CN102782063A - 降低噪声的挤出涂层组合物 - Google Patents

降低噪声的挤出涂层组合物 Download PDF

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CN102782063A
CN102782063A CN2010800649106A CN201080064910A CN102782063A CN 102782063 A CN102782063 A CN 102782063A CN 2010800649106 A CN2010800649106 A CN 2010800649106A CN 201080064910 A CN201080064910 A CN 201080064910A CN 102782063 A CN102782063 A CN 102782063A
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coating
extruding
inorganic particulate
particulate material
polyolefine
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CN102782063B (zh
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K.祖尔彻
A.多梅尼克
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Dow Global Technologies LLC
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Abstract

提供了挤出涂覆基材的方法。该方法包括用挤出涂覆的方法将挤出涂层组合物施用到基材表面上。在这些方法中，挤出涂层组合物包括聚烯烃和平均粒度不大于2μm且颗粒装载量为至少20重量%的无机颗粒材料，以聚烯烃和无机颗粒材料的总重量计。

Description

降低噪声的挤出涂层组合物
背景技术
挤出涂覆(extrusion coating)工艺可以被描述为在高熔融温度和通常至多700米每分钟（mpm）的高速下将熔化的聚合网施用到移动基材的过程。目的在于产生装饰效果的高光泽表面光洁度的挤出涂层会在层压机附近区域产生大量噪声，为了达到公共的工业卫生标准所规定的安全的操作环境通常需要额外的预防措施。噪声代表工艺有关限制因素的指标，它会随着生产线速度的增加而增强。然而，期望高的生产线速度，因为这使挤出涂覆设备成为经济上具有吸引力的操作设备。因此，拥有一种不会出现边缘过渡涂覆问题（即，粘住压力或冷却辊）的稳固的挤出涂覆工艺是有益的，因为边缘过渡涂覆会导致工艺中断，包括损失过渡涂层和破坏聚合物粘附。
发明内容
本发明一方面提供了挤出涂覆基材的方法，该方法通过挤出涂覆将挤出涂层组合物施涂到基材表面上，由此挤出涂层组合物接触冷却辊表面。在该方法中，挤出涂层组合物包含聚烯烃和平均粒度不大于2μm且颗粒装载量为至少20重量%的无机颗粒材料，其中以涂层组合物中聚烯烃和无机颗粒材料的总重量计。在该方法的一些具体实施方式中，聚烯烃包含密度不大于940g/cc的聚乙烯或聚乙烯互聚物。
在该方法的一些实施方式中，挤出涂层组合物的特征在于，与利用缺乏无机颗粒材料的相同挤出涂层组合物进行的同样的挤出涂覆工艺相比，该组合物使冷却辊释放点的挤出涂覆噪声减少了至少3分贝。为了达到公开的目的，噪声降低是针对以下材料测量的：在320℃的模头的挤出物温度和250mm的空气间隙，以25（g/m2）的涂层重量和在300mpm的生产线速度或者以12g/m2的涂层重量和在500mpm的生产线速度施涂到表面粗糙度为0.5μm的镀铬的光滑冷却辊上的聚烯烃挤出涂层组合物。在一些实施方式中，挤出涂层组合物的特征在于使冷却辊释放点的挤出涂覆噪声减少了至少10分贝。可以利用对准正离开模头的挤出物的红外辐射式测温仪测量挤出物温度。
在该方法的一些实施方式中，无机颗粒材料的平均粒度不大于1.5μm，以及颗粒装载量为至少30重量%，以涂层组合物中聚烯烃和无机颗粒材料的总重量计。无机颗粒材料可以是碳酸钙。
本发明另一方面提供了包含基材和涂覆在基材表面上的涂层组合物的涂覆的基材，其中涂层组合物包含聚烯烃和平均粒度不大于2μm的无机颗粒材料，以及颗粒装载量为至少20重量%，以涂层组分中聚烯烃和无机颗粒材料的总重量计。
在一些实施方式中，基材包含纸制品。
在一些实施方式中，无机颗粒材料的平均粒度不大于1.5μm，以及颗粒装载量为25重量%，以聚烯烃和无机颗粒材料的总重量计。
在一些实施方式中，聚烯烃包含密度不大于940g/cc的聚乙烯或聚乙烯互聚物，无机颗粒材料包含矿物。
附图说明
图1(a)是挤出涂覆基材体系的侧面示意图。
图1(b)是图1(a)中体系的俯视图。
具体实施方式
本发明的发明人出乎意料地发现，通过将适当装载量的具有合适粒度分布的无机颗粒材料添加到挤出涂层组合物的聚烯烃中，能够在不降低挤出涂层和涂覆基材间的粘附的情况下实现极好的冷却辊释放，因此能显著减少噪声。
因此，本发明一方面提供了挤出涂覆基材的方法，该方法包括通过挤出涂覆将挤出涂层组合物施用到基材表面上。在这些方法中，挤出涂层组合物包含聚烯烃和平均粒度不大于2μm且颗粒装载量至少为20重量%的无机颗粒材料，以聚烯烃和无机颗粒材料的总重量计。
不希望使本发明束缚于任何特殊的理论，相信是具有适当粒度分布和装载量的颗粒材料，在挤出工艺中为挤出涂层和冷却辊表面的分界面上提供了充分的无机粒子，因此能显著减少挤出涂层粘附到冷却辊上，而不降低挤出涂层和涂覆基材间的粘附。
聚烯烃：
挤出涂层包括至少一种聚烯烃。"聚烯烃"，"PO"和类似的术语是指源自单纯烯烃的聚合物。代表性的聚烯烃包括聚乙烯，聚丙烯，聚丁烯，聚异戊二烯和它们的多种互聚物。本发明的方法特别适用于使用包括聚烯烃，例如低密度的聚乙烯及其互聚物(例如，共聚物)的挤出涂层，因为已知这样的聚烯烃在挤出涂覆时会大量粘附在冷却辊上，因此会产生大量噪声。
聚烯烃可以是，例如低密度聚乙烯（LDPE），聚丙烯（PP），高密度聚乙烯（HDPE）及其他较低密度的聚烯烃，例如增强聚乙烯（EPE），聚烯烃塑性体（POPs），聚烯烃弹性体（POEs），基于聚丙烯的塑性体（PBP）和聚烯烃嵌段弹性体（PBEs），例如烯烃嵌段共聚物（OBCs）。合适的较低密度的聚烯烃包括超低线密度聚乙烯（VLDPEs），包括茂金属聚乙烯和聚乙烯共聚物。可用于制备聚乙烯共聚物的共聚单体包括α-烯烃，例如C3-C20α-烯烃（例如，C4-C10α-烯烃)。α-烯烃共聚单体可以是直链或支化的，如果需要也可以使用两种或更多种共聚单体。聚乙烯共聚物的实例包括乙烯丙烯酸（EAA）共聚物，离聚物，乙烯甲基丙烯酸（EMAA）共聚物，乙烯丙烯酸乙酯（EEA）共聚物，乙烯丙烯酸甲酯（EMA）共聚物，乙烯丙烯酸丁酯（EBA）共聚物和乙烯-乙酸乙烯基酯（EVA）共聚物。
通常使用的聚烯烃的密度不大于约0.940g/cc。这包括其中聚烯烃为密度为约0.916g/cc至约0.940g/cc的聚乙烯的实施方式，更进一步地包括其中聚乙烯的密度为低于0.916g/cc（例如，为约0.860g/cc至约0.915g/cc）的实施方式。在一些实施方式中，包含聚乙烯和/或聚丙烯的聚烯烃的密度为约0.860g/cc至约0.905g/cc。这包括其中聚乙烯和/或聚丙烯的密度为约0.860g/cc至少于0.890g/cc的实施方式。为了公开的目的，密度是按ASTM D-1505测量的。
以挤出涂层组合物中聚烯烃和无机颗粒材料的总重量计，本发明的挤出涂层组合物的聚烯烃含量通常为至多约80重量百分比（wt.%）。这包括其中以挤出涂层组合物中聚烯烃和无机颗粒材料的总重量计，挤出涂层组合物的聚烯烃含量为至多约为75wt.%的实施方式。
无机颗粒材料：
无机颗粒材料可以是多种形式的材料，只要它具有本申请描述的降低噪声能力就可以。通常，可以使用能被磨碎成粒度小于涂层厚度且在挤出涂覆工艺期间不与聚合物相互作用的稳定的任何矿物。在一些实施方式中，颗粒材料包含矿物，例如碳酸钙。
无机颗粒材料中的粒子的平均粒度（d50）不大于约2μm。在一些实施方式中，颗粒材料的粒子的平均粒度不大于约1.5μm。在本申请中公开的粒度是利用光散射在灰化材料(ashed material)上来测量的。
以挤出涂层组合物中聚烯烃和无机颗粒材料的总重量计，无机颗粒以装载量至少为20wt.%（例如，约20wt.%至约60wt.%）存在。这包括其中以挤出涂层组合物中聚烯烃和无机颗粒材料的总重量计，无机颗粒物以装载量至少为25wt.%存在的实施方式。
多层涂覆和预处
在一些实施方式中，挤出涂层组合物与一种或多种任选的另外的挤出组合物共挤出，以提供多层的挤出涂覆基材，条件是本发明的挤出涂层组合物作为与冷却辊接触的外层共挤出。可替换地，多层涂覆的附加层可以通过挤出层压工艺来生产。可以共挤出或者层压以得到多层挤出涂层的聚合物材料的实例包括，聚烯烃，聚酰胺和聚酯。
为了提高挤出涂层和下面的基材的粘结力或者多层涂层的层间粘结力，可以对涂层和/或基材进行预处理。例如，挤出涂层和挤出层压工艺可以对基材或层压网幅使用电晕处理、阻燃或等离子体处理，或对熔融的挤出涂层组合物进行臭氧处理以增强层间粘附力。
任选的组分：
除了聚烯烃和无机颗粒材料外，挤出涂层组合物可以包括其他的添加剂，例如那些在挤出涂层组合物中发现的典型材料。这些包括，例如，稳定剂，阻燃剂，填料，增滑剂和防粘连剂等等。当存在这些添加剂时，其含量少于挤出涂层组合物的约2wt.%。在一些实施方式中，挤出涂层组合物中没有上文描述的降低噪声的无机颗粒填料以外的颗粒填料。
基材：
可以用本发明的方法进行挤出涂覆处理的基材包括纸，纸板，聚合物膜，金属箔，镀金属聚合物膜，SiOx涂膜，织造和非织造纤维或带等等。在一些实施方式中，与不含无机颗粒材料的涂层同等物相比，涂层中的无机颗粒材料对基材的粘附更强。这种增强功能是可以测量的，例如，使用剥离实验就可以测量。
挤出涂覆：
图1(a)和(b)提供了挤出涂覆的系统的示意图。在挤出涂覆工艺的基本实施方式中，挤出涂层组合物作为熔融的网幅102从模头100被挤出出到移动基材104上，基材接着滑过由压紧辊108和冷冻辊（"冷却辊"）110限定的夹106，冷却辊使基材上熔融的网幅冷却变成固体聚合物涂层112。
在这个挤出涂覆工艺中，聚合物涂层是从冷却辊剥离下来的，因此在释放点114产生的噪声强度（颤动）是冷却辊释放的指标。噪声水平越低，冷却辊释放越好。
与在同样的方法中利用缺乏无机颗粒材料的挤出涂层组合物相比，在本发明的方法中，挤出涂覆到基材上的挤出涂层组合物在冷却辊释放点产生的噪声水平显著降低。在一些实施方式中，与同样的方法中利用缺乏无机颗粒材料的挤出涂层组合物相比，冷却辊释放点的噪声水平减少了至少3分贝（dB）。这包括其中与同样的方法中利用缺乏无机颗粒材料的挤出涂层组合物相比，冷却辊释放点的噪声水平减少了至少5分贝、至少10分贝、或甚至至少15分贝的实施方式。
虽然挤出涂覆工艺的噪声水平可依赖于冷却辊表面的类型和结构材料，但本发明的涂层组合物和方法可用于在多种不同的冷却辊表面实现噪声降低，包括用不同的表面电镀材料例如铬等制成的光滑的、不光滑、以及压花的冷却辊。
实施例
该实施例说明将填充的聚烯烃组合物的挤出涂覆到牛皮纸基材上的一种实施方式。
在冷却辊释放点噪声的减少量可依赖于冷却辊的表面粗糙度和生产线速度。因此，为了公开的目的，这些实施例中，噪声降低量是对以300mpm生产线速度涂覆到靠着表面粗糙度RT相当于0.3到0.5微米的光滑镀铬冷却辊的牛皮纸上的25g/m2涂层和对以500mpm生产线速度涂覆到靠着表面粗糙度RT相当于0.3到0.5微米的光滑镀铬冷却辊的牛皮纸上的12g/m2涂层来测量的。在将本发明挤出涂层组合物产生的噪声水平和那些不包含降低噪声的无机颗粒物的对比挤出涂层组合物产生的噪声水平进行比较时，测试这两个样品期间，影响冷却辊释放点噪声水平的其它全部挤出涂覆参数都保持相同。
例如通过干燥共混颗粒填充混配物(即母料，MB)和聚烯烃能够制备挤出涂层组合物。填充的混配物包括载体树脂中的高装载量的无机颗粒材料。填充的混配物物可以通过混炼挤出机，在轧辊上或者在Banbury混合机里混配，或者用任何其他的可使填料和载体树脂一起共混产生适合用作挤出涂层组合物的均匀分散体的适当方法制备得到。各填充的混配物的性质列在表1中。
图1母料
Figure BDA00002069207600061
在该实施例中，制备了用作挤出涂层组合物的两种工作母料（MB1和MB2）。母料中使用了两种类型的来自Imerys的碳酸钙矿物填料。使用的填料是以商标出售的表面修饰的超细湿型大理石。两种测试的碳酸钙间的差异在于粒度分布。也测试了一种来自Borealis的对比填充的混配物。Borealis CA8200是一种滑石填充的混配物。
适于用在挤出涂层组合物中的聚烯烃的实例列在表2中，本发明的挤出涂层组合物和对比挤出涂层组合物的配方列在表3中。
表2
Figure BDA00002069207600063
Figure BDA00002069207600071
为了公开的目的，挤出涂层是在挤出涂覆生产线(例如，Davis标准(Erwepa)涂覆生产线)上，用直径为900毫米、表面粗糙度(RT)等于0.3到0.5微米的镀铬的光滑的冷却辊进行的。挤出涂覆加工条件如下。挤出涂层设定的熔融温度是320℃。空气间隙是250mm，夹朝向压紧辊的偏移量是15mm。挤出涂层为25g/m2时线速度是300mpm，涂层为12g/m2时线速度是500mpm。
利用RealisticTM声级分贝仪表（Tandy Corp.)在规定的位置进行噪声测量，该位置代表在操作中靠近层压机的操作者的工作环境。测量挤出涂覆工艺噪声的结构列在图1(b)中。仪表116与冷却辊的释放点相邻，并且直接指向由冷却辊释放点限定的噪声源。为测量噪声和评估任何噪声降低量，噪声仪表116和基材宽度120的中心线118之间的距离(在图1(b)中以'x'表示）是1200mm。在相当于500-10,000赫兹频率加权选择“A”下进行测量。噪声测量的结果列在表3中。
表3.以分贝计的冷却辊释放点的噪声水平。
Figure BDA00002069207600072
(降低3分贝相当于50%的噪声降低量。这个百分比代表以母料和聚烯烃的总重量计，母料在挤出涂层组合物中的重量百分比。)
本申请所有提及的元素周期表是指由CRC Press，Inc.于2003出版并享有版权的元素周期表。同样，任何提及的族应该为在使用编号族的IUPAC系统的这个元素周期表中所反映的族。除非指出，从上下文暗示或现有技术惯例，所有的份和百分比均基于重量，而且所有的测试方法是与本申请的提交日期同步的。针对美国专利实践的目的，任何涉及的专利、专利申请或公开的内容在此全部引入作为参考(或其等价的US同族也引入作为参考)，特别是关于本领域中的合成技术、产品和工艺设计、聚合物、催化剂、定义(不与本申请具体提供的任何定义不一致)和常识的披露。
数值范围包括以1个单位增加的从下限值到上限值的所有数值，条件是在任意较低值与任意较高值之间存在至少2个单位的间隔。例如，如果记载组分、物理或其它性质是100至1,000，意味着明确地列举了所有的单个数值，如100、101、102等，以及所有的子范围，如100至144、155至170、197至200等。对于包含小于1的数值或者包含大于1的分数(例如1.1、1.5等)的范围，适当时将1个单位看作0.0001、0.001、0.01或0.1。对于包含小于10(例如1至5)的个位数的范围，通常将1个单位看作0.1。这些仅仅是具体所意指的内容的示例，并且所列举的最低值与最高值之间的数值的所有可能组合都被认为清楚记载在本申请中。
定义：
“聚合物”指通过聚合相同或不同类型的单体制备得到的聚合物化合物。因此，一般性术语聚合物包含术语均聚物(通常用于表示仅由一种类型的单体制备的聚合物)和术语互聚物。“互聚物”表示由至少两种不同类型的单体聚合制备的聚合物。该一般性术语包括经常用来指由两种不同类型的单体制备的聚合物的共聚物，以及由多于两种不同类型的单体制备的聚合物，例如，三元共聚物、四元共聚物等。
“组合物”、“制剂”和类似术语指两种或更多种组分的混合物或共混物。
术语“包括”及其派生词不排除任何附加组分、步骤或过程的存在，而不管本申请是否披露过它们。为消除任何疑问，除非特别说明，否则任何通过使用术语“包含”限定的工艺或组合物可以包括任何额外的步骤、设备、添加剂、辅料、或化合物(不管是否为聚合的)。相反，除了对于操作性能不必要的那些，术语“基本上由…组成”将任何其它组分、步骤或过程排除在任何以下叙述的范围之外。术语“由…组成”不包括未特别描述或列出的组分、步骤或过程。除非说明，否则术语“或”指列出的单独成员或其任何组合。在此处描述的本发明的实施方式中，那些描述为“包含”或者“包括”某些组分、步骤、要素等的实施方式可以通过用短语“由...组成”或者“基本上由...组成”替换术语“包含”或者“包括”而转化成另外的实施方式。
尽管已经通过上述描述、附图和实施例以相当多的细节描述了本发明，但是该细节仅针对说明的目的。在不背离所附权利要求书所描述的本发明的精神和范围的情况下，本领域技术人员能够进行很多变型和修改。

Claims (10)

1.挤出涂覆基材的方法，该方法包括通过挤出涂覆将挤出涂层组合物施用到基材表面，由此挤出涂层组合物接触冷却辊表面，挤出涂层组合物包含：
(a)聚烯烃；和
(b)平均粒度不大于2μm且颗粒装载量为至少20重量%的无机颗粒材料，以所述涂层组合物中聚烯烃和无机颗粒材料的总重量计。
2.权利要求1的方法，其中聚烯烃包含密度不大于0.940g/cc的聚乙烯或者聚乙烯互聚物。
3.权利要求2的方法，其中所述挤出涂层组合物的特征在于，与利用缺乏无机颗粒材料的相同挤出涂层组合物进行的同样的挤出涂覆工艺相比，该组合物使冷却辊释放点的挤出涂覆噪声减少了至少3分贝，测量是在表面粗糙度为0.5μm的镀铬的光滑的冷却辊上，以320℃的挤出物温度和250mm的空气间隙，针对以300mpm的生产线速度施用的25g/mm2的挤出涂层或者针对以500mpm的生产线速度施用的12g/mm2的挤出涂层来进行的。
4.权利要求2的方法，其中所述无机颗粒材料的平均粒度不大于1.5μm，以及颗粒装载量为至少30重量%，以涂层组合物中聚烯烃和无机颗粒材料的总重量计。
5.权利要求2的方法，其中所述无机颗粒材料是碳酸钙。
6.权利要求1的方法，还包含在所述基材和所述挤出涂层组合物之间挤出一个或更多额外挤出涂层来提供多层的挤出涂覆的基材，其中所述挤出涂层组合物与冷却辊接触。
7.一种涂覆的基材，包含：
(a)基材；和
(b)涂覆在所述基材表面上的涂层组合物，所述涂层组合物包含∶
(i)聚烯烃；和
(ii)平均粒度不大于2μm且颗粒装载量至少为20重量%的无机颗粒材料，以聚烯烃和无机颗粒材料的总重量计。
8.权利要求7的涂覆的基材，其中所述基材包含纸制品，所述无机颗粒材料包含矿物。
9.权利要求7的涂覆的基材，其中所述无机颗粒材料的平均粒度不大于1.5μm，以及以聚烯烃和无机颗粒材料的总重量计的颗粒装载量为至少25重量%，聚烯烃包含密度不大于0.940g/cc的聚乙烯或者聚乙烯互聚物。
10.权利要求7的涂覆的基材，进一步包含布置在所述基材和所述涂层组合物之间的一个或多个额外涂层。
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