CN1232428A - 结合用于可印刷塑料薄膜的涂料的热转印法 - Google Patents

结合用于可印刷塑料薄膜的涂料的热转印法 Download PDF

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CN1232428A
CN1232428A CN97198530A CN97198530A CN1232428A CN 1232428 A CN1232428 A CN 1232428A CN 97198530 A CN97198530 A CN 97198530A CN 97198530 A CN97198530 A CN 97198530A CN 1232428 A CN1232428 A CN 1232428A
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coating
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P·C·卢
G·L·穆施洛
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Abstract

本发明提供结合涂料组合物的在塑料薄膜上的热转印方法。该方法包括提供具有涂料组合物的塑料薄膜。该涂料组合物含有含乙烯基型不饱和键的羧酸聚合物和/或共聚物的粘结剂、至少一种细微的颗粒填料和表面活性剂。然后按需印刷到塑料薄膜上图象的形状加热热成象元件,如含染料层的色带。加热使得染料层按图象的形状熔融。使涂有该涂料组合物的塑料薄膜与该热成象色带接触,并使染料层从色带转印到塑料薄膜上。这种在涂覆塑料薄膜上的热转印提供了许多用途,如户外塑料标签。

Description

结合用于可印刷塑料薄膜的涂料的热转印法
本发明涉及能提高塑料表面(特别是塑料薄膜)可印刷性的涂料组合物。具体地说，本发明涉及结合使用涂料组合物来改善塑料薄膜上这种可印刷性的热转印法。
开发热转印法是为了满足“即时”型印刷要求。然而，这种热转印一般限制在印刷由纸构成的表面，而不是塑料表面。这主要由于塑料表面在热转印工艺中差的印刷性和差的耐久性。在热转印工艺中，提供用于印刷的印刷表面基材，和提供用于把图象转印到基材上的印刷头型加热元件。把含有固体油墨和热成象色带放在印刷表面基材和印刷头之间。印刷头包括许多加热元件，这些加热元件可按所需的印刷图象逐一加热。操作时，把热成象色带夹在印刷头和印刷表面基材之间，使印刷头接触热成象色带，而热成象色带又接触印刷表面基材。按需印刷的图象加热各个加热元件。这种夹置和加热同时对热成象色带施加压力和热量，这样使热成象色带上所含的固体油墨在加热的部分印刷头上熔化或液化。因为热成象色带与印刷表面基材接触，熔融的油墨按所需的图象形式从热成象色带转印到印刷表面基材上。
虽然热转印方法已很流行，但由于在塑料薄膜上印刷困难和与这种薄膜有关的高成本，这种方法通常主要用于纸基材。例如，商品(如Madico GraphicFilms,Woburn,Mass．销售的01-180和01-181号产品和Kimberly Clark销售的Kimdura K-100)是可用于热转印法的可印刷聚合物薄膜。虽然现已证实这些薄膜是纸的有用替代品，但它们显然比纸贵。因此，由于成本上的考虑，它们不适合于“即时”型印刷用途。
Ohba等的美国专利5,233,924描述了一种“合成纸”型产品，它是据称可用于热转印法中的替代基材的一个实例。该专利揭示了一种加入了无机细粉末的细多孔性不透明聚烯烃薄膜，在该聚烯烃薄膜层的一面或两面有乙烯-乙烯醇共聚物薄膜层，而且还可包括无机材料之类的涂层。虽然现已证明这种薄膜能在热转印工艺中提供足够的印刷质量，但这些材料的高成本使其明显不实用。另外，乙烯-乙烯醇共聚物的光滑表面在许多印刷用途中似乎是一种妨碍。
本发明涉及一种可印刷涂料组合物，它含有丙烯酸类乳液。这种乳液包括无机颗粒和表面活性剂。在一个实施方式中本发明包括紫外线稳定添加剂。本发明特有的涂料配方克服了塑料薄膜印刷(特别是平版印刷或热转印)时现有困难。
所述的丙烯酸类粘结剂含有含乙烯基型不饱和键的羧酸(如丙烯酸或甲基丙烯酸或这些酸的酯)的热塑性聚合物或共聚物。上述的丙烯酸类物质含有低级烷基，如含1-16个碳原子的烷基。具体的实例包括甲基、乙基、丁基、月桂基和硬脂基。有用的丙烯酸类树脂可用非丙烯酸类单体(如丙烯腈、丁二烯和/或苯乙烯)改性。
丙烯酸类聚合物粘合剂在本领域中是众所周知的，且描述在美国专利3,753,769；4,058,645和4,749,616。
特别有用的热塑性共聚物是以商品名称Michem(特别是Michem-4983)购自Michelman公司的乙烯-丙烯酸共聚物。乙烯-丙烯酸共聚物一般通过乙烯和丙烯酸的高压共聚制得。当乙烯与丙烯酸共聚时，由于沿该共聚物的主链和侧链无规嵌入体积大的羧酸基而明显改变了分子结构。羧基没有形成键，且与任何聚合物基材相互作用。
市售的乙烯-丙烯酸共聚物是由Dow Chemical Co．出售的Primacor 4983，固体含量为25％和由15％摩尔丙烯酸和85％摩尔乙烯间反应制得的一种水性分散液。可用的其它丙烯酸类乳液是Valspar公司以商品名Acrylic(特别是Acrylic 79XW318A、89XW055和90XW067)出售的乳液。
按涂料组合物的总重量计，粘结剂的总量约为20-80％重量，较好约为30-60％重量。
该粘结剂可以完全是丙烯酸类聚合物，或可以完全是乙烯-丙烯酸共聚物。对于某些用途，丙烯酸类聚合物和乙烯-烯丙醚类共聚物的混合物是优选的。一般当不含丙烯酸类聚合物时，颜料的分散性较差，涂层对基底的粘合性也较差。如果不含乙烯-丙烯酸共聚物时，涂层会对湿气敏感的。因此，丙烯酸类聚合物和乙烯-丙烯酸共聚物间的平衡是优选的。当使用混合物时，丙烯酸类聚合物的优选含量为5-50％重量，乙烯-丙烯酸共聚物的优选含量为95-50％重量。按混合物的总重量计，典型的配方含有5-20％重量丙烯酸类聚合物和95-80％重量乙烯-丙烯酸共聚物。
该配方的另一种组分含有至少一种能提高油墨接受性的颗粒添加剂。
这种颗粒添加剂(通常称作填料)含有细微的无机固体材料，如二氧化硅(包括热解法二氧化硅)、滑石、硅藻土、硅酸钙、膨润土和粘土。填料的含量占涂料重量的较大百分数，按涂料的总重量计一般约为20-80％，较好约为30-60％。颗粒的粒径一般较小，一般为1-10微米，较好为约3-7微米。填料的具体实例包括高岭土、二氧化硅(已知有抗粘连性)、硅酸铝、粘土和滑石。也可使用纸浆。
也可使用提高不透明性的颗粒，这些颗粒可能提高涂层的油墨接受性。它们是相对惰性的物质。碳酸钙广泛用于热塑性塑料中，碳酸钙是较廉价的，且易于使用。可以使用天然型的碳酸钙，但也可使用用化学方法制得的“沉淀碳酸钙”。有时，为了降低增塑剂的吸附用树脂涂覆碳酸钙颗粒，且也可以使用这种形式的碳酸钙。
也可使用有着色作用的颗粒。上述的颜料是粒径很少小于1微米的有机和无机物质。常见的颜料包括炭黑和二氧化钛。碳酸钙也可用作颜料。也可用于本发明的其它颜料是金属颜料，如铝、铜、金、青铜或锌的颗粒。这些颜料通常是薄片状颗粒，当加入涂料溶剂中时，它们能反射光线。
通常结合使用吸墨材料，遮盖性颗粒和/或颜料，这取决于所要求的半透明或不透明程度。一般遮盖性颗粒和/或颜料的浓度范围为涂料的总颗粒浓度的约5-70％，较好的为涂料的总颗粒浓度的约10-45％。
除上述颗粒以外，可用于本发明的其它颗粒的实例包括乙炔黑、α型纤维素、硅酸铝、硫酸钡、硅酸钙、硫酸钙、纤维素、粘土、硅藻土、玻璃片、角蛋白、木质素、锌钡白、云母、微球、二硫化钼、霞石正长岩、纸、纸浆、石英、壳粉、滑石、蛭石和木粉。
本发明还包括任选的紫外线稳定添加剂。它是能吸收或筛除超过可见辐射光谱紫外端的辐射的化学试剂，以防止能降解塑料的辐射催化反应。常见的紫外吸收剂是二苯酮、苯并三唑(包括羟苯基苯并三唑)、取代的丙烯腈、水杨酸衍生物和镍配合物。对于某些紫外稳定剂(如二苯酮)必须小心，因为它们可用作增稠剂。上述的紫外稳定剂购自Ciba-Geigy的市售苯并三唑“Tinuven1130”，购自Cytec的“UV5411”和购自Fairmont的“Mixxim BB/200”。市售的二苯酮可以商品名“Uvinul 3048”购自BASF或以商品名“Syntase230”购自Great Lakes Chemical。另一种市售的紫外吸收剂是以商品名“VPSanduvor VSU”购自Sandoz的N,N′-二苯基乙二酰胺。紫外吸收剂一般与能终止紫外催化剂反应的自由基清除剂组合使用。常见的自由基清除剂包括受阻胺(包括受阻氨基醚)光稳定剂。上述市售的受阻胺包括Ciba-Geigy销售的“Tinuven123”、Enichem销售的“Uvasil 299”和Mayzo销售的“BLS1770”．工业上制备的紫外吸收剂/自由基清除剂组合物(packages)例如以“VP sanduvor 3225”购自Sandoz。一般当组合使用紫外吸收剂和自由基清除剂时，按所用的紫外稳定添加剂剂的总量计，自由基清除剂的浓度约为10-60％重量，较好约为20-40％重量。用于本发明涂料组合物中的紫外稳定添加剂组合物的总量约占涂料组合物总重量的1-15％，较好占2-8％。紫外稳定剂通常与烃类溶剂混合，特别是与能与水溶混的醇类溶剂混合。醇的用量一般足以溶解紫外稳定添加剂，按涂料的总重量计它的用量约为0.5-5％重量。
该涂料组合物还含有较少量的能促进颗粒分散的表面活性剂。这种组分对于分散紫外稳定剂特别重要。可以使用能提高涂料稳定性的任何合适的表面活性剂。可使用阴离子乳化剂。它们包括具有8-18个碳原子的醇的硫酸酯的碱金属盐和铵盐(如十二烷基硫酸钠)、芳族磺酸(十二烷-1-磺酸和辛二烯-1-磺酸)的碱金属盐和铵盐、芳烷基磺酸盐(如异丙基苯磺酸钠、十二烷基苯磺酸钠和异丁基萘磺酸钠)、磺化二元羧酸酯的碱金属盐和铵盐(如磺基丁二酸二辛酯钠和N-十八烷基磺基丁二酰胺酸二钠)、复合有机单和二磷酸酯的游离酸的碱金属盐或铵盐等。也可使用非离子乳化剂，如辛基或壬基苯基聚乙氧基乙醇等。也可使用上述物质的混合物。具体的乳化剂是以商品名称Aerosol A-102购自American Cyanamide Company的磺基丁二酸的乙氧基化醇(C10-C12)半酯二钠或磺基丁二酸的乙氧基化壬基苯酚半酯二钠(Aerosol A-103)。另一种具体的乳化剂是以商品名称“Triton X-200”购自Rohm and Haas Company的烷基芳基聚醚磺酸钠盐或“Triton X-405”环氧乙烷衍生物。还有一种有用的乳化剂是“Tergitol 15-5-9”。
可以使用足以分散紫外稳定剂和颗粒的有效量的表面活性剂。这种用量约占涂料总重量的0.5-10％重量，较好约占涂料总重量的1-7％重量。
在本发明的涂料中也可含有常规的涂料添加剂。这些物质一般包括用于改善摩擦系数、表面滑爽性和抗粘连性的改性剂。这种改性剂的具体实例包括天然蜡(如石蜡、微晶蜡、蜂蜡、巴西棕榈蜡、褐煤蜡)等和合成蜡(如氢化蓖麻油、氯化烃蜡、长链脂肪酰胺等)。可加入涂料混合物的其它改性剂包括一种或多种湿润剂、交联剂、稳定剂、催化剂、增塑剂、消泡剂、滑爽剂、抗静电剂和抗氧剂。
该涂料的制备方法是，依次或同时混合所有的组分，然后在室温和常压条件下用常规混合装置混合或掺合。该涂料一般是用水性介质，按最终涂料组合物的总重量计，固体含量约为10-80％，一般为25-60％。
用本发明涂料处理的薄膜的形成方法一般是在200-250℃温度下用平片挤出模头挤塑聚烯烃树脂(如聚丙烯)，然后把该薄膜流延在冷却鼓上并将其骤冷。然后在纵向(MD)取向机中将片材拉伸3-7倍，再在横向(TD)取向机中拉伸5-10倍。
用本发明涂料处理的薄膜可包括可形成薄膜的任何单层或多层热塑性材料。上述的材料包括各种聚烯烃，如聚丙烯、聚乙烯、聚丁烯、聚苯乙烯、聚氯乙烯、它们的共聚物和共混物。上述的其它薄膜材料包括聚对苯二甲酸乙二醇酯和尼龙。在多层薄膜中，有位于热塑性芯层的至少一个表面上的一个或多个表层。该表面层可包含聚乙烯(包括中和高密度聚乙烯)、聚丙烯、它们与C2-C5α-烯烃的共聚物或三元共聚物或共混料。该薄膜的至少一个表面可包括热合或压合表面。常见的热合材料包括乙烯和丙烯均聚物、共聚物或三元共聚物(如乙烯-丙烯、乙烯-丙烯-1-丁烯和聚偏氯乙烯聚合物)。为提高基材的白度或颜色或为了提高抗粘连性，各种材料可含有无机颗粒，如二氧化钛。
底涂层能提高本发明涂层与未涂覆薄膜间的粘合性。常见的底涂层是与未涂覆薄膜有良好粘合性的聚合物，如聚乙烯亚胺和环氧树脂。
在本发明的一个实施方式中，将最终印刷好的薄膜粘贴到物体上。可用任何常规的粘合剂粘贴该薄膜。上述的粘合剂是可压合、热熔或水基的。本发明的涂料不影响这种粘合剂。因此，可将粘合剂涂布在该薄膜的印刷面，使印刷的表面面对粘贴的物体。当需要透过物体(如玻璃窗或透明塑料容器)看到印刷物时，这是有用的。
一般在用本发明最终配制的组合物涂覆薄膜之前，为产生足以与底涂层或其它涂层粘合的高能量表面环境对薄膜表面进行处理，如用火焰或电晕处理法或能氧化薄膜表面的其它方法。进行电晕处理的方法是当薄膜在有一定间距的电极之间通过时，将薄膜表面置于高压电晕放电之下。对薄膜表面进行电子处理后，就可涂覆涂料。
或者该涂料用任何常规方法离线涂布。例如，该薄膜可用辊涂法、喷涂法、缝隙涂布法或浸涂法涂布。凹槽辊涂布法或反向直接凹槽辊涂布法也是可采用的方法。过量的涂料溶液可用挤压辊或刮刀除去。
不管采用那一种涂布方法，涂布量应使得干燥时形成光滑、均匀分布的涂层。优选的涂布重量约为3-9克/米2。
基材可有任何合适的厚度，虽然对高速设备而言其厚度一般为20-100微米。
在本发明的一个方面，该涂料用于拉伸包装薄膜的标签上。
在所有情况下，本发明的涂料组合物可涂布在该薄膜的两个表面上。或者，一个表面可涂上另一种涂料组合物，或一个表面可有基底，如另一种聚合物薄膜或层压膜、金属箔(如铝箔)、纤维素膜、纸、纺丝粘合聚烯烃纤维、合适的粘合剂(如热熔或室温密封粘合剂或水基粘合剂)。
因此，本发明涉及热转印图象的形成方法。由于用热转印法在塑料薄膜上难于产生具有清晰分辨率的图象，所以热转印法一般用于纸基材上的印刷。通过结合本发明的涂料组合物，就可容易地在塑料基材上进行热转印图象的形成方法。
本发明可用于许多应用中的热转印法，包括“即时”型数字印刷，且特别适用于压敏标签、条形码、指向用途识别标签(如航空行李标签)、参观人员识别标志等。因为本发明在塑料薄膜上进行热转印，所以预料有许多用途。这些用途不受把纸用作印刷表面时上述缺陷的限制。例如，本发明可用于户外用途的防水基材。
本发明涉及用任何已知的方法进行热转印。一个典型的热转印法揭示在Anczurowski和Sanders发表在Journal of Imaging Technology 13:97-102(1987)中的“热转印材料”一文中。
在优选的方法中，提供包括具有染料或油墨层的载体的热成象元件，如热成象色带。油墨层的熔融温度低于色带基底的熔融温度，且与印刷头的加热温度相匹配。当加热印刷头时，色带上的油墨层应能被熔融，而不会使色带载体降解。油墨层的熔融温度较好约为60-80℃。或者可用升华型染料或油墨。市售热成象色带的一个实例是Sony公司制造的4065。热成象色带放在具有涂层组合物的热塑性基材和包含许多加热元件的印刷头之间。印刷头上的加热元件可按图象的形状加热，从而可按所需印刷的图象分别加热印刷头的特定元件。按图象形状加热热成象色带使热成象色带的固体油墨组分按所需图象的形状熔融。然后把这样熔融的油墨转印到上面有涂层的热塑性基材上。因为热成象色带是按图象形状加热的，所以仅使图象中加热的部分热成象元件上的固体油墨熔融。
在染料升华型热转印方法中，为转印图象无需使基材表面与热成象元件直接接触。实际上，热成象色带上包含升华型染料。当印刷头按所需图象加热热成象色带时，升华型染料升华成气体。把涂有涂料组合物的印刷表面基材放在热成象色带附近，并保持在低于热成象元件的温度。升华成气体的染料转印到冷的基材上，并被冷凝，从而染料按转印的图象形状从热成象色带转印到印刷表面基材上。
本发明也可使用本发明的热转印方法结合用于塑料薄膜的涂料组合物在塑料薄膜上进行彩色印刷。
实施例
如下实施例1-3对未涂覆的聚丙烯薄膜和现有合成纸与涂有本发明各种涂料组合物的可用于热转印工艺的聚丙烯薄膜进行比较。
实施例1
本实施例描述本领域中已知的不含本发明涂料组合物的塑料薄膜。该薄膜由Mobil Chemical Company以160LL302销售的双轴取向聚丙烯薄膜构成。
实施例2
本实施例描述Kimberly Clark以商品名Kimdura销售的现有高价合成纸产品。Kimdura产品是双轴取向的聚丙烯薄膜，它具有矿物填料的表层和含粘土的面涂层。据称，该薄膜是按美国专利5,233,924揭示的方法(4)制造。据称该薄膜是细多孔性聚烯烃型合成纸，在每个表面涂有乙烯-乙烯醇共聚物，上面有加入粘土的面涂层。
实施例3
本实施例描述结合本发明涂料组合物的塑料薄膜，以提供高质量、低成本的热转印表面。
提高印刷性的涂料按如下方法制备，即在水溶液中混合19.9％乙烯-丙烯酸共聚物、10.3％丙烯酸类聚合物、32.4％粘土、25.8％滑石、6.4％二氧化钛和5.2％市售抗静电剂、悬浮助剂和消泡剂添加剂。将该混合物制成固体含量为46-48％。
将Mobil Chemical Company以260LLG202销售的双轴取向聚丙烯薄膜处理成达因水平为38dynes/cm。该薄膜涂有Daubert Chemical出售的聚乙烯亚胺底涂料。这种涂料含有1.9％聚乙烯亚胺、0.5％己糖溶纤剂(hexocellosolve)和97.6％水。用逆向凹槽辊涂布机把提高印刷性的涂料涂布在底涂层表面上，涂布重量达3.75克/米2。在93℃温度下将涂料组合物空气干燥。
印刷表面基材可用Zebra Corp.制造的Zebra 140Xi印刷机结合如下色带进行印刷：
Ⅰ    Iimak Corp.制造的I-21色带，表明结合硬蜡载体的色带。
Ⅱ    Iimak Corp.制造的I-28色带，表明结合快蜡载体的色带。
Ⅲ    Iimak Corp.制造的R2主色带，表明结合树脂载体的色带。
Ⅳ    Iimak Corp.制造的SP330色带，表明结合树脂载体的色带。
Ⅴ    Iimak Corp.制造的PM260色带，表明结合优等树脂载体的色带。
Ⅵ    由Sony Corp.制造的4065色带，表示结合蜡/树脂载体的色带。
Ⅶ    由Sony Corp.制造的4075色带，表示结合树脂载体的色带。
Ⅷ    由Sony Corp.制造的4080色带，表示结合蜡/树脂载体的色带。

Claims (10)

1．热转印图象的形成方法，其特征在于它包括：
(a)提供在至少一个表面上具有涂层组合物的热塑性基材，该涂层含有：
(ⅰ)按涂层的总重量计，约20-80％重量选自含乙烯基型不饱和键的羧酸聚合物、含乙烯基型不饱和键的羧酸共聚物和它们的混合物的至少一种粘结剂；
(ⅱ)按涂层的总重量计，约20-80％重量至少一种细微颗粒填料；和
(ⅲ按涂层的总重量计，约0.5-10％重量的表面活性剂；
(b)按图象形状加热热成象元件，该热成象元件包括含染料层的载体；
(c)把染料图象转印到具有上述涂层的上述基材表面上。
2．如权利要求1所述的方法，其特征在于所述的按图象形状加热步骤(b)使所述的染料层熔融，且通过使所述的印刷表面与包含所述熔融染料层的热成象元件直接接触来完成所述的转印步骤(c)。
3．如权利要求1所述的方法，其特征在于所述的按图象形状加热步骤(b)使所述的染料层升华，且通过把所述的印刷表面放在所述热成象元件附近，使所述升华的染料层冷凝在所述的印刷表面上来完成所述的转印步骤(c)。
4．如权利要求1所述的方法，其特征在于所述的羧酸聚合物由丙烯酸、甲基丙烯酸或它们的酯制成。
5．如权利要求1所述的方法，其特征在于所述的羧酸共聚物是乙烯-丙烯酸共聚物。
6．如权利要求1所述的方法，其特征在于按混合物的总重量计，所述的粘结剂含有约5-50％重量丙烯酸类聚合物和约95-50％重量乙烯-丙烯酸共聚物。
7．如权利要求1所述的方法，其特征在于所述的表面活性剂是阴离子乳化剂或非离子型乳化剂。
8．如权利要求7所述的方法，其特征在于所述的表面活性剂选自烷基芳基聚醚磺酸钠盐、环氧乙烷衍生物及它们的混合物。
9．如权利要求1所述的方法，其特征在于所述的颗粒填料选自二氧化硅、滑石、硅藻土、硅酸钙、膨润土、粘土及它们的混合物。
10．热转印图象，其特征在于它包括：
在至少一个表面上用含如下组分的涂层组合物处理的聚烯烃基材：
(a)按涂层的总重量计，约20-80％重量选自含乙烯基型不饱和键的羧酸聚合物、含乙烯基型不饱和键的羧酸共聚物和它们的混合物的至少一种粘结剂；
(b)按涂层的总重量计，约20-80％重量至少一种细微颗粒填料；和
(c)按涂层的总重量计，约0.5-10％重量的表面活性剂；
在涂有上述组合物的表面上的热转印染料图象，所述的染料图象用热转印法转印到所述的聚烯烃基材上。
CN97198530A 1996-09-11 1997-07-29 结合用于可印刷塑料薄膜的涂料的热转印法 Pending CN1232428A (zh)

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US08/705,349 US5891552A (en) 1996-01-04 1996-09-11 Printed plastic films and method of thermal transfer printing
US08/705,349 1996-09-11

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CA2265543A1 (en) 1998-03-19
KR20000036043A (ko) 2000-06-26
US5891552A (en) 1999-04-06
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WO1998010938A1 (en) 1998-03-19
TW345545B (en) 1998-11-21
JP2001500807A (ja) 2001-01-23
ID19374A (id) 1998-07-02
DE69715889T2 (de) 2003-02-20
EP0925192A1 (en) 1999-06-30
AR009745A1 (es) 2000-05-03
BR9711760A (pt) 2002-03-05
ES2184125T3 (es) 2003-04-01
EP0925192B1 (en) 2002-09-25
DE69715889D1 (de) 2002-10-31
EP0925192A4 (en) 1999-11-10

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