CN1366010A - 含有天然橡胶胶乳的压敏粘合带 - Google Patents

含有天然橡胶胶乳的压敏粘合带 Download PDF

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CN1366010A
CN1366010A CN02101883A CN02101883A CN1366010A CN 1366010 A CN1366010 A CN 1366010A CN 02101883 A CN02101883 A CN 02101883A CN 02101883 A CN02101883 A CN 02101883A CN 1366010 A CN1366010 A CN 1366010A
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W·B·小格里菲斯
A·G·博恩
I·E·尤尔
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Rohm and Haas Co
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Abstract

粘合带,包括:(a)聚合物膜;(b)在所述聚合物膜上的底涂层;和(c)在底涂层上的粘合剂层,它包括:(i)天然橡胶胶乳;和(ii)增粘剂。

Description

含有天然橡胶胶乳的压敏粘合带
背景
本发明一般性涉及包括增粘橡胶胶乳和底漆的粘合带。
天然橡胶在压敏粘合剂中的使用是众所周知的。这种粘合剂使用溶剂型天然橡胶，其中通过离心天然橡胶胶乳获得的橡胶被素炼和由溶剂溶液应用于基底材料。素炼方法降低了橡胶的分子量，这据信产生了改进的粘合力，但可能以损失内聚强度为代价。
到目前为止，还没有从水基橡胶制备粘合涂料的大规模工业生产，虽然事实是环境和健康因素需要水基橡胶的使用。在天然橡胶胶乳粘合带中粘合剂与膜状基底材料(filmic backing)的固着性是关键问题。当粘合带的卷筒被拆卷时，经常发生层离和粘合剂转移到保留在卷筒上的膜的背面。相关的问题是，粘合带在工业生产线产生了相当大的噪音，当它们被拆卷用于纵切成小卷的粘合带时。
自从20世纪40年代以来，当开发了许多方法使水不溶性固体增粘剂引入到水性分散体时，由水基天然橡胶胶乳制成的粘合带已经被大家所知。固着性问题通过引入加成聚合物乳液得到解决。遗憾的是，加成聚合物对粘合带的粘合性能是有害的，因此不能工业上应用。
日本专利申请，JP 11-172212(1999)提出了包括天然橡胶胶乳、合成橡胶胶乳和乙烯-乙酸乙烯酯-丙烯酸酯共聚物乳液的粘合剂提供了良好的固着性。没有EVA共聚物的所有实施例都具有低劣的固着性和由于逐级层离产生的高拆卷噪音。然而，该参考文献承认EVA共聚物的使用对粘合性能具有有害的影响，缺点通过使用合成橡胶得到部分克服。
由本发明解决的问题是发现含有天然橡胶胶乳并具有各种粘合剂性能的良好平衡以及固着性的压敏粘合带。压敏粘合带的其它益处是在拆卷时的低噪音。
本发明的阐述
本发明涉及包括以下组分的粘合带：(a)聚合物膜；(b)在所述聚合物膜上的底涂层；和(c)在底涂层上的粘合剂层，该粘合剂层包括：(i)天然橡胶胶乳；和(ii)增粘剂。
详细描述
术语“粘合带”例如包括包装带、可印带、特种带和保护膜。
术语“聚合物膜”是指适合用于生产粘合带的膜形式的任意聚合物。优选的聚合物膜是由聚烯烃，包括但不限于聚丙烯、聚乙烯及它们的共聚物和结合物；聚酯；和聚氯乙烯(PVC)制备的那些。最优选的聚合物膜是取向聚丙烯膜(OPP)。优选的是，在用底漆和粘合剂涂敷之前，聚合物膜已经进行了电晕或火焰处理以改进固着性。
术语“丙烯酸类聚合物”是指丙烯酸、甲基丙烯酸和它们的酯的聚合物，和主要包括前述单体的共聚物。
术语“增粘剂”是指树脂或树脂的结合物，它能够赋予尤其在粘合带的上下文叙述中的粘合剂配方以粘性。优选的增粘剂包括松香增粘剂，多萜烯树脂，脂族烃树脂，芳族石油树脂，酚树脂，苯乙烯树脂和苯并呋喃-茚树脂。“松香增粘剂”是从松香衍生的增粘剂，包括但不限于松香、松香酯，松香衍生物，氢化松香，氢化松香酯和氢化松香衍生物。松香增粘剂作为固体树脂或作为液体分散体或乳液包括。优选的松香增粘剂是松香酯增粘剂。
术语“底漆”是指应用于聚合物膜基底材料以形成底涂层，从而增加粘合带粘合剂与膜的固着性的溶剂型或水性材料。在一个优选的实施方案中，底涂层包括天然橡胶和交联聚合物相；该底涂层一般通过将包括以下组分的底漆施涂到聚合物膜上来形成：(i)天然橡胶；(ii)含有适合于交联的官能团的至少一种其它聚合物组分；和(iii)交联剂。优选的是，在底漆中的其它聚合物组分的至少一种具有不高于-10℃的Tg。在另一个优选的实施方案中，底漆是溶剂型或水性聚合物组合物，其中主要的本体聚合物相具有不高于-10℃的Tg。优选的是，底漆包括水性聚合物组合物，其中至少一种聚合物组分具有不高于-10℃的Tg，以及它含有交联剂。最优选的是，底漆含有单一聚合物相。优选的底漆包括溶剂型或水性丙烯酸类聚合物，乙烯-乙酸乙烯酯共聚物，乙烯-乙酸乙烯酯-丙烯酸类共聚物，以及天然和合成橡胶如聚异戊二烯，聚异丁烯，苯乙烯-丁二烯共聚物，以及苯乙烯-丁二烯-丙烯腈共聚物，以及前述聚合物的共聚物或者混合物。非必需的是，底漆包括其它添加剂如增塑剂或增粘剂。在本发明的优选实施方案中，底漆的聚合物组分包括至少0.2％的带有适合交联的官能团，例如，羧酸、羟基和胺的单体单元；更优选至少1％。还更优选的是，聚合物组分包括具有不高于-10℃的Tg的丙烯酸类聚合物，该丙烯酸类聚合物包括1％-5％的丙烯酸或甲基丙烯酸单体单元，最优选1.5％-2.5％。在本发明的一个优选实施方案中，底漆包括含有至少0.2％的具有羧酸官能团的单体单元的丙烯酸类聚合物，天然橡胶胶乳，增粘剂和异氰酸酯交联剂。
优选的是，将至少一种交联剂加入到底漆中，优选在聚合物膜上涂敷底漆之前。交联剂是有效用于例如通过羟基或羧酸官能团在水性介质或在溶剂中进行交联的材料。优选的是，本领域中众所周知的交联剂之一与包括携带适合官能团的聚合物组分的底漆一起使用。这些交联剂包括但不限于二官能或者多官能异氰酸酯，封闭的异氰酸酯，碳化二亚胺，二胺，三胺，多胺，氮丙啶，胺官能树脂，例如蜜胺和脲-甲醛树脂，环氧树脂，环氧化物，酸，酸酐和具有共轭不饱和度的聚合物。优选的交联剂是有效用于通过羟基或者羧酸官能团，或者二者进行交联的那些，尤其二官能或多官能异氰酸酯和碳化二亚胺。优选的是，将交联剂以底漆总重量的1-20％，最优选底漆总重量的1-10％的含量加入到底漆中。
一般将底漆涂敷到膜上以形成具有0.5-6g/m2，优选2-3g/m2干燥涂料重量的底涂层。将粘合剂层施涂于底涂层上。优选的是，在施涂粘合剂层之前，干燥底涂层。在本发明的优选实施方案，底涂层已经通过存在于底漆中的交联剂来交联。
优选的是，粘合剂层含有低于25％的合成橡胶。最优选的是，粘合剂层基本上无合成橡胶，例如聚异戊二烯或者苯乙烯-丁二烯橡胶，或者其它合成聚合物。
在本发明的一个实施方案中粘合剂含有1-10％的胶乳颗粒，各个颗粒具有空隙和50-500nm的粒度，如在U.S.专利No.5,663,213中所述那样。这些颗粒在粘合剂中用作UV吸收剂。优选的是，粘合剂含有3-6％的所述胶乳颗粒。
粘合带非必需含有一般用于粘合带的其它添加剂，例如抗氧化剂、UV稳定剂、机械稳定剂、表面活性剂、消泡剂、颜料、湿润剂和增塑剂。
本发明也涉及通过以下步骤生产的粘合带：(a)将底漆施涂于聚合物膜上以形成底涂层；和(b)将包括以下组分的粘合剂施涂于底涂层上：(i)天然橡胶胶乳；和(ii)增粘剂。优选的是，天然橡胶胶乳和增粘剂被混合形成粘合剂，然后再施涂于底涂层上。优选的是，底涂层在施涂粘合剂之前干燥。
实施例
粘合带样品用Centex LATZ天然橡胶胶乳与各种底漆和增粘剂一起制备。对于用底漆制备的样品，干燥底涂层的重量是大约2.5g/m2，和粘合剂的涂料重量是大约13g/m2。对于没有用底漆制备的样品，粘合剂的涂料重量是大约17g/m2。所有涂料重量在干燥之后测量。样品被命名为1A-1E，2A-2E，3A-3E，4A-4E，5A和5D。在样品中使用的增粘剂如下所示：“A”样品含有购自Hercules Co.(Wilmington，DE)的TACOLYN1070，烃(α-甲基苯乙烯)增粘剂；“B”样品含有购自AkzoNobel(Maastricht，荷兰)的SNOWTACK 780G，松香酯增粘剂；“C”样品含有购自Akzo Nobel(Maastricht，荷兰)的SNOWFACK 790G，松香酯增粘剂；“D”样品含有购自Akzo Nobel(Maastricht，荷兰)的SNOWTACK 880G，混合烃/松香酯增粘剂；以及“E”样品含有购自ND Dispersions(Dax，法国)的DERMULSENE TR 501，萜烯酚树脂增粘剂。
样品如下所示进行固着性和粘合性试验。在拆卷时的固着性通过拆开卷绕的粘合带样品和观测粘合剂转移到粘合带背面的程度从“无”到“完全”来进行评价。通过用手摩擦粘合剂层(最初一次，然后重复)和按0-10的等级评定粘合剂被除去的程度来进行“指摩擦”评价试验。通过在室温下使粘合带的粘合剂面与粘合剂面的另一段接触，然后分离粘合剂面(初始一次，然后用附加的剪切力重复)和按0-10的等级评价粘合剂的固着性来评价粘合剂面对面固着性。对于“指摩擦”和面对面固着性评价，得分0表示粘合剂容易转移，得分5-7表示有一些固着性，以及得分10表示即使在压力下也很少或没有粘合剂的转移。粘合剂剥离根据ASTM #D 3330/D 3330M-00(方法A)在不锈钢上测量，但有十分钟的停留时间。结果按N/10mm报道。在数字结果后面的“A”表示破坏的是粘合剂。在表中提供了样品的描述和试验结果。
样品 底漆     固着性 剥离
拆卷(转移量) 指摩擦试验 面对面固着性
一次 重复 一次 重复
1A 无 无 0 0 0 0 2.1A
1B 无 完全 0 0 0 0 2.1A
1C 无 完全 0 0 0 0 2.3A
1D 无 完全 0 0 0 0 2.2A
1E 无 部分 0 0 0 0 2.5A
2A1 橡胶/MMA2 - - - - - -
2B 橡胶/MMA2 无 0 0 0 0 1.2A
2C 橡胶/MMA2 无 0 0 0 0 1.6A
2D 橡胶/MMA2 无 0 0 0 0 1.5A
2E 橡胶/MMA2 无 0 0 0 0 2.0A
3A 丙烯酸类3 无 5 5 5 5 1.8A
3B 丙烯酸类3 无 6 5 6 5 1.3A
3C 丙烯酸类3 无 6 5 6 5 1.8A
3D 丙烯酸类3 无 7 5 7 6 1.5A
3E 丙烯酸类3 大部分 6 5 7 6 1.8A
4A 丙烯酸类/NCO4 无 10 9 10 9 1.5A
4B 丙烯酸类/NCO4 无 10 8 10 9 1.5A
4C 丙烯酸类/NCO4 无 10 8 10 9 1.8A
4D 丙烯酸类/NCO4 无 10 8 10 9 1.7A
4E 丙烯酸类/NCO4 几乎完全 9 7 7 5 1.5A
5A 丙烯酸类/nrl/NCO5 无 10 10 10 10 1.7A
5D 丙烯酸类/nrl/NCO5 无 10 10 0 10 1.6A
1、粘合剂不能在底漆上涂敷。
2、由80％天然橡胶和20％MMA接枝体组成的HEVEATUF 1320胶乳聚合物(购自Heveatex Corp.，Fall River，MA)。
3、PRIMAL PR9599水性丙烯酸类底漆(购自Rohm and Hass Company，Phi1adelphia，PA)。
4、在前面样品中使用的丙烯酸类底漆，具有5％(湿/湿)BASONATPLR8878脂族二异氰酸酯(购自BASF，Ludwigshafen，德国)。
5、用于粘合剂层的天然橡胶胶乳/增粘剂混合物，以上的丙烯酸类底漆和2.5％(湿/湿)的以上二异氰酸酯。

Claims (13)

1、粘合带，它包括：
(a)聚合物膜；
(b)在所述聚合物膜上的底涂层；所述底涂层包括天然橡胶和交联聚合物相；和
(c)在所述底涂层上的粘合剂层，该粘合剂层包括：(i)天然橡胶胶乳；和(ii)增粘剂。
2、权利要求1的粘合带，其中底涂层进一步包括增粘剂。
3、权利要求2的粘合带，其中聚合物膜选自聚烯烃膜、聚酯膜和PVC膜。
4、权利要求3的粘合带，其中交联聚合物相选自由丙烯酸类聚合物、乙烯-乙酸乙烯酯共聚物，乙烯-乙酸乙烯酯-丙烯酸类共聚物，天然橡胶，合成橡胶，它们的共聚物和结合物组成的交联聚合物中。
5、权利要求4的粘合带，进一步包括1-10％的胶乳颗粒，各颗粒具有空隙和50-500nm的粒度。
6、通过包括以下步骤的方法制备的粘合带：
(a)将包括：(i)天然橡胶；(ii)含有适合于交联的官能团的至少一种其它聚合物组分；(iii)交联剂，的底漆施涂于聚合物膜上以形成底涂层；和
(b)将包括：(i)天然橡胶胶乳；和(ii)增粘剂的粘合剂施涂于底涂层上。
7、权利要求6的粘合带，其中在底漆中的所述至少一种其它聚合物组分的至少一种聚合物组分具有不高于-10℃的Tg。
8、权利要求7的粘合带，其中交联剂是二官能或多官能异氰酸酯，二官能或多官能胺或氮丙啶。
9、权利要求8的粘合带，其中所述适合于交联的官能团选自羧酸基团、羟基和氨基。
10、权利要求9的粘合带，其中所述至少一种其它聚合物组分是丙烯酸类聚合物。
11、权利要求10的粘合带，其中底漆进一步包括增粘剂。
12、权利要求11的粘合带，其中交联剂是二官能或多官能异氰酸酯。
13、权利要求12的粘合带，进一步包括1-10％的胶乳颗粒，各颗粒具有空隙和50-500nm的粒度。
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