CN1113084A - 基于乙烯和丙烯聚合物的膜及其应用 - Google Patents

基于乙烯和丙烯聚合物的膜及其应用 Download PDF

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CN1113084A
CN1113084A CN94190565A CN94190565A CN1113084A CN 1113084 A CN1113084 A CN 1113084A CN 94190565 A CN94190565 A CN 94190565A CN 94190565 A CN94190565 A CN 94190565A CN 1113084 A CN1113084 A CN 1113084A
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D·赖斯
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Abstract

本发明涉及基于丙烯和乙烯的聚合物的膜，其在 必要时可含有加工助剂、填料、颜料或其他添加剂。 该膜的特征在于，它含有a)一种丙烯均聚物，其 MFI值(230℃/2.16kg)为约0.8—3.0g/10min，熔 点Tm为约154—168℃(按DSC测定)，且杨氏模数为约900—1500N/mm2(按DIN53457测定)，和b)一种乙烯均聚物，其MFI值(190℃/2.16kg)为约1.5—3.0g/10min，熔点Tm为约110—130℃，杨氏模数为约200—400N/mm2，其中每100重量份丙烯均聚物，有约5至20重量份乙烯均聚物。该膜可以以可掩盖任何物体的自粘合复合膜存在。

Description

本发明涉及基于丙烯和乙烯聚合物的塑料膜，它在需要时可含有加工助剂、填料、颜料或其它添加剂，以及这种膜以自粘装饰膜形式用于涂装任意物体或成形件的用途。
EP-A-0343491已经公开了用于掩饰任意物体的表面膜。该膜以染色、未染色和/或印有图案的形式涂覆在例如用塑料、木材、木质材料、金属或类似材料或基体制成的门、框架、外壳等物体的表面上，以保护其不受各种不利因素的影响，例如腐蚀、光致变色或机械作用。在某些情况下要用它按要求形成所述物体的表面。尽管所用的物体的性质、结构、表面或颜色不适合，但可通过用这种印有图案的膜进行表面掩饰而给人以优质木材的印象。由EP-A-0343491公开的表面膜具有一层甲基丙烯酸酯基聚合物基膜。该聚合物可以通过加入聚丙烯酸酯类而改性。特别合适的是由聚甲基丙烯酸丁酯（PBMA）柔韧化的聚甲基丙烯酸甲酯（PMMA）。该公知表面膜应具有改进的耐光性和耐气候影响性。该膜的检验证明，它仍需改进。因此，柔韧化的PMMA具有相当高的白断口（Weiβbruch）。即使将该材料调节成耐冲击的，也仅有很低的缺口冲击韧性。此外，其润湿性或表面张力值也低得不能令人满意。若要将其贴在一种基体上，则对于基膜的耐压性及粘贴性（粘贴层和基膜之间的粘合）而言，高的表面张力值是很重要的。而PMMA基膜的表面张力仅仅为36至38达因/厘米（按DIN53364测定）。
DE-OS 4121599公开了一种开关所述类型的膜，它有一层含乙烯-丙烯共聚物的基膜，它含有加工助剂和/或添加剂并在需要时还含有至少一种混合染料和/或填料。基膜的下表面或下侧面有一层粘贴层以及需要时的覆盖层及隔离层（Releaseschicht）。同时，基膜需要时还可有一压花和/或彩印层。50至150μm厚的基膜所用的乙烯-丙烯共聚物的MFI值（230℃/2kg）为3g/10min以上，抗拉强度在30N/mm2以上。该膜作为自粘装饰膜用于涂装玻璃、板、纸、纸板以及金属、木材和木质材料的其它物体或成形体。该已知膜优选的肖氏硬度D为55至70。基于该已知膜的特殊原材料，其刚性不能令人满意。在这种膜用于掩饰木材和其它部件时，刚度很重要。刚度高可使掩饰膜降低打印和擦刮损害的可能性。
基于以上所述的现有技术，本发明的任务在于开发一种开头所述的膜，以特别是提高上膜的表面张力值，改进其缺口冲击韧性，并尽可能排除其白断口。当它用作掩饰膜时，贴上的膜受打印和擦刮损害的可能性应较低。
本发明完成了这一任务，其方案是含有：
（a）一种丙烯均聚物，其MFI值（230℃/2.16kg）为约0.8至3.0g/10 min，熔点Tm为约154至168℃（用DSC测定），杨氏模数（E-Modul）为约900至1500 N/mm2（按DIN53457测定），和
（b）一种乙烯均聚物，其MFI值（190℃/2.16kg）为约1.5至3.0g/10min，熔点Tm为约110至130℃，杨氏模数为约200至400N/mm2，
其中，对100重量份丙烯均聚物而言，乙烯均聚物约为5至20重量份。
缩写“DSC”表示差示扫描量热法，由Marti等人详述在“Angewandte Chemische Thermodynamik und Thermoanalytik（Experimenta Suppl.37）”，Basel：Birkhauser 1979中。
本发明塑料膜的上述物理参数值的一种特殊形式如权利要求2所述。
丙烯均聚物优选具有窄分子量分布。这种产品可在市场上作为CR一产品得到（CR＝有控流变学）。特别合适作为乙烯均聚物的是含有一种低密度线性结构乙烯均聚物（LLDPE）或一种在高压下制备的低密度聚乙烯（LDPE）的产品。本发明所称术语“均聚物”指该聚合物基本上由乙烯或丙烯组成。无论如何它决不涉及现有技术意义上的“共聚物”。因此，只要不影响本发明追求的效果，可以含有微量其它单体单元。一般地，本发明意义上的“均聚物”也包括那些除乙烯或丙烯外还含有最高达约10Mol%一种或多种共聚单体的聚合物，尤其是异戊二烯、1，3-丁二烯、乙烯（在丙烯均聚物情况下）、丙烯（在乙烯均聚物情况下）、丁烯、已烯和辛烯或它们的异构体。
本发明塑料膜的性能可以通过在热塑性塑料中加入的添加物来改变。例如塑料中可以含有填料如金属氧化物、金属碳酸盐特别是碳酸钙和白云石、金属二氧化物和金属氢氧化物;润滑剂如C12-C36脂肪酸、脂肪族醇、脂肪酸酯和脂肪酰胺;颜料形式的染色剂如二氧化钛或炭黑，以及有机染料：稳定剂如氧化延迟剂和热稳定剂，例如空间受阻的苯酚类、氢醌类、被取代的该组代表和它们的混合物;紫外线稳定剂，例如各种取代的间苯二酚类、水杨酸酯类、苯并三唑类和苯酮类，以及其它常见的改性剂。添加物也可涉及加工助剂如高分子丙烯酸酯类或丙烯酸酯共聚物。它们在加工时控制熔化过程的流动性能。用含有上述化合物的混合原料，可由任意技术制备薄膜，例如用挤压法、压延法等等。
本发明塑料膜一种特别优选的实施方案还含有一种乙烯-丙烯共聚物，其中对100重量份丙烯均聚物而言，乙烯-丙烯共聚物约为5至40重量份，特别是约10至25重量份。其中优选乙烯-丙烯共聚物的MFI值（230℃/2.16kg）为约1至4g/10min，熔点Tm为约140至155℃，杨氏模数为约400至700N/mm2。若将该膜包括在此后更详细描述的掩饰膜中，则掩饰到任意物体上的膜可明显降低打印和擦刮损害的可能性并具有最佳的刚性和硬度。
本发明的膜可以多种形式用于各种提到的应用领域。例如可使膜含有颜料，然后可在其背面涂上一层底层（Primerschicht），这里事先进行过表面处理例如电晕放电处理。此后可在底层上涂覆一层粘合剂以及需要时的隔离层或可除去的保护膜。优选在膜的上面同样在先进行电晕放电表面处理的条件下涂上一层底层，然后接着涂上一层透明的尤其是聚丙烯酸酯和聚酯基的封漆。最后这一层明显降低了上膜表面打印损坏的可能性。
本发明膜的一个特别优选的应用场合是如下形成复合膜结构：这里以前述方式处理上膜的上侧。在下侧涂上底层（在前述电晕处理时）后再涂一层穿过透明上膜可看见的印花装饰层。上侧可有压花。上述印花装饰层后接有一层下膜，该层通过热紧缩与以上述方式形成的上膜相结合。下膜优选由与上膜相同的组分组成，但含颜料，以突出装饰作用，其背面又有一层底层（用上述电晕处理），底层跟有一粘贴层并在需要时有一隔离层例如为聚硅氧烷纸。在有一层上膜和一层下膜的上述复合膜中，上膜厚度优选为约100至300μm，特别是约150至250μm，复合膜本身约厚400至800μm，特别是400至600μm。含有本发明膜的复合膜特别适用于作为自粘装饰膜来涂装玻璃、板、纸、纸板以及其它金属、木材、木质材料和塑料物体或成形体。
用本发明的膜可以调节所需的物理性能，如在基本上消除白断口的情况下的高缺口冲击韧性和高表面张力。根据其不同的制造方法，表面张力为约46至52达因/厘米（按DIN  53364）。这明显高于开头所述现有技术的表面膜所达到的值（那里为36至38达因/厘米）。高的表面张力值改善了例如涂加彩色图案时的可印花性和对粘合剂层的粘附。此外，本发明的膜还具有有利的杨氏模数、抗拉强度、硬度、耐光性以及热耐光性（Heiβlichtechtheit）。另外，它还有极低的打印损坏可能性、高的抗擦刮性、良好的耐化学腐蚀性，并在高程度上满足了耐光性的要求（根据DIN  54004）。由于上述涂漆的可能性，保证了耐化学腐蚀性能。该材料可在常规生产设备中压延和挤压。可用一台印花设备使表面带上不同的斑痕。在本发明的范围内，不必使用含金属或含硫的稳定剂即可取得所追求的效果，这与必须使用上述稳定剂的含PVC的混合塑料不同。除此之外，本发明的膜不必含增塑剂。它不含卤素，这对热循环是有利的。它在黑暗的热影响下（没有光作用）显示了有利的老化性能。本发明还可达到所需的最佳硬度，从而可有利地影响上述擦刮和打印损坏的可能性。本发明的膜可以多种方式掩饰到各种基体上，尤其是以所述复合膜的形式。因此，有可能同时进行向载体上的掩饰和模塑，例如对非平面表面，用带有膜、气压和模塑醌的相应装置操作。
下面用实施例进一步说明本发明。
实施例1至3：
用一个5-L-辊式压延机由下表列出的配方制得约0.2mm厚的含颜料的上膜。测量该上膜的相应的各种性能并也列在下表中。
表
组成(重量%)
原料  实施例  实施例  实施例
1  2  3
丙烯均聚物
(MFI值(230℃/2.16kg)约1.1g/10min);
熔点Tm约164-166℃(DSC);  80  60  50
杨式模数1135 N/mm2
乙烯均聚物
(MFI值(190℃/2.16kg)2.3g/10min);
熔点Tm 110至115℃;  10  10  10
杨式模数230 N/mm2
乙烯-丙烯共聚物
(MFI值(230℃/2.16kg)1.5g/10min);
熔点Tm约144-150℃(DSC);  10  30  40
杨式模数550 N/mm2
主抗氧剂
空间受阻的苯酚
(Hoechst公司的Hostanox 03)  0.2  0.2  0.2
双[3,3-双(4'-羟基-3'-叔丁基
苯基)-丁酸]-乙二醇酯
UV-吸收剂:
空间受阻的胺  0.3  0.3  0.3
(Hoechst公司的Hostavin N20)
颜料/填料
二氧化钛 6份*)6份*)6份*)
性能
耐光性  7-8  7-8  7-8
按DIN 54004
抗化学腐蚀性  正常  类似  类似
按DIN 68861-1B
抗擦刮性  正常  类似  类似
按DIN 68862-4C
肖氏硬度D  71  68  66
按DIN 53505
＊）以100份混合聚合物为基准。

Claims (12)

1、基于丙烯和乙烯聚合物的塑料膜，其在必要时含有加工助剂、填料、颜料或其它添加物，其特征在于，它含有
(a)一种丙烯均聚物，其MFI值(230℃/2.16kg)为约0.8至3.0g/10min，熔点Tm为约154至168℃(用DSC法测定)，和杨氏模数为约900至1500N/mm2(按DIN53457测定)，和
(b)一种乙烯均聚物，其MFI值(190℃/2.16kg)为约1.5至3.0g/10min，熔点Tm为约110至130℃，和杨氏模数为约200至400N/mm2，
其中对100重量份丙烯均聚物而言，乙烯均聚物约为5至20重量份。
2、按权利要求1所述的膜，其特征是其含有
（a）一种丙烯均聚物，其MFI值（230℃/2.16kg）为约1至2g/10min，熔点Tm为约158至164℃和杨氏模数为约1100至1300 N/mm2，特别是以CR-产物形式存在，和
（b）一种乙烯均聚物，其MFI值（190℃/2.16kg）为约1.8至2.8g/10min，熔点Tm为约112至120℃和杨氏模数为约250至350 N/mm2。
3、按权利要求1或2所述的塑料膜，其特征是其含有一种低密度的线性结构的乙烯的均聚物（LLDPE）和/或一种在高压下制备的低密度聚乙烯（LDPE）。
4、按权利要求2或3所述的膜，其特征是，对约100重量份丙烯均聚物而言，聚乙烯均聚物为约8至12重量份。
5、按权利要求5所述的膜，其特征是，它还含有一种乙烯-丙烯共聚物，其中对100重量份丙烯均聚物而言，乙烯-丙烯共聚物为约5至40重量份，特别是约10至25重量份。
6、按上述权利要求中至少一项所述的膜，其特征是，乙烯-丙烯共聚物的MFI值（230℃/2.16kg）为约1至4g/10min，熔点Tm为约140至155℃，杨氏模数为约400至700 N/mm2。
7、按权利要求6所述的膜，其特征是，乙烯-丙烯共聚物的MFI值（230℃/2.16kg）为约1.2至2.0g/10min，熔点Tm为约142至150℃，杨氏模数为500至600 N/mm2。
8、按上述权利要求中至少一项所述的膜，其特征是，其上侧有一漆层和/或一层印花或斑痕，而下侧有一粘合层和需要时还有一层隔离层。
9、由上述权利要求中至少一项所述的塑料膜作上膜和常见的底层形成的复合膜，其特征是，上膜含有颜料和/或带有压花。
10、由上述权利要求中至少一项所述的塑料膜作上膜和常见的底层形成的复合膜，其特征是，上膜是透明的，其下侧有一彩印层，该层接有一层起保护作用的下膜、一层粘合层以及一种隔离层。
11、按权利要求10所述的复合膜，其特征是，上膜厚约100至300μm，特别是约150至250μm，且复合膜厚约400至800μm，特别是400至600μm。
12、权利要求9至11所述的复合膜作为自粘装饰膜用于涂敷玻璃、板、纸、纸板以及金属、木材、木质材料和塑料制的其它物体或成形件的用途。
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