CN1578805A - 热收缩聚酯薄膜 - Google Patents
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Abstract
一种热收缩聚酯薄膜,其包括聚酯基薄膜和在聚酯基薄膜一侧或两侧上形成的涂层,其中所述涂层包括带有羧基末端的且Tg为70℃-80℃的共聚聚酯,这种热收缩薄膜表现出优异的性能,适合用于标记或收缩包装容器。
Description
技术领域
本发明涉及一种热收缩聚酯薄膜,更具体涉及一种具有改良性能特征的用于标记、包装容器等的热收缩聚酯薄膜。
发明背景
热收缩薄膜已经广泛应用于例如标记瓶子、电池或电解电容器,以及包装容器和其他产品。这种热收缩薄膜由聚氯乙烯、聚苯乙烯或聚酯制成,要求具有好的密封性和收缩性,以及具有好的耐热性、耐化学性、耐候性和可印性。
由聚氯乙烯或聚苯乙烯制成的常规热收缩薄膜具有相对差的耐热性、耐化学性、耐候性和热收缩性。特别是基于聚氯乙烯的热收缩薄膜,由于它们在焚化时会放出有毒的污染物,所以近来变得愈加失宠。另一方面,聚苯乙烯薄薄膜的问题是可印性差,需要特殊用途的墨水。聚苯乙烯薄膜在长期储存中具有自发收缩的倾向。
由聚对苯二甲酸乙二酯(PET)制成的热收缩聚酯薄膜具有令人满意的耐热性、耐化学性、耐候性和收缩性。然而,PET薄膜的收缩应力和收缩率通常高的令人不能接受,从而使收缩包装不均匀,结果必然造成印在包装上的图像扭曲。
日本专利公开特许63-139725、7-53416、7-53737、7-216107、7-216109和9-254257公开了,PET薄薄膜的收缩均匀性可以通过以特定比例掺和聚对苯二甲酸乙二酯及聚对苯二甲酸丁二酯来改进,或者通过使二羧酸组分如对苯二酸和间苯二酸与二醇组分如乙二醇和1,4-环己烷二甲醇共聚来改进。虽然这种热收缩薄膜在收缩均匀性方面有所改进,但是由于它具有聚集静电的倾向、无法接受的低Tg和差的滑动性能,所以很难对它进行处理。
发明内容
因此,本发明的主要目的是提供一种热收缩薄膜,其具有改进的热收缩性、粘合性、耐水性、可印性、滑动性和防粘性。
本发明的上述目的可通过提供一种热收缩聚酯薄膜来实现,所述热收缩聚酯薄膜包括聚酯基薄薄膜和在聚酯基薄薄膜一侧或两侧上形成的涂层,其中所述的涂层包括具有羧基末端的且Tg为70-80℃的聚酯共聚物。
具体实施方式
本发明的热收缩聚酯薄膜包括涂层,该涂层含有具有羧基末端且Tg为70-80℃的聚酯共聚物。
本发明的聚酯共聚物可以通过共聚二羧酸组分和二醇组分来制备,所述二羧酸组分例如为对苯二酸或其酯、间苯二酸或其酯、2,6-萘二甲酸或其酯、癸二酸、己二酸、5-磺基间苯二甲酸、偏苯三酸、草酸、马来酸、琥珀酸、戊二酸、庚二酸、壬二酸,或1,2,4,5-苯四酸,所述二醇组分例如为乙二醇、1,3-丙二醇、二甘醇、己二醇、2,2-(4-氧苯酚)丙二醇衍生物、二甲苯二醇(xylene glycol)、二缩三(乙二醇)、聚丁二醇、2,2′-氧双乙醇或2,2-二甲基-1,3-丙二醇。
这种聚酯共聚物带有羧基末端,Tg在70-80℃范围内,优选温度范围在73-78℃。倘若Tg低于70℃,在容器洗涤或填充过程中容器的标签就会粘在一起;如果Tg高于80℃,在收缩包装时涂层就会发生降解。
为提高滑动性,本发明中使用的涂层还可包括无机润滑剂,如二氧化硅、氧化铝、二氧化钛、碳酸钙、硫酸钡或它们的混合物,优选胶体氧化硅。以聚酯共聚物为基础,无机润滑剂的含量优选范围是0.1-0.5重量%。
包括无机润滑剂的聚酯共聚物可以涂在聚酯基薄膜的一侧或两侧。涂层可以利用常规涂覆方法涂在聚酯基薄膜的表面上,例如,利用照相凹板辊涂法,翻转照相凹板辊涂法,Meyer棒涂法或刮涂法。
通过测量涂料组分的量可以控制涂层的厚度。优选涂料组合物的量在0.01-0.1g/m2的范围内,更优选0.02-0.08g/m2。如果涂料的量低于0.01g/m2,则薄薄膜趋向于变粘。另一方面,如果该量高于0.1g/m2,则在辊上缠绕薄膜过程中会发生阻塞。
在其上形成涂层的聚酯基薄薄膜可以为常规热收缩聚酯薄膜,优选为包含对苯二酸和乙二醇组分的聚酯共聚物。然而,希望聚酯基薄膜包含亚丙基对苯二酸酯重复单元,以便提高热收缩性和透明性。分别以全部组分为基准,聚酯基薄膜优选包括45-90摩尔%的对苯二酸乙二酯重复单元、5-25摩尔%的亚丙基对苯二酸酯重复单元和5-30摩尔%的二甲基(1,3-亚丙基)对苯二酸酯重复单元。
以全部组分为基准,亚丙基对苯二酸酯重复单元含量优选为5-25摩尔%。如果所述的重复单元含量低于5摩尔%,相对于主要收缩方向的横向上的收缩率会变得非常大,在50℃下的自动收缩率变大,薄薄膜的透明性变差;如果所述的重复单元含量高于25摩尔%,在拉伸过程中会发生过多的结晶,导致在主要收缩方向上收缩程度降低。
以全部组分为基准,对苯二酸乙二酯重复单元的含量优选为45-90摩尔%。如果重复单元含量低于45摩尔%,聚酯薄膜的耐热性和延展性会变差;如果摩尔含量高于90%,薄薄膜的收缩率就不符合要求并且粘合性变差。
以全部组分为基准,二甲基(1,3-亚丙基)对苯二酸酯重复单元的含量优选为5-30摩尔%。如果所述的摩尔含量低于5摩尔%,在收缩包装过程中就不能进行充分的热收缩,单轴拉伸薄膜在横向方向上的强度会降低,反之,如果其高于30摩尔%,薄膜的耐热性和延展性会变差。
在聚酯薄膜的制造中,优选将聚亚丙基对苯二酸酯和聚对苯二甲酸乙二酯与2,2-二甲基-1,3-丙二醇共聚聚酯掺合,该2,2-二甲基-1,3-丙二醇共聚聚酯是由对苯二酸或对苯二甲酸二甲酯与乙二醇和2,2-二甲基-1,3-丙二醇共聚制得。
在优选实施方案中,2,2-二甲基-1,3-丙二醇共聚聚酯包含15-25摩尔%的二甲基(1,3-亚丙基)对苯二酸酯重复单元。如果二甲基(1,3-亚丙基)对苯二酸酯重复单元的含量低于15摩尔%,热收缩率就会不符合要求,如果含量高于25摩尔%,薄膜就会成为非晶形的。
2,2-二甲基-1,3-丙二醇共聚聚酯的固有粘度优选为0.5-0.7。聚亚丙基对苯二酸酯和聚对苯二甲酸乙二酯的固有粘度优选分别为0.7-0.95和0.5-0.65。
本发明的聚酯基薄膜可以进一步包括另外共聚的二羧酸组分和二醇组分,所述二羧酸组分如间苯二酸及其酯、2,6-萘二甲酸及其酯、癸二酸、己二酸、5-磺基间苯二酸、偏苯三酸、草酸、马来酸、琥珀酸、戊二酸、庚二酸、壬二酸及1,2,4,5-苯四酸,所述二醇组分如乙二醇、1,3-丙二醇、二甘醇、己二醇、2,2-(4-氧苯酚)丙二醇衍生物、二甲苯二醇、二缩三(乙二醇)、聚-1,4-丁二醇、2,2′-氧双乙醇、2,2-二甲基-1,3-丙二醇或它们的混合物。
本发明中使用的聚酯基薄膜可以包含添加剂,如分散剂、防结块剂、润滑剂等,其用量不对薄膜的性能造成不利影响。
用于基薄膜的聚酯树脂可以利用传统方法如直接酯化法或酯交换法合成。聚酯基薄膜的制备是聚酯树脂熔融挤出形成熔融薄片,冷却,使熔融的薄片凝固,最后用拉幅机单轴或双轴拉伸凝固的薄片。
在优选实施方案中,本发明的热收缩薄膜的厚度在12-125μ的范围内。
本发明在实施例中进一步描述和说明,然而本发明的范围并不仅仅局限于这些实施例。
合成例1-6
固有粘度为0.62的聚对苯二甲酸乙醇酯(A)按如下的公知方法合成。
将100摩尔份数的对苯二甲酸二甲酯和140摩尔份数的1,3-丙二醇装至配有混和器和蒸馏柱的高压釜中,以对苯二甲酸二甲酯为基准,加入0.05重量%量的四亚丁基钛酸酯(酯交换催化剂)。当除去生成的甲醇后,升温到220℃进一步反应。待酯交换反应完成后,以对苯二甲酸二甲酯为基准,加入0.045重量%量的磷酸三甲酯(稳定剂),并且10分钟后,加入用量为对苯二甲酸二甲酯重量0.02%的三氧化锑(聚合催化剂)。5分钟后,将所得产物转移至配有真空装置的第二反应器,在280℃反应约180分钟,得到固有粘度为0.85的聚亚丙基对苯二甲酸酯(B)。
将100摩尔份数的对苯二甲酸二甲酯、110摩尔份数的乙二醇和40摩尔份数的新戊二醇(2,2-二甲基1,3-丙二醇)装至配有混和器和蒸馏柱的高压釜中,加入乙酸锰(酯交换催化剂),用量为对苯二甲酸二甲酯重量的0.07%。当反应生成的甲醇除去后,升温到220℃进一步反应。待酯交换反应完成后,加入用量为对苯二甲酸二甲酯重量0.04%的磷酸三甲酯。5分钟后,加入用量分别为对苯二甲酸二甲酯重量0.035%的三氧化锑和0.005%的四亚丁基钛酸酯,并搅拌10分钟。将结果产物转移至配有真空装置的第二反应器,在压力缓慢降低的同时升温至285℃,保持在温度约210分钟,得到固有粘度为0.60的共聚聚酯(C)。
将聚酯A、B和C以不同比例混合,每个混合物都在280℃熔融、挤出、然后用保持在20℃的压延辊冷却,得到非晶形的片材。将非晶形的片材用保持在80℃的拉幅机以3.6的拉伸率单轴拉伸,得到厚度为50μ的聚酯基薄膜。其组成列于表1。
表1
合成例 | 重复单元的含量(摩尔%) | ||
对苯二甲酸乙二酯 | 亚丙基对苯二酸酯 | 2,2-二甲基(-1,3-亚丙基)对苯二酸酯 | |
1 | 51 | 25 | 24 |
2 | 61 | 25 | 14 |
3 | 66 | 20 | 14 |
4 | 75 | 14 | 11 |
5 | 82 | 10 | 8 |
6 | 88 | 5 | 7 |
合成例7
利用二羧酸组分和二醇组分合成聚酯树脂,所用的二羧酸组分由80摩尔%的对苯二甲酸二甲酯、15摩尔%的间苯二甲酸二甲酯和5摩尔%的2,6-萘二甲酸二甲酯组成,所用的二醇组分由15摩尔%的丙二醇、10摩尔%的2,2-二甲基-1,3-丙二醇和75摩尔%的乙二醇组成。树脂经干燥、280℃熔融、挤出、用保持在20℃的压延辊冷却、将得到的非晶形薄片用拉幅机单轴拉伸,得到聚酯基薄膜。
实施例1
将50重量份的1,3-苯二甲酸和50重量份的2,2′-氧双乙醇装至配有混和器和蒸馏柱的高压釜中,在150℃下,加入0.05重量份的乙酸锰(酯交换催化剂)。当除去反应生成的水和甲醇后,升温到220℃并保持120分钟。待酯交换反应完成后,加入0.02重量份的磷酸三甲酯。10分钟后,加入0.02重量份的三氧化锑,并搅拌10分钟。将结果产物转移至配有真空装置的第二反应器,在压力缓慢降低的同时升温至280℃,保持该温度约140分钟,得到共聚聚酯。共聚聚酯的Tg为76℃(用DSC(Perkin-Elmer制造)测得,升温速率10℃/分钟)。
将上述共聚聚酯(涂料组分)用Meyer棒涂法涂在合成例1中制备的聚酯基薄膜的一侧,然后经干燥后得到带有涂层的热收缩聚酯薄膜,干燥后涂层的量为0.03g/m2。
实施例2-6
除了在每个实施例中以合成例2-6中制备的聚酯基薄膜分别代替合成例1的基薄膜外,重复实施例1的过程。
实施例7
除了在用于涂层的共聚聚酯中加入0.5重量份的胶体二氧化硅外,重复实施例1中过程。
实施例8
除了干燥后涂层的量为0.02g/m2外,重复实施例1的过程。
实施例9
除了干燥后涂层的量为0.05g/m2外,重复实施例1的过程。
比较例1-6
除了合成例1-6中制备的聚酯基薄膜不用共聚聚酯涂覆外,重复实施例1的过程。
比较例7
除了将带有SO3端基且Tg为64℃的WR901树脂(JapaneseSynthesis Co.Ltd.,)涂覆在聚酯基薄膜的一侧上,干燥后涂层的量为0.03g/m2外,重复实施例1中的过程。
比较例8
除了将包含常规的三聚氰胺固化剂的丙烯酸树脂涂覆在聚酯基薄膜上,干燥后涂层的量为0.05g/m2外,重复实施例1中的过程。
比较例9
除了将常规的水性聚氨酯涂覆在聚酯基薄膜上,干燥后涂层的量为0.03g/m2外,重复实施例1中的过程。
性能测试I
测试了实施例1-9和比较例1-9中制备的热收缩聚酯薄膜的以下性能。结果列于表2。
(1)粘合性能
将1,3-二氧戊环涂覆在试样薄膜的表面上,然后将另一个薄膜试样覆盖在上面。大约10秒钟后,将薄膜彼此撕开。按下面的标准评价粘合性能。
○:拉伸时彼此粘在一起
△:脱落,带有粘合的印迹
×:很容易分开,没有粘合的印迹
(2)耐水性和粘性
将两个试样薄膜片材在室温下流动的水中洗30分钟,空气中晾干,在热梯度下将它们压在一起(28psi,10秒钟,100-140℃,梯度:10℃),然后将它们彼此撕开。按下面的标准评价粘性。
○:很容易分开
△:脱落,带有粘合的印迹
×:彼此粘在一起,直至破坏
(3)滑动性(摩擦系数)
按照ASTM D1894在200克负载下测量静摩擦系数。
表2
例 | 粘合性能 | 静摩擦系数 | 耐水性 | 粘性 | ||||||||
100℃ | 110℃ | 120℃ | 130℃ | 140℃ | 100℃ | 110℃ | 120℃ | 130℃ | 140℃ | |||
实施例1 | ○ | 0.65 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
实施例2 | ○ | 0.64 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
实施例3 | ○ | 0.65 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
实施例4 | ○ | 0.65 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
实施例5 | ○ | 0.66 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
实施例6 | ○ | 0.65 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
实施例7 | ○ | 0.50 | ○ | ○ | ○ | ○ | △ | ○ | ○ | ○ | ○ | △ |
实施例8 | ○ | 0.45 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
实施例9 | ○ | 0.42 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
比较例1 | ○ | 0.75 | × | × | × | × | × | × | × | × | × | × |
比较例2 | ○ | 0.77 | × | × | × | × | × | × | × | × | × | × |
比较例3 | ○ | 0.78 | × | × | × | × | × | × | × | × | × | × |
比较例4 | ○ | 0.75 | × | × | × | × | × | × | × | × | × | × |
比较例5 | ○ | 0.76 | × | × | × | × | × | × | × | × | × | × |
比较例6 | ○ | 0.78 | × | × | × | × | × | × | × | × | × | × |
比较例7 | ○ | 0.50 | △ | △ | △ | × | × | △ | △ | △ | × | × |
比较例8 | × | 0.40 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
比较例9 | × | 0.52 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
从表2可以看出,比较例1-6中表面没有涂层的薄膜,表现出较差的粘合性、滑动性、耐水性和粘性。比较例7-9中分别涂有WR901、含常规的三聚氰胺固化剂的丙烯酸树脂和水性聚氨酯涂层的薄膜表现出较差的物理性能,包括粘合性。
相反,本发明中的涂有共聚聚酯涂层的聚酯薄膜在所有的各类性能中都表现出优异的特性。
性能测试II
实施例1-9中制备的聚酯薄膜进行了以下的性能测试。结果列于表3。
(1)热收缩率
将试样薄膜切成15mm×200mm(长)的片,在80℃水中处理,然后测量片的长度,按下面公式计算热收缩率:
热收缩率(%)=[(L-l)/L]×100
其中L是热处理前薄膜的长度,l是热处理后薄膜的长度。
(2)可印性
将硝化纤维素墨水涂在试样薄膜的表面,用刀片印上预定的网格图案。将粘合强度为40克/毫米的半透明的胶带压在薄膜的被墨水涂过的表面上。按下列标准,通过胶带从表面撕下时转移到胶带上的墨水的量评价可印性。
○:没有墨水转移到胶带上
△:70%或少于70%的墨水转移到胶带上
×:70%或多于70%的墨水转移到胶带上
(3)玻璃瓶上的包装性能
将10mm×10mm的网格摹制到热收缩薄膜上,利用四氢呋喃使之卷曲成型为直径为65mm的圆柱形薄膜。然后用这个圆柱形的热收缩薄膜在85℃或90℃的水中包装商业上用的玻璃瓶(容量334ml)。包装性能按下面标准评价:
○:玻璃瓶上的网格没有扭曲,90℃收缩包装后,薄膜与瓶盖形状的相配性好
△:玻璃瓶上的网格没有扭曲,85℃收缩包装后,薄膜与瓶盖形状的相配性好
×:网格发生扭曲,85℃收缩包装后,薄膜与瓶盖形状的相配性差
(4)延展性
观测了薄膜拉伸后的外观和厚度均匀程度,并按下面标准评价:
○:薄膜厚度均匀性好,没有发白。
×:薄膜变得发白或在厚度上不均匀。
◇:由于薄膜的不规则展开性,无法评价延展性
(5)断裂强度
用抗张强度试验机(型号:6021,Instron Co.制造)测试了薄膜的断裂强度。使用10cm×15mm的薄膜试样来测量断裂强度。
(6)浊度
用浊度测试仪(型号:x1-211,Gardner Neotech制造)测量了薄膜试样的浊度。
表3
实施例序号 | 收缩率(%) | 可印性 | 包装性 | 延展性 | 断裂强度(kgf/mm2) | 浊度(%) | |
MD* | TD* | ||||||
1 | -1.9 | 68 | ○ | ○ | ○ | 5.7 | 3.9 |
2 | -1.0 | 61 | △ | △ | ○ | 6.8 | 3.9 |
3 | 0 | 72 | ○ | ○ | ○ | 5.5 | 4.2 |
4 | 0 | 72 | ○ | ○ | ○ | 5.2 | 4.7 |
5 | 0.8 | 72 | ○ | ○ | ○ | 5.4 | 5.2 |
6 | 1.1 | 65 | ○ | △ | ○ | 4.9 | 5.3 |
7 | -1.8 | 68 | ○ | ○ | ○ | 5.7 | 4.0 |
8 | -1.9 | 69 | ○ | ○ | ○ | 5.7 | 3.9 |
9 | -1.9 | 69 | ○ | ○ | ○ | 5.8 | 4.2 |
*MD和TD分别代表薄膜在轴向和横向上的收缩率
如表3所示,本发明的实施例1-9中制备的热收缩聚酯薄膜表现出优异的热收缩率、可印性、延展性、断裂强度、粘合性和透明性。因此,具有这样理想性能的创造性热收缩薄膜可有利地用在标记或包装各种容器的用途中。
当本发明以上述具体实施方案描述时,应理解本领域技术人员可对本发明进行的各种修改和变化也落入所附权利要求中限定的本
发明范围内。
Claims (17)
1.一种热收缩聚酯薄膜,其包括聚酯基薄膜和在该聚酯基薄膜一侧或两侧上形成的涂层,其中所述涂层包括具有羧基末端的且Tg为70-80℃的共聚聚酯。
2.权利要求1的热收缩聚酯薄膜,其中所述共聚聚酯是使用二羧酸和二醇组分共聚而成,所述二羧酸选自以下组中:对苯二酸或其酯、间苯二酸或其酯、2,6-萘二甲酸或其酯、癸二酸、己二酸、5-磺基间苯二甲酸钠、偏苯三酸、草酸、马来酸、琥珀酸、戊二酸、庚二酸、壬二酸、1,2,4,5-苯四酸以及它们的混合物,所述二醇选自以下组中:乙二醇、1,3-丙二醇、二甘醇、己二醇、2,2-(4-氧苯酚)丙二醇衍生物、二甲苯二醇、二缩三(乙二醇)、聚丁二醇、2,2′-氧双乙醇、2,2-二甲基-1,3-丙二醇以及它们的混合物。
3.权利要求1的热收缩聚酯薄膜,其中所述涂层的量为0.01-0.1g/m2。
4.权利要求1的热收缩聚酯薄膜,其中以共聚聚酯为基准,所述聚酯基薄膜还包括用量为0.1-0.5重量%的无机润滑剂。
5.权利要求4的热收缩聚酯薄膜,其中所述无机润滑剂选自以下组中:二氧化硅、氧化铝、二氧化钛、碳酸钙、硫酸钡和它们的混合物。
6.权利要求1的热收缩聚酯薄膜,其中所述聚酯基薄膜包括亚丙基对苯二甲酸酯重复单元。
7.权利要求6的热收缩聚酯薄膜,其中所述聚酯基薄膜还包括对苯二甲酸乙二酯和2,2-二甲基(1,3-亚丙基)对苯二酸酯重复单元。
8.权利要求7的热收缩聚酯薄膜,其中所述亚丙基对苯二甲酸酯重复单元的含量为5-25摩尔%,所述对苯二甲酸乙二酯重复单元的含量为45-90摩尔%,所述2,2-二甲基(1,3-亚丙基)对苯二酸酯重复单元的含量为5-30摩尔%。
9.权利要求7或8的热收缩聚酯薄膜,其中所述聚酯基薄膜是通过掺合聚亚丙基对苯二甲酸酯、聚对苯二甲酸乙二酯和2,2-二甲基-1,3-丙二醇共聚聚酯而制备的。
10.权利要求9的热收缩聚酯薄膜,其中所述聚亚丙基对苯二甲酸酯和聚对苯二甲酸乙二酯的固有粘度分别为0.7-0.95和0.5-0.65。
11.权利要求9的热收缩聚酯薄膜,其中所述2,2-二甲基-1,3-丙二醇共聚聚酯是通过对苯二酸或对苯二甲酸二甲酯与乙二醇和2,2-二甲基-1,3-丙二醇的混合物共聚而制备的。
12.权利要求11的热收缩聚酯薄膜,其中所述2,2-二甲基-1,3-丙二醇共聚聚酯的固有粘度为0.5-0.7。
13.权利要求11的热收缩聚酯薄膜,其中所述2,2-二甲基-1,3-丙二醇共聚聚酯包括75-85摩尔%的对苯二甲酸乙二酯重复单元和15-25摩尔%的2,2-二甲基(1,3-亚丙基)对苯二酸酯重复单元。
14.权利要求6的热收缩聚酯薄膜,其中所述亚丙基对苯二甲酸酯重复单元是通过对苯二酸或对苯二甲酸二甲酯与丙二醇聚合而制备的。
15.权利要求14的热收缩聚酯薄膜,其中所述二羧酸组分还包括间苯二甲酸二甲酯和2,6-萘二甲酸二甲酯,而所述二醇组分还包括2,2-二甲基-1,3-丙二醇和乙二醇。
16.权利要求15的热收缩聚酯薄膜,其中所述二羧酸组分包括70-100摩尔%的对苯二甲酸二甲酯、0-20摩尔%的间苯二甲酸二甲酯和0-10摩尔%的2,6-萘二甲酸二甲酯。
17.权利要求15的热收缩聚酯薄膜,其中所述二醇组分包括5-20摩尔%的丙二醇、5-20摩尔%的2,2-二甲基-1,3-丙二醇和60-90摩尔%的乙二醇。
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CNB02821692XA Expired - Lifetime CN1249133C (zh) | 2001-11-02 | 2002-11-02 | 热收缩聚酯薄膜 |
Country Status (7)
Country | Link |
---|---|
US (1) | US7018689B2 (zh) |
EP (1) | EP1448679B1 (zh) |
KR (1) | KR100443194B1 (zh) |
CN (1) | CN1249133C (zh) |
DE (1) | DE60219512T2 (zh) |
HK (1) | HK1074213A1 (zh) |
WO (1) | WO2003037967A1 (zh) |
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CN103930274A (zh) * | 2011-10-14 | 2014-07-16 | 艾利丹尼森公司 | 用于标签的收缩膜 |
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-
2002
- 2002-11-02 US US10/492,825 patent/US7018689B2/en not_active Expired - Lifetime
- 2002-11-02 CN CNB02821692XA patent/CN1249133C/zh not_active Expired - Lifetime
- 2002-11-02 DE DE60219512T patent/DE60219512T2/de not_active Expired - Lifetime
- 2002-11-02 KR KR10-2002-0067622A patent/KR100443194B1/ko active IP Right Grant
- 2002-11-02 WO PCT/KR2002/002043 patent/WO2003037967A1/en active IP Right Grant
- 2002-11-02 EP EP02788908A patent/EP1448679B1/en not_active Expired - Lifetime
-
2005
- 2005-08-02 HK HK05106605A patent/HK1074213A1/xx not_active IP Right Cessation
Cited By (12)
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CN100526065C (zh) * | 2005-04-20 | 2009-08-12 | 郡是株式会社 | 收缩标签 |
CN102066465B (zh) * | 2008-06-11 | 2013-08-21 | Skc株式会社 | 热收缩性聚酯薄膜 |
CN102272205A (zh) * | 2009-03-19 | 2011-12-07 | Skc株式会社 | 热收缩聚酯薄膜及其制备方法 |
CN102272205B (zh) * | 2009-03-19 | 2015-03-04 | Skc株式会社 | 热收缩聚酯薄膜及其制备方法 |
CN102206331A (zh) * | 2010-03-30 | 2011-10-05 | 中国石油化工股份有限公司 | 一种聚酯及其膜的制法 |
CN102206331B (zh) * | 2010-03-30 | 2013-04-24 | 中国石油化工股份有限公司 | 一种聚酯及其膜的制法 |
CN103930274A (zh) * | 2011-10-14 | 2014-07-16 | 艾利丹尼森公司 | 用于标签的收缩膜 |
CN103930274B (zh) * | 2011-10-14 | 2016-12-14 | 艾利丹尼森公司 | 用于标签的收缩膜 |
US10525678B2 (en) | 2011-10-14 | 2020-01-07 | Avery Dennison Corporation | Shrink film for label |
US9339995B2 (en) | 2012-01-11 | 2016-05-17 | Avery Dennison Corporation | Multi-layered shrink film with polyolefin core |
CN103147301A (zh) * | 2013-03-27 | 2013-06-12 | 吴江市金平华纺织有限公司 | 一种热缩纱布 |
CN103147301B (zh) * | 2013-03-27 | 2015-02-11 | 海泰纺织(苏州)有限公司 | 一种热缩纱布 |
Also Published As
Publication number | Publication date |
---|---|
KR100443194B1 (ko) | 2004-08-04 |
DE60219512T2 (de) | 2007-12-27 |
KR20030036104A (ko) | 2003-05-09 |
EP1448679A1 (en) | 2004-08-25 |
DE60219512D1 (de) | 2007-05-24 |
EP1448679B1 (en) | 2007-04-11 |
CN1249133C (zh) | 2006-04-05 |
US7018689B2 (en) | 2006-03-28 |
HK1074213A1 (en) | 2005-11-04 |
US20040265607A1 (en) | 2004-12-30 |
WO2003037967A1 (en) | 2003-05-08 |
EP1448679A4 (en) | 2005-01-12 |
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