CN1039890C - 含有用于压敏粘合剂的含水剥离涂料组合物的制品 - Google Patents

含有用于压敏粘合剂的含水剥离涂料组合物的制品 Download PDF

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CN1039890C
CN1039890C CN93114396A CN93114396A CN1039890C CN 1039890 C CN1039890 C CN 1039890C CN 93114396 A CN93114396 A CN 93114396A CN 93114396 A CN93114396 A CN 93114396A CN 1039890 C CN1039890 C CN 1039890C
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M·M·威廉姆
R·J·特拉汉
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Abstract

本发明的目的是包括衬料层、至少一个压敏粘合剂层和含水剥离涂料层的制品，其中，至少衬料层的一面贴有压敏粘合剂，剥离涂料层包括聚合物(优选具有酸官能基)和具有至少一个脂肪酸酯基和至少一个季铵基的有机化合物的水溶液或水分散体。
本文还公开了聚合物(优选具有酸官能基)与具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物的水溶液或水分散体的混合物用作剥离涂料的方法。
即使在长期贮存及经受极端温度和湿度条件以后，含水剥离涂料层仍可以使压敏涂料层和衬料层容易地分开。含水剥离涂料不会迁移进入压敏粘合剂层而影响压敏粘合剂的粘合性能。

Description

含有用于压敏粘合剂的含水剥离涂料组合物的制品
本发明涉及含有用于压敏粘合剂的含水剥离涂料组合物的制品。
压敏粘合剂已广泛用作膜、箔、和胶带纸、标签纸、印花纸的粘合剂。这里将膜、箔、胶带纸、标签纸和印花纸统称为“衬料”(“backing”)。粘合剂可以涂敷于衬料的单面或双面。这里将以粘合剂涂敷的衬料的那一面称为“衬料涂有粘合剂面”。
例如，对于胶带，粘合剂涂敷的衬料通常要自卷成卷儿，其中衬料涂有粘合剂面在卷中与邻近的一层衬料的上表面(通常不含有粘合剂)直接接触。不涂有粘合剂、但涂有起到剥离剂作用的物质衬料的表面这里称为“衬料涂有剥离剂面”。在某些情况下，衬料的双面都可能涂有粘合剂，同时在这些衬料涂有粘合剂面的单面或双面使用含有另外的衬料和剥离涂料的剥离涂料纸。这里将双面都涂有粘合剂的衬料称为“双面涂有粘合剂的衬料”，并且将含有剥离涂料纸的面称为“剥离涂料纸面”。粘合剂必须可以干净地从“衬料涂有剥离剂面”或“剥离涂料纸面”剥离而不损坏该面或在该面上留下任何粘合剂残留物。
卷成卷儿的涂有粘合剂衬料对粘合剂有另外的要求。粘合剂必须对衬料的二个面有不同的亲和力，这样，粘合剂倾向于附着在涂敷的衬料面上而在展开时不会转移至邻近层的未涂敷的衬料面上。
有两个方法可以使粘合剂对衬料的两个面有不同的亲和力-底层涂布方法和剥离涂料方法。在底层涂布方法中，选择不粘合衬料的粘合剂，使用底层涂料使粘合剂粘合在衬料上。底层涂料首先涂敷于衬料上，然后再将粘合剂涂敷于底层涂层上。涂有粘合剂的衬料卷起时，“衬料涂有粘合剂面”上的粘合剂与不含粘合剂的衬料面接触，但不与它粘合。该方法的例子是；未增塑的聚氯乙烯膜上涂布溶剂基天然橡胶粘合剂，取向聚丙烯膜上涂布水基丙烯酸类粘合剂，其中，衬料被涂布的面先用电晕放电处理而“衬底”
在剥离涂料方法中，剥离涂料涂敷于不含有粘合剂的衬料面(“衬料涂有剥离涂料面”)，粘合剂涂敷于衬料的另一面(“衬料涂有粘合剂面”)。剥离涂料对衬料有很强的亲和力，但对粘合剂的亲和力微弱。溶剂基天然橡胶粘合剂和热熔体嵌段共聚物涂布于取向的聚丙烯膜上时，通常使用剥离涂料。
另外，剥离涂料也可以涂敷于另外的衬料上(这里称为“剥离涂料纸”)，然后附在衬料涂有粘合剂面上。
用作剥离涂料的涂料必须符合几个要求。衬料卷成卷儿时，剥离涂料对将与其直接接触的粘合剂必须只有低的亲和力。这种低的亲和力必须能够长期保持，并在变化及极端恶劣的温度、湿度条件下仍能保持。但是，剥离涂料不可将衬料和粘合剂之间的粘合力降低至这样的程度，以至于使胶带卷成了套筒(“telescopes”)。剥离涂料还必须坚固地粘结在衬料面上，以防止使用侵蚀性粘合剂时剥离涂料脱层。另外，剥离涂料的组分不能迁移进入粘合剂而损害粘合剂的性能。
由于安全、健康和环境原因，还希望使用含水的而不含溶剂的剥离涂料。
本发明的目的是含有衬料层、至少一个压敏粘合剂层和含水剥离涂料层的制品，其中，至少衬料层的一面贴有压敏粘合剂层，而且含水剥离涂料层含有聚合物(优选具有酸官能基的聚合物)和具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物的水溶液或水分散体。
本发明的另一目的是包括两面贴有压敏粘合剂层的衬料层和至少一个与压敏粘合剂层接触的剥离涂料层的制品，其中的剥离涂料纸层包括具有酸官能基的聚合物和具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物的水溶液或水分散体。
含水剥离涂料层使压敏粘合剂层与衬料层容易分开，即使在长期贮存和置于极端温度、湿度条件下以后。含水剥离涂料不会迁移进入压敏粘合剂层而影响压敏粘合剂的粘合性能。
本发明的压敏粘合剂制品如胶带、膜和标签至少由三种组分组成：
(1)衬料；
(2)压敏粘合剂；和
(3)水基剥离涂料。其中，或者(1).压敏粘合剂涂敷于衬料的一面(“衬料涂有粘合剂面”)而剥离涂料涂敷于衬料的另一面(“衬料涂有剥离涂料面”)；或者(2).衬料的两面都涂有压敏粘合剂(“粘合剂双面涂敷衬料”)而随后在至少一个“衬料涂有粘合剂面”上附着的剥离涂料纸含有剥离涂料。
本发明的衬料是传统材料，例如，包括未增塑的聚氯乙烯、聚乙烯、聚丙烯、聚酯的塑料，以及用于自卷带的其它基料；纸(包括皱纹纸或平光纸和那些用于蒙版粘带的纸)；非织布(包括纤维素塑料)；等等。衬料的典型厚度为约20μm-约40μm。
本发明的压敏粘合剂是传统材料，例如，含水丙烯酸类粘合剂；溶剂基橡胶粘合剂(包括顺式聚1，4-异戊二烯)；热熔体嵌段共聚物粘合剂；合成橡胶(包括苯乙烯-丁二烯橡胶)；等等。
本甲请人发明了新型的压敏粘合剂制品，它含有传统的衬料材料、传统的压敏粘合剂和新型的剥离涂料组合物。用于本发明的剥离涂料组合物必须含有聚合物和具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物的水溶液或水分散体。用量占聚合物干重的约0.1％(干重)-约50％(干重)的具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物与聚合物合并，优选用量为1％(干重)-10％(干重)。
本发明的剥离涂料组合物含有水溶性聚合物、胶乳聚合物或它们的混合物。
水溶性聚合物的例子包括聚丙烯酸酯类、聚丙烯酰胺类、聚乙烯醇、纤维素聚合物等等。
这里使用的“胶乳聚合物”意指不溶于水的聚合物，它可用传统的聚合物方法如乳液聚合制备。用于剥离涂料组合物的胶乳聚合物可用本领域熟知的乳液聚合方法制备。
可以使用很多单体或单体混合物制备胶乳聚合物。例如，丙烯酸酯单体，它包括丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸异丙酯、丙烯酸丁酯、丙烯酸异丁酯、丙烯酸仲丁酯、丙烯酸叔丁酯、丙烯酸戊酯、丙烯酸新戊酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸异辛酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸异癸酯、丙烯酸十二烷酯、丙烯酸冰片酯、丙烯酸异冰片酯、丙烯酸十四烷酯、丙烯酸十五烷酯、丙烯酸十八烷酯等；甲基丙烯酸酯单体，它包括甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸异丙酯、甲基丙烯酸丁酯、甲基丙烯酸异丁酯、甲基丙烯酸己酯、甲基丙烯酸辛酯、甲基丙烯酸异辛酯、甲基丙烯酸癸酯、甲基丙烯酸异癸酯、甲基丙烯酸十二烷酯、甲基丙烯酸冰片酯、甲基丙烯酸异冰片酯、甲基丙烯酸十四烷酯、甲基丙烯酸十五烷酯、甲基丙烯酸十八烷酯等；也可以使用丙烯酸、甲基丙烯酸、衣康酸、马来酸、富马酸、苯乙烯、取代的苯乙烯、丁二烯、丙烯腈、乙烯、乙酸乙烯酯、丙烯酰胺等。
用于本发明剥离涂料组合物的水溶性聚合物或胶乳聚合物优选含有酸官能基。将含酸基单体接入聚合物中，可以便酸官能基接入聚合物。可用的含酸基单体包括那些含有羧酸官能基的单体，如丙烯酸、甲基丙烯酸、衣康酸、富马酸、柠康酸；甲基丙烯酸二氧磷基乙酯等。
用于本发明剥离涂料组合物的聚合物优选是非离子稳定化的。合适的非离子稳定剂包括具有C7-C18的烷基、约6-约60的氧亚乙基重复单元的烷基苯氧基聚环氧乙烷，如庚基苯氧基聚环氧乙烷
甲基辛基苯氧基聚环氧乙烷等等；聚环氧乙烷以亚甲基连接烷基苯酚的衍生物；含硫试剂如约6-约60摩尔氧化乙烯与壬硫醇、十二硫醇等或与烷基硫代苯酚(其中烷基为C6-C16的烷基)缩聚制得的试剂；氧化乙烯的长链羧酸衍生物，这些酸例如月桂酸，肉豆蔻酸，棕榈酸，油酸等或酸的混合物，如(木浆)浮油中发现的每分子含有6-60个氧亚乙基单元的混合酸；长链醇如辛醇、癸醇、十二烷醇或十六烷醇、氧化乙烯的带有疏水性烃链的醚化或酯化多羟基化合物的衍生物的亚乙基式缩合物，如含有6-60个氧代亚乙基单元的脱水山梨糖的单硬脂酸酯；以及与一个或多个疏水的氧化丙烯链段结合的氧化乙烯链段。也可以使用苯磺酸烷基酯和乙氧基化的烷基苯酚的混合物。
有用的具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物包括甘油二酯和甘油三酯，其中以季铵官能基取代一个脂肪酸基。这些化合物例子包括卵磷脂，羟基化的卵磷脂和卵磷酯衍生物如Phos-Phalidycholine和磷脂酰乙醇胺，以及脂油的季铵盐。脂肪族羟基化(Fattyhydroxylated)、乙氧基化和丙氧基化的季铵和二季铵也可用于本发明的剥离涂料组合物中。许多化合物是天然产物。例如，卵磷脂是天然产物的磷脂混合物，它存在于绝大多数的生物细胞中，即有亲水部分又有疏水部分。商用卵磷脂的主要来源是大豆。
另外，传统的涂料组分如颜料、粘结剂、载色剂、扩链剂、分散剂、表面活性剂、凝结剂、润湿剂、流变改进剂、增厚剂、干燥延缓剂、消饱剂、着色剂、蜡、防腐剂、热稳定剂、紫外吸收剂等可用于本发明的剥离涂料中。
本发明剥离涂料可用刀涂、辊涂和印花涂布方法涂布于衬料上。剥离涂料涂布于柔软的衬料上以后，可以通过加热干燥。根据选择的衬料、压敏粘合剂和涂布方法，用于本发明的剥离涂料的干重是约0.01克/米2至约10克/米2。优选约0.1克/米2至约2.0克/米2。
下列实施例为了详细说明本发明，但并不限制本发明。对于本领域的一般技术人员，本发明的其它应用是显而易见的。
实施例1
剥离涂料组合物的制备
将列于表1的组分一起混合，制备剥离涂料组合物。剥离涂料用
                           表1
          组    分   剥离涂料1   剥离涂料2   剥离涂料3
  水含水氢氧化铵卵磷脂(在水甲，重量为水的12.5％)1牛脂三甲基氯化季铵盐(在水中重量为水的27％)2丙烯酸胶乳聚合物(固体量45.2％)3丙烯酸胶乳聚合物4(固体量46％)4水溶性聚合物5(在水中，重量是水的14)5剥离涂料固体量pH   --1.70克-27.6克--43.3％8.5-9.0   2.00克80.30克-1.85克-13.59克6-38％8.5-9.0     2.18克--1.85克-13.59克62.78克635％8-9
  注：1 American Lecithin Company的分散的Alcdec FF-100卵磷
    脂，用氢氧化铵调整PH值至5.5-9。
  2 Akzo Chemicals，lnc，的牛脂三甲基氯化季铵盐(Arquad T-
    27W)。
  3 Rohm和Haas Company的低分子表面活性剂RES68510(带
    有酸官能基阴离子稳定化的丙烯酸胶乳。
  4 Rohm和Haas Company的无酸官能基非离子稳定化的丙烯酸胶乳
    (RES3112)。
  5 Rohm和Haas Company的带有酸官能基的水溶性聚合物(RES
    8615-3)。
  6 加至胶乳聚合物中以前，预先混合在一起。
水稀释至固体含量为35％，得剥离涂料1，稀释至固体含量为28％，得剥离涂料2和3。然后将剥离涂料刮刀涂布于14.5千克/令的皱纹纸衬料上，在135℃下干燥1分钟，得到的增量为1.6千克/令。
实施例2
测试样品的制备
评价剥离涂料(剥离涂料1，2和3)，以鉴定它们用作压敏粘合剂的剥离涂料的效果。
测试样品的粘合
商用蒙版粘带条(2.54厘米宽、25.4厘米长)与实施例1制备的皱纹纸衬料的涂有剥离涂料面上的压敏粘合剂放在一起，制备测试样品。剪去测试样品上多余的衬料。然后将测试样品置于0.5×105Pa的压力下，以保证蒙版粘带的压敏粘合剂和皱纹纸衬料上的剥离涂料完全粘合。
或者在室温下制备测试样品并且马上测试，或者在82℃的热箱中制备并老化3天以模拟长期贮存。用一个2.54厘米的金属棒压在置于热箱中的测试样品以产生1.93×103Pa的压力，以模拟传统胶带中承受的压力。
测试样品的重新粘合
商用蒙版胶带条(2.54厘米宽、25.4厘米长)置于实施例1制备的皱纹纸衬料的涂有剥离涂料面上的压敏粘合剂放在一起，制备测试样品。剪去测试样品上多余的衬料。然后将测试样品置于0.5×105Pa的压力下，以保证蒙版粘带的压敏粘合剂和皱纹纸衬料上的剥离涂料完全粘合。
或者在室温下制备测试样品并且马上测试，或者在82℃的热箱中制备并老化3天以模拟长期贮存。用一个2.54厘米的金属棒压在置于热箱中的测试样品以产生1.93×103Pa的压力，以模拟传统胶带中承受的压力。
然后将蒙版粘带部分和剥离涂料部分用手分开。根据PressureSensitive Tape Council(PSTC)的标准，将蒙版粘带置于不锈钢板上。
实施例3
剥离涂料组合物粘合力的测试
在Instron Testing Machine(Model 1011)上，使用T-Peel测试方法评价测试样品的粘合性能。T-Peel试验在室温下、30.48厘米/分钟的条件下测试。结果列于表2。
         表2
             剥离量(千克/米)
             起始时   老化后
剥离涂料1    8.8      10.7
剥离涂料2    6.4      13.7
剥离涂料3    9.4      13.6
与没有涂布剥离涂料的典型压敏粘合剂的性能相比，涂布于压敏粘合剂以后马上测试时，每个剥离涂料都表现出良好的性能。在82℃的热箱中老化3小时模拟长期贮存后剥离量的增加仍是可接受的。
实施例4
剥离涂料组合物的重新粘合力测试
根据Pressure Sensitive Tape Conncil(PSTC)标准，使用180°Peel、90°Peel和90°Quik-Stick测试方法，评价测试样品的重新粘合性能。结果列于表3。
            表3
       重新粘合(千克/米)
       180°Peel     90°Peel      90°Quick-Peel
       起始时 老化后 起始时 老化后 起始时 老化后剥离涂料1  37.4   34.0   25.9    23.3  18.8   17.8剥离涂料2  32.7   29.2   21.2    20.1  12.4   11.3剥离涂料3  36.3   30.8   23.6    21.3  14.2   12.1
与没有涂布剥离涂料的典型压敏粘合剂的性能相比，涂布于压敏粘合剂以后马上测试时，每个剥离涂料都表现出良好的性能。在82℃的热箱中老化3小时模拟长期贮存后表现出可接受的重新粘合力的降低，这表明剥离涂料没有大量迁移进压敏粘合剂中，并且对压敏粘合剂的粘合和重新粘合性能没有大的不利影响。

Claims (12)

1.包括衬料层、至少一个压敏粘合剂层、含水剥离涂料层的制品，其中，所述衬料层的至少一面贴有所述压敏粘合剂层，所述含水剥离涂料包括聚合物和具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物的水溶液或水分散体。
2.权利要求1的制品，其中聚合物含有酸官能基。
3.权利要求2的制品，其中酸官能基是羧酸官能基。
4.权利要求1的制品，其中有机化合物是卵磷脂。
5.权利要求1的制品，其中有机化合物是脂肪族羟基化，乙氧基化或丙氧基化的季铵或脂肪族羟基化、乙氧基化或丙氧基化的二季铵。
6.权利要求1的制品，其中有机化合物是脂油的季铵盐。
7.包括两面贴有压敏粘合剂层的衬料层和至少一个与压敏粘合剂层接触的剥离涂料层的制品，其中的剥离涂料纸层包括具有酸官能基的聚合物和具有至少一个脂肪酸酯基及至少一个季铵基的有机化合物的水溶液或水分散体。
8.权利要求7的制品，其中聚合物含有酸官能基。
9.权利要求8的制品，其中酸官能基是羧酸官能基。
10.权利要求7的制品，其中有机化合物是卵磷脂。
11.权利要求7的制品，其中有机化合物是脂肪族羟基化，乙氧基化或丙氧基化的季铵或脂肪族羟基化、乙氧基化或丙氧基化的二季铵。
12.权利要求7的制品，其中有机化合物是脂油的季铵盐。
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