CN101098943B - 具有光吸收性能的用于生产液晶显示器或将其粘合在一起的双面压敏胶带 - Google Patents
具有光吸收性能的用于生产液晶显示器或将其粘合在一起的双面压敏胶带 Download PDFInfo
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Abstract
本发明涉及一种压敏胶带,特别是用于光学液晶数据显示器(LCD)生产或将其粘合在一起的胶带,其包含顶面和底面。所述压敏胶带还包含具有顶面和底面的载体膜,以及该压敏胶带在顶面和底面上都配备有压敏胶粘剂层。所述压敏胶带的特征在于所述载体膜具有小于4000ppm的抗粘连剂含量,以及在所述载体膜与压敏胶粘剂层之间配备至少一个光吸收发色层。
Description
本发明涉及具有多层载体结构以及具有光吸收性能的双面压敏胶带,特别是用于生产或粘合液晶显示器的双面压敏胶带。
工业化时代中,压敏胶带是普遍使用的加工辅件。特别是在计算机工业中的应用,对压敏胶带提出了非常严格的要求。具有低除气性的同时,压敏胶带应当适合于应用在宽的温度范围内以及应当满足一定的光学性能。
应用领域之一是计算机、电视、膝上型电脑、PDAs、手机、数字照相机等需要的液晶显示器领域。这类应用的一种非常普遍的LCD模块示于图1中。
该领域中,在液晶显示器各处非常频繁地使用隔离带(spacer taps),所述隔离带具有光吸收功能。一方面意图避免来自外部的光线落到显示器上。另一方面意图阻止来自液晶显示器光源的光线穿透到外部。图1示意性地显示用于光吸收的双面黑色胶带的原理;标号的定义如下:
1 LCD玻璃
2 双面黑色胶带
3 压敏胶粘剂
4 光源(LED)
5 光束
6 双面胶带
7 光波导
8 反射膜
9 LCD框架
10 可见区
11 “盲”区
目前,该工业中存在着具有更高分辨率的更轻组件以及日益更大的液晶显示器(LC显示器,LCDs)的趋势。更强和日益更有效的光源也与该趋势有联系,其又对胶带的光吸收性能提出更高的要求。
一般而言,目前将黑色双面胶带用于该应用。对于这些胶带及其所需载体的制备,存在众多方法。
制备黑色双面压敏胶带的一种方法在于载体材料的着色。在电子工业中,由于其很好的可冲切性,非常优选使用具有PET载体的双面压敏胶带。为了实现光吸收,可以使PET载体用炭黑或其他黑色颜料着色。这类体系目前例如作为tesaTM 51965可购得。该现有方法的缺点在于光吸收水平低。在很薄的载体层中,可能仅仅混入相对少量的炭黑或其他黑色颜料的颗粒,结果光的吸收不完全。用眼观察,以及在相对强的光源下(在大于600堪的亮度下),则可以确定不足的吸收。
制备黑色双面压敏胶带的另一方法涉及借助于共挤出制备双层或多层载体材料。载体膜一般通过挤出制成。作为共挤出的结果,与常规的载体膜一起,共挤出第二层以及任选的第三层黑色层,实现光吸收的功能。该方法也具有多种缺点。例如,为了挤出必须使用抗粘连剂,其在产物中造成称作针孔的情况。这些针孔是光学点缺陷(光穿过这些孔)而且不利地影响LCD的机能。
粘连是指聚合物膜等等的不受欢迎的特性,该特性为在一定温度(粘连温度)以上即使是仅在轻的压力下也会彼此粘住。用抗粘连剂(防粘连剂,防粘剂)抑制粘连。
因此,抗粘连剂是这样的物质,其减少或防止例如热塑性聚合物膜自身或者与其他材料由于冷流或静电充电的粘连。
对于例如PET膜的生产操作,所用的抗粘连剂通常是例如二氧化硅(如二氧化硅颗粒)、含硅白垩(siliceous chalk)或其他白垩、以及沸石。
抗粘连剂意欲阻止片状聚合物膜在压力和温度下焙烧在一起(bakingtogether)而结块。通常将抗粘连剂加入到热塑性混合物中。该颗粒则作为隔离物起作用。
层厚度造成另外的问题,因为两层或三层首先在模具中独立地成型,因此总的说来可能只是获得相对较厚的载体层,结果膜变得相对较厚和不易弯曲,因此其对于有待粘合的表面的顺应性差。此外,黑色层同样必须相对较厚,因为否则不可能实现完全的吸收。另一缺点在于载体材料被改变的机械性能,共挤出至少一层黑色层,因为该黑色层的机械性能与初始载体材料(如纯PET)的机械性能不同。双层形式的载体材料的另一缺点在于胶粘剂对共挤出载体材料的锚固上的差异。在这种情况下,双面胶带中总是存在薄弱点。
另一种方法中,将黑色着色的涂层涂布到载体材料的一面或两面上。该涂布可以在该载体上单面或双面地进行。该方法也有多种缺点。一方面,这里也容易形成缺陷(针孔),其在膜挤出操作期间由抗粘连剂引起,而且不能被覆盖。对于在液晶显示器中的应用,这些针孔是不能接受的。此外,最大吸收性能不符合要求,因为可能只是施加相对较薄的涂膜。这里同样地,对于层厚度存在上限,因为否则载体材料的机械性能会遭受改变。
在液晶显示器的开发中有着一种发展趋势。一方面,液晶显示器要变得更轻以及更扁平,而且对于分辨率不断提高的日益增大的显示器有着增加的需求。
为此,显示器的设计已经改变,因此光源与LCD面板靠得越来越近,结果越来越多的光从外部穿透到LCD面板边缘区域(“盲区”)中(参见图1)的风险增加。因此,在这种进展下,对双面胶带的遮掩性能(遮蔽性能)所提出的要求也在提高,由此需要新的方法制备黑色胶带。
JP 2002-350612描述了具有光防护性能的用于LCD面板的双面胶带。借助于施加在载体膜一面或两面上的金属层实现该功能,另外,载体膜也可以是已经着色的。然而,仅仅尝试用载体膜的双面金属化来补偿针孔的形成。该方法没有避免针孔本身。
JP 2002-023663同样描述了具有光防护性能的用于LCD面板的双面胶带。这里同样地,借助于施加在载体膜一面或两面上的金属层实现该功能。此外,该专利包括着色的胶粘剂。和JP 2002-350612类似,又是仅仅尝试借助于载体膜的双面金属化来补偿针孔的形成。
因此,对于LCD显示器的粘合以及对于其生产,仍然需要没有上述不足之处或者这些不足之处有所克服的双面PSA带。
本发明的目的在于提供一种双面压敏胶带,其中避免或降低在应用中点缺陷(针孔)的影响,以及能够完全吸收光线。
令人惊讶地已经发现,借助于适当的预处理,技术人员所无法预料地,含有抗粘连剂的膜适合作为用于制备下文所述类型的具有光吸收性能的特定双面压敏胶带的载体材料,这可以提高该最终用途的可达性,而且用这种方法得到的胶带出乎意料地相对现有技术具有所期望的优点。特别是,令人惊讶地,在光学性能方面没有注意到不利的影响。
因此本发明涉及压敏胶带,特别是用于光学液晶显示器(LCDs)粘合的那些,压敏胶带具有顶面和底面,压敏胶带进一步包含具有顶面和底面的载体膜,所述压敏胶带在所有情况下在所述顶面和底面上都配备有压敏胶粘剂层,以及所述载体膜具有小于4000ppm的抗粘连剂含量,以及所有情况下在所述载体膜与所述压敏胶粘剂层之间存在至少一层光吸收发色层。
所述压敏胶带本身由于该光吸收发色层而在两面上具有光吸收性能。
本发明意义上的抗粘连剂可以例如特别是硅石颗粒,然而还可以是例如其他二氧化硅、含硅白垩或其他白垩、或者沸石。
所述压敏胶粘剂层可以相同或者不同。
抗粘连剂的减少或完全排除可减少或消除潜在针孔缺陷的数目。这借助于<1000ppm、优选<500ppm以及非常优选0ppm的抗粘连剂含量以改进的方法实现。
所述载体膜优选4-250μm,更优选8-50μm,非常优选12-36μm厚。其优选是透明的或半透明的,或者例如由于着色而具有低的半透明度。
有利地,所用的载体膜在至少一面上经过粗糙化。在这种情况下优选的粗糙度为优选大于50nm以及小于400nm,特别是小于300nm。粗糙度可以例如借助于AFM(原子力显微术)确定。因此该粗糙度数据理解为RMS粗糙度。按照本发明更有利地,可以使所述膜在两面上粗糙化,在该情况下任一面或者两面可以显示出上述的有利粗糙度值。
在本发明的有利实施方案中,可以在载体膜一面上配备金属反射层(金属闪光和反光)。在更有利的设计中,在载体膜的两面上配备金属反射层。所述金属反射层优选是金属涂层。在本发明的一种优选形式中,载体膜在两面上带有气相沉积的金属,例如铝或银,该金属特别有利地通过阴极雾化涂布工艺(溅射)施加。金属反射层的厚度优选是5nm-200nm。
发色层尤其是在所有情况下层厚度优选为0.01-5μm的涂膜。除第一发色层以外,在胶带的两面上可以有更多的发色层。该情况下,这些层同样有利地是上述厚度的涂膜。在一种非常优选的形式中,所述发色层中的至少一个是黑色,特别地最外面的发色层是黑色。所述发色层可以在其化学性质上有差异以及可以包含不同的发色颜料,对于光吸收性能而言这具有有利的结果。
在所有情况下PSA层优选具有5μm-250μm的厚度。本发明的另一部分在于所述双面PSA带内各层的独立层厚度的选择,以及因此可以例如施加厚度不同的PSA层。
下面,意欲突出本发明PSA带的某些有利的实施方案(图2至5),不希望由于所述实例的选择而强加任何不必要的限制。
图中的标记具有下列含义:
(a)载体膜层
(b)金属反射层
(c)(第一)发色层
(c’)另外的发色层
(d)PSA层
(d’)PSA层
在本发明第一个有利的实施方案中,在载体膜在两面上配备金属涂层。此类PSA带经由图2中的实例显示。本发明的PSA带由下列层组成:含有减少的抗粘连剂含量或不含抗粘连剂的载体膜层(a),两个金属反射层(b),发色层(c),以及两个PSA层(d)和(d’),所述PSAs可以彼此相同或不同。
在本发明的另一优选实施方案中,本发明的PSA带具有图3所示的产品构造。
这里,该双面PSA带由下列层组成:具有减少的抗粘连剂含量或完全没有抗粘连剂的载体膜(a),两个金属反射层(b),一层覆盖在另一层上的至少两个发色层(c)和(c’),以及两个PSA层(d)和(d’),所述PSAs可以彼此相同或不同。
在本发明的另一优选实施方案中,本发明的PSA带具有符合图4的产品构造。
这里,该双面PSA带由下列层组成:具有减少的抗粘连剂含量或完全没有抗粘连剂的载体膜(a),仅在一面上存在的金属反射层(b),两个经涂布的发色层(c)和(c’),以及两个PSA层(d)和(d’),所述PSAs可以彼此相同或不同。
在本发明的另一有利的实施方案中,本发明的PSA带具有按照图5的产品构造。
这里,该双面PSA带由下列层组成:具有减少的抗粘连剂含量或完全没有抗粘连剂的载体膜(a),一个金属反射层(b),一层覆盖在另一层上的至少两个发色层(c)和(c’),以及两个PSA层(d)和(d’),所述PSAs可以彼此相同或不同。
下文将给出本发明PSA带的更详细的描述,不存在描述应当限于上述举例的实施方案的意图。
作为膜载体,原则上可以使用所有的膜状聚合物载体,特别有利的是透明的那些。因而可以例如使用聚乙烯、聚丙烯、聚酰亚胺、聚酯、聚酰胺、聚甲基丙烯酸酯、氟化的聚合物膜等。在一种特别优选的形式中,使用聚酯膜,更优选PET(聚对苯二甲酸乙二醇酯)膜。所述膜可以是松弛形式或者可以具有一个或多个优先方向(preferential directions)。优先方向通过在一个或两个方向上拉伸获得。
用于本发明PSA带的膜是抗粘连剂即便有的话含量也非常小的膜。这种膜的实例是例如来自Mitsubishi的HostaphanTM 5000系列聚酯膜(PET5211、PET 5333、PET 5210)。
特别地,对于非常薄的PET膜(例如厚12μm的膜)的制备,如果PET膜在两面上用金属涂布以及如果该膜不含抗粘连剂或含有显著减少的抗粘连剂含量的话,这是非常有利的。这里在避免针孔方面已经获得特别优良的结果。此外,12μm PET膜由于它们为双面胶带提供很好的粘合性能而是特别有利的,因为在这种情况下膜很柔软并且能够良好地适应于有待粘合的基材的表面粗糙度。
为了改善涂膜或气相沉积金属的锚固,预处理膜是非常有利的。所述膜可以进行蚀刻(如三氯乙酸或三氟乙酸)、电晕预处理或等离子体预处理、或涂布底漆(如Saran)。
此外,所述膜可以用彩色颜料或发色颗粒着色。例如,炭黑适合于黑色着色而二氧化钛颗粒适合于白色着色。然而,颜料或颗粒应当有利地在直径上总是小于载体膜最终的层厚度。基于所述膜材料,以5-40wt%颗粒含量可以获得最佳的着色。
特别地借助于用金属例如铝或银单面或双面气相沉积涂布所述膜,在该膜上产生反射层以及因此光吸收层。有利地将铝或银非常均匀地施加到膜上。金属层的使用具有防止或减少光透过载体材料的作用。另外可以补偿载体膜的表面粗糙度。
所述发色层可以实现多种功能。在本发明的一种有利形式中,彩色层具有完全吸收外部光线的功能。在这种情况下,双面PSA带在300-800nm波长范围内的透射率<0.5%,更优选<0.1%,非常优选<0.01%。在一种优选实施方案中,这是以黑色涂膜作为发色层而实现的。所述层优选由涂料基质(固化的粘结剂基质,优选热固性体系,然而也可以是辐射固化体系)组成,彩色颜料混入该涂料基质中。可以使用的涂料的实例包括聚酯类、聚氨酯类、聚丙烯酸酯类或聚甲基丙烯酸酯类,连同技术人员已知的涂料添加剂一起。在本发明一种非常优选的实施方案中,所述彩色颜料是黑色的;作为发色颗粒,优选将炭黑或石墨颗粒混入粘结剂基质中。在很高的添加水平(>20wt%)下,该添加具有不仅产生完全的光吸收而且另外产生导电性的效果,以至于本发明的双面PSA带同样具有抗静电性能。
为了增强优选作为发色层外侧的黑色层的吸收特性,另外的发色层、优选进一步向内部设置的发色层可以另外以白色颜料提供。适合的白色颜料优选是二氧化钛颜料。
在一种优选的实施方案中,本发明PSA带两面上的PSA层是相同的。然而,在一种特定的工艺中,所述PSA带顶面和底面上的PSAs在层厚度和/或化学组成方面相互有区别,这也可能是有利的。这样可以例如设定不同的压敏粘合性能。用于本发明的双面PSA带的PSA体系是丙烯酸酯、天然橡胶、合成橡胶、有机硅或EVA胶粘剂。然而原则上也可以使用技术人员已知的所有其他PSAs。
对于天然橡胶胶粘剂,将天然橡胶研磨至不低于约100 000道尔顿的分子量(重均分子量),优选不低于500 000道尔顿,并加入添加剂。
在橡胶/合成橡胶作为胶粘剂原材料的情况下,存在广泛的变化可能性。可以使用天然橡胶或合成橡胶,或者可以使用天然橡胶和/或合成橡胶的任何期望的共混物,按照所需的纯度等级和粘度等级,原则上可以从所有现有的等级中选择一种或几种天然橡胶,例如绉片、RSS、ADS、TSR或CV级,以及可以从无规共聚的苯乙烯-丁二烯橡胶(SBR)、丁二烯橡胶(BR)、合成聚异戊二烯(IR)、丁基橡胶(IIR)、卤代丁基橡胶(XIIR)、丙烯酸酯橡胶(ACM)、乙烯-乙酸乙烯酯共聚物(EVA)和聚氨酯和/或其共混物中选择一种或几种合成橡胶。
进一步优选地,为了改善橡胶的加工性能,可以向其中添加以弹性体总量计重量含量为10-50wt%的热塑性弹性体。作为代表,在这方面可以具体提及特别相容的苯乙烯-异戊二烯-苯乙烯(SIS)和苯乙烯-丁二烯-苯乙烯(SBS)类型。
在本发明的一种优选实施方案中,使用丙烯酸酯PSAs和/或甲基丙烯酸酯PSAs。
通过自由基加成聚合可获得的(甲基)丙烯酸酯PSAs包含至少50wt%来自下列通式化合物的至少一种丙烯酸系单体:
其中R1为H或CH3以及基团R2为H或CH3或者选自支化或未支化的具有1-30个碳原子的饱和烷基。
优选地选择单体以使得所得到的聚合物能够在室温或更高温度下用作PSAs,特别是使得所得到的聚合物具有压敏粘合性。
在另一本发明实施方案中,选择共聚单体组成以使得该PSAs能够用作可热活化的PSAs。
可以优选通过使单体混合物聚合获得聚合物,该单体混合物由丙烯酸酯和/或甲基丙烯酸酯和/或其游离酸组成,具有式CH2=CH(R1)(COOR2),其中R1为H或CH3以及R2为具有1-20个碳原子的烷基链或H。
所用聚丙烯酸酯的摩尔质量(重均)Mw优选达Mw≥200 000g/mol。
在一种非常优选的方案中,使用丙烯酸系或甲基丙烯酸系单体,其包括具有含4-14个碳原子、优选含4-9个碳原子的烷基的丙烯酸酯和甲基丙烯酸酯。不希望受该列举限制地,具体实例为丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸正戊基酯、丙烯酸正己基酯、丙烯酸正庚基酯、丙烯酸正辛基酯、甲基丙烯酸正辛基酯、丙烯酸正壬基酯、丙烯酸月桂酯、丙烯酸硬脂酯、丙烯酸二十二烷基酯,及其支化的异构体,例如丙烯酸异丁酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸异辛酯和甲基丙烯酸异辛酯。
可以使用的其他类化合物为由至少6个碳原子组成的桥联环烷基醇的单官能丙烯酸酯和/或甲基丙烯酸酯。该环烷基醇也可以被例如C-1-6烷基、卤素原子或氰基取代。具体实例为甲基丙烯酸环己基酯、丙烯酸异冰片基酯、甲基丙烯酸异冰片基酯和丙烯酸3,5-二甲基金刚烷基酯。
一种有利的方案中使用带有极性基团的单体,所述基团如羧基、磺酸和膦酸基、羟基、内酰胺和内酯、N-取代酰胺、N-取代胺、氨基甲酸酯、环氧、硫醇、烷氧基或氰基、醚等。
适度碱性的单体例如为N,N-二烷基-取代的酰胺,诸如N,N-二甲基丙烯酰胺、N,N-二甲基甲基丙烯酰胺、N-叔-丁基丙烯酰胺、N-乙烯基吡咯烷酮、N-乙烯基内酰胺、甲基丙烯酸二甲基氨基乙酯、丙烯酸二甲基氨基乙酯、甲基丙烯酸二乙基氨基乙酯、丙烯酸二乙基氨基乙酯、N-羟甲基甲基丙烯酰胺、N-(丁氧基甲基)甲基丙烯酰胺、N-羟甲基丙烯酰胺、N-(乙氧基甲基)丙烯酰胺、N-异丙基丙烯酰胺,该列举并非穷举。
其他优选的实例为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯、烯丙基醇、马来酸酐、衣康酸酐、衣康酸、甲基丙烯酸缩水甘油基酯(glyceridyl methacrylate)、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙基酯、甲基丙烯酸2-丁氧基乙酯、丙烯酸2-丁氧基乙酯、甲基丙烯酸氰基乙酯、丙烯酸氰基乙酯、甲基丙烯酸甘油酯、甲基丙烯酸6-羟基己基酯、乙烯基乙酸、丙烯酸四氢糠基酯、β-丙烯酰氧基丙酸、三氯代丙烯酸、富马酸、巴豆酸、乌头酸和二甲基丙烯酸,该列举并非穷举。
在一种进一步非常优选的方案中,使用乙烯基酯、乙烯基醚、乙烯基卤化物、亚乙烯基卤化物和α-位上具有芳环和杂环的乙烯基化合物作为单体。在此同样地,可以非排他性地提及一些实例:乙酸乙烯酯、乙烯基甲酰胺、乙烯基吡啶、乙基乙烯基醚、氯乙烯、偏二氯乙烯和丙烯腈。
此外,在有利的方案中,可以使用具有可共聚双键的光引发剂。适宜的光引发剂包括Norrish I和II光引发剂(Norrish I型反应:羰基化合物光裂解(α分裂)成酰基和烷基;Norrish II型反应:由光化学激发的羰基诱导的羰基γ位上氢原子的分子内抽取,产生双自由基,其可以分解成烯醇和链烯(β分裂)或者环化以形成环丁醇)。实例包括产自UCB(Ebecryl P 36)的丙烯酸酯化的二苯甲酮和苯偶姻丙烯酸酯。原则上可以使技术人员已知的而且能够在UV照射下通过自由基机理交联聚合物的任何光引发剂共聚。
在另一优选方案中,将所述共聚单体与静态玻璃化转变温度高的单体混合。适宜的组分包括芳族乙烯基化合物,例如苯乙烯,其中该芳基核优选由C4-C18单元构成以及还可以包含杂原子。特别优选的实例为4-乙烯基吡啶、N-乙烯基苯邻二甲酰亚胺、甲基苯乙烯、3,4-二甲氧基苯乙烯、4-乙烯基苯甲酸、丙烯酸苄基酯、甲基丙烯酸苄基酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸叔丁基苯酯、甲基丙烯酸叔丁基苯酯、丙烯酸4-联苯基酯、甲基丙烯酸4-联苯基酯、丙烯酸2-萘基酯、甲基丙烯酸2-萘基酯及这些单体的混合物,该列举并非穷举。
由于芳族化合物含量的增加,PSA的折射率提高。
为进一步改进,可以向PSA中混入树脂。作为添加的增粘树脂,可以使用本领域技术人员已知的增粘剂树脂。可以提及的代表包括蒎烯树脂、茚树脂和松香,它们的歧化、氢化、聚合和酯化衍生物及其盐,脂族和芳族烃树脂、萜烯树脂和萜烯-酚醛树脂,还包括C5、C9及其他烃树脂。为了按照要求调节所得胶粘剂的性能,可以使用这些以及其他树脂的任何所需的组合。通常来说,可以使用与所述聚丙烯酸酯相容(可溶)的任何树脂:具体地说,可以提及所有脂族、芳族和烷基芳族烃树脂、基于单一单体的烃树脂、氢化烃树脂、官能化烃树脂和天然树脂。
此处同样地,优选使用与聚合物高度相容的透明树脂来改善PSA的透明度。氢化或部分氢化的树脂往往具有这些性能。
另外,可以任选地添加增塑剂、其他填料(例如纤维、炭黑、氧化锌、白垩、实心或空心玻璃珠、其他材料制成的微珠、二氧化硅、硅酸盐)、成核剂、导电材料如共轭聚合物、掺杂的共轭聚合物、金属颜料、金属颗粒、金属盐、石墨等、膨胀剂、配合剂和/或防老化剂,该防老化剂是以例如主抗氧化剂和辅助抗氧化剂的形式或以光稳定剂的形式。
在本发明PSA带的另一实施方案中,所述PSA可以同样与例如作为填料的光吸收颗粒进行混合,如炭黑颜料或炭黑颗粒或石墨颗粒。
另外,可以混合交联剂和交联促进剂。用于电子束交联和UV交联的适宜的交联剂的实例包括双官能或多官能的丙烯酸酯、双官能或多官能的异氰酸酯(包括封端形式的那些)以及双官能或多官能的环氧化物。另外还可以加入可热活化的交联剂,如路易斯酸、金属螯合物或多官能异氰酸酯。
对于任选的用UV光的交联,可以向PSAs中添加吸收UV的光引发剂。其应用非常有效的可用光引发剂为苯偶姻醚、如苯偶姻甲基醚和苯偶姻异丙基醚,取代的苯乙酮、如2,2-二乙氧基苯乙酮(出自Ciba Geigy的Irgacure651)、2,2-二甲氧基-2-苯基-1-苯乙酮、二甲氧基羟基苯乙酮,取代的α-酮醇如2-甲氧基-2-羟基苯丙酮,芳族磺酰氯如2-萘基磺酰氯、以及光敏肟如1-苯基-1,2-丙烷二酮2-(O-乙氧羰基)肟。
上述光引发剂和可以使用的其他光引发剂,以及Norrish I或Norrish II型的其他光引发剂,可以有利地含有下列基团:二苯甲酮、苯乙酮、联苯酰、苯偶姻、羟基烷基苯酮、苯基环己基酮、蒽醌、三甲基苯甲酰膦氧化物、甲基苯硫基吗啉酮、氨基酮、偶氮苯偶姻、噻吨酮、六芳基双咪唑、三嗪、或芴酮,这些基团中的每一个都可以另外被一个或多个卤素原子和/或一个或多个烷氧基和/或一个或多个氨基或羟基所取代。
可以如下制备丙烯酸酯PSAs:
对于聚合而言,有利地选择单体以使得所得到的聚合物能够在室温或更高温度下用作PSAs。
按照以上的论述,为了获得PSAs中≤25℃的优选的聚合物玻璃化转变温度Tg,非常优选的是,选择单体以及有利地选择单体混合物的定量组成,以便获得所期望的聚合物Tg,其符合类似于Fox方程式(E1)的方程式(E1)(参考T.G.Fox,Bull.Am.Phys.Soc.1(1956)123)。
该方程式中,n表示所用单体的序号,Wn为各单体n的质量分数(wt%)以及Tg,n为各单体n的均聚物相应的玻璃化转变温度,其单位为K。
对于聚(甲基)丙烯酸酯PSAs的制备,进行常规的自由基聚合是有利的。对于自由基进行的聚合,优选使用还含有用于该聚合的其他自由基引发剂的引发剂体系,特别是热分解形成自由基的偶氮或过氧化引发剂。然而,原则上技术人员熟悉的用于丙烯酸酯的所有常规引发剂都是适宜的。在Houben Weyl,Methoden der Organischen Chemie,Vol.E 19a,第60-147页中对C-中心基团的生产进行了描述。优选类似地采用这些方法。
自由基源的实例为过氧化物、氢过氧化物和偶氮化合物;在此可以提及的典型自由基引发剂的一些非限制性实例包括过氧化二硫酸钾、过氧化二苯甲酰、氢过氧化异丙苯、过氧化环己酮、过氧化二-叔丁基、偶氮二异丁腈、环己基磺酰基乙酰基过氧化物、过碳酸二异丙基酯、叔丁基过辛酸酯(t-butyl peroctoate)和苯频哪醇。在一种非常优选的形式中所用的自由基引发剂为1,1’-偶氮二(环己烷-腈)(产自DuPont的Vazo88TM)或偶氮二异丁腈(AIBN)。
非常优选选择自由基聚合中形成的PSAs的平均分子量(重均)Mw以使得其处于200 000-4 000 000g/mol的范围内;特别是对于进一步用作具有回弹性的导电热熔PSAs来说,制得平均分子量Mw为400 000-1 400 000g/mol的PSAs。平均分子量由尺寸排阻色谱法(GPC)或基质-辅助激光解吸/离子化质谱法(MALDI-MS)测定。
聚合可以在无溶剂下、在一种或多种有机溶剂存在下、在水存在下、或在有机溶剂和水的混合物中进行。其目的是使所用溶剂的量最小化。适宜的有机溶剂为直链烷烃(如己烷、庚烷、辛烷、异辛烷),芳烃(如苯、甲苯、二甲苯)、酯(如乙基、丙基、丁基或己基乙酸酯)、卤代烃(如氯苯)、烷醇(如甲醇、乙醇、乙二醇、乙二醇单甲基醚)和醚(例如二乙基醚、二丁基醚)或其混合物。为了确保单体转化期间反应混合物以均相的形式存在,可以将水可混溶的或亲水性的助溶剂加入到含水的聚合反应中。可以有利地用于本发明的助溶剂选自脂族醇、二元醇、醚、二元醇醚、吡咯烷、N-烷基吡咯烷二酮(pyrrolidinone)、N-烷基吡咯烷酮、聚乙二醇、聚丙二醇、酰胺、羧酸及其盐、酯、有机硫化物、亚砜、砜、醇衍生物、羟基醚衍生物、氨基醇、酮等,以及它们的衍生物及混合物。
根据转化率和温度,聚合时间为2-72小时。可以选择的反应温度越高,即,反应混合物的热稳定性越高,所选择的反应时间可以越短。
至于聚合的引发,对于热分解引发剂,引入热量是必要的。对于这些引发剂,根据引发剂类型,可以通过加热到50-160℃来引发聚合。
对于制备,聚合(甲基)丙烯酸酯PSA而不使用溶剂也是有利的。这种情况下使用的特别适宜的技术是预聚合技术。用UV光引发聚合,然而仅达到约10-30%的低转化率。然后,将得到的聚合物浆熔接(welded),例如成膜(在最简单的情况下,方块冰),然后在水中聚合直到高转化率。可以将这些粒料随后用作丙烯酸酯热熔胶粘剂,对于熔融操作,特别优选使用与聚丙烯酸酯相容的膜材料。对于该制备方法,还可以在聚合之前或之后,添加导热材料。
另一种有利的聚(甲基)丙烯酸酯PSAs的制备方法为阴离子聚合。在这种情况下,优选使用的反应介质含有惰性溶剂,如脂族和脂环族烃,或者如芳烃。
在这种情况下,活性聚合物通常由结构PL(A)-Me表示,其中Me是I族金属,如锂、钠或钾,以及PL(A)为来自丙烯酸酯单体的生长着的聚合物。制备时,通过引发剂浓度与单体浓度的比例来控制聚合物的摩尔质量。适宜的聚合引发剂的实例包括正丙基锂、正丁基锂、仲丁基锂、2-萘基锂、环己基锂和辛基锂,然而该列举并非穷举。此外,基于钐络合物的引发剂已知用于丙烯酸酯的聚合(Macromolecules,1995,28,7886)而且可在此应用。
此外,还可以使用双官能的引发剂,如1,1,4,4-四苯基-1,4-二锂丁烷(dilithiobutane)或1,1,4,4-四苯基-1,4-二锂异丁烷(dilithioisobutane)。同样可以使用辅助引发剂。适宜的辅助引发剂包括锂卤化物、碱金属醇盐和烷基铝化合物。在一种非常优选的形式中,选择配体和辅助引发剂以使得丙烯酸单体如丙烯酸正丁酯和丙烯酸2-乙基己酯可以直接聚合而不必通过与相应的醇进行酯交换在聚合物中生成。
适于制备分子量分布窄的聚(甲基)丙烯酸酯PSAs的方法还包括受控的自由基聚合法。在这种情况下,优选将下列通式的控制剂用于聚合:
其中R§和R#彼此独立地选择或者相同,为
-支化和未支化的C1-C18烷基;C3-C18烯基;C3-C18炔基;
-C1-C18烷氧基;
-被至少一个OH基团或卤素原子或甲硅烷基醚取代的C1-C18烷基;C3-C18烯基;C3-C18炔基;
-碳链中具有至少一个氧原子和/或一个NR*基团的C2-C18杂烷基,R*为任意的基团(特别是有机基团);
-被至少一个酯基、胺基、碳酸酯基、氰基、异氰基和/或环氧基和/或被硫取代的C1-C18烷基;C3-C18烯基;C3-C18炔基;
-C3-C12环烷基;
-C6-C18芳基或苄基;
-氢。
(I)型控制剂优选由下列化合物组成:
其中的卤素原子优选为F、Cl、Br或I,更优选Cl和Br。各种取代基中特别适宜的烷基、烯基和炔基包括直链和支链。
含有1-18个碳原子的烷基的实例为甲基、乙基、丙基、异丙基、丁基、异丁基、叔丁基、戊基、2-戊基、己基、庚基、辛基、2-乙基己基、叔辛基、壬基、癸基、十一烷基、十三烷基、十四烷基、十六烷基和十八烷基。
具有3-18个碳原子的烯基的实例为丙烯基、2-丁烯基、3-丁烯基、异丁烯基、正-2,4-戊二烯基、3-甲基-2-丁烯基、正-2-辛烯基、正-2-十二碳烯基、异十二碳烯基、和油烯基。
具有3-18个碳原子的炔基的实例为丙炔基、2-丁炔基、3-丁炔基、正-2-辛炔基和正-2-十八碳炔基。
羟基取代的烷基的实例为羟丙基、羟丁基和羟己基。
卤素取代的烷基的实例为二氯丁基、一溴丁基和三氯己基。
适宜的在碳链中具有至少一个氧原子的C2-C18杂烷基的实例为-CH2-CH2-O-CH2-CH3。
C3-C12环烷基的实例包括环丙基、环戊基、环己基和三甲基环己基。
C6-C18芳基的实例包括苯基、萘基、苄基、4-叔丁基苄基和其他取代的苯基,例如乙基,甲苯、二甲苯、均三甲苯、异丙基苯、二氯苯或溴甲苯。
上述列举只是作为化合物相应基团的实例,以及并非穷举。
还可以用作控制试剂的其他化合物包括下列类型的那些:
其中R§和R#如上所定义,以及R&又独立于R§和R#可以选自这些基团的上述组中。
在常规‘RAFT’法的情况下,为了产生很窄的分子量分布,通常聚合只进行到低的转化率(参见WO 98/01478 A1)。然而,作为低转化率的结果,这些聚合物不能用作PSAs,特别是不能用作热熔PSAs,因为高含量的残留单体不利地影响工业粘合性;残留单体在浓缩操作中污染溶剂循环物;以及相应的自粘胶带会显示出很高的除气性。为了防止低转化率的这种缺点,在一种特别优选的方案中,两次或多次引发聚合。
作为另外的受控自由基聚合方法,可以进行硝基氧-受控聚合。为了自由基稳定,在有利的方案中,使用(Va)或(Vb)型的硝基氧:
其中R3、R4、R5、R6、R7、R8、R9和R10彼此独立地表示下列化合物或原子:
i)卤素,如氯、溴或碘,
ii)具有1-20个碳原子的线性、支化、环状和杂环烃,其可以是饱和的、不饱和的或是芳族的,
iii)酯-COOR11、醇盐-OR12和/或膦酸酯-PO(OR13)2,其中R11、R12或R13表示选自ii)的基团。
还可以将(Va)或(Vb)型化合物连到任意种类的聚合物链上(主要是使得至少一种上述基团构成这种聚合物链),以及因此可以用于聚丙烯酸酯PSAs的合成。更优选地,选择下列类型化合物的聚合用受控调节剂:
·2,2,5,5-四甲基-1-吡咯烷基氧基(PROXYL),3-氨基甲酰基-PROXYL,2,2-二甲基-4,5-环己基-PROXYL,3-氧代-PROXYL,3-羟亚胺-PROXYL,3-氨甲基-PROXYL,3-甲氧基-PROXYL,3-叔丁基-PROXYL,3,4-二叔丁基-PROXYL
·2,2,6,6-四甲基-1-哌啶基氧基(TEMPO),4-苯酰氧基-TEMPO,4-甲氧基-TEMPO,4-氯-TEMPO,4-羟基-TEMPO,4-氧代-TEMPO,4-氨基-TEMPO,2,2,6,6-四乙基-1-哌啶基氧基,2,2,6-三甲基-6-乙基-1-哌啶基氧基
·N-叔丁基1-苯基-2-甲基丙基硝基氧
·N-叔丁基1-(2-萘基)-2-甲基丙基硝基氧
·N-叔丁基1-二乙基膦酰基-2,2-二甲基丙基硝基氧
·N-叔丁基1-二苄基膦酰基-2,2-二甲基丙基硝基氧
·N-(1-苯基-2-甲基丙基)1-二乙基膦酰基-1-甲基乙基硝基氧
·二-叔丁基硝基氧
·二苯基硝基氧
·叔丁基叔戊基硝基氧。
一系列其他聚合反应方法可以选自现有技术,按照这些方法可以通过供替代的工艺制成PSA:
US 4,581,429 A公开了一种受控生长自由基聚合方法,其使用式R’R”N-O-Y的化合物作为引发剂,其中Y是能够聚合不饱和单体的自由基物种。然而,通常该反应具有低转化速率。具体的问题在于丙烯酸酯的聚合,它只是以很低的收率和摩尔质量进行。WO 98/13392 A1描述了具有对称取代形式的开链烷氧基胺化合物。EP 735 052 A1公开了一种用于制备摩尔质量分布窄的热塑性弹性体的方法。WO 96/24620 A1描述了一种聚合方法,其中使用非常特殊的自由基化合物,例如基于四氢咪唑的含磷硝基氧。WO 98/44008 A1公开了特殊的基于吗啉、哌嗪酮和哌嗪二酮的硝酰基。DE199 49 352 A1描述了在受控生长自由基聚合中作为调节剂的杂环烷氧基胺。烷氧基胺或对应的游离硝基氧的相应进一步开发改善了聚丙烯酸酯的制备效率。
作为其他的受控聚合方法,可以有利地使用原子转移自由基聚合(ATRP)以合成聚丙烯酸酯PSAs,在该情况下优选使用单官能或双官能的仲或叔卤化物以及用于夺取卤化物的Cu、Ni、Fe、Pd、Pt、Ru、Os、Rh、Co、Ir、Ag或Au的络合物(EP 0 824 111 A1;EP 826 698 A1;EP 824 110 A1;EP 841346 A1;EP 850 957 A1)作为引发剂。在US 5,945,491 A、US 5,854,364 A和US 5,789,487 A的说明书中对ATRP的各种可能性进行了进一步的描述。
本发明进一步涉及制备双面胶带的方法,该胶带特别用于LCD制造或LCD粘合。该方法由于已经如上所述的载体膜的使用而值得注意,该载体膜具有小的抗粘连剂含量或者没有抗粘连剂。
这类膜难以或者不可能通过已知方法加工。
令人惊讶地已经发现,如上所述用于PSA带中的具有低的抗粘连剂含量或没有抗粘连剂的膜,如果将该膜涂布在耐热的生产中(in-process)的膜上,在其上所述膜(例如PET膜)能够在卷绕之前冷却,可以使得该膜易处理。在本发明方法的一种形式中,将耐热的生产中的膜也卷绕起来。如此可以避免膜的粘连(各层焙烧在一起)而在膜的光学性能方面没有任何不利的改变。
此外,令人惊讶地已经发现,如果载体膜在制备PSA带之前进行粗糙化,以及特别是如果将其进行粗糙化以至于粗糙度小于400nm、优选小于300nm、以及优选大于50nm(RMS粗糙度形式的数据),具有低的抗粘连剂含量或没有抗粘连剂的膜可以进一步进行加工以得到所期望的PSA带,而且同时具有PSA带所需的性能。
借助于纳米压花可以有利地获得所述粗糙度,例如通过其中将非织造和/或机织织物压到膜表面上的层压操作(“交织”)。关于这一点,一种有利的层压台由至少两根辊组成,在所述辊之间可以产生所期望的压制压力。然后在辊间使非织造或机织织物层压到膜上,由此将其表面结构转移到膜上。
在本发明方法的另一形式中,借助于所述辊之一自身的表面在膜表面上产生表面结构。
通过相应抛光剂的选择,可以将抛光操作用于微调所述膜表面的微细粗糙度。在这种情况下也可以具有两个或多个相继的抛光过程。
为改善后续层对所述膜的粘附性,可以使膜在粗糙化之前或之后,通过蚀刻、通过电晕或等离子体处理和/或通过用底漆处理而进行预处理。
在上述方法的一种进一步发展中,特别地将涂布到耐热的生产中的膜上与粗糙化相结合,在本发明的操作程序中进行上述两者。
为了在膜上产生反射层以及因此同样地光吸收层,使所述膜层用金属、例如铝或银蒸汽涂布在一面或两面上。为了获得特别突出的反射和光吸收性能,有利的是通过阴极雾化涂布方法(即溅射)操作,有利地进行控制用于气相沉积的溅射操作以使得铝或银得以非常均匀地施加。此外,在一种非常优选的实施方案中,在一个加工步骤中使PET膜用铝蒸汽涂布在一面或两面上。金属层的使用具有减少或避免光透过载体膜以及补偿载体膜表面粗糙度的作用。
在另一步骤中,施加发色层。有利地可以如下得到该层:在固化粘结剂基质(优选热固性体系,然而辐射固化体系也可以)中,将彩色颜料混入涂料基质中,特别是选择黑色颜料。所用的涂料可以是例如聚酯、聚氨酯、聚丙烯酸酯或聚甲基丙烯酸酯,连同技术人员已知的涂料添加剂一起。在一种非常优选的本发明实施方案中,混入粘结剂基质中的发色颗粒是炭黑或石墨颗粒。在很高的添加水平(>20wt%),这样的添加不仅导致完全的光吸收,而且产生导电性,以至于本发明的双面PSA带同样具有抗静电性能。
对于以压敏胶粘剂的处理,在一种优选的方案中,将压敏胶粘剂从溶液涂布到载体膜上(或者,更准确地,涂布到已经施加至载体膜的各层上),所述膜特别是用上述方法制成的。为了提高PSA的锚固,可以任选地预处理金属反射层和/或发色层。因而,例如可以通过电晕或通过等离子体,可以从熔体或从溶液涂布底漆,或者可以用化学方法进行蚀刻,而进行预处理。
然而,特别地在黑色涂膜的情况下,应当使电晕功率最小化,因为否则会将膜烧上针孔。对于从溶液涂布PSA,例如在烘道中施加热量以除去溶剂,以及适当的话,引发交联反应。
此外,上述聚合物也可以作为热熔体系(即从熔体)涂布。对于该制备方法,由此可能必须从PSA中除去溶剂。在这种情况下,原则上可以使用技术人员已知的任何技术。一种非常优选的技术是用单螺杆或双螺杆挤出机浓缩的技术。双螺杆挤出机可以同向或反向操作。优选在两个或多个真空段蒸馏出溶剂或水。根据溶剂的蒸馏温度还进行逆向加热。残余的溶剂含量总计优选<1%,更优选<0.5%,以及非常优选<0.2%。
从该熔体进行热熔体的进一步加工。
为了作为热熔体涂布,可以采用不同的涂布方法。在一种方式中,通过辊涂法涂布PSAs。在Donatas Satas的“Handbook of Pressure SensitiveAdhesive Technology”(van Nostrand,New York 1989)中描述了不同的辊涂法。在另一形式中,通过熔体模头来进行涂布。在进一步优选的方案中,通过挤出进行涂布。优选使用挤出模头来进行挤出涂布。所用的挤出模头有利地可以来自下列三种类型之一:T-模头、鱼尾模头和衣架式模头。这些类型的区别在于其流道设计不同。通过涂布,还可以使PSAs进行取向。
另外,PSA可能必须进行交联。在一种优选形式中,用电子和/或UV辐射进行交联。
根据所用的UV光引发剂,以波长为200-400nm的短波紫外照射进行UV交联照射;具体地,用输出功率为80-240W/cm的高压或中压水银灯进行照射。照射强度适应于UV光引发剂相应的量子产率以及所设定的交联程度。
此外,在一种实施方案中,可以用电子束来交联PSA。可以使用的典型的照射设备包括线型阴极系统、扫描器系统和分段阴极系统(segmentedcathode system),其中使用电子束加速器。在Skelhorne,Electron BeamProcessing,in Chemistry and Technology of UV and EB formulation forCoatings,Inks and Paints,Vol.1,1991,SITA,London中给出了该技术领域的详细描述和最重要的工艺参数。典型的加速电压设定在50kV-500kV之间,优选80kV-300kV之间。所用的分散量(scatter dose)的范围在5-150kGy之间,具体地在20-100kGy之间。
也可以并用这两种交联方法或其他可以高能照射的方法。
本发明进一步提供本发明双面压敏胶带用于光学液晶显示器(LCDs)的粘合或生产的用途,其用于LCD玻璃粘合的用途,以及在其构造中具有本发明压敏胶带的液晶显示器。为了用作压敏胶带,所述双面压敏胶带可以用一片或两片隔离膜或隔离纸衬里。在一种优选实施方案中,使用硅化或氟化的膜或纸,如玻璃纸、HDPE或LDPE涂覆的纸,其又具有基于有机硅或氟化聚合物的剥离涂层。
实施例
以下对本发明进行描述,不希望由实施例的选择造成任何不必要的限制。
采用下列测试方法。
测试方法
A.透射率
用来自Biotek Kontron的Uvikon 923,在190-900nm的波长范围内测量透射率。绝对透射率(absolute transmittance)作为550nm处的值以%记录。
B.针孔
给予商业上常用类型的极强光源(如Liesegangtrainer 400KC型649高射投影仪,36V卤素灯,400W)完全不透光的遮蔽。该遮蔽物在其中央含有直径5cm的圆孔。将双面LCD胶带放在所述圆孔的上面。在完全黑暗的环境中,用电子仪器或目测数出针孔的数目。接通光源时,这些针孔作为半透明点可见。
聚合物1
将2400g丙烯酸、64kg丙烯酸2-乙基己酯、6.4kg N-异丙基丙烯酰胺和53.3kg丙酮/异丙醇(95∶5)加入到通常用于自由基聚合的200L反应器中。在搅拌下使反应器通氮气45分钟后,将反应器加热到58℃,并加入40g 2,2’-偶氮异丁腈(AIBN)。随后,将外部热浴加热到75℃,在该外部温度下持续进行反应。反应1小时后,再加入40g AIBN。在5小时和10小时后,每次用15kg的丙酮/异丙醇(95∶5)进行稀释。在6小时和8小时后,每次加入100g的二环己基过氧化二碳酸酯(Perkadox 16,Akzo Nobel),在所有情况下其都是以800g丙酮中的溶液加入。在24小时的反应时间后,终止反应并将反应混合物冷却到室温。
交联
将PSAs从溶液涂布到硅化处理的隔离纸(来自Loparex的PE涂覆的隔离纸)上,在干燥箱中于100℃下干燥10分钟,然后在200kV加速电压下以25kGy剂量交联。涂布重量在所有情况下都是50g/m2。
膜(Al蒸汽涂布):
将没有抗粘连剂存在下挤出的来自Mitsubishi的12μm PET膜(HostaphanTM 5210)用13g/m2的纸幅层压,以便防止粘连。在该状态下,可以将该膜卷绕并储存。
在退绕并除去纸幅之后,该PET膜在两面上用铝进行蒸汽涂布直至将完整的铝层施加到两面上为止。通过溅射法以300mm的宽度蒸汽涂布该膜。在该方法中,使带正电荷的离子化的氩气通入高真空的室中。接着带电离子撞击在带负电荷的Al板上,在分子水平上使铝粒子分离,其然后沉积在经过该板上方的聚酯膜上。
参照膜(Al蒸汽涂布):
来自Mitsubishi RNK 12μm的标准12μm PET膜在两面上用铝进行蒸汽涂布直至将完整的铝层施加到两面上为止。通过溅射法以300mm的宽度蒸汽涂布该膜。在该方法中,使带正电荷的离子化的氩气通入高真空的室中。带电离子撞击在带负电荷的Al板上,在分子水平上使铝粒子分离,其然后沉积在经过该板上方的聚酯膜上。
黑色油墨的制备:
由4份固化剂CVL No.10(来自Dainippon Ink and Chemicals,Inc.)和35份DaireducerTM V No.20(来自Dainippon Ink and Chemicals,Inc.)以及100份PanaceaTM CVL-SPR805油墨(来自Dainippon Ink and Chemicals,Inc.,氯乙烯/乙酸乙烯酯基的油墨)制成黑色油墨。
“黑色油墨A”的制备以及与所述油墨相关而经提到的性能,有关上述这些的US 2004/0028895的公开内容明确地包含在本说明书的公开内容中。
白色油墨的制备:
由2份固化剂CVL No.10(来自Dainippon Ink and Chemicals,Inc.)和35份DaireducerTM V No.20(来自Dainippon Ink and Chemicals,Inc.)以及100份PanaceaTM CVL-SP709油墨(来自Dainippon Ink and Chemicals,Inc.,氯乙烯/乙酸乙烯酯基的油墨)制成白色油墨。
“白色油墨W”的制备以及与所述油墨相关而经提到的性能,有关上述这些的US 2004/0028895的公开内容明确地包含在本说明书的公开内容中。
膜1(黑/黑):
将黑色油墨施加在所述Al涂布膜(基于HostaphanTM 5210)的两面上并在45℃干燥48小时。用黑色涂料涂布的面是完全而均匀的黑色。涂布量在所有情况下约为2g/m2。
膜2(黑/黑):
将白色油墨施加在所述Al涂布膜(基于HostaphanTM 5210)的两面上并在45℃干燥48小时。涂布量在所有情况下为2g/m2。然后再次用黑色油墨涂布该两面。同样在45℃进行干燥48小时。用涂料双重涂布的面是完全而均匀的黑色。每一面上两种油墨的涂布量为4g/m2。
参照膜1(黑/黑):
将黑色油墨施加在所述Al涂布膜(基于HostaphanTM RNK 12μm)的两面上并在45℃干燥48小时。用黑色涂料涂布的面是完全而均匀的黑色。涂布量在所有情况下约为2g/m2。
参照膜2(黑/黑):
将白色油墨施加在所述Al涂布膜(基于HostaphanTM RNK 12μm)的两面上并在45℃干燥48小时。涂布量在所有情况下为2g/m2。然后再次用黑色油墨涂布该两面。同样在45℃进行干燥48小时。用涂料双重涂布的面是完全而均匀的黑色。每一面上两种油墨的涂布量为4g/m2。
实施例1
以50g/m2在两面上用聚合物1通过层叠涂覆膜1。
实施例2
以50g/m2在两面上用聚合物1通过层叠涂覆膜2。
参照例1
以50g/m2在两面上用聚合物1通过层叠涂覆参照膜1。
参照例2
以50g/m2在两面上用聚合物1通过层叠涂覆参照膜2。
结果
使实施例1和2连同参照例1和2一起按照测试方法A和B进行测试。结果列于表1中。
实施例 | 透射率(测试A) | 针孔(测试B) |
1 | <0.1% | 0 |
2 | <0.1% | 0 |
参照1 | <0.1% | 32 |
参照2 | <0.1% | 25 |
从表1的结果,显然在光学缺陷(没有针孔)方面,实施例1至2显著优于参照例1和2。因此在LCD应用的情况下可以避免光学缺陷。
因此该结果证明仅仅以没有抗粘连剂的膜就可以使针孔数目减少到0。
有创造性地和令人惊讶地,本发明的PSA带在其生产的任意阶段都不会显示粘连。这对于单面或双面金属化的膜也一样,而且即使在单面或双面涂布后也仍然是这样。上述的有利特性不可能由技术人员所预期。
本发明还使得可以第一次提供非常薄的压敏胶带(通过使用非常薄的膜,例如12μm的膜),其中仍然存在非常优良的黑色着色以及因此存在优异的(很高的)光吸收性。这些压敏胶带在液晶显示器的生产以及安装(粘合)中提供充分更优化的粘合可能性。
Claims (24)
1.一种压敏胶带,
其具有顶面和底面,
其进一步包含具有顶面和底面的载体膜,
在所有情况下,所述压敏胶带在所述顶面和所述底面上配备有压敏胶粘剂层,
其特征在于,
所述载体膜具有小于4000ppm的抗粘连剂含量,
所述载体膜的至少一面具有小于400nm的粗糙度,和
在所有情况下,在所述载体膜与所述压敏胶粘剂层之间存在至少一层光吸收发色层。
2.权利要求1的压敏胶带,其特征在于
所述载体膜的至少一面具有小于300nm的粗糙度。
3.权利要求1的压敏胶带,其特征在于
所述载体膜的至少一面具有大于50nm的粗糙度。
4.权利要求1-3任一项的压敏胶带,其是用于光学液晶显示器(LCDs)的生产或粘合的压敏胶带。
5.权利要求1-4任一项的压敏胶带,其特征在于
所述载体膜具有小于1000ppm的抗粘连剂含量。
6.权利要求5的压敏胶带,其特征在于
所述载体膜具有小于500ppm的抗粘连剂含量。
7.权利要求5的压敏胶带,其特征在于
所述载体膜具有0ppm的抗粘连剂含量。
8.前述权利要求中任一项的压敏胶带,其特征在于
所述载体膜的厚度为250μm-4μm。
9.权利要求8的压敏胶带,其特征在于
所述载体膜的厚度为50μm-8μm。
10.权利要求8的压敏胶带,其特征在于
所述载体膜的厚度为36μm-12μm。
11.前述权利要求中任一项的压敏胶带,其特征在于
所述载体膜在其至少一面上配备有金属反射涂层。
12.权利要求11的压敏胶带,其特征在于
所述载体膜在其至少一面上配备有金属涂层。
13.权利要求1-3任一项的压敏胶带,其特征在于
所述载体膜在两面上配备有金属反射涂层。
14.权利要求13的压敏胶带,其特征在于
所述载体膜在两面上配备有金属涂层。
15.制备上述权利要求中任一项的压敏胶带的方法,其特征在于
在制备所述压敏胶带之前,将所述载体膜至少一面上的表面进行粗糙化。
16.权利要求15的方法,其特征在于
将所述载体膜至少一面上的表面进行粗糙化以使得其粗糙度小于400nm。
17.权利要求15的方法,其特征在于
将所述载体膜至少一面上的表面进行粗糙化以使得其粗糙度小于300nm。
18.权利要求15-17任一项的方法,其特征在于
将所述载体膜至少一面上的表面进行粗糙化以使得其粗糙度大于50nm。
19.权利要求15的方法,其特征在于
通过非织造和/或机织织物的加压施加和/或通过用表面带有结构的辊进行处理,以及适当的话通过抛光精制,而得到所述粗糙度。
20.权利要求19的方法,其特征在于
在粗糙化之前或之后,通过蚀刻、通过电晕或等离子体处理和/或通过用底漆处理,对所述载体膜进行预处理。
21.权利要求20的方法,其用于制备权利要求11-14之一的压敏胶带,其特征在于
通过溅射,即阴极雾化涂布得到所述金属反射涂层。
22.权利要求1-14中任一项的压敏胶带或者通过权利要求15-20中任一项的方法可得到的压敏胶带的用途,其用于光学液晶显示器(LCDs)的生产或粘合。
23.权利要求22的用途,其用于粘合LCD玻璃。
24.包含权利要求1-14中任一项的压敏胶带的液晶显示器(LCD)。
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DE102004058281.5 | 2004-12-02 | ||
DE102004058281A DE102004058281A1 (de) | 2004-12-02 | 2004-12-02 | Doppelseitige Haftklebebänder zur Herstellung bzw. Verklebung von LC-Displays mit lichtabsorbierenden Eigenschaften |
PCT/EP2005/056398 WO2006058912A1 (de) | 2004-12-02 | 2005-12-02 | Doppelseitige haftklebebänder zur herstellung bzw. verklebung von lc-displays mit lichtabsorbierenden eigenschaften |
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EP (1) | EP1819795A1 (zh) |
JP (1) | JP2008521990A (zh) |
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CN (1) | CN101098943B (zh) |
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DE102016220687A1 (de) | 2016-10-21 | 2018-04-26 | Tesa Se | Plasmabehandlung einer Mehrlagenverklebung |
DE102016220691A1 (de) * | 2016-10-21 | 2018-04-26 | Tesa Se | Mehrlagenverklebung |
KR102491041B1 (ko) * | 2018-04-12 | 2023-01-25 | 삼성디스플레이 주식회사 | 차광 테이프, 이의 제조 방법 및 이를 포함하는 표시 장치 |
GB2580211B (en) * | 2018-12-21 | 2022-11-30 | Rogers Corp | Single-sided pressure-sensitive adhesive tape |
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US5789487A (en) * | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
FR2757865B1 (fr) * | 1996-12-26 | 1999-04-02 | Atochem Elf Sa | Procede de polymerisation ou copolymerisation radicalaire controlee de monomeres (meth)acryliques, vinyliques, vinylideniques et dieniques et (co)polymeres obtenus |
JP3352943B2 (ja) * | 1998-04-23 | 2002-12-03 | ダイセル化学工業株式会社 | バリア性フィルム及びその製造法 |
JP3952668B2 (ja) * | 2000-07-10 | 2007-08-01 | 株式会社コスモテック | 粘着シート及びそれを用いた液晶表示装置 |
JP3879899B2 (ja) * | 2001-02-09 | 2007-02-14 | 大日本インキ化学工業株式会社 | 遮光性粘着シート |
JP2002350612A (ja) * | 2001-05-25 | 2002-12-04 | Dainippon Ink & Chem Inc | 遮光性フィルム、遮光性粘着シート、およびそれを使用した表示パネル |
JP2003307621A (ja) * | 2002-04-18 | 2003-10-31 | Nitto Denko Corp | 粘着型光学フィルムおよび画像表示装置 |
JP3902162B2 (ja) * | 2002-08-12 | 2007-04-04 | 大日本インキ化学工業株式会社 | 光反射性と遮光性を併有するlcdモジュール用粘着テープ |
KR100987679B1 (ko) * | 2002-08-12 | 2010-10-13 | 디아이씨 가부시끼가이샤 | 광반사성과 차광성을 겸비한 lcd 모듈용 점착 테이프 |
JP4517572B2 (ja) * | 2002-11-15 | 2010-08-04 | Dic株式会社 | 反射・遮光粘着テープ |
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JP2005060435A (ja) * | 2003-08-14 | 2005-03-10 | Three M Innovative Properties Co | 両面粘着シート |
-
2004
- 2004-12-02 DE DE102004058281A patent/DE102004058281A1/de not_active Withdrawn
-
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- 2005-12-02 US US11/720,389 patent/US20090120574A1/en not_active Abandoned
- 2005-12-02 DE DE112005002882T patent/DE112005002882A5/de not_active Withdrawn
- 2005-12-02 JP JP2007543852A patent/JP2008521990A/ja active Pending
- 2005-12-02 CN CN2005800464310A patent/CN101098943B/zh not_active Expired - Fee Related
- 2005-12-02 WO PCT/EP2005/056398 patent/WO2006058912A1/de active Application Filing
- 2005-12-02 EP EP05813500A patent/EP1819795A1/de not_active Withdrawn
- 2005-12-02 KR KR1020077015161A patent/KR20070092722A/ko not_active Application Discontinuation
- 2005-12-02 TW TW094142565A patent/TW200632065A/zh unknown
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US20120111830A1 (en) | 2012-05-10 |
KR20070092722A (ko) | 2007-09-13 |
CN101098943A (zh) | 2008-01-02 |
DE102004058281A1 (de) | 2006-06-08 |
WO2006058912A1 (de) | 2006-06-08 |
EP1819795A1 (de) | 2007-08-22 |
TW200632065A (en) | 2006-09-16 |
DE112005002882A5 (de) | 2007-10-11 |
US20090120574A1 (en) | 2009-05-14 |
JP2008521990A (ja) | 2008-06-26 |
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