平方米，是基重的量度，其中该量度是定量表示膜或层压物的厚度或单位质量的行业标准术语。
“水头压”可依据方法AATCC 127-2008被测量,并且可用单位磅每平方英尺或psi表示。本发明的所述膜具有至少200psi的水头压。
“皮肤层”意味着多层膜的作为所述膜外表面的一个或两个外层。
“抗扯强度”或“拉扯力”反映了所述膜撕开的易度或难度，且用单位克表示。于此，抗扯强度可通过经引用并入本文中的埃尔门多夫切口抗扯测试ASTM D-1922和/或本文描述或根据ASTM D-5587的梯形抗扯测试(“trap测试”)测量。所述测试可在CD或MD方向且对于有切口的或无切口的膜进行。除非另有注明，此处抗扯强度是切口抗扯强度。需注意，抗扯强度与膜厚度有关，且任何抗扯强度的比较需考虑到比较样本的相对基重。
“抗张强度”意味着在CD或MD上膜内引发断裂(“在断裂时的负载”)所需的负载。抗张强度用单位牛/厘米或与此等同的单位表示，并且通过ASTM方法D822-02使用下述参数确定：样品方向＝MD x CD；样品尺寸＝1英寸宽x6英寸长；测试速度＝20英寸/分钟；夹持距离＝2英寸。夹持尺寸＝3英尺宽的橡胶面夹均匀地夹持样品。
“WVTR”意味着“水蒸气传输速率”，并且是膜透气性的量度。WVTR用克水/24小时/平方米或与等同的单位表示，并且可根据ASTM方法D-6701-01被测量。
膜
本发明的所述膜是热塑性单层或多层膜并且可有从大约5gsm到大约20gsm的基重，可替换的从大约5到大约15gsm，可替换的从大约10到大约15gsm，可替换的从大约8到大约13gsm，可替换的从大约10gsm到大约12gsm，可替换的少于大约15gsm，可替换的少于14gsm，可替换的少于大约12gsm，并且可替换的少于大约10gsm。本发明的多层膜可包括至少2层，可替换的至少3层，可替换的至少5层，可替换的至少7层，可替换的至少9层，可替换的至少11层，可替换的从2到大约20层，可替换的从3到大约11层，并且可替换的从5到11层。膜可以包括或不包括降低一个或者两个外表面的粘着性的皮肤层。
本发明的所述膜的CD断裂负载大于0.7牛/厘米，可替换的大于大约0.8牛/厘米，可替换的大于大约0.9牛/厘米，可替换的从大约0.7牛/厘米到大约3.0牛/厘米，并且可替换的从大约0.7牛/厘米到大约2.0。本发明的所述膜的MD断裂负载至少大约2.0牛/厘米，可替换的至少大约2.5牛/厘米，可替换的至少大约3.0牛/厘米，可替换的从大约2.0牛/厘米到大约6.0牛/厘米并且可替换的从大约3.0牛/厘米到大约6.0牛/厘米。
然而，本发明重要的和创新的方面是MD与CD断裂负载的比例，这是这些性质之间改进平衡的度量且没有展现在之前公开的膜中。不希望受到理论限制，应理解这个有优势的比例通过以此处公开的过程减少膜内的机器方向定向实现。本发明的膜的MD断裂负载与CD断裂负载的比例从大约1到大约15，可替换的从大约1到大约10，可替换的从大约1到大约9，可替换的从大约1到大约8，可替换的从大约1到大约5，可替换的小于大约10，可替换的小于大约9，可替换的小于大约8，可替换的小于大约5，可替换的小于大约4，并且可替换的小于大约1。
本发明的膜进一步具有的水蒸气传输速率(WVTR)为至少500克水/24小时/平方米，可替换的至少1000克水/24小时/平方米，可替换的至少2000克水/24小时/平方米，可替换的至少3500克水/24小时/平方米，可替换的至少4500克水/24小时/平方米，可替换的至少大约6000克水/24小时/平方米，可替换的至少大约7000克水/24小时/平方米，可替换的至少大约9000克水/24小时/平方米，以及可替换的从大约1000克水/24小时/平方米到大约10000克水/24小时/平方米。
本发明的膜进一步具有的机器方向上的埃尔门多夫抗扯强度为至少大约5克，可替换的至少大约10克，可替换的至少大约15克，可替换的从大约5克到大约50克，可替换的从大约10克到大约45克，以及可替换的从大约15克到大约45克。
本发明的膜进一步具有的机器方向上的梯形(“trap”)抗扯强度为至少大约15克，可替换的至少大约20克，可替换的至少大约25克，可替换的从大约15克到大约150克，可替换的从大约15克到大约100克，以及可替换的从大约15克到大约85克。
本发明的所述膜进一步包括一种或者多种热塑性聚合物。适合用于所述膜的聚合物包括但不仅限于聚烯烃，例如，聚乙烯均聚物和共聚物、聚丙烯、聚丙烯均聚物和共聚物、官能化聚烯烃、聚酯、聚(酯-醚)、聚酰胺(包括尼龙)、聚(醚-酰胺)、聚砜、含氟聚合物、聚氨酯、和其混合物。聚乙烯均聚物包括那些具有低、中或高密度的和/或那些通过高或低压聚合反应形成的。聚乙烯和聚丙烯共聚物包括但不仅限于含有C4-C8α-烯烃单体的共聚物，包括1-辛烯、1-丁烯、1-己烯和4-甲基戊烯。聚乙烯可以大体是线性或支线性的，并且可以通过所属领域中已知的运用催化剂的各种流程形成，催化剂比如Ziegler-Nata催化剂、金属茂或者单活性位点催化剂(single-site catalysts)或者其它所属领域广为知晓的催化剂。合适的共聚物的例子包括但不仅限于比如聚(乙烯-丁烯)、聚(乙烯-己烯)、聚(乙烯-辛烯)和聚(乙烯-丙烯)的共聚物、聚(乙烯-醋酸乙烯酯)、聚(乙烯-丙烯酸甲酯)、聚(乙烯-丙烯酸)、聚(乙烯-丙烯酸丁酯)、聚(乙烯-丙二烯)、聚(甲基-丙烯酸甲酯)和/或其聚烯烃三元共聚物。在一个实施例中，膜包括聚乙烯、聚丙烯、和其组合物。合适的商业上可得到的基于聚乙烯的树脂的一个例子是Exxon生产的ExceedTM3527PA。合适的商业上可得到的聚丙烯共聚物的一个例子是Borealis生产的Borealis BD712。
合适的烯烃聚合组合物的另外的非限制性例子包括烯嵌段共聚物、烯无规共聚物、聚氨酯、橡胶、乙烯亚芳基和共轭二烯、聚酯、聚酰胺、聚醚、聚异戊二烯、聚氯丁橡胶、任一上述的共聚物、和其混合物。另外，本发明的膜，或其层，可包括脆性聚合物，其非限制性示例在美国专利7,879,452中公开。在一个实施例中，膜包括烯烃嵌段共聚物。
在一个实施例中，烯烃嵌段共聚物是基于聚丙烯的。适合的基于聚丙烯的烯烃嵌段共聚物非限制性例子是密歇根州米德兰市的Dow化学公司以商标INFUSETM、德克萨斯州休斯顿市的ExxonMobil化学公司以商标
Figure BDA0002890091470000091
和商标为Exxon
Figure BDA0002890091470000092
的共聚物(比如ExxonPD7623)销售。聚丙烯以及聚酯，都被知晓为提高形成的聚合物膜的熔化温度，改善膜的抗烧穿性。在可替换的实施例中，本发明的膜可包括基于乙烯的烯烃嵌段共聚物。
上述热塑性聚合物可以0％到大约95％的量出现在膜中或在膜的单层中，可替换地从大约0％到大约40％，可替换地从大约10％到大约50％，可替换地从大约35％到大约50％，可替换地从大约20％到大约40％，并且可替换地从大约1％到大约10％。
在一个实施例中，膜、或多层膜的一层或多层包括从大约0.1％到大约90％、可替换地从大约1％到大约60％、可替换地从大约20％到大约50％、可替换地从大约20％到大约40％、可替换地从大约1％到大约10％的聚丙烯、基于聚丙烯的组合物或共聚物、乙烯、基于乙烯的组合物或共聚物、或其组合。
本发明的膜或其单层可包括一种或多种弹性聚合物，包括苯乙烯嵌段共聚物、弹性烯烃嵌段共聚物和其组合。合适的苯乙烯嵌段共聚物(SBC)的非限制性例子包括苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-异戊二烯-苯乙烯(SIS)、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)、苯乙烯-乙烯-丙烯(SEP)、苯乙烯-乙烯-丙烯-苯乙烯(SEPS)、或苯乙烯-乙烯-乙烯-丙烯-苯乙烯(SEEPS)嵌段共聚物弹性体、聚苯乙烯、和其混合物。在一个实施例中，膜包括苯乙烯-丁二烯-苯乙烯、聚苯乙烯、和其混合物。合适的SBC树脂已可从德克萨斯州休士顿市的
Figure BDA0002890091470000101
聚合物、洛杉矶市Planquemine的DexcoTM聚合物有限合伙公司、或德克萨斯州Pasadena市SeptonTM美国公司得到。
本发明的膜可包括可选择地组分，比如填料，填料比如碳酸钙、增塑剂、增容剂、取样聚合物(draw down polymers)、加工助剂、防粘连剂、减粘聚合物、和类似物。其它添加剂可包括颜料、染料、抗氧化剂、抗静电剂、滑剂、起泡剂、热或光稳定剂、UV稳定剂、和类似物。合适的加工助剂和防粘连剂的例子包括但不限于可以从Ampacet公司得到的AmpacetTM。在一个实施例中，聚合组合物可包括从大约0％到大约75％、可替换地1％到30％和可替换地从大约30％到大约60％的填料。在一个实施例中，聚合组合物可包括从大约0％到大约15％、以及可替换地从大约0％到大约10％、以及可替换地从大约0.5％到大约5％的合适的加工助剂。
在一个实施例中，膜大体上不含二氧化钛，以及可替换地包括少于0.1％的二氧化钛。膜可以具有大于50％、可替换地大于55％、以及可替换地大于大约60％的不透明度。
装置
图1描述膜形成装置10的示例设计，其适合形成本发明的膜。应用于膜或无纺织物材料的“机器方向”意味着当其在膜形成装置中处理时平行于膜或无纺织物的进行方向的方向。“横向方向”意味着垂直于机器方向的方向。在一个非限制性实施例中，并且如图1所述，膜形成装置10包括浇铸/拖拽工段12、机器方向定向(MDO)工段14、和横向交叉辊(CDI)工段16。可选择地，膜形成装置10可包括对于所属领域技术人员显而易见的附加工段，比如炼韧器工段、卷线机、附加的机器方向定向工段、和/或电晕处理工段。在其它实施例中，如同样将被所属领域技术人员理解的，其工段或部件的顺序可不同于描述于图1中的那些。
浇铸/拖拽工段12包括挤出机24，随后是至少一激冷辊28，其中第一缝隙26在挤出机和激冷辊之间。如将被所属领域技术人员理解的，挤出机24相对于激冷辊28的位置可从图1所示的位置改变至比所示的稍许更下游的位置，但其中挤出机24仍然在将包括挤出物的熔化幕沉积到激冷辊28上的位置。激冷辊28的下游(其具有温度T1并且以速度V1转动)是拉伸辊30，其具有温度T2并且以速度V2转动。激冷辊28通过第二缝隙32与拉伸辊30分离。在操作中，挤出机24熔化挤出物并将挤出物挤出穿过缝隙26至激冷辊28之上，形成网、或膜15。膜15穿过缝隙32进入轧点33，其中该轧点形成于从动辊34和拉伸辊30之间。膜15随后穿过空转辊39至机器方向定向工段14。
本发明的网或膜可通过被所属领域技术人员理解的方法形成，并且可被浇铸、吹制、压光、单独挤出、共挤出、冷浇铸、压印(nip embossed)、或任何其它的可使膜相容于此处所述的流程的方法处理。
在一个实施例中，热塑性聚合膜的配方可被混入挤出机24，例如在从大约210摄氏度到大约280摄氏度的温度下。准确的温度将取决于聚合组合物的配方。包括聚合组合物的网或“熔化幕”可被挤出(或共挤出，如果多层膜正在被形成)于激冷辊28上。激冷辊28的温度T1被精确地控制，以使得当膜15离开激冷辊28时，膜15处于足够高的温度使其在没有很大程度的MD分子定向的情况下拉伸至理想的厚度，但该温度低于聚合组合物的熔点。因此，温度T1和T2取决于膜的组分。T1可能大于80摄氏度、可替换地从大约80摄氏度到大约160摄氏度、可替换地从大约90摄氏度到大约160摄氏度、可替换地从大约100摄氏度到大约140摄氏度、可替换地从大约80摄氏度到大约120摄氏度、可替换地从大约100摄氏度到大约120摄氏度、以及可替换地小于160摄氏度。拉伸辊30的温度T2可大于40摄氏度、可替换地从大约40摄氏度到大约100摄氏度、可替换地从大约60摄氏度到大约100摄氏度、可替换地从大约60摄氏度到大约90摄氏度、可替换地从大约85摄氏度到大约90摄氏度、以及可替换地小于大约100摄氏度。
应注意在本发明中，激冷辊28的温度T1和拉伸辊30的温度T2显著高于任何之前公开的MDO流程。在之前的应用中，T1通常是从大约10摄氏度到大约60摄氏度，并且T2通常是从大约10摄氏度到大约40摄氏度。本发明使用平衡膜加工性和允许控制MDO的量的需求的温度。
在一个实施例中，至少有两根激冷辊，每一根均具有速度V和温度T。每根激冷辊的速度和温度可以是相同的或不同的，然而都将会足够使膜在没有很大程度上的MD分子定向的情况下被拉伸至理想的厚度，但该温度低于聚合组合物的熔化温度。仅通过非限制性例子的方式，温度将相差5摄氏度、10摄氏度、或更大。激冷辊可能每个各自是光滑的、有特定纹理的、涂覆的(例如利用释放处理)，其中在每个辊上将相同或不同。
挤出机24和激冷辊28之间的第一缝隙26的长度是挤出机24和激冷辊28之间的最短距离，并且大于之前的铸造MDO流程。在一个实施例中，第一缝隙26的长度大于2.5厘米、可替换地从大约2.5厘米到大约25厘米、可替换地从大约3厘米到大约15厘米、以及可替换地从大约3厘米到大约7.6厘米。挤出物可在缝隙26中经历熔化幕拉伸，伴随着相应的厚度减少从10倍到大约25倍(大约10X到大约25X)。
在一个实施例中，如美国专利7,442,332中描述，装置可在挤出机24与激冷辊28之间包括附加的辊和轧点。在另一个实施例中，装置可包括一个或多个附加的激冷辊。在又一个实施例中，激冷辊28可以被两根辊取代，其中辊形成附加的轧点。辊可以是金属辊和橡胶辊，并且金属辊可选择地有压纹。在轧点中膜的温度是大约120摄氏度或以下，并且可替换地是大约100摄氏度或以下。在通过附加的轧点之后，膜前进穿过轧点33并且进一步经历此处描述的流程。
辊的速度比V2/V1提供膜拉伸的相对长度。因此，1/1(1x)的比指示了膜还没被拉伸。5/1(5x)的比指示了，在拉伸伴随着相应膜厚度减小之前，膜已被拉伸了其长度的5倍，即膜厚度是拉伸之前其厚度的0.2倍。在一个实施例中，V2/V1的比至少为2、可替换地至少为5、可替换地从大约2到大约8、可替换地从大约3到大约8、以及可替换地小于5。
在激冷辊28与拉伸辊30处的轧点33之间的第二缝隙32的长度是激冷辊28与拉伸辊30之间的最短距离，并且在一个实施例中为至少大约7.5厘米、可替换地从大约7.5到大约30厘米、可替换地从大约7.5到大约20厘米、可替换地从大约7.5到大约10厘米、可替换地大约30厘米、可替换地大约20厘米、可替换地大约15厘米、以及可替换地小于10厘米。在激冷辊28与拉伸辊30之间被拉伸后，膜15本质上是在MD上具有有限分子定向的无孔膜。
于此，“把有限机器方向定向传递于膜”意味着产生足够的MD定向来给予膜至少2.0牛/厘米的MD断裂负载与至少0.7牛/厘米的CD断裂负载。另外，膜将具有从大约1到大约15的MD断裂负载与CD断裂负载的比。虽然MDO的量将不会直接被量化，MDO的量相关于膜的性质。具有有限的MDO的膜将具有特别提升的CD性质(比如CD埃尔门多夫和梯形抗扯强度、CD抗张断裂强度)和相对于之前所述的膜的CD和MD抗张强度的提升的平衡。
从浇铸/拖拽工段12的下游，膜15可从拉伸辊30围绕空转辊39穿过达到第一及其方向定向(MDO)工段14。这个工段的目的是进一步在机械方向上拉伸膜，同时仍避免显著的MD定向。MDO工段14可包括加热辊35a和35b，随后是拉伸辊36a和36b和/或冷却辊37。在加热辊35a-35b处，膜15加热到温度T3。T3将取决于膜的组分，并且将足够避免显著的MD定向。在一个实施例中，T3是从大约80摄氏度到大约150摄氏度、可替换地大于95摄氏度、以及可替换地大于120摄氏度。
所属领域技术人员将理解，第一MDO工段14内的拉伸辊、加热辊和冷却辊的数量以及MDO工段的数量可以改变。因此，在可替换的实施例中，装置可包括一个或多个附加组的拉伸辊、加热辊、和/或冷却辊，来给予其理想的物理和美学特性，比如多孔性和不透明度。通过例子的方式，第二组加热辊、拉伸辊和/或冷却辊可位于第一MDO工段14中，拉伸辊36a和36b的下游和冷却辊37的上游。在可替换的实施例中，第二组加热辊、拉伸辊和/或冷却辊位于CDI工段16的下游、在第二MDO工段中。
膜15以V3的速度移向MDO工段14的下游。在一个实施例中，V3/V1的比大于1、可替换地大于2、可替换地小于25、可替换地从大约2到大约25、可替换地从大约5到大约15、可替换地从大约5到大约25。在一个实施例中，V3/V2和/或V2/V1的比大于1、可替换地大于2、可替换地小于5、可替换地从大约1到大约5、以及可替换地从大约2到大约5。
如果具有横向交叉辊(CDI)工段16，其可包括张紧辊38，随后是交叉辊40、42。在本发明中，交叉辊40、42被设计用于沿横向拉伸膜，导致附加的膜活化并且给予透气性。在一个实施例中，在CDI工段16之前或之后，机械方向交叉辊被用于替换横向交叉辊40、42处或另外地使用。合适的横向交叉辊在美国专利7,442,332中被描述。
替代在MDO工段和或CDI工段或除了这些工段之外，膜可以用拉幅架(未示出)被拉伸。这可被用于达到MDO与CDO的效果。
膜15可从CDI工段16移至其它可选的部件，包括但不仅限于，电晕处理工段、退火工段、第二MDO工段和/或卷线机，其中膜15之后可准备好被用于所欲想的用途。本发明的膜可被用于多种用途，包括例如用于关于比如一次性吸收性产品的个人卫生用品。非限制性实施例包括尿布、训练裤、成人失禁垫和裤、泳衣、卫生巾、卫生棉、护垫等。在一个实施例中，本发明关于包括此处描述的膜的吸收性物品。在一个实施例中，吸收性物品是尿布。
本发明进一步描述包括本发明的膜的层压物。层压物包括第一层，其包括此处描述的透气的热塑性膜；和基底，其接合于膜的一或者两面。基底可以是任何适合与热塑性膜一起使用的纺织或无纺织物材料，并且在一个实施例中是纺粘型无纺织物。基底的基重是100gsm或更少、可选择地50gsm或更少、可选择地25gsm或更少、可选择地15gsm或更少、以及可选择地10gsm或更少。基底可通过各种方法(比如粘附层压、超声粘合、挤出粘合等)接合于膜。
本发明的膜和/或层压物适于用作尿布底片或耳部(闭合凸片(closure tabs))，并且可形成用于包装、包裹产品(比如个人卫生物品)以及食物(比如三明治、水果、蔬菜和类似物)的保护套、透气的塑料袋(比如透气的尿布塑料袋)。可使用本发明的层压物的物品的其它非限制性的例子包括建筑应用，比如屋顶和墙衬和用于地板和地毯的底片。
本发明将在接下来详细例子的叙述下被进一步描述。
不透明度
膜的不透明度可被按照如下测量：方法使用与白背面组合的样品和与黑背面组合的同样的样品的反射比的比。Hunterlab色度计D25A根据制造商的说明书被校准和被标准化。样本被切得足够大来覆盖仪器的检查孔开口。样本被置于端口上，其中橡胶卷到一边或向上卷起。样本被用未校准的白片覆盖。“Read”和“xyz”键将被按。白片被移除。样本被黑玻璃片覆盖。100％被按。样本的“y”值以及不透明度值将以百分比被显示。在所有例子中，样本受到CD增量拉伸(CDI)。
可替换地，膜的不透明性可根据ASTM D1746被测量。
水头压
水头压可根据描述于AATCC127-2008的方法被测量。具体地，Textest InstrumentFX 3000 Hydrotester III,05/07s/n 597或更高可被应用。标准测试梯度是60mbar/min，并且70gsm纺粘/图案接合的聚丙烯无纺织物被用作支撑物。测试终点是第三滴点，并且当第一、第二和第三滴点穿透样本的压力和/或样品破裂时的压力以mbar为单位被记录。如果没有水穿透被观测到，最大测试压被记录。
Trap抗扯强度
样品样板被切成具有3”x6”的尺寸。从这个样板，标记梯形样板，其中该梯形样板有4”的长边、1”的平行短边、和3”的高(平行边之间、垂直于边测量的距离)。从短边边缘的中间开始，切出垂直于短边的、具有5/8”长度的小缝。将样板放置在Intron模型1122,4301的钳夹或等同的张力试验测试单元内，其中该单元具有恒定的拉伸率。夹钳之间的距离被设置为1”。根据指导，调试并且标准化负荷元件。对于装有Series IX软件的张力试验器，从软件的“method”菜单中选择合适的Series IX测试方法。
设置测试单元的负载范围，来使最大负载发生在85％的满标度负荷。将十字头运行速率设置在十二英寸(12”)每分钟。将样板沿梯形的标记的不平行的边固定于上下夹钳内，以此来使夹钳的一端边缘对齐于梯形的一英寸(1”)边，并且剪切位置在钳夹的中间。启动测试装置并且记录试样的拉扯力。
实施例1
按照之前描述的方法形成膜。聚合物配方以重量计包括48％的聚乙烯、45％的碳酸钙、6％的聚丙烯和1％的加工助剂。该配方在大约260摄氏度的温度下熔化混合并且挤出成为单层，并且挤出于激冷辊上，其中该激冷辊以大约45.7米每分钟的速度并且在116摄氏度的温度下转动。膜在拉伸辊被拉伸，其中该拉伸辊以142米每分钟的速度V2并且在88摄氏度的温度下操作。接下来它在以278米每分钟的速度并且在小于95摄氏度的温度下操作的MDO处被拉伸。形成的膜具有基重11.4gsm和CD断裂负载1.14牛顿/厘米。横向断裂伸长率是446％。在机器方向上，断裂负载是3.16牛顿/厘米。机器方向断裂伸长率是269％。不透明度是59.4％，并且没有加入TiO2。水蒸气传输速率(WVTR)是9,083克水/24小时/平方米。这些数据点都超过了减少材料的16gsm基重的膜的参数。
实施例2-11
运用例1中公开的方法，附加的铸造膜被形成。样品含有如下所示的1％的加工助剂、聚丙烯和填料，以及包括聚乙烯的组合物残留物。膜的物理特性在表1中被示出。除非另有表述，膜包括50％碳酸钙并且不包含二氧化钛。
根据实施例2，三层膜被形成，其中皮肤层包括含有4％聚丙烯的聚乙烯，并且芯层包括含有33％聚丙烯的聚乙烯。层A/B/A厚度的百分比是15/70/15。
在实施例3中，单层膜被形成，其中包括聚乙烯、11％的聚丙烯和47％的碳酸钙填料。
在实施例4中，单层膜被形成，其中包括9％的聚丙烯。V2/V1的比是2.2并且V3/V2的比是2.0。
在实施例5中，单层膜被形成，其中包括16％的聚丙烯。V2/V1的比是3.2并且V3/V2的比是2.5。
在实施例6和7中，单层膜被形成，其中包括33％的聚丙烯。V2/V1的比分别是4.0和3.5并且V3/V2的比分别是1.5和1.3。
在实施例8中，包括三层的多层膜被形成，其中外层包括0％的聚丙烯并且内层包括33％的聚丙烯。V2/V1的比是3.2并且V3/V2的比是2.0。层A/B/A厚度的百分比是15/70/15。
在实施例9和10中，包括33％聚丙烯以及橡胶添加剂的单层膜被形成。V2/V1的比是3.5并且V3/V2的比对于实施例9是1.3并且对于实施例10是1.5。
在实施例11中，单层膜被形成，其中包括21％的聚丙烯和46％的碳酸钙。V2/V1的比是3并且V3/V2的比是2。
表1
Figure BDA0002890091470000171
在本发明的所有实施例中，所有范围被包含并且可合并。所有数值被理解为通过词“大约”被修改除非另有详细说明。从程度上来说词“包含”、“包含着”、“包括”、或“包括着”被用于说明书或权利要求，它们意图为包含性的，其在形式上相似于词“包括”当那个词作为权利要求中的过渡词使用时的释义。
所有的在发明详细描述引用的文件是，部分相关于，在此接合于参考文件；对于任何文件的引用不会被理解为关于本发明的现有技术的许可。从某种程度上说，任何在这个文件中词的意思或定义与任何包含于参考文献的文件中的同样词的意思或定义矛盾，在这个文件中给予这个词的意思或定义应该主导。
然而本发明特别的实施例已被说明和描述，多种其它的改变和修改在没有偏离发明意思和范围的情况下，可被做出应该是对于所属领域技术人员明显。因此应试图包括本发明中所有这类在发明范围内的改变和修改。

Claims (7)

1.一种热塑性膜，所述膜包括聚乙烯、聚丙烯和填料，其中所述膜在适合于产生这样的膜的温度在激冷辊和拉伸辊之间在机器方向上进行拉伸：该膜具有有限的机器方向定向，从大约1到大约5的MD断裂负载与CD断裂负载比，15gsm或更少的基重和大于约50％的根据ASTM D-1746测量的透明度。
2.根据权利要求1所述的膜，其中所述膜进一步在横向方向上进行拉伸以导致这样的膜：该膜具有至少大约3500克水/24小时/平方米的水蒸气传输速率。
3.根据权利要求2所述的膜，其中所述膜用交叉辊在横向方向上进行拉伸。
4.根据权利要求1所述的膜，其中所述膜具有至少5克的机器方向切口埃尔门多夫抗扯强度或者至少15克的机器方向切口梯形抗扯强度。
5.根据权利要求1所述的膜，其中所述膜具有至少200psi的水头压。
6.根据权利要求1所述的膜，其中所述膜具有至少400psi的水头压。
7.根据权利要求1所述的膜，其中所述填料是碳酸钙、二氧化钛或其组合。
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