CN1281492A - 防滑制品 - Google Patents
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Abstract
本发明提供一种背面有粘合剂的制品,其制造方法和包括这种制品的一套制品。本发明的制品作为防滑产品,它包含背衬和施涂到背衬主表面上的耐油粘合剂。按本发明的一个方面,所提供的制品包含:具有第一和第二主表面的背衬,第一主表面是有纹理的,形成防滑表面;和位于背衬第二主表面上的压敏粘合剂,将该粘合剂制成在处于油性环境下的使用过程中能防剥离,该粘合剂包含下述各组分的聚合反应产物:(a)丙烯酸;(b)至少一种含N-乙烯基的单体;(c)至少一种选自丙烯酸异辛酯、丙烯酸2-乙基己酯和它们组合的丙烯酸酯;(d)任选地小于约20重量%的氟烷基硅氧烷;和(e)任选的交联剂。
Description
本发明涉及用于提供防滑表面的制品,制造这种制品的方法和包含至少一个这种制品的一套制品。
某些表面如商业厨房的地面例如由于油和油脂的累积而变滑。许多商业厨房包括由通常称为“方砖”的含硅多孔素烧砖组成的地面。由于其多孔性,方砖一般会保留剩余的油脂和油,即使在严格的清洗工作之后。已知这些剩余的油脂和/或油随时间会从方砖向外迁移。
多种商品可以施加到各种地面表面上,以降低地面的滑移性,或提高表面的耐摩擦性。这种“防滑”制品一般包含背衬,其中该背衬的一个主表面是用摩擦颗粒或类似物构成的。背衬的另一主表面一般用直接施涂到地面上的压敏粘合剂涂覆。与处在油性状态下的地面如上述在商业厨房中的方砖有关的一个问题是压敏粘合剂与通常处于这种环境下的油性状态的不相容性。吸附在砖孔内的剩余的油脂和油通常从砖向外迁移,在比较短的时间内导致粘合失效。在某些情况下,使用溶剂基的接触胶结材料作为这种地面的底漆,涂到防滑制品的下面。然而,这些接触胶结材料一般具有边缘效应(marginal performers)并且包括不希望有的溶剂。
因此,迫切需要一种防滑制品,它较好可以通过使用压敏粘合剂施加到地面或其它表面上,所述压敏粘合剂能耐通常在地面(如一般在商业厨房或类似环境中的地面)上存在的油脂和油。
本发明提供背面有粘合剂的制品,如包含背衬和施涂到背衬主表面上的耐油粘合剂的防滑产品。按本发明的一个方面,提供一种制品,它包含:
具有第一和第二主表面的背衬,第一主表面是有纹理的,形成防滑表面;和
位于背衬第二主表面上的压敏粘合剂,将该粘合剂制成在处于油性环境下的使用过程中能防剥离,该粘合剂包含下述各组分的聚合反应产物:
(a)丙烯酸;
(b)至少一种含N-乙烯基的单体;
(c)至少一种选自丙烯酸异辛酯、丙烯酸2-乙基己酯和它们组合的丙烯酸酯;和
(d)任选的氟烷基硅氧烷。
本发明的制品可以具有有纹理的表面(textured surface),这种有纹理的表面是通过将许多摩擦颗粒压花或粘合到背衬的第一主表面上形成的。通常,背衬可以包含各种材料如布料、纸张、非织造织物、聚合膜、纤维、金属片和上述材料的层压片中的任何一种。以聚酯背衬为佳。N-乙烯基单体较好是选自N-乙烯基-2-吡咯烷酮、N-乙烯基己内酰胺和它们的组合。
本发明的另一个方面是提供一种制造上述制品的方法,它包括:
提供具有第一和第二主表面的背衬,第一主表面是有纹理的,形成防滑表面;和
将上述压敏粘合剂施涂到背衬的第二主表面上;和
将剥离衬里施加到粘合剂上。
本发明的再一个方面是提供一套制品,它包含:
至少一种上述防滑制品;
底漆组合物;
适于容纳至少一种制品和底漆组合物的包装。
鉴于对包括较好实例的详细描述、实施例和所附权利要求书在内的其余内容的披露,本领域的技术熟练者将会进一步认识本发明。
在描述本发明的较好实例中,将参考各种附图,其中:
图1是包含摩擦颗粒的本发明防滑片材料部分的放大横截面图;和
图2是包括压花摩擦表面的本发明另一种防滑片材料部分的放大横截面图。
本发明提供适用于包括地砖在内的各种表面的防滑制品。本发明的制品尤其能很好地适用于某些通常被认为不利于压敏粘合剂使用的环境。本发明的制品特别可用压敏粘合剂涂覆,所述压敏粘合剂能很好地粘合到多孔表面如商业厨房中的方砖上。本发明的粘合剂将粘合到砖上并保持粘牢,即使与一般在这种环境下存在的油脂和油接触时。
参照图1,防滑片材料10包含背衬11,该背衬具有上表面12和下表面13。第一粘合剂材料的第一层14(“构造”涂层(“make”coating))粘合到上表面12上。第二粘合剂材料的第二层15(“上胶”涂层(“size”coating))覆盖在第一层14上。许多能经得起行人车辆的挤压而不会发生明显破裂的摩擦颗粒16均匀地分布在背衬片11的上表面12上,并通过构造涂层14和上胶涂层15牢固地粘合在该上表面上,从而使摩擦颗粒16的顶部在上胶涂层15的暴露面的一般平面上向上凸起,这样就形成了摩擦或防滑表面。应注意到上胶涂层会覆盖摩擦颗粒的某些凸起部分,因为在制造片材料中上胶涂层施涂到摩擦颗粒上。在这种情况下,摩擦颗粒的顶端在构造涂层的上表面的平面上凸起,而一层不同厚度的上胶涂层覆盖在顶端上,从而获得由上胶涂覆的磨粒组成的突起。在使用过程中,上胶涂层会磨损掉,从而露出磨粒的凸起顶端。构造涂层14和上胶涂层15的总厚度足以将颗粒16粘合在其上,并在行人步行中充分地防止颗粒损失。
压敏粘合剂层17涂覆在背衬片11的下表面13上,以便于将防滑片材料粘合到诸如地面等的基材表面上。任选地如美国专利4,328,274(Tarbutton等)中所披露的,若背衬片、构造涂层、上胶涂层和压敏粘合剂是透明的,则可以对背衬片11的底表面13或上表面12进行印刷,以获得装饰性的图案、信息或其它标记。较好的是粘合剂层17被合适的剥离衬里19所保护,所述剥离衬里19可以由此用途已知的片材料如硅氧烷涂覆的牛皮纸等制成。
构造涂层和上胶涂层可以由相同的可固化的涂料组合物制成。或者,构造涂层和上胶涂层可以得自两种不同的涂料组合物。本领域的技术熟练者将明白必须确保构造涂层有效地粘合到背衬片和任何添加的矿物或填料上,并且确保上胶涂层粘合到同样的矿物以及构造涂层本身上。构造涂层和上胶涂层的涂层重量将视摩擦颗粒的大小而变,粘合剂越多,则颗粒就可以越大。构造涂层和上胶涂层应有足够厚度,以便能粘合颗粒,但不应厚得遮住颗粒而减小或消除所需的摩擦表面。对于构造涂层来说,典型的涂层重量约为85-200克/米2,对于上胶涂层来说,典型的涂层重量约为45-145克/米2。
背衬片是从已知用于此用途的片材料如布料、纸张、非织造织物、聚合膜、纤维、金属片及其层压片或处理过的形式制成。其例子包括,但不局限于玻璃、聚酯、聚酰胺、人造纤维、棉花或它们组合的织物或非织造物,聚酰胺、聚氯乙烯、聚乙烯、聚丙烯或它们组合的聚合膜,聚对苯二甲酸乙二醇酯和聚丙烯的双轴取向膜,退火的铝箔,聚甲基丙烯酸甲酯和乙烯-甲基丙烯酸共聚物。一般来说,背衬片不需要具有非常高的强度,尽管有这种强度是适宜的。背衬片应具有足够的强度,以便能加工(即涂覆和处置),并能安置在基材上,若需要的话从这种基材上揭去。可以对背衬片的表面涂上底漆或以其它方式进行处理,以改进对其上涂层的粘合性。为此可以采用多种已知的表面处理方法。较好的背衬是聚酯背衬,如采用在如美国专利4,749,617(Canty)中所述的氮丙啶处理液按美国专利5,057,371(Canty等)中所述制造的涂过氮丙啶底漆的聚酯膜。
各种摩擦颗粒中的任何一种都可以用来制造本发明的防滑和磨料制品。合适的摩擦颗粒包括,但不局限于磨料颗粒如碳化硅、熔凝氧化铝(fused aluminumoxide)、陶瓷氧化铝、热处理过的氧化铝、白色氧化铝、氧化铝氧化锆、金刚石、铈土、立方氮化硼、石榴石、由溶胶-凝胶得到的磨料颗粒等,以及软木、橡胶、玻璃和得自聚酯、脲-甲醛、蜜胺、丙烯酸类、聚烷基二甘醇碳酸酯和酚醛树脂的聚合颗粒。颗粒可以是透明或不透明的。它们可以是有规则形状或无规则形状的,带有或没有尖锐的边缘(尽管对磨料制品来说尖锐边缘是较好的)。术语“摩擦颗粒”也包括粘合在一起形成附聚物的单个颗粒。颗粒大小的范围可视特定的用途而变,这对本领域的普通技术人员来说是皆知的。
本发明所用较好的粘合剂是包含交联三元共聚物的压敏粘合剂,所述三元共聚物是选自丙烯酸异辛酯、丙烯酸乙基己酯和它们组合的丙烯酸酯,含N-乙烯基的单体如N-乙烯基己内酰胺或N-乙烯基吡咯烷酮,和可自由基聚合的羧酸如较好是丙烯酸的反应产物。在较好的配方中,丙烯酸酯是丙烯酸异辛酯。以单体的总重量计,起初存在于粘合剂配方中的丙烯酸酯的浓度约为80-90重量%。以单体的总重量计,丙烯酸或其它合适的可自由基聚合的羧酸的初始浓度较好约为5-10重量%。N-乙烯基单体(如N-乙烯基吡咯烷酮)的初始浓度较好约为4-8重量%。
任选地可以将少量的氟烷基硅氧烷加到配方中,以改进粘合剂的防水和耐溶剂性。特别合适的氟烷基硅氧烷披露于Kumar等的美国专利5,349,004中,其内容在此参考引用。当使用本发明的粘合剂配方时,氟烷基硅氧烷在配方中存在的初始浓度一般小于约20重量%,较好小于约10重量%。当硅氧烷存在于配方中时,其一般可被部分丙烯酸酯并且可被少量的其它组分所代替。
本发明的制品可按本领域普通技术人员已知的常规技术制得。例如,采用刷涂、辊涂、挤出涂覆、帘流涂布、喷涂、刮刀涂布等方法将可固化的涂料组合物施涂到背衬片上。然后可以采用多种已知的方法如磨料制造领域中已知的方法将摩擦颗粒施加到此第一层粘合剂(即构造涂层)上。一种较好的将摩擦颗粒涂覆到背衬片上的方法是采用下落式涂布(drop coating),其中使摩擦颗粒在空气中下落到背衬片的刚涂覆好的表面上,从而使其均匀地分布在涂覆的表面上。随后,可以固化构造涂层,或者立刻施涂上胶涂层并同时固化两层涂层。
在制备粘合剂的过程中,将上述单体与合适的自由基引发剂如2,2’-偶氮二(异丁腈)在溶剂中混合,使其反应,形成所需的三元共聚物。一般来说,将各单体、合适的溶剂和引发剂加到合适的容器如适当体积的广口玻璃瓶中,以形成混合物。用氮气,一般以1升/分钟的速度吹扫所得的混合物5分钟。然后密封反应容器,在55-65℃的恒温浴中滚动,直到如用气相色谱法测定的%转化率大于约98.5%。当达到所需的转化率时,在四氢呋喃(THF)中以下述实施例中所述的方式测定特性粘度(Ⅳ)。特性粘度通常与聚合物的分子量有关。一般来说,反应好的聚合物的Ⅳ落在约0.33-0.97分升/克的范围内。Ⅳ更好地在约0.4-0.5 dl/g的范围内。一般来说,反应好的聚合物的分子量(数均)在约30,000-70,000的范围内,较好约为35,000-50,000。
宜将交联剂加到聚合物/溶剂的混合物中,而后将该混合物涂覆到合适的表面如背衬片11或剥离衬里19上。在配方中宜包含交联剂,以在最终的粘合剂中达到一定的交联度,使耐油性、剥离强度和粘合剂的剪切强度达到最佳。以单体的重量计,加到配方中的交联剂的浓度一般约为0.1-1重量%,较好为0.1-0.5重量%。
合适的交联剂包括,但不局限于热活化、湿活化和紫外辐射(UV)活化的交联剂。热活化交联剂的例子包括,但不局限于选自多官能氮丙啶酰胺如N,N’-双-1,2-亚丙基对苯二甲酰胺,金属配合物如乙酰丙酮铝,金属离子如以可溶性金属盐的形式存在的Zn2+、Zr2+和Ni2+。湿活化的交联剂的例子包括,但不局限于选自硅烷如三甲氧基甲硅烷基丙基甲基丙烯酸酯(三),氨基硅烷,环氧硅烷和它们的混合物。UV-活化的交联剂的例子包括,但不局限于选自在如美国专利4,330,590(Vesley)和美国专利4,329,384(Vesley等)中所述的三嗪,和在如美国专利4,737,559和美国专利4,847,137(Kellen等)中所述的可共聚合的芳族酮单体,所有这些专利的内容都在此参考引用。一种特别好的交联剂是热活化剂N,N’-双-1,2-亚丙基对苯二甲酰胺。
将粘合剂涂覆的背衬一般在室温下干燥,随后在升高的温度下另外再加热。在室温下典型的干燥时间是15分钟,随后在约93℃的升高温度下大约20分钟,以进一步干燥粘合剂层,并且上述过程也在热活化交联剂存在下进行,以完成交联反应。然后使膜冷却,接着将剥离衬里层压到粘合剂上。
如上所述,将上述可自由基聚合的单体和自由基引发剂在合适的溶剂如甲乙酮或乙酸乙酯中混合。本领域的技术熟练者将明白选择溶剂会影响聚合反应,这例如是通过影响反应速度或最终聚合物中的支化度而达到的。一般来说,在粘合剂中最少量的支化是适宜的。在上述两种溶剂中,乙酸乙酯中形成的支化比甲乙酮的少。然而,这些溶剂都是合适的,并且本领域的技术熟练者将明白也可以采用其它溶剂。在单体混合物中所包含的合适的链转移剂是巯基乙醇,以单体的重量计,其在上述单体混合物中加入的重量百分数约为0.05-0.2%。对这种链转移剂的需求取决于溶剂的选择和本领域技术熟练者己知的用于控制最终聚合物的特性粘度和分子量等的其它因素。
本发明的制品在无需背衬片的情况下也可用于防滑产品。也就是说,组合物可以固化成独立式涂层(free-standing coating),而粘合剂层可以施涂到独立式固化涂层的一个表面上。与使用背衬片的那些制品相比,独立式固化涂层可能较为贴合。这种独立式固化涂层可被压花(在形成涂层之前或之后)或其中包含混合的摩擦颗粒。为了制备独立式固化涂层,将可固化的涂料组合物涂覆到非粘性的表面(例如可以是聚乙烯或未处理的聚酯制成的压花模具)上,而后固化。可以在剥离衬里上的粘合剂层而后施涂到固化涂层上。或者,粘合剂在如涂覆到剥离衬里上之后可以先固化,然后在粘合剂上施涂合适的组合物制成独立式涂层。接着,剥离衬里、粘合剂和固化涂层从非粘性的表面上以整体结构揭下来。这种独立式固化涂层然后可以直接施加到基材上,其中有粘合剂***层,而无背衬片。
参照图2,防滑片材料20包括独立式涂层21,该涂层具有上表面22和下表面23。压敏粘合剂层27涂覆在独立式涂层21的下表面23上,以便于将防滑片材料粘合到基材表面上。较好的是粘合剂层27被合适的剥离衬里29所保护,所述剥离衬里29可以由此用途已知的片材料如硅氧烷涂覆的牛皮纸等制成。
本发明的制品尤其能很好地适用于处在油性或油脂状态下如在商业厨房等中的地面。本发明制品所用的粘合剂在其耐油和油脂(包括吸附在通用类型的常规方砖孔中的油和油脂)上出乎意料地优异,并且它可用作商业厨房的地面。与其它压敏粘合剂相比,用于本发明在此所述的粘合剂配方能提供比已有技术中所揭示的其它压敏粘合剂更高的剥离强度和更好的抗剪强度。
按本发明的一个方面,上述制品可以以包含至少一种上述制品和底漆组合物的一套制品中的一个部分的形式提供。将制品和底漆组合物包装在合适的商品包装中,然后将其运送或销售给消费者或用户,以用于为商业地面等提供防滑性。用于本发明合适的底漆组合物包括购自Minnesota Mining and Manufacturing Company,St.Paul,Minnesota(“3M”)的3M Concrete Protector & Restorer;同样购自3M的3M Cornerstone Floor Sealer;或水性氟化物组合物,如那些在美国专利5,383,639中所披露的。其它产品也适用于本发明,本领域的技术熟练者将明白本发明并不局限于在此所述制品中使用的特定选择的底漆。
在将本发明的制品施加到地面上如商业厨房的地面上时,一般需要先用合适的洗涤剂或脱脂剂清洗地面,从地面的表面上去除过量的油和油脂。然后施涂上述底漆,以提供比较清洁并且无油脂或油的表面,接着再将本发明的制品施加到上面。将制品施加到这样准备好的地面上,办法是从粘合剂处理过的表面上去除背衬,将制品的粘合剂处理过的表面牢固地粘贴到地面上。应对制品施加合适的压力,以确保将其粘贴到地面上,希望使用手辊,以便在将制品粘贴到地面上时对制品的表面施加均匀的压力。
本发明的制品特别能应用于为地面提供防滑性,尤其是为经常处在油和/或油脂环境下的表面提供这种性能。这样,本发明的制品特别能应用于商业厨房如在饭店设施等中。即使当处在食品行业中常见的油脂和油中,上述压敏粘合剂也将提供长时间合适的粘性、抗剥离性和优良的剪切强度。本发明制品的剥离强度一般大于约30牛顿/分米(N/dm),较好大于76 N/cm。
下述非限制性实施例进一步说明本发明的各个方面。
实施例
在实施例中,配制各粘合剂组合物并按所述的方法进行测试,其过程如下所述。除非另有说明外,所有的重量都按重量份计。
制备样品
在1升反应器中加入如表1和2所列的可自由基聚合的单体以及指定量的自由基引发剂2,2’-偶氮二(异丁腈)。单体和引发剂在指定的溶剂(甲乙酮或乙酸乙酯)中混合。当使用乙酸乙酯作为溶剂时,在反应混合物中也加入巯基乙醇作为链转移剂。以1升/分钟的气体流速用氮气吹扫混合物5分钟。然后密封容器,在55-65℃的恒温浴中滚动,直到用气相色谱法测定反应达到大于98.5%的转化率。一旦达到所需的转化率,在四氢呋喃(THF)中测定某些样品的特性粘度,Ⅳ测定值结果以分升/克(dl/g)列于表中。
将热活化交联剂(N,N’-双-1,2-亚丙基对苯二甲酰胺)加到这样制得的聚合物中,而后将其施加到如美国专利4,340,276中实施例14所述制备的改性聚酯膜背衬上。所制得的交联剂是其在甲苯中的5%溶液,将0.75克这样的交联剂加到50克各聚合物溶液(40%固体)中。将各粘合剂组合物涂覆到分开的聚酯膜上,达湿膜厚约为0.03厘米。开始在室温下(18-24℃)干燥粘合剂涂覆的背衬15分钟,然后在约93℃的干燥烘箱内再干燥20分钟,从而完成交联反应。将干燥膜冷却,层压到剥离衬里上,而后切成条(1.3-2.54厘米宽,15.2厘米长)。
测试方法A-剥离强度
将得自Century Tile,St.Paul,Minnesota的方砖用花生油(购自PlantersLifesavers Company,Winston-Salem,North Carolina)饱和,方法是将各块砖浸没在花生油中至少五(5)天。5天处理之后,用商品脱脂剂(以商品名“Twist“N Fill”购自Minnesota Mining and Manufacturing Company,St.PaulMinnesota)擦洗各块砖,将它们清洗三次。用纸巾擦干各块砖,施加上述粘合剂涂覆的条,并用手持橡胶辊施加手压将其牢固地粘合到各块砖上。在将条施加到砖上之后让其置于室温下24小时。而后将某些砖再次浸没在花生油中,使粘合条被油所覆盖。浸过的条和砖在65℃保持64小时。用轻质矿物油(以商品名“Klearol”购自Witco-Sonneborn)处理其它粘合的条和砖(如实施例15),以评价烃基油对粘合剂可能产生的影响。矿物油处理包括在如上述花生油处理相同的条件下将砖初始浸没在矿物油中。在初始浸没之后,以如上所述的方式清洗砖,施加粘合剂涂覆的条。将条和砖浸没在矿物油中,在油中保持在室温下100小时。
浸过之后,从油中取出砖,冷至室温。用纸巾擦拭,去除砖上过量的油。然后测定各粘合条的90°剥离粘合力。
在测定粘合到上述一块方砖上的条的90°剥离粘合力时,将各块砖安装在低摩擦的滑板上,并水平地夹在拉伸测试机(Chatillon LR5K)的下夹头上。粘合条的一端从方砖向外剥离,将其夹在拉伸测试机的上夹头上。然后以约30.5厘米/分钟的速度分开夹头,测量以90°的角度揭去条时所需的力。以N/dm标题为“剥离(油)”记录下所有置于油中的样品的剥离强度数据。
将某些样品条粘合到干净的新的方砖上,在室温下保持如上所述的停留时间64小时,不置于油中,然后测试剥离强度。以N/dm标题为“剥离(新)”记录下所有在不存在油时所测得的样品的剥离强度数据。
测试方法B-特性粘度
特性粘度(“Ⅳ”)提供测定特定聚合物的分子量的方法。以分升/克(dl/g)记录下Ⅳ。测定多种粘合剂组合物的Ⅳ,以便提供各实施例所用的粘合剂的分子量的适当比较。特性粘度是通过下述常规方法测量的,使用Schott GerateViscometer(型号为AVS 400)在控制在25℃的水浴中测量1分升聚合物溶液(每分升四氢呋喃溶剂0.2克聚合物)的流动时间和溶剂的流动时间。按下述公式确定Ⅳ的最终值:
Ⅳ=ln(聚合物溶液的流动时间/溶剂的流动时间)/聚合物在聚合物溶液中的浓度
实施例1-6和对比例A-D
使用如表1所列的指定重量份数的可自由基聚合的单体在甲乙酮(MEK)溶剂中配制粘合剂。测定指定粘合剂样品的Ⅳ。按上述步骤,制造背面有粘合剂的条,将其固定到方砖上,而后置于油中。置于油中之后,测试粘合条的剥离强度。剥离强度数据列于表1中。
通常,使用丙烯酸异辛酯、丙烯酸和N-乙烯基吡咯烷酮制得的粘合剂提供最佳的剥离强度。令人惊奇的是,这些粘合剂具有很好的性能,即使在基本上置于油中之后它们也能保持粘合在多孔方砖上。使用丙烯酸2-乙基己酯制得的实施例5的样品显示出较低但可接受的剥离强度。实施例6的样品和对比例D的样品的剥离强度数据是估计的。
表1
剥离强度:实施例1-6,和对比例A-D
实施例 | IOA1 | AA2 | NVP3 | MAA4 | NVC5 | EHA6 | AAM7 | MEK8 | Ⅳ(dl/g) | 剥离(油)N/dm |
1 | 45 | 3 | 2 | 7.5 | 66.4 | |||||
2 | 45 | 3 | 4 | 82.5 | 90.3 | |||||
3 | 45 | 5 | 2 | 78 | 111.9 | |||||
4 | 45 | 5 | 4 | 81 | 0.4 | 174.4 | ||||
对比例A | 45 | 3 | 72 | 9.2 | ||||||
5 | 16.7 | 13.3 | 150 | 270 | 0.57 | 27.0 | ||||
对比例B | 150 | 0.0 | 13.3 | 16.7 | 270 | 0.59 | 0.4 | |||
对比例C | 156.6 | 5.4 | 14.4 | 3.6 | 270 | 0.5 | 0.4 | |||
6 | 200 | 22.2 | 0.0 | 17.8 | 360 | 0.43 | 估计100 | |||
对比例D | 195.5 | 21.7 | 34.8 | 378 | 0.4 | 估计<10 |
1.丙烯酸异辛酯
2.丙烯酸
3.N-乙烯基吡咯烷酮
4.甲基丙烯酸
5.N-乙烯基己内酰胺
6.丙烯酸2-7基己酯
7.丙烯酰胺
8.甲乙酮
实施例7-15和对比例E
制备实施例7-15和对比例E,按实施例1-6和对比例A-D相同的方式测量剥离强度。在三个实施例中使用按美国专利5,349,004实施例6所述制得的氟烷基硅氧烷,确定其对剥离强度的可能的影响。用包括少量邻苯二甲酸二异壬酯的粘合剂来制备对比例E,所述邻苯二甲酸二异壬酯是一种已知的增塑剂,它在将粘合剂施涂到条上之前加到粘合剂中。在乙酸乙酯中制得的粘合剂包括0.024份巯基乙醇作为链转移剂。将实施例15的样品置于矿物油中后,测试该样品的剥离强度。将所有其它样品置于花生油中之后,测试这些样品的剥离强度。剥离强度测试值列于表2中。
按上述测试方法测定特性粘度,同样记录下来。对于在MEK溶剂中制得的合剂,剥离强度通常比使用乙酸乙酯制得的粘合剂的低,这可能是因为对在MEK中制得的粘合剂来说在聚合物主链中的支化度较高。对于那些单一系列的粘合剂(如使用相同溶剂制得的)在IV超过约0.5之前,剥离力通常随特性粘度的提高而增加。Ⅳ值大于0.5通常伴随剥离强度下降。对于最佳的产品性能(即综合剪切和剥离力),特性粘度较好为0.4-0.5 dl/g。
从剥离强度数据看出,少量的硅氧烷似乎对粘合有某些积极的影响。在粘合剂中加入增塑剂对粘合剂保持粘合在基材(尤其是油处理过的基材)上的能力有明显的负面影响。使用丙烯酸异辛酯、丙烯酸和N-乙烯基吡咯烷酮制得的粘合剂能提供最佳的剥离强度。
表2
剥离强度:实施例7-14,和对比例E
实施例 | IOA1 | AA2 | NVP3 | FSI4 | DINP5 | MEK/EtOAc6 | IV7(dl/g) | 剥离(新)N/dm | 剥离(油)N/dm |
7 | 130.9 | 14.5 | 11.6 | 2.9 | 240/0 | 0.41 | 170.8 | 38.2 | |
8 | 132.1 | 14.7 | 11.7 | 1.5 | 240/0 | 0.41 | 161.7 | 39.4 | |
9 | 132.7 | 14.7 | 11.8 | 0.74 | 240/0 | 0.41 | 171.3 | 40.1 | |
对比例E | 133.3 | 14.8 | 11.9 | 2.9 | 240/0 | 0.42 | 202.5 | 33.6 | |
10 | 133.3 | 14.8 | 11.9 | 240/0 | 0.42 | 201.8 | 39.7 | ||
20 | 2.2 | 1.8 | 0/36 | 0.28 | 277.8 | 81.0 | |||
12 | 20 | 2.2 | 1.8 | 0/36 | 0.32 | 246.9 | 84.9 | ||
13 | 20 | 2.2 | 1.8 | 0/36 | 0.41 | 235.3 | 77.2 | ||
14 | 20 | 2.2 | 1.8 | 0/36 | 0.64 | 169.8 | 57.9 | ||
15 | 20 | 2.2 | 1.8 | 0/36 | 72.9 |
1.丙烯酸异辛酯
2.丙烯酸
3.N-乙烯基吡咯烷酮
4.按美国专利5,349,004中实施例6制得的氟烷基硅氧烷
5.邻苯二甲酸二异壬酯
6.甲乙酮/乙酸乙酯
7.特性粘度
Claims (11)
1.一种施加到地面或其它表面上用于提供防滑表面的制品,该制品包含:
具有第一和第二主表面的背衬,第一主表面是有纹理的,形成防滑表面;和
位于背衬第二主表面上的压敏粘合剂,将该粘合剂制成在处于油性环境下的使用过程中能防剥离,该粘合剂包含下述各组分的聚合反应产物:
(a)丙烯酸;
(b)至少一种含N-乙烯基的单体;
(c)至少一种选自丙烯酸异辛酯、丙烯酸2-乙基己酯和它们组合的丙烯酸酯;和
(d)任选的氟烷基硅氧烷。
2.如权利要求1所述的制品,其中第一主表面是有纹理的,有许多摩擦颗粒粘合到或位于背衬的第一主表面上。
3.如权利要求1所述的制品,其中背衬包含选自布料、纸张、非织造织物、聚合膜、纤维、金属片和上述材料的层压片的材料。
4.如权利要求1所述的制品,其中N-乙烯基单体主要选自N-乙烯基-2-吡咯烷酮、N-乙烯基己内酰胺和它们的组合。
5.如权利要求1所述的制品,其中粘合剂主要由丙烯酸、N-乙烯基-2-吡咯烷酮和丙烯酸酯的交联聚合反应产物组成。
6.如权利要求5所述的制品,其中粘合剂包含约5-10重量%反应的丙烯酸,约4-8重量%反应的N-乙烯基-2-吡咯烷酮,和余量的反应的丙烯酸酯。
7.如权利要求1所述的制品,其中粘合剂提供剥离强度大于约30 N/dm的制品并且粘合剂的特性粘度约为0.4-0.5 dl/g。
8.如权利要求1所述的制品,其中聚合物包含约5-10重量%反应的丙烯酸,约4-8重量%反应的N-乙烯基-2-吡咯烷酮,约80-90重量%反应的丙烯酸酯,和小于约20重量%反应的氟烷基硅氧烷。
9.如权利要求1所述的制品,它包括粘合在粘合剂上的可除去的剥离衬里。
10.一种制造施加到地面或其它表面上用于提供防滑表面的制品的方法,该方法包括:
提供具有第一和第二主表面的背衬,第一主表面是有纹理的,形成防滑表面;
将压敏粘合剂施涂到背衬的第二主表面上,该粘合剂包含下述各组分的聚合反应产物:
(a)丙烯酸;
(b)至少一种含N-乙烯基的单体;
(c)至少一种选自丙烯酸异辛酯、丙烯酸2-乙基己酯和它们组合的丙烯酸酯;和
(d)任选的氟烷基硅氧烷;和
将剥离衬里施加到粘合剂上。
11.一套制品,它包含:
至少一种如权利要求1所述的制品;
底漆组合物;
适于容纳至少一种制品和底漆组合物的包装。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/989,099 US6132844A (en) | 1997-12-11 | 1997-12-11 | Slip resistant articles |
US08/989,099 | 1997-12-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1281492A true CN1281492A (zh) | 2001-01-24 |
Family
ID=25534750
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN98812100A Pending CN1281492A (zh) | 1997-12-11 | 1998-04-10 | 防滑制品 |
Country Status (12)
Country | Link |
---|---|
US (1) | US6132844A (zh) |
EP (1) | EP1037953B1 (zh) |
JP (1) | JP2001525483A (zh) |
KR (1) | KR20010032927A (zh) |
CN (1) | CN1281492A (zh) |
AU (1) | AU7466698A (zh) |
BR (1) | BR9813724A (zh) |
CA (1) | CA2312398A1 (zh) |
DE (1) | DE69804011T2 (zh) |
ES (1) | ES2169516T3 (zh) |
ID (1) | ID27990A (zh) |
WO (1) | WO1999029796A1 (zh) |
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CN106883784A (zh) * | 2017-04-19 | 2017-06-23 | 韩德辉 | 一种多功能胶带 |
CN106995666A (zh) * | 2017-04-19 | 2017-08-01 | 湖南万祺科技有限公司 | 一种新式防滑胶带 |
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-
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- 1998-04-10 CN CN98812100A patent/CN1281492A/zh active Pending
- 1998-04-10 ES ES98922032T patent/ES2169516T3/es not_active Expired - Lifetime
- 1998-04-10 WO PCT/US1998/007516 patent/WO1999029796A1/en not_active Application Discontinuation
- 1998-04-10 BR BR9813724-7A patent/BR9813724A/pt not_active IP Right Cessation
- 1998-04-10 KR KR1020007006271A patent/KR20010032927A/ko not_active Application Discontinuation
- 1998-04-10 AU AU74666/98A patent/AU7466698A/en not_active Abandoned
- 1998-04-10 JP JP2000524375A patent/JP2001525483A/ja active Pending
- 1998-04-10 EP EP98922032A patent/EP1037953B1/en not_active Expired - Lifetime
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- 1998-04-10 DE DE69804011T patent/DE69804011T2/de not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102328701A (zh) * | 2009-05-13 | 2012-01-25 | Cvg管理股份有限公司 | 隔热和隔音的车辆地板*** |
CN102328701B (zh) * | 2009-05-13 | 2015-09-30 | Cvg管理股份有限公司 | 隔热和隔音的车辆地板*** |
CN106883784A (zh) * | 2017-04-19 | 2017-06-23 | 韩德辉 | 一种多功能胶带 |
CN106995666A (zh) * | 2017-04-19 | 2017-08-01 | 湖南万祺科技有限公司 | 一种新式防滑胶带 |
Also Published As
Publication number | Publication date |
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US6132844A (en) | 2000-10-17 |
KR20010032927A (ko) | 2001-04-25 |
ES2169516T3 (es) | 2002-07-01 |
ID27990A (id) | 2001-05-03 |
DE69804011D1 (de) | 2002-04-04 |
EP1037953B1 (en) | 2002-02-27 |
JP2001525483A (ja) | 2001-12-11 |
AU7466698A (en) | 1999-06-28 |
BR9813724A (pt) | 2000-10-10 |
WO1999029796A1 (en) | 1999-06-17 |
DE69804011T2 (de) | 2002-11-28 |
EP1037953A1 (en) | 2000-09-27 |
CA2312398A1 (en) | 1999-06-17 |
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