CN1141351C - 压敏粘合剂 - Google Patents
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Abstract
公开了一种涂布了丙烯酸压敏粘合剂,以获得对聚合物低能表面的高的或永久性附着力的乙烯基图案印标膜或标签。除了对低能表面的高附着力外,图案印标膜或标签具有微孔或微观粗糙的边缘,当试图揭去时能引起撕裂。这类制品保持了易于制造图案印标膜或标签的柔性和膜强度。
Description
本发明领域
本发明涉及粘合剂,尤其是提高了对低能表面的粘合特性的丙烯酸压敏粘合剂。
本发明背景
在此使用的术语“膜”指薄的柔性单层或多层聚合物片。该术语可与术语“背衬”和“载体卷材”互换使用。由涂布了丙烯酸压敏粘合剂(PSA)的乙烯基膜形成的图案印标膜或标签在本领域是众所周知的。但是,目前还不具备提供具有对低能表面(如高密度聚乙烯和聚丙烯塑料)的高粘合强度(即不可除去),又不损害粘合剂的重要性能(如剪切强度和粘结强度)的标签和图案印标膜的能力。
在此使用的术语“低能表面”用以指显示低极性和低临界表面张力(约小于40达因/厘米2)特性的那些表面。低能表面的一个例子是聚烯烃塑料的表面。在PSA类中,已知丙烯酸基的PSA对低表面能的聚烯烃塑料的粘合特性比橡胶基的PSA差。这一作用是由于与橡胶PSA和聚烯烃表面间的极性差相比,丙烯酸PSA和聚烯烃表面间的极性差较大的结果。但是,不幸的是在许多应用中都非常需要使用丙烯酸PSA,因为丙烯酸PSA具有优良的户外耐久性,而橡胶PSA由于其烃弹性体的化学不饱和性,显示差的紫外线稳定性和氧化稳定性。
获得压敏粘合剂对聚烯烃塑料的高粘合强度的普通物理方法包括火焰处理(它氧化塑料的表面)、用强酸提高粘合表面极性的化学蚀刻、或使用含氯化聚烯烃的底涂层和顶涂层。例如,日本专利No.平-1(1989)-242676讨论了与压敏粘合剂有关的氯化聚烯烃树脂的使用。这样的表面处理方法的一个缺点是在将图案印标模或标签施用到低能表面时需增加额外的处理步骤而使效率低。这样不是很理想,因为图案印标膜和标签的工业规模的使用者要求这些产品能以简单的一个步骤方便地施用,而不需要额外的费时的表面制备方法。
对永久性图案印标模和标签的应用,要求具有与橡胶基PSA同样的粘合特性和兼备丙烯酸PSA的户外耐久性。提高丙烯酸PSA对低表面能聚烯烃塑料的粘合强度的一种方法是在粘合剂中加入一种相容的增粘剂,如松香酯、萜烯酚醛树脂或烃树脂。尽管使用增粘剂明显提高了由低速下剥离力测定的粘合强度,同时这些增粘剂提高了PSA的玻璃化转变温度(Tg),导致降低低温性能,还引起在较快的剥离速度下的“跳跃”或“拉链(zippy)”式剥离特性。这种“跳跃”或“拉链”式剥离是不合需要的性能,会导致膜和标签易于揭下,并使膜和标签的抗擅自移动性(tamper-resistant)变小。
另外,如果在PSA中加入大量增粘剂或增塑剂,也观察到粘合剂的剪切强度和粘结强度的损失。
在许多应用中,要求图案印标膜或标签一旦贴到表面,就要难以揭去。要达到这点可以通过向图案印标膜或标签膜提供一种手段,使得试图揭去它们将会导致撕裂图案印标膜或标签,或造成其它损害。提高涂布了PSA的乙烯基标签或图案印标膜的可损坏性的一种方法是使乙烯基膜背衬具有较小的弹性或成为“脆性”。可通过加入硬性丙烯酸树脂,减少乙烯基膜的增塑剂用量达到这点。
美国专利5,141,790(Calhoun等人)和5,296,277(Wilson等人)描述了商业上称作Controltac PlusTM膜(可从3M获得)的粘合剂膜。Controltac PlusTM膜的粘合剂表面的特点是它包括非粘合剂物质的集聚区,称作“栓”,它从粘合剂表面突出一短的距离。该专利还描述了这样的粘合剂膜,其粘合剂表面被赋予微观结构或具有微观拓扑结构。
本发明的概述
本发明涉及在增粘的丙烯酸PSA中加入增塑剂材料。制得的PSA显示聚氯乙烯图案印标膜或标签对低能表面(如高密度聚乙烯塑料)能提供改进了的粘合。
更具体而言,本发明涉及增粘和增塑的丙烯酸PSA组合物,它包括:
a)约100重量份丙烯酸共聚物,所述的丙烯酸共聚物包括约70-98%重量的一种或多种有1-14个碳原子的非叔烷基的单官能丙烯酸酯,和约30-2%重量的极性单体;
b)约10-40重量份的增粘剂;
c)约3-10重量份的增塑剂;和
d)任选的交联剂。
本发明还涉及结合了这种增粘的粘合剂的膜,以及这些膜作为图案印标膜和标签的用途。
当加入到增粘的丙烯酸压敏粘合剂中,特定化学类型的增塑剂提高了粘合剂对低能表面的粘合特性。已发现在增粘的丙烯酸粘合剂中加入增塑剂能提高对低能表面的浸湿或“快粘合”。加入增塑剂抵销了增粘剂引起的玻璃化转变温度的升高,并且提高了粘合强度。当每100重量份粘合剂中加入的增塑剂小于约10重量份时,增塑剂的存在对粘合剂的剪切性能或粘结强度几乎没有影响。
所发现的用以提高粘合特性的增塑剂有聚乙二醇醚、聚环氧乙烷、磷酸酯、脂族羧酸酯、苯甲酸酯、以及它们的组合。另外,还鉴定了能提高对低能表面粘合强度的其它增塑剂,但是发现这些增塑剂会引起粘结强度的某些下降。这些增塑剂包括磺酰胺和芳族羧酸酯。
和丙烯酸相容的增粘剂一起加入特定的增塑剂能够构成一种提高了对低能表面,特别是高密度聚乙烯表面的附着力的户外耐久的乙烯基标签或图案印标膜,而不必对表面进行物理或化学处理。在一个技术方案中,标签或图案印标膜的结构可以包括可破坏的乙烯基膜背衬,用于抗破坏的应用。该技术方案中,用一微孔的或微观粗糙的钢尺模切图案印标膜或标签,当试图揭下时就会引起撕裂。图案印标膜或标签的改进的附着力特性会进一步阻止揭去。除了对膜的这些改进外,制品保持了柔韧性和膜强度,而易于制造图案印标膜或标签。
附图简述
图1是乙烯基膜标签的剖面示意图。
图2是对各种粘合剂组合物的180°剥离附着力的直方图。
图3是对各种粘合剂组合物的膜收缩的直方图。
本发明的详细描述
丙烯酸压敏粘合剂
一般用于乙烯基装饰图案膜商业应用的许多丙烯酸压敏粘合剂包括具有约70-98%重量的一种或多种有1-14个碳原子的非叔烷基的丙烯酸酯和约30-2%重量的极性单体的丙烯酸共聚物。
在一个较好的技术方案中,丙烯酸PSA是烯不饱和的丙烯酸烷基酯(C1-C14)的共聚物,如丙烯酸异辛酯、丙烯酸2-乙基己酯、丙烯酸2-甲基丁酯(MBA)、丙烯酸N-丁酯、丙烯酸甲酯(MA)、丙烯酸乙酯和丙烯酸异冰片酯(IBA)。极性单体包括烯不饱和的羧酸,如甲基丙烯酸、丙烯酸(AA)、衣康酸、丙烯酸β-羧基乙酯、富马酸、丙烯酰胺(Acm)或其它极性单体,如N-乙烯基吡咯烷酮、N-乙烯基己内酯、丙烯酸2-羟乙酯等。
这类粘合剂能非常好地粘合在涂布过的基材上,并至少部分由于极性单体而具有优良的粘结强度。使用极性单体可制备具有优良粘结强度的粘合剂,但这些单体赋予粘合剂的高玻璃化转变温度在配制用于低能表面的“快速浸湿”的粘合剂时成为一个缺点。
用于低能表面的一种较好的PSA配方,经测定丙烯酸异辛酯/丙烯酸的比例为95/5。该配方配制的组合物在过多的丙烯酸(会使PSA配方“硬化”,导致差的“浸湿”)和过少的丙烯酸(导致PSA组合物差的粘结强度)间很好地进行综合。
几种可应用于本发明的压敏粘合剂列于下表I:
表I
增粘剂
丙烯酸压敏粘合剂 | ||
聚合物化学 | 分子量 | |
90/10 | IOA/AA | 1.5×106 |
93/7 | IOA/AA | 1×106 |
93/7 | IOA/AA | 5×105 |
. 94/6 | IOA/AA | 5×105 |
95/5 | IOA/AA | 2×105 |
98/2 | IOA/AA | 1×106 |
70/22.5/7.5 | IOA/MA/AA | 2×105 |
96/4 | 2-MBA/ACM | 2×105 |
90/10 | 2-MBA/AA | 5×105 |
68/28/4 | IOA/IB/AA | 2×105 |
要获得对低能表面的高粘合特性,最普通的用于丙烯酸压敏粘合剂的增粘剂包括萜烯酚醛、松香、松香酯、氢化松香酯、合成烃树脂以及它们的组合。在下表II列出评价的增粘剂:
表II
普通的丙烯酸PSA增粘剂 | ||
公司 | 商品名称 | 化学类 |
Hercules | Foral85 | 氢化松香甘油酯 |
Hercules | Hercolyn-D | 氢化松香甲酯 |
Arizona Chemical | Nirez2019 | 萜烯酚醛树脂 |
Union Camp | Uni-Tac-70 | 松浆油松香 |
Hercules | Regalrez6108 | 芳族烃树脂 |
Exxon | ECR-180 | 石油烃树脂 |
氢化松香酯,因为其性能优点,包括高“粘性”、户外耐久性、耐氧化性、与热熔处理的相容性、以及在丙烯酸PSA的后交联中有限的干扰,是优选的增粘剂。
增粘剂一般的加入量为,每100份干的丙烯酸PSA加入约10-40份增粘剂,可获得要求的“粘性”。但是,如上所述,加入这些类型的增粘剂会降低剪切强度或粘结强度,升高丙烯酸PSA的Tg,而这是不希望的。
交联剂
为了提高丙烯酸压敏粘合剂的剪切强度或粘结强度,通常在PSA中加入交联添加剂。一般常用两种类型的交联添加剂。第一类交联添加剂是热交联添加剂,如多官能氮丙啶。一个例子是1,1’-(1,3-苯二羰基)-二(2-甲基氮丙啶)(CASNo.7652-64-4),在此称作“双酰胺”。聚合后在基于溶剂的PSA中加入这样的化学交联剂,并由在炉内干燥涂布后粘合剂期间由热活化该交联剂。
在另一个技术方案中,使用有赖于自由基来进行交联反应的化学交联剂。如过氧化物的试剂可用作自由基的前体来源。当充分加热时,这些前体会产生自由基,导致聚合物链上的交联反应。常用的产生自由基的试剂是过氧化苯甲酰。仅需要少量的自由基产生剂,但完成交联反应需要的温度一般要比双酰胺试剂高。
第二类化学交联剂是光敏交联剂,需通过高密度紫外光(UV)活化。用于热熔丙烯酸PSA的两种常用的光敏交联剂是二苯酮和可共聚到PSA聚合物中的4-丙烯酰氧二苯酮。另一种光交联剂是三嗪,它可以后加入到聚合物溶液,并由紫外光活化,例子有2,4-二(三氯甲基)-6-(4-甲氧基-苯基)-s-三嗪。这些交联剂可由人工光源,如中压汞灯产生的UV光活化。根据交联剂类型,化学交联剂的量一般不超过约0.5%重量就能达到要求的交联。
除了使用热交联剂或光敏交联剂,还可以采用高能电磁辐照,如γ辐照或电子束辐照达到交联。
也可以采用物理交联剂。在一个技术方案中,物理交联剂是高Tg的macromer,如基于聚苯乙烯和聚甲基丙烯酸甲酯的那些,其用量为每100重量份干粘合剂,约2-6重量份交联剂。
据报道二异氰酸酯也可作为基于丙烯酸共聚物粘合剂的交联剂。
其它添加剂由于丙烯酸压敏粘合剂具有优良的氧化稳定性,所以一般不需要诸如抗氧化剂和UV光吸收剂的添加剂。与之不同,基于橡胶的PSA一般要包括这些添加剂。
在热熔丙烯酸PSA中可使用少量热稳定剂(约小于0.3%重量),以提高加工期间的热稳定性。
尽管不作要求,但是在一些具体的应用中,可以使用填料(粘土)或色剂(TiO2或炭黑)作为添加剂,赋予粘合剂不透明性和色泽,或使粘合剂体系更便宜。背衬
在本发明的一个技术方案中,使用增塑的柔性聚氯乙烯膜,来构成装饰膜、标签或图案印标膜。改性的聚氯乙烯膜有益于可破坏型或抗破坏型标签或图案印标膜。通过降低PVC膜配方中增塑剂量和加入一种丙烯酸甲酯/丙烯酸丁酯的共聚物树脂(ElvaciteTM2013,可从Imperial Chemical Industries,Wilmington,DE获得),使这种膜成为“脆性”或“可撕裂”的。通过流延有机溶胶溶液,或通过压延可挤出的PVC树脂,制造这些膜。
其它有兴趣的背衬包括但不限于:聚酯、聚烯烃、纸、箔、聚丙烯酸酯、聚氨酯、全氟聚合物、聚碳酸酯、乙烯乙酸乙烯酯等。还有包括乙烯基膜背衬、纺织或无纺片材、纺织或无纺织物、纸和逆向反射片材。
增塑剂
用于本发明的增塑剂可选自很宽范围内的各种可购得的材料。代表性的增塑剂列于表III。
表III
丙烯酸PSA增塑剂 | |||
公司 | 商品名称 | 化学类 | 化学名称 |
ICIAmericasMonsantoMonsantoMonsantoMonsantoAkzo NobelVelsicolVelsicolRhone-PoulencSartomerSartomer | Pycal 94Santicizer 97Santicizer 141Santicizer 154DOAKetienflex 8Benzoflex 9-88Benzoflex P-200Alkapol SQR-490Sartomer 660(Cryoflex)Sartomer 650(Wareflex) | 聚环氧乙烷己二酸酯磷酸酯磷酸酯己二酸酯磺酰胺苯甲酸酯苯甲酸酯聚环氧丙烷甲酸酯己二酸酯 | 聚氧乙烯芳基醚己二酸二烷酯磷酸2-乙基己基二苯酯磷酸叔丁基苯基二苯酯己二酸二(2-乙基己基)酯甲苯磺酰胺二丙二醇二苯甲酸酯聚乙二醇二苯甲酸酯聚氧丙烯芳基醚二丁氧基乙氧基乙基缩甲醛己二酸二丁氧基乙氧基乙酯 |
在每种情况下,加入的增塑剂必须与配方中使用的丙烯酸PSA相容。PSA配方中加入的增塑剂的量取决于粘合剂的分子量。最好使用最小量的增塑剂。具体而言,本发明的一个特征就是达到提高了基材粘合特性,又不丧失粘结强度或剪切强度性能。一般在每100份粘合剂中可加入多达约10重量份的增塑剂,对高分子量(Mw约大于1×106)的粘合剂不会损害粘结强度。在较低分子量(Mw约小于3×105)情况,每100份粘合剂需要的增塑剂不超过5重量份。
制备增塑的丙烯酸PSA的方法
在粘合剂配制过程的多个点都可以在丙烯酸压敏粘合剂中加入增塑剂。例如,可以在聚合前或紧随聚合之后,在丙烯酸共聚物或三元共聚物溶液中加入增塑剂,增塑剂也可以在涂布时掺合到热熔丙烯酸PSA的熔体中,还可以加入到紫外光聚合或热聚合的丙烯酸酯PSA的单体浆料中,或加入到水基的丙烯酸酯PSA乳状液中。
对这些方法,优选增塑剂能与丙烯酸酯PSA或其溶液混溶,能溶于存在的任何溶剂,在热熔应用中为热稳定的,基本上不会干扰聚合反应或交联过程,并能与水基的粘合剂配方中的丙烯酸酯PSA一起形成稳定的乳状液。
本发明特别可应用于图案印标膜和标签的乙烯基膜。在一个技术方案中,乙烯基膜可以是一种可延性聚氯乙烯背衬,用于装饰性标签和图案印标膜。如上所指出的,还可以制备抗擅自移动性的乙烯基膜。这样的抗擅自移动性膜特别可应用于警告性、指示性或安全的标签,当移动时破碎,使标签难以或不能揭去。
图1所示为典型的膜结构,图1中的膜10包括一膜层12,如2密尔(0.05毫米)厚的乙烯基/丙烯酸酯膜,在膜的一个表面涂布了丙烯酸PSA14。剥离衬料16,如涂布硅的纸或膜,粘合到PSA上,直到膜准备粘合到一个表面上。
通过用60T微孔钢尺模切膜层12,使膜成为抗擅自移动性。赋予该膜的“微观粗糙”边缘增强了它的“撕裂”或“破碎”特性。
图1中所绘的这类膜可施用到低能的塑料表面,如高密度聚丙烯(HDPP)和高密度聚乙烯(HDPE)部件上。这样的部件在许多户外应用中有用,户外应用包括但不限于草坪和花园设备、娱乐车、各种地形的车辆、摩托雪橇、摩托车和水运工具。具体的部件包括但不限于盖、蓬和防护板,这些部件用膜装饰,形成乙烯基的图案印标膜、警告用标签和指示用标签。
对本发明的膜,在约90英寸(230厘米)/分钟的中等剥离速度下测定的剥离附着力应大于4磅/英寸(18牛顿/25毫米宽),以达到对高密度聚乙烯的足够粘合特性。要求按下面所述的PSTC-7静态剪切试验(1.6厘米2×1.6厘米2/1千克)测定的静负载剪切性能(dead load shear performance)为10,000分钟或更大。但是,对乙烯基图案印标膜或标签膜施用到上述部件的应用,不要求达到这一水平的全负荷剪切性能。但是最好PSA有足够的粘合强度,以抵抗收缩力,收缩力是由施用了粘合剂的图案印标膜或标签膜引起的。
实施例
试验方案
1.
180°剥离附着力PSTC-1:根据压敏带评议会(PSTC)的试验标准,将1英寸(2.54厘米)宽涂布了PSA的2密尔(0.05毫米)厚乙烯基膜带层叠在高密度聚乙烯试验样板上。该试验样品用标准的2密尔乙烯膜背衬来加固。使该施用后的试验样品在72°F(22℃)和约50%相对湿度下平衡约24小时。然后使用Lloyd,Instron或IMASS剥离试验仪,在约12或90英寸(30或230厘米)/分钟的速度下,以180°的角度剥离该试验样品。以磅/英寸宽或千克/2.54厘米宽报道剥离附着力测定结果。
2.
静态剪切PSTC-7:将1/2英寸2(1.6厘米2)的涂布PSA样品的刚性箔或聚酯膜层叠在#304不锈钢上,试验固定力或粘结强度。在施用1千克重物之前,使该样品在约72°F(22℃)和约50%相对湿度下平衡约24小时。在约72°F(22℃)和约50%相对湿度条件下进行试验。记录断裂的时间,即样品与样板分离时的时间(分钟)。还记录断裂的机理,可能是“爆脱”,其中没有粘合剂残余物留在样板或背衬上,或是“内聚”,其中粘合剂留在试验样板和试验样品上。
3.
膜收缩:该试验是额外的试验,用于测定内附着力或剪切强度。它与产品的实际使用条件直接相关。该试验测定PSA“把乙烯基膜固定在原地”的能力或抵抗乙烯基膜引起的收缩力的能力。将
英寸(6.35厘米)×4英寸(10.2厘米)涂布了PSA的乙烯基膜样品施用到一块铝板上。用薄剃刀片在横向和纵向剖切施用后的乙烯基膜样品,使样品处于150°F(65.6℃)下定型24小时。以千分之一英寸(密尔)剃刀切口扩增值记录测定值。对于具有差的内强度或内聚强度的粘合剂剃刀切口趋于分开或加宽。一般10密尔或更大的裂缝开口表明该PSA的剪切强度差,而具有优良的剪切强度或内聚强度的粘合剂则显示小的裂缝开口,小于10密尔,能将乙烯基膜固定在位。实施例1-溶液流延样品
配制用于低能表面的压敏丙烯酸粘合剂,方法为在100份(固体)高分子量(Mw大于1×106)的93/7丙烯酸异辛酯/丙烯酸(IOA/AA)共聚物溶液(乙酸乙酯中25%的固体)中加入20份Foral、10份Hercolyn-D和10份Pycal94。向该配方中,每100份粘合剂(甲苯中5%的溶液)加入0.6份双酰胺交联剂。该溶液混合1分钟并再摇晃1小时,减少空气夹带。将粘合剂组合物涂布在硅氧烷剥离衬料上,然后在200°F(93.3℃)烘箱内干燥5分钟。达到0.6克/24英寸2(155厘米2)的涂层重量的目标。
将这一实施例涂布的压敏粘合剂层叠到各种膜上,制备标签和图案印标膜。在一个技术方案中,膜是聚氯乙烯膜,该膜由于存在一种与PVC相容的增塑剂而成为柔性,或当其含有与PVC相容的增塑剂和共聚物树脂(如丙烯酸甲酯/丙烯酸丁酯共聚物树脂)时,为脆性可破坏的聚氯乙烯膜。实施例2-热熔样品
用有100重量份低分子量(Mw小于3×105)的95/5/0.4的丙烯酸异辛酯/丙烯酸/4-丙烯酰氧二苯酮的三元共聚物、15重量份Foral85、5重量份Hercolyn-D和5重量份Pycal94的组合物配制的粘合剂,制备涂布压敏丙烯酸粘合剂的用于低能表面的乙烯基图案印标膜。
该配方物热熔涂布在硅氧烷剥离衬料上,涂层重量为0.6克/24英寸2(155厘米2),并经525mj/cm2UV光辐照(国立标准和技术研究所,根据EIT和MIL-STD45662A)。按实施例1中所述制备涂布压敏粘合剂的乙烯基膜。性能数据
图2中的数据显示了增粘剂和增塑剂对高密度聚乙烯塑料的剥离附着力的作用。当用Pycal94增塑剂配制增粘的压敏粘合剂时,达到了以30厘米/分钟的剥离速度,大于17牛顿/25毫米宽的180°剥离附着力值。对剥离速度增加至230厘米/分钟,Pycal94增塑的PSA显示剥离附着力大于20牛顿/25毫米宽。这些结果的独特之处在于观察到了用Pycal94增塑的增粘丙烯酸PSA的最高剥离附着力。在230厘米/分钟的快剥离速度下,在高密度聚乙烯上的180°剥离附着力的差别,对Pycal94改性的各种丙烯酸粘合剂较之那些没有增塑剂的粘合剂更大。
内粘合强度是另一个重要的性能特性。在用丙烯酸PSA涂布的乙烯基图案膜或移画印花图案的应用中,粘合剂必须有足够的内强度,抵御乙烯基固有的收缩倾向。最常采用的测定粘合强度的方法为如PSTC-7中所述的静荷载或静态剪切试验。测定粘合强度的另一种方法是测定涂布PSA的乙烯基膜的膜收缩度。
图3数据显示了向增粘的PSA中加入Pycal94如何影响膜的收缩性。Pycal94加入PSA配方中确实引起了膜收缩性的少量改变。但是,这种轻微的改变在PSA涂布的乙烯基的总性能上是可以忽略的。
表IV中的数据显示使用不同类型的增塑剂可以达到要求的性能特性。这些数据包括对高密度聚乙烯的180°剥离附着力、用或没有用含丝网印刷油墨的溶剂的膜收缩度测定值、静态剪切值。这些数据表明不同类型的增塑剂,当加入到PSA配方中,在高密度聚乙烯上显示超过15牛顿/25毫米宽的剥离附着力,同时保持小于0.25毫米的膜收缩性能。
对用溶剂油墨印刷的涂布PSA的乙烯基膜的收缩度测定值也列于表IV。涂布PSA的乙烯基膜的抵御溶剂油墨印刷对膜的收缩作用的能力对产品是一个很重要的性能。一般地,用溶剂油墨印刷的涂布PSA的乙烯基膜的膜收缩值是未经丝网印刷的涂布PSA的乙烯基膜的两倍。表IV中,在膜收缩的3900溶剂油墨一栏,膜涂布了丝网印刷油墨和一层透明涂料。该方法的第一步,用225目的聚酯丝网,将黑色溶剂油墨(ScotchcalTM3905,可从3M获得)丝网印刷到膜上。印刷后的膜在强制通风的烘箱内,在150°F(66℃)干燥1小时。该方法的第二步,用同样的丝网在印刷了黑色的膜上再涂布一层透明涂料(ScotchcalTM3920,可从3M获得),并在150°F(66℃)再干燥1小时。
表IV中的静态剪切数据与膜收缩试验结果相关。小于10,000分钟剪切的那些增塑PSA样品显示内聚合或内附着力的失败。在1.6厘米2面积的样品上用1000克重物,在23℃进行这些测定。表IV还给出具有高的膜收缩或低的静态剪切值的增塑剂。尽管希望不受任何特定理论的限制,仍可以指出那些增塑剂与丙烯酸PSA的不相容性。
总之,表IV和图2和3中的数据表明,加入增粘剂和特定的增塑剂可以达到提高对低能表面(如高密度聚乙烯)的剥离附着力,而不必损害内粘合强度。
表IV
有15份Foral85和5份Hercolyn-D增粘剂的95/5/0.4的IOA/AA/ABP聚合物 | |||||
增塑剂 | 180°剥离附着力(牛顿/25毫米) | 膜收缩(毫米) | 在23℃的静态剪切(分钟) | ||
30厘米/分钟 | 230厘米/分钟 | 无油墨 | 3900溶剂油墨 | 底涂铬的铝 | |
5.0%Pycal 94 | 19.8 | 22.9 | 0.150 | 0.250 | 10,000+ |
5.0%Santicizer 97 | 11.0 | 19.4 | 0.175 | 10,000+ | |
5.0%Santicizer 141 | 15.4 | 21.6 | 0.175 | 0.250 | 10,000+ |
5.0%Santicizer 154 | 16.3 | 21.6 | 0.175 | 0.275 | 10,000+ 爆脱 |
5.0%DOA | 12.3 | 0.0 | 0.175 | 0.275 | 10,000+ |
5.0%Ketjenflex 8 | 16.7 | 18.0 | 0.250 | 0.650 | 80 内聚 |
5.0%Benzoflex P-200 | 15.4 | 21.6 | 0.175 | 0.325 | 1,500 内聚 |
5.0%Benzoflex 9-88 | 15.4 | 21.1 | 0.175 | 0.375 | 90 内聚 |
5.0%Alkopol SQR-490 | 17.2 | 20.2 | 0.200 | 0.300 | 10,000 爆脱 |
5.0%Sartomer 660 | 14.1 | 22.0 | 0.200 | 0.325 | 10,000+ |
5.0%Sartomer 650 | 12.3 | 20.7 | 0.150 | 0.300 | 10,000+ |
下面表V中的数据表示用增塑剂改性,以提高对低能塑料的附着力的PSA共聚物和三元共聚物的广泛范围。试验了由丙烯酸异辛酯/丙烯酸(IOA/AA)共聚物、丙烯酸2-甲基丁酯/丙烯酸(2-MBA/AA)共聚物、丙烯酸2-甲基丁酯/丙烯酰胺(2-MBA/Acm)共聚物、丙烯酸异辛酯/丙烯酸甲酯/丙烯酸(IOA/MA/AA)三元共聚物、丙烯酸异辛酯/丙烯酸异冰片酯/丙烯酸三元共聚物(IOA/IBA/AA)构成的压敏粘合剂。由整体溶液聚合制得压敏粘合剂配方1-14。配方15由无溶剂的紫外光聚合制得。由GPC测定平均分子量(Mw)。在PSA配制中使用了各种增粘剂和交联方法。
在PSA中加入Pycal94增塑剂时,对高密度聚乙烯的180°剥离附着力提高了。例如,在100份由96份丙烯酸2-甲基丁酯和4份丙烯酰胺组成的共聚物中加入5份Pycal94,在230厘米/分钟剥离速度下,对高密度聚乙烯基材的附着力从2.2牛顿/25毫米宽提高到6.6牛顿/25毫米宽。在100份由76份丙烯酸异辛酯、21.5份丙烯酸异冰片酯和2.5份丙烯酸组成的三元共聚物粘合剂中加入7.5份Pycal94,在30厘米/分钟剥离速度下,剥离附着力从4.4牛顿/25毫米宽提高到17.2牛顿/25毫米宽。
对本领域的技术人员来说,对本发明可以做出各种修改和变化而不背离本发明的范围和精神。应理解本发明不受在此提出的说明性技术方案和实施例的限制,举例方式提出的这些实施例和技术方案,仅由下面提出的权利要求书限制本
发明的范围。
表V
PSA配方100份 | 交联剂 | 增粘剂份 | 增塑剂份 | Mw | 180°剥离附着力(牛顿/25毫米) | 膜收缩(毫米)无油墨 | ||
30厘米/分钟 | 230厘米/分钟 | |||||||
1 | 98/2IOa/AA | 0.6%氮丙啶 | 25Foral85 | 5 Pycal94 | 1×106 | 17.2 | 20.7 | 0.350 |
2 | 95/5IOA/AA | 0.3%ABP | 11Regalrez6108 | 5 Pycal94 | 2×105 | 13.2 | 0.125 | |
3 | 95/5IOA/AA | 0.4%ABP | 15Foral85/5Hercolyn-D | 5 Pycal94 | 2×105 | 19.8 | 22.9 | 0.200 |
4 | 93/7IOA/AA | 0.6%氮丙啶 | 25ECR-180/10Hercolyn-D | 10 Pycal94 | 1×106 | 15.0 | 23.3 | 0.075 |
5 | 94/6IOA/AA | 1.5%氮丙啶 | 12Nirez2019/7.5Unitac70 | 11 Pycal94 | 5×105 | 20.2 | 0.150 | |
6 | 90/102-MBA/AA | 1.1%氮丙啶 | 无 | 无 | 5×105 | 2.2 | 0.9 | 0.125 |
7 | 90/102-MBA/AA | 1.1%氮丙啶 | 无 | 5 Pycal94 | 5×105 | 11.0 | 2.2 | 0.150 |
8 | 96/42-MBA/Acm | 0.2%ABP | 无 | 无 | 2×105 | 7.9 | 2.2 | 0.175 |
9 | 96/42-MBA/Acm | 0.2%ABP | 无 | 5 Pycal94 | 2×105 | 10.6 | 6.6 | 0.300 |
10 | 76/21.5/2.5IOA/IBA/AA | 0.6%氮丙啶 | 20Regalrez6108 | 无 | 1×106 | 4.4 | 2.2 | 0.100 |
11 | 76/21.5/2.5IOA/IBA/AA | 0.6%氮丙啶 | 20Foral85 | 7.5 Pycal94 | 1×106 | 17.2 | 17.6 | 0.150 |
12 | 76/21.5/2.5IOA/IBA/AA | 0.6%氮丙啶 | 20Regalrez6108 | 7.5 Pycal94 | 1×106 | 17.2 | 3.5 | 0.125 |
13 | 70/22.5/7.5IOA/MA/AA | 0.15%ABP | 无 | 5 Pycal94 | 2×105 | 13.6 | 11.0 | 0.200 |
14 | 85/10/5IOA/MA/AA | 0.4%ABP | 15Foral/5Hercolyn-D | 5 Pycal94 | 2×105 | 19.4 | 23.3 | 0.125 |
15 | 90/10IOA/AA | 0.2%三嗪 | 无 | 4Santicizer141 | 1.5×106 | 6.6 | 0.250 |
Claims (18)
1.一种丙烯酸压敏粘合剂,它包括:
a)100重量份丙烯酸共聚物,所述的丙烯酸共聚物包括70-98%重量的一种或多种有1-14个碳原子的伯烷基或仲烷基的丙烯酸酯,和30-2%重量的极性单体;
b)10-40重量份的增粘剂;
c)3-10重量份的增塑剂;和
d)任选的交联剂。
2.如权利要求1所述的丙烯酸压敏粘合剂,其特征还在于所述丙烯酸酯选自烷基有1-14个碳原子的烯不饱和的丙烯酸烷基酯。
3.如权利要求1所述的丙烯酸压敏粘合剂,其特征还在于所述极性单体选自烯不饱和的羧酸和丙烯酰胺。
4.如权利要求1所述的丙烯酸压敏粘合剂,其特征还在于所述增粘剂选自萜烯酚醛、松香、松香酯、氢化松香酯、合成烃树脂以及它们的组合。
5.如权利要求1所述的丙烯酸压敏粘合剂,其特征还在于所述增塑剂选自聚乙二醇醚、聚环氧乙烷、磷酸酯、脂族羧酸酯、苯甲酸酯、以及它们的组合。
6.如权利要求1所述的丙烯酸压敏粘合剂,其特征还在于所述增塑剂选自磺酰胺、芳族羧酸酯以及它们的组合。
7.一种适用于临界表面张力小于14达因/厘米2的低能表面的粘合剂膜,它包括:
a)聚合物背衬;和
b)施用到聚合物背衬表面上的压敏粘合剂,该压敏粘合剂包括:
i)100重量份丙烯酸共聚物,所述的丙烯酸共聚物包括70-98%重量的一种或多种有1-14个碳原子的伯烷基或仲烷基的丙烯酸酯,和30-2%重量的极性单体;
ii)10-40重量份的增粘剂;
iii)3-10重量份的增塑剂;和
iv)任选的交联剂。
8.如权利要求7所述的粘合剂膜,其特征还在于聚合物背衬包括选自乙烯基膜、纺织和无纺片材、纺织和无纺织物、纸和逆向反射片材的材料。
9.如权利要求7所述的粘合剂膜,其特征还在于所述丙烯酸酯选自烷基有1-14个碳原子的烯不饱和的丙烯酸烷基酯。
10.如权利要求7所述的粘合剂膜,其特征还在于所述极性单体选自烯不饱和的羧酸和丙烯酰胺。
11.如权利要求7所述的粘合剂膜,其特征还在于所述增粘剂选自萜烯酚醛、松香、松香酯、氢化松香酯、合成烃树脂以及它们的组合。
12.如权利要求7所述的粘合剂膜,其特征还在于所述增塑剂选自聚乙二醇醚、聚环氧乙烷、磷酸酯、脂族羧酸酯、苯甲酸酯、以及它们的组合。
13.如权利要求7所述的粘合剂膜,其特征还在于所述增塑剂选自磺酰胺、芳族羧酸酯以及它们的组合。
14.如权利要求7所述的粘合剂膜,其特征在于它还包括剥离衬料。
15.一种由权利要求7所述的粘合剂膜形成的并具有可视表面的图案印标或标签,其中的可视表面能传递信息或提供装饰。
16.一种由权利要求7所述的粘合剂膜形成的并有可视表面的图案印标或标签,它具有微观粗糙的边缘。
17.一种制备如权利要求1所述的粘合剂的方法,该方法包括下面的步骤:
a)热熔涂布该粘合剂;和
b)用紫外光固化该粘合剂。
18.一种制备如权利要求1所述的粘合剂的方法,该方法包括下面的步骤:
a)流延该粘合剂的浆料;和
b)用紫外光固化该粘合剂。
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US60698896A | 1996-02-26 | 1996-02-26 | |
US08/606,988 | 1996-02-26 | ||
US08/664,730 | 1996-06-17 | ||
US08/664,730 US5874143A (en) | 1996-02-26 | 1996-06-17 | Pressure sensitive adhesives for use on low energy surfaces |
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- 1996-06-17 US US08/664,730 patent/US5874143A/en not_active Expired - Lifetime
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1997
- 1997-01-16 WO PCT/US1997/000609 patent/WO1997031076A1/en active IP Right Grant
- 1997-01-16 DK DK97902032T patent/DK0932654T3/da active
- 1997-01-16 EP EP97902032A patent/EP0932654B1/en not_active Expired - Lifetime
- 1997-01-16 DE DE69722021T patent/DE69722021T2/de not_active Expired - Lifetime
- 1997-01-16 JP JP53014597A patent/JP4035636B2/ja not_active Expired - Lifetime
- 1997-01-16 CN CNB971925429A patent/CN1141351C/zh not_active Expired - Lifetime
- 1997-01-16 BR BR9707681A patent/BR9707681A/pt active Search and Examination
- 1997-01-16 ES ES97902032T patent/ES2193350T3/es not_active Expired - Lifetime
- 1997-01-16 AU AU15795/97A patent/AU717994B2/en not_active Ceased
- 1997-01-16 KR KR1019980706513A patent/KR100484048B1/ko not_active IP Right Cessation
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1999
- 1999-02-12 US US09/248,946 patent/US6280557B1/en not_active Expired - Lifetime
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- 2001-01-23 US US09/767,533 patent/US6582791B2/en not_active Expired - Lifetime
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CN101687560B (zh) * | 2007-06-29 | 2013-03-06 | 汉高两合股份公司 | 具有水溶性紫外光固化粘合剂的标签 |
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US6582791B2 (en) | 2003-06-24 |
DK0932654T3 (da) | 2003-09-15 |
US6280557B1 (en) | 2001-08-28 |
JP4035636B2 (ja) | 2008-01-23 |
KR19990087122A (ko) | 1999-12-15 |
AU1579597A (en) | 1997-09-10 |
AU717994B2 (en) | 2000-04-06 |
EP0932654A1 (en) | 1999-08-04 |
JP2000513390A (ja) | 2000-10-10 |
CN1212007A (zh) | 1999-03-24 |
DE69722021D1 (de) | 2003-06-18 |
BR9707681A (pt) | 1999-07-27 |
EP0932654B1 (en) | 2003-05-14 |
ES2193350T3 (es) | 2003-11-01 |
US5874143A (en) | 1999-02-23 |
KR100484048B1 (ko) | 2006-01-27 |
US20010012551A1 (en) | 2001-08-09 |
DE69722021T2 (de) | 2004-04-01 |
WO1997031076A1 (en) | 1997-08-28 |
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