CN1276287A - 单轴或双轴拉伸的聚酯树脂发泡片材和膜 - Google Patents

单轴或双轴拉伸的聚酯树脂发泡片材和膜 Download PDF

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CN1276287A
CN1276287A CN00117688A CN00117688A CN1276287A CN 1276287 A CN1276287 A CN 1276287A CN 00117688 A CN00117688 A CN 00117688A CN 00117688 A CN00117688 A CN 00117688A CN 1276287 A CN1276287 A CN 1276287A
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H·阿尔加塔
S·科尔鲁尔
T·塞韦里尼
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Sinco Research S P A
Sinco Ricerche SpA
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Abstract

单轴或双轴拉伸的聚酯树脂发泡片材和膜,其中聚酯树脂在280℃时的熔体强度大于1×10－2牛顿,在280℃时的熔体粘度至少为1500Pa.s,剪切比趋于零,该树脂的结晶速率为在120℃时加热10分钟结晶度值可高达30—35%。

Description

单轴或双轴拉伸的聚酯树脂发泡片材和膜
本发明涉及具有高机械性能和有价值的光学性能的从聚酯树脂制得的单轴和双轴拉伸的发泡膜和片材。
聚酯树脂膜由于其优良的机械、电学和耐化学性能而广泛地用于各种技术领域。
特别是聚对苯二甲酸乙二醇酯的双轴拉伸膜在尺寸稳定性和拉伸性能上优于其它的膜，这特别是由于其高的弹性模量。
然而，聚酯膜具有诸多缺点，这主要是由于其非常高的相对密度以及在信息技术领域如电子白板和类似器件中的应用要求它们高度填充白色颜料来达到充分不透明的情况。各种制造聚酯树脂的发泡膜或片材的方法是已知的。
由聚酯树脂制成的厚的低密度发泡材料由于其高的隔热性能(当它们从挤出机中排出时这种性能会阻止材料内部件的有效冷却)具有难以减小的较高的结晶度。
迄今为止还没有解决密度小于600-700kg/m3并且具有结晶度或可结晶的由聚酯树脂制成的单轴或双轴拉伸发泡片材这个问题的方案。
在所述低密度发泡片材的单轴和双轴拉伸中遇到的主要困难在于其在拉伸过程中可能会断裂。
在WO 97/33948中得知从聚酯发泡膜来制造标签，所述聚酯发泡膜从非晶形树脂如聚(1，4-二羟甲基环hexile)对苯二甲酸酯或非晶形共聚对苯二甲酸-间苯二甲酸乙二醇酯制得时也可以单轴或双轴拉伸。
表观密度低并且结晶度足够高的单轴和双轴拉伸的聚酯树脂发泡片材或膜可以提供相当多的优点，尤其是从所述片材和膜会具有的改进的机械性能来看。
现在意想不到地发现可以单轴和双轴拉伸堆积密度小于700kg/m3，较好小于400kg/m3的芳族聚酯树脂发泡片材和膜，而不会产生破裂问题或其它缺点，其中该树脂的结晶速率为在120℃时加热10分钟结晶度值可高达30-35％，从而获得表观密度较低的拉伸片材或膜，该拉伸片材或膜具有高的机械性能，尤其是高的模量和高的抗冲击性以及良好的与闪光反射性能(sparkling reflectanceproperties)有关的不透明性或半透明性。
在120℃时加热10分钟可提高的结晶度较好为5-35％。
与拉伸前片材和膜所具有的相比，所得拉伸片材或膜的高抗冲击性令人惊奇地相当高。
业已发现若所述片材是从具有高于某些给定限值的足够高熔体强度和熔体粘度值的聚酯树脂制得，则可以单轴和双轴拉伸具有上述指定厚度、结晶度和密度特性的发泡片材。
有用树脂的熔体强度在280℃时至少为1×10-2牛顿，熔体粘度在280℃时至少为1500Pa.s，剪切速率趋于零。
可以方便地采用10-150×10-2牛顿或更大的熔体强度和2,000-20,000Pa.s的熔体粘度。
在制造发泡片材或膜的树脂上所测得的熔体强度值低于用于制备片材和膜的树脂所测得的值。
特性粘度通常为0.8-1.5dl/g。
上述指定的流变性能是指在经挤出-发泡过程之前的树脂，但是在所述过程中可以到达上述指标。
用于制备具有上述指定流变性能的树脂的芳族聚酯树脂可以按已知的方法由芳族二元羧酸与含2-12个碳原子的二元醇经缩聚反应制得，或者可以由二元羧酸的低级烷基酯与含2-12个碳原子的二元醇进行酯交换反应随后使二醇酯进行缩聚反应制得。
对苯二甲酸、间苯二甲酸和萘二甲酸是较好的芳族酸。
聚对苯二甲酸乙二醇酯及其共聚物，其中1至高达20-25个，较好1-25个来自对苯二甲酸的单体单元被来自间苯二甲酸和/或萘二甲酸的单元所取代，这是较好的树脂。
具有上述指定流变性能的聚酯树脂宜这样制得，在特性粘度小于约0.7dl/g的聚酯树脂中加入0.05-2重量％较好是芳族四羧酸二酐，特别是均苯四酸二酐，经固态缩聚反应(SSP)，该操作是在将树脂的熔体强度和熔体粘度提高到所选数值的这样的温度条件和这样的持续时间下进行的。
SSP之后树脂的特性粘度一般提高到大于0.8dl/g的值。
上述固态缩聚反应按已知的方法进行。
特别合适的方法描述于美国专利5,243,000中，其内容在此参考引用。
其它适用于达到本发明熔体强度和熔体粘度值的方法披露于美国专利5,288,764和5,229,432中，其内容同样在此参考引用。
聚酯树脂可以与其它热塑性聚合物，尤其是以与用量约为2-50重量％的聚酰胺树脂的混合物的形式使用。这种类型的混合物或合金描述于WO 94/09069中，其制备方法在此参考引用。
尤其当希望获得改进的气体阻隔性能(氧气和CO2)时特别合适的聚酰胺是聚己二酰间苯二甲胺。
这种聚酰胺与聚酯树脂熔融混合，而聚酯树脂还可与用量为聚酯树脂重量的0.05-2％的芳族四羧酸二酐，特别是均苯四酸二酐熔融预混合。
其它可以使用的聚合物是可从脂族二元羧酸和二元醇或脂族羟基酸(hydroxides-acids)或相应的内酯或交酯制得的脂族聚酯树脂。
聚-ε-丙内酯是代表性的树脂。
这些树脂的加入量达40重量％，它们能为这样混合的树脂提供生物降解性。
本发明的另一个方面是发现在聚酯树脂中加入0.5-10重量％的高或低分子量的脂族或芳族聚酰胺能明显减少在拉伸发泡片材和膜中存在的未反应的均苯四酸二酐量和乙醛量。
适合于单轴和双轴拉伸的发泡片材的堆积密度约为50-700kg/m3。厚度一般为0.5-5毫米。
为了制造厚度降至大约30微米的薄的双轴拉伸的发泡膜，初始发泡片材的厚度约为0.6-2毫米；当改为希望获得双轴拉伸的片材时，可采用较厚的片材(2-5毫米)。
在双轴拉伸的情况下，拉伸后的堆积密度有相当大的提高(对于4∶1的拉伸甚至是四倍)。
然而，当使用烃作为发泡剂时，由于将片材或膜加热到适于拉伸的温度所进行的加热，封在孔中的残余的烃会膨胀。这样就可能获得密度低于拉伸前密度的双轴拉伸的片材或膜。
在单轴拉伸的情况下，密度通常减小(这是由于在单轴拉伸中所用的设备与双轴拉伸的不同)。
在两种情况下，这样来进行操作，使拉伸后的密度较好地小于500kg/m3。
根据在挤出发泡过程中所采用的条件，如成核剂和发泡剂的种类以及用量，在初始发泡材料中孔的平均大小可以在0.01-1毫米的范围内变化。
该值在0.2-0.4毫米的范围内是具代表性的。
双轴拉伸后在片材和膜中孔的平均大小相对于拉伸前的大小有所增加，在单轴拉伸中，孔拉长了。
双轴拉伸可按常规方法进行，它可在高于聚酯树脂的Tg但低于熔点的温度下操作。
温度为80-120℃是合适的，在拉伸过程中的停留时间为几秒钟到40秒或更长。
拉伸前片材和膜的结晶度保持低得足以能够容易地进行拉伸(较好低于10％)。
在两个方向上的双轴拉伸比通常为1.5∶1-5∶1，较好达3∶1，在两个方向上的拉伸可以同时或顺次进行。
单轴拉伸在纵向或横向上进行。拉伸比通常为1.1∶1-4∶1。
拉伸通常在一系列加热到95-110℃的温度并以不同速度旋转的压延单元上进行。
在许多情况下，较好的是将双轴和单轴拉伸的材料经热稳定处理，该热稳定处理是在如160-220℃的温度下操作几秒钟(通常10-120秒钟)。
上述处理能使材料达到良好的尺寸稳定性并改进其机械性能。
相对于不稳定的材料而言，热定形材料具有比较低的热收缩值(例如在180℃时加热几分钟的热收缩值小于5％)。
拉伸后的结晶度高于拉伸前的结晶度，其值可以达到30％，并且在将拉伸的片材和膜经热定形处理的情况下该值还可以达到更高。
正如所述的，与拉伸前的相比，单轴和双轴拉伸的发泡片材和膜的机械性能有了相当大的改进。
弹性模量和抗冲击性特别高。
例如，在厚度为40微米的双轴拉伸膜的情况下，模量可达2GPa或更大，最终的拉伸强度为50-60MPa，断裂伸长率为50％。
拉伸材料的不透明度是高的，在双轴拉伸膜的情况下其通常为40-80％。相对于未拉伸的发泡材料，光泽性得到相当大的改进。半透明片材，尤其是那些双轴拉伸过的整块片材都显示出闪光反射性，这就使该片材特别适用于诸如全息印刷的应用。
本发明单轴和双轴拉伸片材或膜的特征在于热收缩程度高。例如，厚度为0.04毫米并且拉伸比为3∶1的双轴拉伸膜在加热到180℃几分钟后所显示出的收缩量为20-30％。这个特性可用于许多用途，尤其是用来贴标签于聚酯树脂瓶，利用加热瓶时所述标签会发生收缩这一特性将标签粘合到瓶上。
由于其柔韧性、透气性和对水蒸气的高渗透性，单轴和双轴拉伸片材或膜尤其可用于纺织领域。
而且其易于上油墨的性能使其尤其适用于替换纸或卡纸板的应用。
单轴和双轴拉伸片材和膜还可以包括在多层材料中，其中一层如由用玻璃纤维增强的聚酯树脂或由低熔点聚酯树脂或由其它材料组成的层邻近拉伸片材或膜的一个或两个侧面。
低熔点聚酯通常是包含大于7摩尔％间苯二甲酸单元的共聚对苯二甲酸/间苯二甲酸乙二醇酯。
多层材料可以这样制得，即从一组挤出机中共挤出待发泡的树脂和一种或多种形成邻近层的树脂，而后拉伸所得的多层材料，或者将一层或多层其它材料胶合到发泡片材或膜上，或者将它们粘合到所述片材或膜上。
最后，双轴拉伸发泡膜和片材的高度不透明性和其高的机械性能使其尤其适用于信息技术和照相用途中。
在此没有述及的其它应用对技术熟练者来说是显而易见的。
给出下述实施例用于说明本发明，但它们并不限制本发明的范围。
测量方法
特性粘度按ASTM D 4603-86的方法在25℃时在60/40重量比的苯酚和四氯乙烷的溶液中进行测量。
流变测试按ASTM D 3835标准方法在280℃时使用Goettfert流变仪进行。
熔体强度通过测量拉伸从Goettfert Rheograph 2002流变仪的毛细管中挤出的材料所需的以cN(10-2牛顿)表示的力而确定。
为了进行测量，将Rheotens单元施加到Goettfert Rheograph 2002流变仪的毛细管出口上。
挤出条件如下：
活塞速度：0.2mm/sec
模头直径：2mm
毛细管长度：30mm
测试温度：280℃
测试是将加速设置为2.4cm/sec2时进行的。
重复各个测量，取两次测量的平均值。
结晶度百分数是从与聚对苯二甲酸乙二醇酯的结晶度百分数相关的反式和旁式构型之比(非晶形相可与旁式构型有关，而结晶相可与反式构型有关)通过水平ATR(衰减全反射)加以确定。
将ATR测试仪安装到Perkin型号2000 FT-IR上，为了达到更好的清晰度，以8cm-1的分辨率，累积16次扫描进行测量。
用PET样品进行测试仪的校准，所述PET样品的结晶度数值用常规密度-柱法进行测定，为7-65％。
相关系数高于0.98。
在1410cm-1处的吸收作为参照带。
实施例1
将90 kg/h聚对苯二甲酸乙二醇酯共聚物连续地送入螺杆直径为90毫米的双螺杆挤出机中，所述共聚物包含2％间苯二甲酸(IPA)，其在280℃时的熔体强度为150×10-2牛顿，在300℃和10弧度/秒时的熔体粘度为1800 PA.S，特性粘度为1.24dl/g，在熔融状态DSC曲线(冷却速度为5EC/min)上的结晶峰在191EC处，ΔH为34J/g，该共聚物是在210℃在0.4％PMDA存在下对聚合物进行再分级(regrading)获得的。
将静态混合器放在螺杆的下游，以改进混合物各种组分的均匀性。
在挤出机熔融区域中的温度设置在280℃，在压缩区域中的温度为280℃，在混合区域中的温度为270℃，在挤出头的温度为265℃。
以18rpm使挤出机螺杆转动。
在聚合物熔融后将3.6重量％的氮气(发泡剂)加到挤出机区域内的树脂中，使其与聚合物基体彻底地混合，而后冷却。
一旦混合并冷却后，将树脂/氮气组合物通过直径为60毫米并且挤出出口大小为0.29毫米的环形头挤出。
挤出头的下游是直径为200毫米、长度为750毫米并且用20℃的水冷却的冷却定径芯。
一旦发泡材料离开模头，立刻将其装到模芯上，切割，拉伸而后以5米/分钟的速度用制造线轴的缠绕机将其绕到辊上。
片材具有下述特性：
密度：                      0.400g/cm3
厚度：                      0.7mm
孔的平均直径：              230微米
结晶度：                    8％
在100℃时以在两个方向上的拉伸比为3∶1将片材在两个方向上同时进行双轴拉伸。表1列出了拉伸前后片材的某些性能。
拉伸后片材的不透明度为70％；拉伸前该值为92％。
在20℃时拉伸后的光泽为32％，在60℃时为109％。
未拉伸片材的相应值为7.5％和28％。
实施例2
重复实施例1的过程，不同点仅在于挤出头的出口大小为0.35毫米，而非0.29毫米，并且发泡材料以3.9米/分钟的速度收集到辊上。
在110℃时在拉伸比为3∶1和4∶1的情况下进行双轴拉伸。表1列出了拉伸前后片材的性能。
实施例3
重复实施例2的过程，不同点仅在于使用1.8重量％的正戊烷作为发泡剂。
所得的片材具有下述特性：
密度：                      0.148g/cm3
厚度：                      1.4mm
孔的平均直径：              300微米
结晶度：                    8％
实施例4
重复实施例1的过程，不同点仅在于使用2.4重量％的CO2作为发泡剂。
所得的片材具有下述特性：
密度：                      0.280g/cm3
厚度：                      1mm
孔的平均直径：              220微米
结晶度：                    8％
在100℃时以3∶1的拉伸比对片材进行双轴拉伸后片材的机械性能与实施例1中拉伸后片材的机械性能相类似。
实施例5
按实施例1相同的过程，不同点仅在于使用这样一种共聚对苯二甲酸乙二醇酯，它包含7.5％的IPA，在冷却速度为5℃/分钟的来自熔体的DSC曲线上其在160℃时有吸热峰，ΔH为24J/g。
所得的片材具有下述特性：
密度：                      0.395g/cm3
厚度：                      1.2mm
孔的平均直径：              208微米
结晶度：                    8％
在100℃时以在两个方向上的拉伸比为3∶1对片材进行双轴拉伸。
拉伸片材的厚度为0.04mm；密度为910kg/m3；不透明度为75％。
实施例6
对实施例2的拉伸片材(拉伸比为3∶1)进行210℃的热稳定处理10秒钟。弹性模量为1.2GPa，最终的拉伸强度为29MPa，断裂伸长率为33％。
                               表1
 实施例     样品  堆积密度(kg/m3)    厚度(mm)    双轴拉伸比    模量(GPa)   最终的拉伸强度(MPa)  伸长率(％)
   1    照原样     400     0.7     0.8     12   154
  拉伸过的     985     0.04     3∶1     2     56   49
   2    照原样     400     1.4     0.5     9   173
  拉伸过的     533     0.13     3∶1     1     28   35
    710     0.06     4∶1     1.6     47   22
   3    照原样     148     1.4     0.2     4   18
  拉伸过的     70     0.42     3∶1     1     30   2
注：机械性能是指纵向上的
实施例7
重复实施例1的制备过程，不同点仅在于除了实施例1所用的共聚对苯二甲酸乙二醇酯和PMDA外，还加入2.5重量％的聚己二酰间苯二甲胺(Mitsubishi GasChemicals，Japan，聚MXD-6 6121)。在两个方向上以3∶1的拉伸比进行双轴拉伸的厚度为0.04毫米的片材的氧气渗透率为80ml/m2/天，而不含聚MXD-6的片材的渗透率为96(在拉伸前，含聚MXD-6的片材的渗透率为13，不含聚酰胺的片材的渗透率为15)。
游离(未反应的)PMDA量为2ppm；乙醛量为2-3ppm。
实施例8
重复实施例1的制备过程，所不同的是使用PET均聚物，该均聚物具有实施例1所述的熔体强度和熔体粘度特性，在冷却速度为5EC/分钟的来自熔体的DSC曲线上其在201℃时有吸热峰，ΔH为38J/g，并且所用的氮气(发泡剂)的量为1.3重量％。所得的片材具有下述性能：
密度：                    0.450g/cm3
厚度：                    1.1mm
孔的平均直径：            300微米
结晶度：                  8％
将片材在一系列加热到95EC并且以不同速度旋转的压延单元上进行拉伸。
将使用Franctovis Ceast冲锤磨(一种测试冲击性的设备)测得的垂直冲击试验结果与所用的拉伸比(在纵向上拉伸)之间的关系列于表2中。
     样品   密度   厚度   冲击强度   峰值能量    总能量
  kg/m3     mm     J/m      J      J
照原样(未拉伸)    450     1.1     407     0.38     0.41
  以1.1∶1拉伸    375     0.7     840     0.48     0.59
   以3∶1拉伸    380     0.4     1030     0.3     0.41
   以4∶1拉伸    330     0.25     1225     0.24     0.31
作为对比，得自商购水果容器的聚乙烯处理过的卡纸板基的厚度为0.45毫米的样品所达到的峰值能量值(开始出现断裂时的能量)为0.16J，并且与冲击后样品穿孔能量相对应的总能量为0.5J。
作为本申请要求优先权的意大利专利申请MI99A001139中所披露的内容在此参考引用。

Claims (15)

1.从芳族聚酯树脂制得的单轴或双轴拉伸的发泡片材和膜，该树脂在280℃时的熔体强度大于1×10-2牛顿，在280℃时的熔体粘度至少为1500Pa.s，剪切比趋于零，其结晶速率为在120℃时加热10分钟结晶度值可达30-35％。
2.如权利要求1所述的单轴和双轴拉伸的片材和膜，其堆积密度为100-1000kg/m3。
3.如权利要求1和2所述的片材和膜，其厚度为0.03-1毫米。
4.如权利要求1至3所述的片材和膜，其中树脂的结晶速率为在120℃时加热10分钟结晶度为5-20％。
5.如权利要求1至4所述的片材和膜，其中聚酯树脂混合有0.5-10重量％的聚酰胺。
6.如权利要求5所述的片材和膜，其中聚酰胺是聚己二酰间苯二甲胺。
7.如权利要求1至6所述的片材或膜，其中聚酯树脂是聚对苯二甲酸乙二醇酯或含2-15摩尔％间苯二甲酸单元的共聚对苯二甲酸-间苯二甲酸乙二醇酯。
8.一种多层材料，它包含如权利要求1至7所述的片材或膜，以及一层或多层粘合到发泡片材或膜一个或两个侧面上的不同的材料。
9.如权利要求8所述的多层材料，其中至少一层粘合到发泡片材或膜上的层是含有2-15摩尔％得自间苯二甲酸的单体单元的共聚对苯二甲酸-间苯二甲酸乙二醇酯。
10.如权利要求1至9所述的片材和膜，它经热定形处理。
11.一种制备如权利要求1至10所述的片材和膜的方法，它包括对密度为60-700kg/m3的聚酯树脂发泡片材进行单轴或双轴拉伸的步骤，其中该树脂的结晶速率为加热到120℃10分钟结晶度值可达30-35％，其在280℃时的熔体强度大于1×10-2牛顿，在280℃时的熔体粘度至少为1500Pa.s，剪切速率趋于零。
12.如权利要求11所述的方法，其中采用1.1∶1-5∶1的拉伸比进行拉伸。
13.如权利要求12所述的方法，其中在纵向和横向上同时或顺次进行双轴拉伸。
14.如权利要求11和12所述的方法，其中在纵向或横向上进行单轴拉伸。
15.由权利要求1至10所述的片材或膜获得的制造制品。
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US6472035B1 (en) 2002-10-29
NO20002657L (no) 2000-11-27
TW572944B (en) 2004-01-21
KR20000077407A (ko) 2000-12-26
ITMI991139A1 (it) 2000-11-24
CA2309227A1 (en) 2000-11-24
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KR20000077408A (ko) 2000-12-26
PL201643B1 (pl) 2009-04-30
NO20002658D0 (no) 2000-05-24
PL201642B1 (pl) 2009-04-30
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EP1055697B1 (en) 2004-09-08
US6696146B1 (en) 2004-02-24
PL340234A1 (en) 2000-12-04
AR024005A1 (es) 2002-09-04
ATE325832T1 (de) 2006-06-15
CA2309283A1 (en) 2000-11-24
DE69931245D1 (de) 2006-06-14
HUP0001986A2 (hu) 2001-12-28
DE69919988T2 (de) 2005-09-29
CN1276286A (zh) 2000-12-13
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DE69931245T2 (de) 2007-01-11
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KR100684815B1 (ko) 2007-02-22
DE69919988D1 (de) 2004-10-14
BR0001862A (pt) 2001-01-02
EP1055698A1 (en) 2000-11-29
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JP2001018942A (ja) 2001-01-23
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