CN1278850C - 可收缩虹彩膜 - Google Patents
可收缩虹彩膜 Download PDFInfo
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Abstract
收缩虹彩膜是多层共挤出的取向虹彩膜,其具有至少10个大体平行的厚度大体均匀的非常薄的层,其中相邻接触层为不同的热收缩的热塑性树脂材料,该材料各自可以在膜平面中至少一个尺度上热收缩,连续相邻的层可以大体上均匀地收缩以具有相差至少0.03的折射指数。通过选择适当的热塑性树脂材料、使其共挤出形成厚膜并然后在低于树脂材料的热固化温度下使该膜取向而制备收缩膜。
Description
发明背景
本发明涉及经外加热能活化而具有足够的弹性记忆水平的膜,其可以用于多种包装用途,例如收缩标签和装饰用收缩包装材料。在下文中,这样的膜有时被称作“收缩膜”。用于此目的的常用膜可以由聚乙烯醇、二元醇改性的对苯二甲酸乙二酯(由乙二醇和环己烷二甲醇和对苯二酸制得)和聚丙烯体系制得,这取决于要求的希望达到的收缩程度和特定的用途。已经可以获得的收缩率达到50%或60%。通常将收缩膜制成管状物,然后将其切割成适当的尺寸而用于容器或者某些其他物体。通常希望该膜能以其与物体形状精确相符的形式围绕物体收缩。
因光干涉而具有窄反射波段的多层共挤出的光反射膜是已知的。当该反射波段出现在可见波长范围内时,膜呈现彩虹色。尽管希望采用这样的虹彩膜作为收缩包装用的收缩膜,但是至今为止尚不能达到此目的。
多层共挤出的虹彩膜由许多大体平行的透明热塑性树脂材料层组成,其中相邻接触层为折射指数相差至少约0.03的不同树脂材料。这些膜包含至少10层,但是更常见包含至少35层,优选地至少约70层。
市售可得的膜通常包含50~100个重复的成对聚合物,其可以产生被称作“彩虹色”的光学效果。各独立层非常薄,并且通常为大约30~500nm。多层共挤出的虹彩膜的质量要求单独层具有并保持大体平行状态以及其具有大体均匀的厚度。偏离这些要求会干扰所期望的光学效果。
传统的多层共挤出的虹彩膜具有较小程度的“弹性记忆”,并且当与热接触时产生某种程度的收缩。然而,这些膜可以达到的收缩量不足以用于收缩包装用的膜,并还会伴有独立层的光学特性的变化,因而使彩虹色变化或者消失和/或干扰连接层之间夹层的粘合致使这些层发生内部分层或分离。
尽管不是为了获得收缩膜,但是过去已经在提高多层共挤出的光反射膜的机械性能方面作了努力。美国专利4,310,584介绍了采用热塑性对苯二酸聚酯或共聚酯树脂作为两层相邻聚合物膜中的一种成分,并在美国专利5,089,318中介绍了另一种改进方法,其中采用热塑性弹性体作为一种树脂材料。尽管作了这些改进,当与传统的膜体系相比时这些膜的机械和光学性能仍旧不足以用于收缩包装的用途。
现已发现通过适当地选择不同的热塑性树脂材料和通过使被选择树脂材料制得的共挤出膜取向的方法可以获得具有满意性能的收缩虹彩膜。
因此本发明的目的是提供适合收缩包装用的收缩虹彩膜。在参考了以下详细描述后,本发明的这个目的和其他目的对本领域的普通技术人员将是显见的。
发明概述
本发明涉及适合收缩包装用的收缩虹彩膜和制备该膜的方法。更确切地说,本发明涉及的多层共挤出的收缩虹彩膜由至少10个大体平行的厚度大体均匀的非常薄的层组成,并且相邻接触层为不同的热收缩的热塑性树脂材料。这些材料各自可以于外部加热下在至少一个尺度上热收缩达至少10%。共挤出的相邻接触层可以于在外部加热下大体均匀地收缩,以使收缩后具有的折射指数相差至少约0.03而产生光学效果。通过以下方法制备该膜:选择适当的热塑性树脂材料、使其共挤出成为较厚的膜、然后在一定温度下采用温度分布图使该膜取向以达到所需的颜色和收缩性能。
1、更具体地讲,本发明的涉及一种厚度为大约12~150μm的多层共挤出的取向虹彩膜,其中所述的膜包含至少10个非常薄的各自具有约30~500nm大体均匀厚度的层,所述的层大体平行并且相邻接触层为不同的可热收缩的热塑性树脂材料,所述热塑性树脂材料各自可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩至少10%,并且其中共挤出的不同的可热收缩的热塑性树脂材料的相邻接触层可以在上述范围内的外部加热下大体上均匀地收缩,并且其折射指数在该收缩后相差至少大约0.03而产生彩虹色。
2、在上述多层共挤出的取向虹彩膜的一种具体方案中,所述的膜包含至少35个非常薄的各自具有约30~500nm大体均匀厚度的层,并且在外部加热下所述热塑性树脂材料各自可以在膜平面中至少一个尺度上热收缩达至少20%。
3、在上述第2项多层共挤出的取向虹彩膜的一种具体方案中,所述热塑性树脂材料的折射指数在该收缩后相差至少大约0.06。
4、在上述笫3项多层共挤出的取向虹彩膜的一种具体方案中,所述膜包含至少70个非常薄的各自具有约30~500nm大体均匀厚度的层,并且所述热塑性树脂材料各自可以于外部加热下在膜平面中的至少一个尺度上热收缩大约40~50%。
5、在上述第4项多层共挤出的取向虹彩膜的一种具体方案中,所述膜的厚度为大约15~75μm。
6、在上述第1项多层共挤出的取向虹彩膜的一种具体方案中,所述热塑性树脂材料的折射指数在该收缩后相差至少大约0.06。
7、在上述第1项多层共挤出的取向虹彩膜的一种具体方案中,所述膜包含至少70个非常薄的各自具有约30~500nm大体均匀厚度的层,并且在外部加热下所述热塑性树脂材料各自可以在膜平面中至少一个尺度上热收缩大约40~50%。
8、在上述第7项多层共挤出的取向虹彩膜的一种具体方案中,所述的膜的厚度为大约15~75μm。
9、在上述第1项多层共挤出的取向虹彩膜的一种具体方案中,所述的膜的厚度为大约15~75μm。
10、本发明还涉及一种制备多层共挤出的取向虹彩膜的方法,其包括选择成对热塑性树脂材料,当形成厚度约12~150μm的取向薄膜时这些材料各自可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩达至少10%,并且这些成对材料可以在所述范围内的外部加热下大体均匀地收缩以使折射指数在所述收缩后相差至少大约0.03;共挤出所述的成对材料使其形成厚度为大约24~750μm的膜,该膜包含至少10个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层,并且其中相邻接触层为不同的可热收缩的热塑性树脂材料;和通过使所述厚度为大约24~750μm的膜取向并同时减小膜厚至大约12~150μm的方式赋予其热收缩性。
11、在上述第10项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,所述的成对被选热塑性树脂材料可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩至少20%,并将该成对材料共挤出成膜,该膜包含至少35个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层。
12、在上述第11项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,选择所述的成对热塑性树脂材料使其在所述收缩后具有的折射指数相差至少大约0.06。
13、在上述第12项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,所述的成对被选热塑性树脂材料可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩大约40~50%,并将该成对材料共挤出成膜,该膜包含至少70个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层。
14、在上述第13项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,所述的共挤出膜的厚度为大约30~375μm并使其减小至大约15~75μm。
15、在上述第10项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,选择所述的成对热塑性树脂材料使其在所述收缩后具有的折射指数相差至少大约0.06。
16、在上述第10项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,所述的成对被选热塑性树脂材料可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩大约40~50%,并将该成对材料共挤出成膜,该膜包含至少70个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层。
17、在上述第16项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,所述的共挤出膜的厚度为大约30~375μm并使其减小至大约15~75μm。
18、在上述第10项的制备多层共挤出的取向虹彩膜的方法的一种具体方案中,所述的共挤出膜的厚度为大约30~375μm并使其减小至大约15~75μm。
发明详述
根据本发明,多层共挤出的收缩虹彩膜可以通过在选择所用的树脂材料、共挤出膜的厚度方面改变传统制备方法和通过取向使该膜具有弹性记忆的方法而制得。
多层共挤出的虹彩膜已为本领域所知。在Cooper、Shetty和Pinksy的美国再颁专利Re31,780和Shetty和Cooper的美国专利5,089,318、5,451,449(这里引用所有这些专利作为参考)中和其他专利中对该膜作了介绍。正如那里介绍的,虹彩膜是具有至少10个非常薄的层、优选至少约35层和更优选至少约70层的透明热塑性树脂共挤出的叠层膜,其中各层通常为大约30~500nm,更优选大约50~400nm,并且这些层大体平行,相邻接触层为不同的折射指数相差至少约0.03、更优选至少约0.06的透明热塑性树脂材料。如果存在,构成表皮的膜的最外层各自为至少大约5%膜的总厚度。
本发明中所用的热塑性树脂材料必需满足几点特征。首先,当形成厚度为大约12~150μm、优选大约15~75μm的薄膜时,该膜必须可以于70~300℃加热下在膜平面中一个或多个尺度上热收缩达至少10%,优选地至少大约20%,更优选地大约40~50%。优选地,作为膜的树脂材料可以在膜平面中所有方向上热收缩且各处的热收缩程度大体相同。第二,当形成相邻接触膜层时,树脂材料还必须在整个层中以大体均匀的速度收缩。膜平面中不同尺度上的收缩速度不必相同,但是对两个相邻的层来说任何给定尺度上的速度必须大体相同。例如,只要两个纵向收缩速度和两个横向收缩速度大体相同,那么纵向收缩可以不同于横向收缩。最后,必须选择树脂材料使得收缩后折射指数相差至少大约0.03,优选至少大约0.06。在取向前折射指数不必相差这些数值,因为取向可以改变给定层的折射指数,并因此对取向前的两个指数相差小于0.03的层进行取向可以使得取向后的差值超过0.03。在大多数情况下,取向后但在收缩前的折射指数的差别和收缩后折射指数的差别近似相同。
只要各材料具有上文所述的特性,并且同样地被选树脂材料的组合具有上文所述的特性,那么至今为止用于制备虹彩膜的任何热塑性树脂材料可以用于本发明。可用组合的典型的非限定性实例包括聚苯乙烯和乙烯乙酸乙烯酯、聚苯乙烯和聚乙烯、PETG-共聚酯(由乙二醇和环己烷二甲醇制得的二元醇改性的聚对苯二甲酸乙二酯)和丙烯酸树脂、以及PETG-共聚酯和乙烯乙酸乙烯酯。
使用改进的常规方法将被选树脂材料制成各个厚度较厚的多层膜,以便在取向过程中减小厚度。例如,可以通过冷却辊浇铸技术采用常规的单集料管平膜模具(single manifold flat film die)结合供料台(feedblock)制备该膜,其中供料台收集来自两个或者更多个挤出机各自的熔体并将它们排布成所需的层模型。例如在美国专利3,565,985和3,773,882中介绍了适宜的供料台。供料台可用于形成具有两种成分(即ABAB...)、三种成分(ABCABCA...或ACBACBC)或者更多种成分的交替层。非常狭窄的多层物流流经单管平膜模具,在那里这些层同时扩散至模具的宽度并且变薄至最后的模具出口厚度。可以通过***不同的供料台组件而改变层数和它们的厚度分布。膜各侧的最外层通常比其他层厚。较厚的表层可以由组成光学芯的其中一种成分构成或者可以是用于赋予所需的机械、热密封或者其他性能的不同聚合物。
只要这些层保持大体均匀的厚度和平行取向,那么就可以在本发明的方法中采用任何常规的膜取向的方法。取向可以是单轴取向或者多轴取向。例如,可以通过在所需方向上施加拉力而对膜进行拉伸,并且拉伸可以借助牵伸辊或者牵伸辊的组合施加的拉力而出现在冷却辊和卷取装置之间。
另一种可用来影响取向的方法是辊压。这里使多层膜通过被安置的辊之间以降低厚度至大约20-50%原始多层膜的厚度。当膜经过两辊之间的辊隙时在该膜上施用润滑剂,并且润滑剂可以直接施涂于膜上或者辊表面上从而当膜通过辊之间的间隙时使润滑剂转移至膜表面。润滑剂可以是任何流体或者是在辊压力作用于膜的区域中充当流体的物质。其用于在辊和膜之间形成全部或者部分的流动膜以通过流体润滑剂使辊表面和膜表面分离,从而在薄片进入辊间间隙时防止接触并提高流动性。水可以用作润滑剂,并且还希望在水中包含表面活性剂。
在取向过程中,通常通过辊接触和/或空气将被取向的膜加热至低于树脂材料的晶体熔点的温度。加工温度取决于被取向的特定的虹彩膜,并可以在大约室温至大约145℃或者更高温度之间变化。取向作用使树脂膜具有弹性记忆,因而在外部加热下该树脂膜会收缩。需要通过热固化或者受限的高温退火来调节特定的收缩虹彩膜的活化范围。如果超过了树脂材料的热固温度,那么具有那种材料的膜将不会按照需要收缩。
下面给出多个实施例以说明本发明。在这些实施例中,正如整个说明书和权利要求一样,如果没有另作说明那么所有份数和百分比以重量计算,所有温度单位为℃。
实施例1
选择聚苯乙烯和乙烯乙酸乙烯酯用作热塑性树脂材料。共挤出树脂材料以制备具有包含大约100个交替层的光学芯的样品膜,该样品的大小适于后续拉伸取向至预定厚度。该样品的表层为聚烯烃。制得的共挤出膜的厚度为35~70μm,并且实际上不表现反射色彩。
然后使用两段Marshall-Williams设备加工无色的共挤出膜,并在不同的取向温度(110~115℃)下拉伸该膜。有效的牵伸比为1.8∶1~2.6∶1,采用的预定最终厚度为12~25μm。取向的结果是产生彩虹色。在整个薄片上进行颜色测试,以确定产生的彩虹色的均匀性。没有迹象显示在垂直于移动薄片的平面中单独微层具有非均匀的拉伸现象。
在200℃下将缠绕于玻璃瓶周围的取向多层膜的样品与热空气流接触5秒钟。即使该膜在取向方向上收缩大约15%,也可以在膜中观察到均匀的彩虹色,而且该膜与玻璃瓶的轮廓相配。通过将玻璃瓶放在烘箱中于225℃下持续5分钟可以得到类似的结果。
实施例2
共挤出共聚树脂和聚甲基丙烯酸甲酯以制备具有包含大约200个交替层的光学芯的样品膜,该样品的大小适于后续拉伸取向至预定厚度。该样品的表层为共聚酯。制得的共挤出膜的厚度为40~120μm,并且实际上不表现反射色彩。然后使用单段Marshall-Williams MDO加工无色的挤出膜,并在不同的取向温度(80~125℃)下拉伸该膜。有效的牵伸比为1.8∶1~3.5∶1,采用的预定最终厚度为25~40μm。取向的结果是产生彩虹色。在整个薄片上进行颜色测试,以确定产生的彩虹色的均匀性。没有迹象显示在垂直于移动薄片的平面中单独微层具有非均匀的拉伸现象。
在200℃下将缠绕于玻璃瓶周围的取向多层膜的样品与热空气流接触5秒钟。即使该膜在取向方向上收缩大约25%,也可以在膜中观察到均匀的彩虹色,而且该膜与玻璃瓶的轮廓相配。将玻璃瓶放在烘箱中于225℃下持续5分钟和175℃下持续3分钟可以得到类似的结果。
实施例3
重复实施例2,不同的是将共聚酯与乙烯-乙酸乙烯酯树脂共挤出,以制备光学芯中具有大约100~200层的总膜厚为75~100μm的膜。通过双轴取向以2∶1~5∶1的拉伸比加工该膜。所得的膜具有彩虹色性质,并且当其与热能接触产生15~50%收缩时可以保持这种彩虹色性质。
实施例4
重复实施例3,不同的是共挤出膜的光学芯中具有大约200层并且总的膜厚为125~300μm。
在没有背离本发明的精神和范围的情况下可以对本发明的方法和制品进行多种变化和修改。例如,向任何聚合物物流加入染料、颜料和加工助剂,这显然是目标光学效果的延伸部分。收缩前的最终膜厚可以被调节至实际上任何实用的膜尺寸或片尺寸。也可以对该膜进行表面涂布或者使其叠压至另一种材料。这里公开的多种实施方案仅仅是为了说明本发明,而不是为了限制本发明。
Claims (18)
1.一种厚度为大约12~150μm的多层共挤出的取向虹彩膜,其中所述的膜包含至少10个非常薄的各自具有约30~500nm大体均匀厚度的层,所述的层大体平行并且相邻接触层为不同的可热收缩的热塑性树脂材料,所述热塑性树脂材料各自可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩至少10%,并且其中共挤出的不同的可热收缩的热塑性树脂材料的相邻接触层可以在上述范围内的外部加热下大体上均匀地收缩,并且其折射指数在该收缩后相差至少大约0.03而产生彩虹色。
2.根据权利要求1的多层共挤出的取向虹彩膜,其中所述的膜包含至少35个非常薄的各自具有约30~500nm大体均匀厚度的层,并且在外部加热下所述热塑性树脂材料各自可以在膜平面中至少一个尺度上热收缩达至少20%。
3.根据权利要求2的多层共挤出的取向虹彩膜,其中所述热塑性树脂材料的折射指数在该收缩后相差至少大约0.06。
4.根据权利要求3的多层共挤出的取向虹彩膜,其中所述的膜包含至少70个非常薄的各自具有约30~500nm大体均匀厚度的层,并且所述热塑性树脂材料各自可以于外部加热下在膜平面中的至少一个尺度上热收缩大约40~50%。
5.根据权利要求4的多层共挤出的取向虹彩膜,其中所述的膜的厚度为大约15~75μm。
6.根据权利要求1的多层共挤出的取向虹彩膜,其中所述热塑性树脂材料的折射指数在该收缩后相差至少大约0.06。
7.根据权利要求1的多层共挤出的取向虹彩膜,其中所述的膜包含至少70个非常薄的各自具有约30~500nm大体均匀厚度的层,并且在外部加热下所述热塑性树脂材料各自可以在膜平面中至少一个尺度上热收缩大约40~50%。
8.根据权利要求7的多层共挤出的取向虹彩膜,其中所述的膜的厚度为大约15~75μm。
9.根据权利要求1的多层共挤出的取向虹彩膜,其中所述的膜的厚度为大约15~75μm。
10.一种制备多层共挤出的取向虹彩膜的方法,其包括选择成对热塑性树脂材料,当形成厚度约12~150μm的取向薄膜时这些材料各自可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩达至少10%,并且这些成对材料可以在所述范围内的外部加热下大体均匀地收缩以使折射指数在所述收缩后相差至少大约0.03;共挤出所述的成对材料使其形成厚度为大约24~750μm的膜,该膜包含至少10个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层,并且其中相邻接触层为不同的可热收缩的热塑性树脂材料;和通过使所述厚度为大约24~750μm的膜取向并同时减小膜厚至大约12~150μm的方式赋予其热收缩性。
11.根据权利要求10的制备多层共挤出的取向虹彩膜的方法,其中所述的成对被选热塑性树脂材料可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩至少20%,并将该成对材料共挤出成膜,该膜包含至少35个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层。
12.根据权利要求11的制备多层共挤出的取向虹彩膜的方法,其中选择所述的成对热塑性树脂材料使其在所述收缩后具有的折射指数相差至少大约0.06。
13.根据权利要求12的制备多层共挤出的取向虹彩膜的方法,其中所述的成对被选热塑性树脂材料可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩大约40~50%,并将该成对材料共挤出成膜,该膜包含至少70个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层。
14.根据权利要求13的制备多层共挤出的取向虹彩膜的方法,其中所述的共挤出膜的厚度为大约30~375μm并使其减小至大约15~75μm。
15.根据权利要求10的制备多层共挤出的取向虹彩膜的方法,其中选择所述的成对热塑性树脂材料使其在所述收缩后具有的折射指数相差至少大约0.06。
16.根据权利要求10的制备多层共挤出的取向虹彩膜的方法,其中所述的成对被选热塑性树脂材料可以于大约70~300℃的外部加热下在膜平面中的至少一个尺度上热收缩大约40~50%,并将该成对材料共挤出成膜,该膜包含至少70个大体平行的各自具有约30~500nm大体均匀厚度的非常薄的层。
17.根据权利要求16的制备多层共挤出的取向虹彩膜的方法,其中所述的共挤出膜的厚度为大约30~375μm并使其减小至大约15~75μm。
18.根据权利要求10的制备多层共挤出的取向虹彩膜的方法,其中所述的共挤出膜的厚度为大约30~375μm并使其减小至大约15~75μm。
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Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/963,239 US6602585B2 (en) | 2001-09-26 | 2001-09-26 | Shrinkable iridescent film |
US09/963,232 | 2001-09-26 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1561287A CN1561287A (zh) | 2005-01-05 |
CN1278850C true CN1278850C (zh) | 2006-10-11 |
Family
ID=25506959
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB028190092A Expired - Fee Related CN1278850C (zh) | 2001-09-26 | 2002-08-28 | 可收缩虹彩膜 |
Country Status (12)
Country | Link |
---|---|
US (1) | US6602585B2 (zh) |
EP (1) | EP1439954B1 (zh) |
JP (1) | JP4276943B2 (zh) |
CN (1) | CN1278850C (zh) |
AT (1) | ATE347996T1 (zh) |
AU (1) | AU2002362596A1 (zh) |
BR (1) | BR0212865A (zh) |
CA (1) | CA2461689A1 (zh) |
DE (1) | DE60216797T2 (zh) |
ES (1) | ES2279005T3 (zh) |
TW (1) | TW564220B (zh) |
WO (1) | WO2003026879A2 (zh) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020102393A1 (en) * | 2001-01-31 | 2002-08-01 | Engelhard Corp. | Decorative iridescent film |
US20030068453A1 (en) * | 2001-10-02 | 2003-04-10 | Dan-Cheng Kong | Multilayer sleeve labels |
EP1640152B1 (en) * | 2003-06-04 | 2018-12-05 | Toray Industries, Inc. | Multilayer film and biaxially oriented polyester film |
US20060024491A1 (en) * | 2004-07-27 | 2006-02-02 | Engelhard Corporation | Optical effect films with customized central layer |
JP4957235B2 (ja) * | 2005-12-26 | 2012-06-20 | 東洋紡績株式会社 | 熱収縮性ポリエステル系フィルム |
US20070231548A1 (en) * | 2006-03-31 | 2007-10-04 | Merrill William W | Process for making an optical film and rolls of optical film |
US20070228586A1 (en) * | 2006-03-31 | 2007-10-04 | Merrill William W | Process for making an optical film |
US7829162B2 (en) | 2006-08-29 | 2010-11-09 | international imagining materials, inc | Thermal transfer ribbon |
US20080083999A1 (en) * | 2006-10-06 | 2008-04-10 | 3M Innovative Properties Company | Process for making an optical film |
US20080085481A1 (en) * | 2006-10-06 | 2008-04-10 | 3M Innovative Properties Company | Rolls of optical film |
US20080274340A1 (en) * | 2007-05-04 | 2008-11-06 | Giammatteo Marc W | Non-specular iridescent films |
US8114485B1 (en) * | 2009-08-14 | 2012-02-14 | Nucoat, Inc. | Water resistant shrinkable medium for receiving ink |
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US3759647A (en) | 1969-04-10 | 1973-09-18 | Turner Alfrey Us | Apparatus for the preparation of multilayer plastic articles |
US3647612A (en) | 1969-06-06 | 1972-03-07 | Dow Chemical Co | Multilayer plastic articles |
US4101698A (en) | 1975-07-14 | 1978-07-18 | Avery International Corp. | Elastomeric reflective metal surfaces |
US4374691A (en) | 1980-05-09 | 1983-02-22 | Minnesota Mining And Manufacturing Company | Material and method for forming pressure transferable graphics |
US4496618A (en) | 1982-09-30 | 1985-01-29 | Pernicano Vincent S | Heat transfer sheeting having release agent coat |
US4548857A (en) | 1983-09-26 | 1985-10-22 | Dennison Manufacturing Co. | Heat transferable laminate |
US5149386A (en) * | 1987-08-10 | 1992-09-22 | Alcan International Limited | Tamper-evident structures |
US5015318A (en) * | 1987-08-10 | 1991-05-14 | Alcan International Limited | Method of making tamper-evident structures |
US4837061A (en) * | 1987-08-10 | 1989-06-06 | Alcan International Limited | Tamper-evident structures |
US5104719A (en) | 1989-08-30 | 1992-04-14 | Revlon, Inc. | Heat activated, quick release decals and associated methods |
US5089318A (en) | 1989-10-31 | 1992-02-18 | The Mearl Corporation | Iridescent film with thermoplastic elastomeric components |
US5149578A (en) * | 1989-12-26 | 1992-09-22 | The Dow Chemical Company | Multilayer film for tamper indication by use of optical interference reflection |
DE4104337A1 (de) | 1991-02-13 | 1992-10-15 | Swarovski & Co | Dekorelement mit mehreren schmucksteinen und verfahren zu dessen herstellung |
US5571557A (en) | 1995-05-09 | 1996-11-05 | Chartpak, Inc. | Faux glass etch product and process of preparing same |
US5631064A (en) | 1995-09-15 | 1997-05-20 | Minnesota Mining And Manufacturing Company | Retroreflective transfer sheet and applique |
US6045894A (en) * | 1998-01-13 | 2000-04-04 | 3M Innovative Properties Company | Clear to colored security film |
US6475608B2 (en) * | 1998-11-16 | 2002-11-05 | Engelhard Corporation | Multi-layer iridescent films |
US6554447B1 (en) * | 2000-04-14 | 2003-04-29 | S. C. Johnson & Son, Inc. | Candle product decorated with heat-shrinkable film and related method |
US20020102393A1 (en) * | 2001-01-31 | 2002-08-01 | Engelhard Corp. | Decorative iridescent film |
-
2001
- 2001-09-26 US US09/963,239 patent/US6602585B2/en not_active Expired - Fee Related
-
2002
- 2002-08-28 ES ES02799558T patent/ES2279005T3/es not_active Expired - Lifetime
- 2002-08-28 CN CNB028190092A patent/CN1278850C/zh not_active Expired - Fee Related
- 2002-08-28 BR BR0212865-9A patent/BR0212865A/pt not_active Application Discontinuation
- 2002-08-28 WO PCT/US2002/027446 patent/WO2003026879A2/en active IP Right Grant
- 2002-08-28 EP EP02799558A patent/EP1439954B1/en not_active Expired - Lifetime
- 2002-08-28 AU AU2002362596A patent/AU2002362596A1/en not_active Abandoned
- 2002-08-28 JP JP2003530495A patent/JP4276943B2/ja not_active Expired - Fee Related
- 2002-08-28 DE DE60216797T patent/DE60216797T2/de not_active Expired - Lifetime
- 2002-08-28 AT AT02799558T patent/ATE347996T1/de not_active IP Right Cessation
- 2002-08-28 CA CA002461689A patent/CA2461689A1/en not_active Abandoned
- 2002-09-03 TW TW091120073A patent/TW564220B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ATE347996T1 (de) | 2007-01-15 |
AU2002362596A1 (en) | 2003-04-07 |
JP4276943B2 (ja) | 2009-06-10 |
JP2005503284A (ja) | 2005-02-03 |
WO2003026879A2 (en) | 2003-04-03 |
DE60216797T2 (de) | 2007-11-08 |
EP1439954B1 (en) | 2006-12-13 |
WO2003026879A3 (en) | 2003-06-05 |
US6602585B2 (en) | 2003-08-05 |
US20030059590A1 (en) | 2003-03-27 |
CA2461689A1 (en) | 2003-04-03 |
ES2279005T3 (es) | 2007-08-16 |
BR0212865A (pt) | 2004-09-14 |
CN1561287A (zh) | 2005-01-05 |
TW564220B (en) | 2003-12-01 |
EP1439954A2 (en) | 2004-07-28 |
DE60216797D1 (de) | 2007-01-25 |
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