CN111032331A - 允许无损移除的粘合剂制品 - Google Patents

允许无损移除的粘合剂制品 Download PDF

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Publication number
CN111032331A
CN111032331A CN201880054804.6A CN201880054804A CN111032331A CN 111032331 A CN111032331 A CN 111032331A CN 201880054804 A CN201880054804 A CN 201880054804A CN 111032331 A CN111032331 A CN 111032331A
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adhesive
core
article
adhesive layer
layer
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CN111032331B (zh
Inventor
布雷特·P·克鲁尔
达乌德·H·坦
布雷德利·W·伊顿
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245Vinyl resins, e.g. polyvinyl chloride [PVC]
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Abstract

本公开提供了粘合剂制品,所述粘合剂制品通过在移除期间减小或消除芯背衬对由所述粘合剂生成的剥离力的贡献可从表面移除而不会损坏。在一些情况下,这可通过在垂直于由主表面限定的平面的方向上失去结构完整性的芯来实现。在其它情况下,通过损害所述芯和可剥离粘合剂层之间的所述界面来减小贡献。

Description

允许无损移除的粘合剂制品
相关申请
本专利申请涉及分别于2017年8月25日、2018年1月26日和2018年8月25日提交的各自题为“允许无损移除的粘合剂”的3M代理人案件79768US002、79768US003和79768WO004,并且各自全文以引用方式并入。
技术领域
本公开整体涉及可剥离粘合剂制品,该粘合剂制品能够附接或粘附到基底,并且可从基底上移除而不对基底造成损坏。本公开整体还涉及制备和使用此类粘合剂制品的方法。
背景技术
革命性的
Figure BDA0002390038780000011
粘合带产品是一系列可拉伸移除的粘合带,该粘合带强力地保持在多种表面(包括油漆、木材和瓷砖)上并且可干净移除—无孔、痕或粘性残余物。这些产品通常在粘结到各种表面或基底方面具有实用性,用于多种应用。
一般来讲,这些产品包含设置在胶带或其它背衬上的拉伸释放粘合剂组合物。可拉伸剥离的粘合剂是高性能的压敏粘合剂,它具有牢固的保持力,又能完全地移除而不产生表面损伤。可拉伸释放的粘合剂产品被设计成将制品(诸如钩(以保持图片或衣物制品)或其它装饰性或实用元件)牢固地粘附到表面(粘附体),但当以低角度从建筑表面拉离时可干净地移除。干净移除方面意指在移除拉伸释放粘合剂之后,在表面上不留下发粘和/或不美观的残余物,并且在移除过程中不对表面造成损坏。在拉伸释放移除的过程中,随着背衬被拉伸,粘合剂层通常保持粘附到胶带背衬上,但从表面(粘附体)释放。
最近,可剥离的粘合剂技术被引入到产品中用于安装。一些示例性可商购获得的可剥离安装产品(例如,Jimmy HookTM产品、GeckoTechTM产品、Elmer’s FreestyleTM产品和Hook UmTM产品)依赖于抽吸技术和摩擦或干燥粘合剂两者以生成安装装置的保持力。安装装置包括半刚性塑料背衬和刚性钩,两者都集成为一体式制品支撑件。刚性钩永久地附接到半刚性塑料背衬的第一主平坦表面。背衬的第二主平坦表面表面可粘附到壁表面。第二主平坦表面包括抽吸技术(例如,多个微创或纳米吸收元件)和/或摩擦粘合剂(其中背衬用橡胶基粘合剂浸渍,以增加基底和背衬之间的摩擦)或干燥粘合剂(其依赖范德华力)中的一种或多种。之后,整个构造可通过剥离移除。
发明内容
现有可剥离粘合剂产品在各种表面上通常不能良好地起作用,包括例如涂漆表面和粗糙表面(例如,干式墙)。另外,现有可剥离产品可具有低剪切强度,并且因此可保持较小的重量或者另选地需要较大的粘合剂表面积/厚度,这可致使当将此类产品从粘附体移除时损坏的可能性增加。已尝试用刚度(模量)较低的那些背衬替换现有背衬,以减小移除时的剥离力。例如,柔软的弹性背衬已被证明会导致较低的剥离力,该剥离力与粘合剂在释放时的明显拉伸(应变)相关。即使在对背衬材料进行有利修改的情况下,本发明人也认识到,某些脆弱表面(例如,纸材和干式墙)仍受到可见损坏,具体地在背衬拉伸能力受损的情况下。由此,本公开的发明人寻求以较高剪切强度的至少一种来配制可剥离安装产品和/或粘合剂制品,其在涂漆或粗糙表面上工作良好,并且/或者能够始终如一地保持较高的重量,所有这些均不会损坏它们所施加的基底。
本公开的发明人认识到,通过减少或消除在移除期间背衬对由粘合剂生成的剥离力的贡献,可改善或增强现有剥离释放粘合剂产品。在一些情况下,这可通过确保芯在垂直于由其主表面限定的平面的方向上失去结构完整性来实现。在其它情况下,通过损害背衬和可剥离粘合剂层之间的界面来减小贡献。通过将剥离力与背衬的特性分离,本公开的粘合剂制品可利用无数背衬材料和构造,而不会不利地影响无损可移除性。在一些情况下,增强的构造允许粘合剂制品保持更大的重量。在一些实施方案中,增强的可移除性允许粘合剂制品用于新表面(例如,脆弱的纸材)上。在一些实施方案中,增强的适形性提高或增强产品在某些表面上的性能(例如,粗糙或纹理化表面,诸如例如墙纸、干墙等)。
本公开的发明人还认识到,在移除过程期间提供对剥离释放力贡献最小的衬垫是一种新颖且有效的方法,以提高粘合剂制品的性能,同时增强产品的无损特征。
在一个方面,本公开提供一种粘合剂制品,该粘合剂制品包括第一可剥离粘合剂层、第二可剥离粘合剂层,以及设置在第一可剥离粘合剂和第二可剥离粘合剂之间并限定芯平面的离散芯。当粘合剂制品以大于35度的角度移除时,任一可剥离粘合剂层与芯脱粘。
在一个方面,本公开提供一种粘合剂制品,该粘合剂制品包括:第一可剥离粘合剂层;第二可剥离粘合剂层;离散芯,所述离散芯设置在所述第一可剥离粘合剂和所述第二可剥离粘合剂之间,并具有第一主表面和第二主表面,其中所述芯限定与所述第一主表面重合的芯平面;以及多个粘合剂接触区域,该多个粘合剂接触区域各自包括第一粘合剂层和第二粘合剂层之间的界面。
在另一方面,本发明提供一种用于将物体安装到表面上的粘合剂制品,该制品包括:第一粘合剂层;第二粘合剂层;芯,该芯限定周边,该芯设置在第一粘合剂层和第二粘合剂层之间;以及多个粘合剂接触区域,其中粘合剂接触区域包括第一粘合剂层和第二粘合剂层之间的界面,并且其中粘合剂接触区域位于芯的周边内。
在另一方面,本发明提供一种用于安装到表面上的物体,该物体包括:具有第一主表面的耐用件;离散芯,该离散芯限定与耐用件接触的第一表面和与第一表面相对的第二表面;以及粘合剂层,该粘合剂层粘结到耐用件的第一主表面和芯的第二表面两者,其中从耐用件移除粘合剂所需的剥离释放力大于将粘合剂与芯脱粘所需的剥离释放力或层离芯所需的剥离力中的至少一种。
在另一方面,本公开提供一种使用粘合剂制品的方法,该方法包括:使本文所述的粘合剂制品中的任何与粘附体表面接触。
如本文所用,“层”是指在表面上连续或不连续的单层。
如本文所用,术语“高度”、“深度”、“顶部”和“底部”仅用于说明目的,并不一定限定表面与侵入特征之间的取向和关系。因此,应认为术语“高度”和“深度”,以及“顶部”和“底部”应被认为是可互换的。
术语“包括”及其变型在说明书和权利要求书中出现这些术语的地方不具有限制的含义。
词语“优选的”和“优选地”是指在某些情况下可提供某些有益效果的本发明实施方案。然而,在相同的情况或其它情况下,其它实施方案也可以是优选的。此外,对一个或多个优选实施方案的表述并不暗示其它实施方案是不可用的,且并非旨在将其它实施方案排除在本发明范围之外。
如本文所述,应该将所有数字视为由术语“约”修饰。
如本文所用,“一个”、“一种”、“所述”、“至少一种(个)”以及“一种(个)或多种(个)”可互换使用。因此,例如,包括凹陷部的“a”图案的芯可被解释为包括“一个或多个”图案的芯。
另外,在本文中,通过端点表述的数值范围包含该范围内所含的所有数值(例如,1至5包含1、1.5、2、2.75、3、3.80、4、5等)。
如本文所用,作为对特性或属性的修饰语,除非另外具体地定义,否则术语“大致”意指该特性或属性将能够容易被普通技术人员识别,而不需要绝对精确或完美匹配(例如,对于可量化特性,在+/-20%内)。除非另外具体地定义,否则术语“大体上”意指高逼近程度(例如,对于可量化特性,在+/-10%内),但同样不需要绝对精确或完全匹配。术语诸如相同、相等、均匀、恒定、严格等应当理解成是在普通公差内,或在适用于特定情况的测量误差内,而非需要绝对精确或完美匹配。
本公开的以上发明内容并不旨在描述本发明的每个公开实施方案或每种实施方式。以下描述更为具体地举例说明了例示性实施方案。在本申请全文的若干处,通过实施例列表提供了指导,这些实施例能够以各种组合使用。在每种情况下,所表述的列表只是作为代表性的组类,不应解释为穷举性的列表。
附图说明
图1是本文通常描述类型的示例性粘合剂制品的一个实施方案的俯视平面图;
图2是图2的粘合剂制品的剖视图;
图3A至图3C是通常属于图1和图2中所识别的类型的粘合剂制品从粘附体表面移除的照片;
图4是本文通常描述类型的示例性粘合剂制品的一个实施方案的剖视图;
图5是本文通常描述类型的示例性粘合剂制品的一个实施方案的剖视图;
图6是本文通常描述类型的示例性粘合剂制品的一个实施方案的俯视平面图;
图7是图6的粘合剂制品的剖视图;
图8是本文通常描述类型的示例性粘合剂制品的一个实施方案的剖视图;
图9是本文通常描述类型的示例性粘合剂制品的一个实施方案的剖视图;
图10是本文通常描述类型的示例性粘合剂制品的另一个实施方案的剖视图;并且
图11是用于对本公开的示例性粘合剂制品进行重量悬挂测试的钩的透视图。
某些描绘的实施方案中的层仅是为了进行示意性的说明,并且并非旨在绝对地限定任何部件的厚度(相对厚度或其它方式的)或位置。虽然上述附图示出了本公开的若干实施方案,但正如说明书中所指出的,还可以想到其它的实施方案。在所有情况下,本公开均以示例性而非限制性方式展示。应当理解,本领域的技术人员可以设计出许多落入本公开原理的范围内及符合本公开原理的实质的其它修改形式和实施方案。
具体实施方式
将详细描述各种实施方案和具体实施。这些实施方案不应理解为以任何方式限制本专利申请的范围,并且在不脱离本发明的实质和范围的前提下,可作出更改和修改。此外,本文仅论述了一些最终用途,但本文未具体描述的最终用途也包括在本申请的范围内。因此,本专利申请的范围应由权利要求书确定。
本公开整体涉及可从基底、壁或表面(通常为粘附体)移除而不造成损坏的粘合剂制品。如本文所用,术语“不造成损坏”或“无损坏”等意指可将粘合剂制品与基底分开而不对油漆、涂层、树脂、覆盖物或下面的基底造成肉眼可见的损坏和/或留下残余物。对基底的肉眼可见损坏可为例如对基底的任何层的刮擦、撕裂、层离、破碎、碎裂、拉紧等形式。可见损坏也可为变色、疲软、光泽度变化、雾度变化、或基底外观的其它变化。
粘合剂制品包括(1)一个或多个可剥离粘合剂层,该一个或多个可剥离粘合剂层邻近(2)离散芯。如本文所用,术语“可剥离的”是指粘合剂制品可通过以介于约1°和约180°之间的角度剥离而从基底或表面移除。在一些实施方案中,通过以30°至120°的角度剥离可从基底或表面移除粘合剂制品。在一些实施方案中,通过以至少约35°的角度剥离可从基底或表面移除粘合剂制品。在剥离释放移除期间,至少第一粘合剂层与芯分离或使芯变形。因此,粘合剂制品被具体设计成模仿“无背衬”构造,其中芯对粘附体受到的粘合剂移除力几乎没有贡献或没有贡献。“无背衬”构造提供剥离力不超过基底(包括例如干式墙、油漆、玻璃等)上的损坏阈值的粘合剂制品。
图1和图2示出了如本文通常所述的粘合剂制品100的示例性实施方案。粘合剂制品100包括具有相对的第一主表面111和第二主表面112的芯110。图1以俯视平面图示出了粘合剂制品100,其中芯110透过粘合剂层140可见。在一些实施方案中,粘合剂140通常可为光学透明的,使得芯至少部分可见。在其它实施方案中,粘合剂层140通常可为不透明的,或者芯在俯视平面图中可为不可视识别的。如图2所示,芯110具有由上边缘113、下边缘114和侧边缘115、侧边缘116限定的正方形形状。芯110的形状没有具体限制,并且可包括任何合适的形状或形状的组合。边缘113至边缘116配合以形成芯周边117,该芯周边117限定芯和粘合剂制品110的其余部分(例如,粘合剂层140)之间的可识别边界。
芯110作为粘合剂制品100的独特结构组件而存在,而不是作为分散或以其它方式分布在一个或两个粘合剂层140、粘合剂层142中的材料而存在。形成芯110的材料可包括纸材、天然或合成聚合物膜、由天然和/或合成纤维以及它们的组合制成的非织造织物、织物增强聚合物膜、纤维或纱线增强聚合物膜或非织造织物、诸如由合成或天然材料(诸如棉、尼龙、人造丝、玻璃、陶瓷材料等)的线形成的织造织物的织物,或这些材料中的任何的组合。芯110也可由金属、金属化聚合物膜或陶瓷片材料形成。在一些实施方案中,芯为具有两个或更多个层的多层膜;在一些此类实施方案中,将多个层层压。例如,芯可由具有任何合适厚度、组成和不透明度或透明度的泡沫、膜或它们的组合形成。在其它实施方案中,芯可包括离散颗粒或粘合剂或具有相对高凝胶含量的其它组合物的排列。下文将进一步详细地探讨芯110的示例性材料和构造。两种或更多种此类组合物和构造的组合也可用于本公开的各种实施方案中。
在图1和图2的具体实施方案中,芯110包括厚度为“T”的单个芯层材料,尽管本文也设想和描述多层或多材料构造。在一些实施方案中,芯的厚度“T”介于约2密耳和约100密耳之间。在一些实施方案中,芯的厚度大于2密耳、大于5密耳、大于8密耳、大于10密耳、大于12密耳、大于15密耳、大于20密耳、大于22密耳或大于24密耳。在一些实施方案中,芯的厚度小于100密耳、小于90密耳、小于80密耳、小于75密耳、小于70密耳、小于65密耳、小于60密耳、小于55密耳、小于50密耳、小于45密耳、小于40密耳、小于38密耳、小于35密耳、小于32密耳、小于30密耳、小于28密耳或小于25密耳。
粘合剂层140沿周边117的每一侧延伸,有效地围绕芯110并限定粘合剂制品100的边界105。如图1所示的粘合剂层140具有与芯110基本上相同的正方形形状。在其它实施方案中,粘合剂层140可改为限定例如矩形、椭圆形或卵形形状。在其它实施方案中,粘合剂层140仅沿侧边缘115、侧边缘116或仅沿芯110的上边缘和下边缘延伸。在又一其它实施方案中,粘合剂层140部分沿单个边缘延伸,或者部分沿多个边缘延伸。
如图2所示,芯110在横截面上大致为矩形,然而芯可具有多种横截面形状。例如,芯110的横截面形状可为多边形(例如,正方形、四面体、菱形、梯形),其可为正多边形或非正多边形,或者芯110的横截面形状可为弯曲的(例如,圆形或椭圆形)。第一芯平面118与第一主表面111重合,而第二芯平面119与第二主表面112重合。芯平面118、芯平面119被平行地示出,但在其它实施方案中可相交并形成斜角。
主表面111、主表面112中的每个邻近可剥离粘合剂层140和可剥离粘合剂层142。可剥离粘合剂层140和142可彼此相同或彼此不同。粘合剂层140和粘合剂层142各自可为单层或可为多层。粘合剂层140和粘合剂层142可各自在芯110的主表面上为连续的或不连续的(例如,图案化的)。粘合剂层140和粘合剂层142中的每个分别包括相对的主表面141、主表面145。制品的可用粘合剂区域由每个粘合剂层的相对的主表面141、主表面145的长度和宽度限定(此处大于芯110的第一主表面111)。主表面141、主表面145的可用粘合剂区域用于将粘合剂制品100联接到例如壁表面或耐用件。
粘合剂层140和粘合剂层142与芯的主表面111、主表面112共延的部分由厚度“T”隔开。因此,芯110与粘合剂层140、粘合剂层142分离,并且包括如上所述的限定的和可识别的几何形状。(一个或多个)粘合剂层的厚度没有具体限制,但在芯的至少主表面上通常为基本上连续的。在目前优选的实施方式中,粘合剂层的厚度不大于芯厚度“T”的95%,不大于90%、不大于80%、不大于75%、不大于60%、不大于50%、不大于40%、不大于30%、不大于20%,并且在一些实施方案中不大于芯厚度“T”的10%。在典型实施方案中,一个或两个粘合剂层140、粘合剂层142的厚度介于约1密耳和约3密耳之间。
在某些具体实施方式中,芯110的主表面上的给定粘合剂层140、粘合剂层142的厚度可大于粘合剂层在粘合剂界面150处的组合厚度,如下所述。
第一粘合剂层和芯的第一主表面111之间的接触限定了第一芯界面120。相似地,第二粘合剂层142和第二主表面112之间的接触限定了与第一芯界面120相对的第二芯界面122。在一些实施方案中,第一界面120和第二界面122包括与芯的粘合剂接触区域,其为至少约5%;至少约10%,至少约25%;至少约30%;至少约35%;至少约40%;至少约45%;至少约50%;至少约55%;至少约60%;至少约65%;至少约70%;至少约75%;或者至少约80%。在一些实施方案中,第一芯界面和第二芯界面包括粘合剂层140、粘合剂层142和芯之间介于约10%和约100%的粘合剂接触区域。在一些实施方案中,第一芯界面120和第二芯界面122包括粘合剂层140、粘合剂层142和芯之间介于约40%和约90%的粘合剂接触区域。每个芯界面140、芯界面142的粘合剂接触区域可相同或不同。在一些实施方案中,包括具有安装到第一可剥离粘合剂层140上的耐用件的实施方案中,第一芯界面140处的粘合剂接触区域大于第二芯界面142处的粘合剂接触区域。在其它实施方案中,第二芯界面142处的粘合剂接触区域大于第二芯界面140处的粘合剂接触区域。
粘合剂层140、粘合剂层142的未被芯110移位的主表面粘结在一起以形成粘合剂界面150。在图1和图2所示的实施方案中,粘合剂界面150限定围绕芯110的周边的接缝。粘合剂界面150放置在大致平行于芯平面118、芯平面119的平面中,但在其它实施方式中可与任一芯平面118、芯平面119共面。
构成芯110和粘合剂层140、粘合剂层142的材料被选择成使得粘合剂界面150处的粘结强度强于:1)第一芯界面120和/或第二芯界面122处或附近的粘结强度;2)芯110在基本上垂直于芯平面118的方向上的结构完整性(例如,内聚强度);或者3)它们的组合。粘合剂界面150处的粘结可为胶粘剂(在以粘合剂层140、粘合剂层142中的相同可剥离粘合剂为特征的实施方案中)、粘合剂,或它们的组合。
芯界面和粘合剂界面之间的关系可表示为剥离比,该剥离比被定义为粘合剂界面处的剥离强度(oz/in2)与芯界面(一个或多个)处的剥离强度的比较。在一些实施方案中,剥离比可为至少1.15∶1;在一些实施方案中,至少1.25∶1;在一些实施方案中,至少1.5∶1;在一些实施方案中,至少2∶1;在一些实施方案中,至少3∶1;在一些实施方案中,至少5∶1;在一些实施方案中,至少10∶1;在一些实施方案中,至少15∶1;在一些实施方案中,至少20∶1;
在某些实施方案中,芯110的材料被选择成使得它与粘合剂层140、粘合剂层142中的任一个或两个形成相对弱的粘结。
另选地,芯110的一个或两个主表面111、主表面112可包括释放材料,以降低或最小化芯界面处的粘结强度。合适的释放材料包括但不限于低表面能材料,诸如硅氧烷、通过光酸生成的交联固化的环氧硅氧烷、氟硅氧烷、硅氧烷丙烯酸酯、全氟聚醚和其它含氟化合物材料、烯烃材料、长链烃功能性材料,以及它们的共聚物和混合物。在其它实施方案中,在芯界面的一部分上施加消音层。消音材料降低或消除了粘合剂在芯界面处的粘合性。示例性消音材料包括(例如)玻璃泡、膜、透明油墨、液体和/或具有较低粘合特性的粘合剂。在一些实施方案中,芯界面中的粘合剂以降低或消除其粘附性的方式处理。一些示例性处理包括例如辐射、UV暴露、电子束或其它用于交联粘合剂或消除粘合剂的粘性的装置。
在其它实施方案中,芯的材料或构造被选择成使得它在移除期间施加在粘合剂制品上生成的力时层离、内聚性地失效或以其它方式分离。
即使在以可破坏芯为特征的实施方案中,芯110仍可沿其分离的一般平面提供足够的强度,使得根据具体应用,基于对用于将物体安装在安装表面上的粘合剂制品100的使用,芯的结构完整性不会失效。芯110可有利地在平行于芯平面118、芯平面119的方向上提供足以支撑物体并且向制品100提供一定程度的回弹力的内部静态剪切强度。
图3A至图3C示出了定位在硬膜190和粘附体180之间的制品100的移除。如图3A至图3C所示,当制品100以超过35度的剥离角度从粘附体移除时,粘合剂层140与芯110的本体的至少一部分脱离。这可由于第一芯界面120处的粘合剂粘结失效而发生,或者可由于芯材料在第一主表面111处或在芯110的主体内的降解(例如,内聚失效或层离)而发生。例如并且如图3B和图3C所示,如果芯110包括非织造材料,则剥离力可致使芯界面处的非织造材料中的纤维或细丝从芯110的其余部分移去,或者致使芯110在芯厚度的大致方向上(即,在基本上垂直于芯平面118、芯平面119中的一者或两者的方向上(图3A至图3C中未示出))被破坏。不受理论的束缚,在芯界面中的一者或两者处的脱粘或降解用于至少减少或潜在地消除芯110对剥离力的贡献,从而允许粘合剂层(一个或多个)独立拉伸并减少对粘附体的潜在损坏。在一些实施方案中,可剥离粘合剂层(一个或多个)140、粘合剂层142的侵蚀性可被选择成使得芯分离或降解发生在粘合剂界面150(图3A至图3C中未示出)层离之前,或者在必要可剥离粘合剂层和粘附体或耐用件之间的粘结的分离之前。
图4示出了根据本公开的粘合剂制品200的另一个实施方案。像图1至图2的胶粘剂制品100一样,粘合剂制品200包括芯210、第一可剥离粘合剂层240和第二可剥离粘合剂层242。芯210包括邻近第一粘合剂层240和第二粘合剂层242的第一主表面211和第二主表面212。第一粘合剂层240和芯的第一主表面211之间的接触限定了第一芯界面220。相似地,第二粘合剂层242和第二主表面212之间的接触限定了与第一芯界面220相对的第二芯界面222。制品200与粘合剂制品100的不同之处在于制品200包括多层芯210。
多层芯210可包括背衬260和联接到背衬260的相对主表面上或其它方式设置在背衬260的相对主表面上的一个或多个表层270。如图所示,多层芯包括两个表层270和表层272。在某些实施方案中,背衬260为可拉伸膜层。例如,背衬260的形式可为具有任何合适厚度、组成和不透明度或透明度的泡沫、膜或它们的组合。背衬260可为单层膜、单层泡沫、多层膜、多层泡沫、多层泡沫和膜、和/或单层或多层粘合剂。在特定实施方案中,芯210包括如PCT申请US2017/016039(Runge等人)中所述的多层膜,其全文以引用方式并入本文。表层270和表层272可彼此相同或彼此不同。表层270、表层272中的每一层可为单层或可为多层。
在某些实施方案中,背衬260包括具有比表层270、表层272中的任一者或两者实质上更高的刚度或模量的材料。较硬的背衬260的用途可为芯210提供结构支撑,以例如改善剪切保持行为,并且也可被选择成影响移除特性,诸如剥离移除角度和剥离移除速率。在一些实施方案中,高刚度区域的刚度比粘合剂安装组件的低刚度区域中的刚度大至少约5%。背衬260(或本文所述的任何层)的刚度由厚度和杨氏模量的组合限定。本文所述的背衬的示例性杨氏模量介于约100PSI和约15,000PSI之间。如本文所用,术语“高刚度”是指刚度比表层高至少约5%的材料层或材料排列。在一些实施方案中,高刚度背衬260的刚度比表层中的刚度大介于约5%和约10,000%之间。在一些实施方案中,高刚度区域的刚度比任一个或两个表层270、表层272中的刚度大至少50%、大至少100%,并且在一些实施方案中大至少1000%。在一些实施方案中,背衬260的杨氏模量介于约660PSI和约2000PSI之间。在一些实施方案中,(一个或多个)表层270、272的杨氏模量介于约600PSI至约1500PSI之间。在另一个实施方案中,高刚度表层层270、表层272的刚度比背衬260中的刚度大介于约5%和约10,000%之间。
图5示出了根据本公开的粘合剂制品300的另一个实施方案,其特征在于被设计用于在从粘附体移除制品300时进行内部分离的芯310。
与粘合剂制品100和粘合剂制品200一样,粘合剂制品300包括芯310、第一可剥离粘合剂层340和第二可剥离粘合剂层342。芯310包括邻近第一粘合剂层340和第二粘合剂层342的第一主表面311和第二主表面312。第一粘合剂层340和芯的第一主表面311之间的接触限定了第一芯界面320。相似地,第二粘合剂层342和第二主表面312之间的接触限定了与第一芯界面320相对的第二芯界面322。芯310包括介于第一背衬层310a和第二背衬层310b之间的可分离连接器360。可分离连接器360包括设置在第一背衬层310a的第二主表面上的第一可分离连接构件362和设置在第二背衬层310b的第二主表面上的第二可分离连接构件364。第一可分离连接构件362和第二可分离连接构件364能够彼此接合以形成可分离连接,从而可分离地连接芯背衬层:在分离可分离连接器360之后,第一可分离连接构件362与第一芯背衬310A保持柔性,并且第二可分离连接构件364与第二芯背衬310B保持柔性。
可分离连接器360可包括用于连接芯背衬层的任何已知或开发的可重复使用的连接器。可分离连接器360允许第一芯背衬层310a和第二芯背衬层310b沿一般平面分离和连接。在一些实施方案中,可分离连接器360可包括例如包括互锁系统的机械类紧固件、具有连接而无宏观机械变形或干涉的相互啮合系统、可释放的接触响应紧固件、可分开的构造等。在其它实施方案中,可分离连接器360包括通过共价键、离子键、氢键和/或范德华力结合的粘合剂、凝胶或凝胶粘合剂的一个或多个层。
在一些实施方案中,第一可分离连接构件362可包括在其第二主表面处粘结有第一芯背衬层310a的钩材料层,并且第二可分离连接构件364可包括在其第二主表面处粘结有第二芯背衬层310b的环材料层。预期,可利用任何可商购获得的钩环式连接器系统(包括购自3M公司的那些)。钩环式连接器系统是由本实施方案提出的仅一种类型的机械互锁连接器系统。通过机械互锁,这意味着在连接器元件中的至少一个连接器元件发生一些宏观变形(优选地地塑性变形)的情况下的那些紧固件使得机械干涉在多个组件之间发生。基于在此类可分离连接器系统的配合层之间的必备力及分离方式来设计互相接合元件的许多不同的修改形式。一些示例性的分离式连接器在例如美国专利6,572,945、7,781,056、6,403,206和6,972,141中有所描述,所有这些专利的全文均以引用方式并入本文。
可分离连接器360的连接区域和类型可被选择成使得分离芯背衬层310a、310b所需的力显著低于从粘附体移除剥离粘合剂层或在粘合剂界面350处使粘结破裂所需的力。此类力可在基本上垂直于连接器360的一般平面的方向上施加。在一些实施方案中,可分离连接构件362、可分离连接构件364可被选择成使得可分离连接器360在粘合剂界面350层离之前,或者在可剥离粘合剂层和粘附体之间的粘结分离之前分离,从而损害芯310的结构完整性。
在某些情况下,即使在剥离移除期间分离之后,可分离连接器也可重构以供重复使用。例如,可分离连接构件362、可分离连接构件364可被重新对齐,并且在主表面上施加压力以引起另一种机械联锁。作为另一示例,以一层或多层粘合剂和/或凝胶为特征的可分离连接器可允许一个或多个键(例如,离子键、范德华)重新形成。
可分离连接器360可沿其分离的一般平面提供足够的强度,使得根据具体应用,基于对用于将物体安装在安装表面上的粘合剂制品的使用,可分离连接器360将不分离。可分离连接器360可在平行于用于支撑所安装的物体(例如,耐用件)的一般平面的方向上提供内部静态剪切强度。
图6和图7示出了根据本公开的另一实施方案的粘合剂制品。粘合剂制品400包括与芯410共延的粘合剂层440。芯包括第一主表面411,其中上边缘413、下边缘414和侧边缘415、侧边缘416配合以形成周边。芯410包括延伸穿过芯材料的厚度“T”的孔470的阵列。在一些实施方案中,芯410包括孔470的排列图案。“排列图案”是排列在预定位置处的多个特征部(例如,孔、凹口、通道等),其以一定程度的规律性排列或以任何期望的方式排列。芯410中的孔470以网格阵列的形式排列,但其它图案和排列也是可能的。在一些实施方案中,孔470作为周期性阵列分布在芯表面上(例如,一维阵列或二维阵列,例如正方形阵列、六边形阵列或其它规则阵列)。例如,孔的排列图案可包括排列的行图案、排列的格状图案(诸如排列的正方形格状图案)、排列的Z字形图案、或排列的放射状图案。排列图案不需要在整个表面上均匀地形成,而是可仅在芯表面的一部分上形成。孔的图案可在制品的任一部分上改变或者保持不变。例如,在相同的平面内可使用类似的或不同的图案。图案内的孔可具有相似的大小和形状,或者可具有不同的尺寸和形状。
为便于参考,图6和图7中包括笛卡尔x-y-z坐标系。第一主表面411和第二主表面412大致平行于x-y平面延伸,并且芯410的厚度对应于z轴。孔470的阵列包括大致沿x轴的横向和大致沿y轴的纵向。阵列或图案中的相邻孔470之间的节距在横向和纵向上可相同。排列图案包括相邻孔470之间限定的间距或节距。可选择任何给定区域中的孔的配置,使得节距471(即,相邻特征部之间的平均质心到质心的距离)为至少0.5毫米,在其它实施方案中为至少1毫米,在其它实施方案中为至少5毫米,在其它实施方案中为至少15毫米,在其它实施方案中为至少20毫米,在其它实施方案中为至少25毫米,并且在又一其它实施方案中为至少30毫米。在某些实施方案中,节距不大于70毫米,在一些实施方案中,不大于60毫米,在一些实施方案中,不大于50毫米,并且,在某些实施方案中,不大于45毫米。
孔470可呈现任何形状的形式。芯410的图示实施方案包括多个圆形开口472。适于孔开口472的形状的非限制性示例包括圆形、三角形、正方形、矩形和其它多边形。相似地,孔470的三维几何形状没有特别限制,只要孔延伸穿过芯410并且可包括圆形圆柱体;椭圆柱形;立方体,例如正方体或长方体;锥形;截头圆锥形等。无论横截面形状如何,每个孔470在开口472处具有最大横截面尺寸。最大横截面尺寸的大小没有具体限制。在示例性实施方案中,最大横截面可不大于80毫米,在一些实施方案中不大于70毫米,并且在一些实施方案中不大于60毫米。最大横截面尺寸可为至少0.5毫米,在其它实施方案中为至少1毫米,在其它实施方案中为至少5毫米,在一些实施方案中为至少10毫米,在一些实施方案中为至少15毫米,并且在一些实施方案中为至少20毫米。
如图所示,孔470沿横向和纵向两者是离散的。在其它实施方案中,孔470可沿一个方向离散,使得孔类似于芯中的通道,或者可在芯的主表面411、主表面412上对角地(相对于图6所示的取向)延伸。此类通道可遵循任何期望的路径,并且可在任何给定方向上在芯的表面上连续或者不连续。
粘合剂层440、粘合剂层442接触以在孔470的体积内形成多个粘合剂界面450。如图7所示,阵列线中的每个孔470包括粘合剂界面450。尽管在某些情况下孔与界面的一对一比率可为优选的,但本公开的其它实施方案可在少于所有可用孔470的范围内包括粘合剂界面450。在其它实施方案中,粘合剂层可不在孔470中的任一个中形成粘合剂界面。
第一剥离粘合剂层440和第二可剥离粘合剂层442在图6和图7中被示为覆盖孔470之间的芯的主表面411、主表面412上的间隙空间。在其它实施方案中,粘合剂层可覆盖空隙空间的较小连续部分,或者可仅覆盖紧围绕孔470的开口或基底的间隙空间。在其它实施方案中,一个或两个粘合剂层仅存在于孔470内,使得芯界面和粘合剂界面两者均位于孔的体积内。在典型实施方案中,粘合剂层440、粘合剂层442不占据给定孔内的所有可用体积。
多个粘合剂界面450存在于芯410的周边内,并且在大致平行于第一芯平面418和第二芯平面419并与第一芯平面418和第二芯平面419偏移的平面中。在其它实施方式中,制品400的芯410可与粘合剂制品100至粘合剂制品300的特征部组合,使得制品包括两者均在周边内并且在芯周边外部延伸的粘合剂界面。
通常,在芯材料中形成孔470之后,将一个或两个粘合剂层440、粘合剂层442层压或以其它方式联接到芯410。孔可通过用于从结构移除材料的任何已知方法形成,诸如模切、激光切割、压印等。在其它实施方案中,芯410可被挤出以包括如美国专利公布2017/0022339(Hanschen等人)和2016/0002838(Ausen等人)中所述的孔,所有这些均全文以引用方式并入本文。
图8示出了本文通常描述的包括耐用件的类型的粘合剂制品500的一个示例性实施方案的横截面表示。粘合剂制品500包括耐用件590、芯510和粘合剂层540、粘合剂层542。芯510可为本文所述的材料和构造中的任何。图8所示的特定耐用件590包括从第一主表面592延伸的钩596,两者与第二主表面594相对且间隔开。关于合适的耐用件的更多细节可见于下文。耐用件590的第二主表面594邻近第二粘合剂层542的主表面545,从而形成耐用件界面598。第二粘合剂层542和第二主表面512之间的接触限定了与耐用件界面598相对的芯界面524。同样,第二粘合剂层542和第一粘合剂层之间的接触限定了与耐用件界面598相对的多个粘合剂界面550。
图9示出了本文通常描述的类型的粘合剂制品600的另一个示例性实施方案,该粘合剂制品600包括耐用件690并且以单个可剥离粘合剂层640为特征。粘合剂制品包括通过粘合剂层640安装到耐用件690上的芯610。芯610可为本文所述的材料和构造中的任一种。耐用件690的第二主表面694邻近第一粘合剂层640的第二主表面643,从而形成与芯平面619大致共面的耐用件界面698。第一粘合剂层640和第一主表面611之间的接触限定了设置在耐用件界面698上方的芯界面620。粘合剂层640的第一主表面641可联接到期望的粘附体(例如,壁表面、机柜表面等)。耐用件界面698处的粘结强度优选强于:1)芯的内聚强度;2)芯界面620处的粘结,或3)它们的组合。粘合剂-粘合剂界面的缺乏可导致粘合剂制品600在从耐用件(或安装表面)移除时几乎完全降解和/或拆卸。然而,在使用者可接受单独设置粘合剂制品600的每个组成元件的情况下,这可为可接受的。
图10示出了本文通常描述的类型的粘合剂制品的另一个示例性实施方案,该粘合剂制品包括耐用件790、开孔芯710和单个可剥离粘合剂层740。芯710可为本文所述的材料和构造中的任何,并且包括延伸穿过芯材料的厚度“T”的孔770的排列阵列。耐用件790的第二主表面794附连到第一粘合剂层740,从而在孔770中的至少一些内与芯平面719大致平行(如果不共面的话)的平面内形成多个耐用件界面798。粘合剂层740和第一主表面711之间的接触限定了设置在耐用件界面798上方的平面中的芯界面720。粘合层740的第一主表面741可用于将制品700固定到期望的粘附体(例如,壁表面、机柜表面等)。多个耐用件界面798处的粘结强度优优选强于:1)芯710的内聚强度;2)芯界面720处的粘结,或3)它们的组合。芯周边内的粘合剂-耐用件界面的数量的增加可改善在剥离移除期间芯710与粘合剂层740的分离,从而确保粘合剂可充分拉伸以避免明显损坏。
芯材料
芯为粘合剂构造的一部分并且妨碍另外的相邻粘合剂层的部分的界面粘结。芯材料可被选择成提供低能量表面,以允许芯和可剥离粘合剂之间的容易分离。芯可为单层或者多层构造。多于一个芯层可存在于芯中。多个芯层可由膜层隔开,该膜层还可包括一个或多个层。在一些实施方案中,芯包括塑料、金属、纸、非织造材料、纺织品、织造材料、泡沫、粘合剂、凝胶和/或细丝增强材料中的至少一种。在一些实施方案中,芯为单层材料或多层膜中的至少一种。在其它实施方案中,芯可为设置在相邻粘合剂层之间的颗粒的排列。
在一些实施方案中,两个或更多个子层可为共挤出的,以便形成芯。在一些实施方案中,芯为柔性的。一些实施方案在芯中包括染料或颜料。一些实施方案在芯的至少一个层中包括至少一种增粘剂。一些实施方案在芯的一个或多个层中包括增塑油。
芯可由任何期望的一种或多种材料制成。适用于芯的代表性示例可包括例如聚烯烃诸如聚乙烯(包括高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯和线性超低密度聚乙烯)、聚丙烯和聚丁烯;乙烯共聚物诸如聚氯乙烯(增塑的和未增塑的)和聚醋酸乙烯酯;烯烃共聚物诸如乙烯/甲基丙烯酸亚乙酯共聚物、乙烯-醋酸乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物和乙烯/丙烯共聚物;丙烯酸类聚合物和共聚物;聚氨酯;以及前述的组合。也可使用任何塑性材料或者塑性材料和弹性体材料的混合物或共混物诸如聚丙烯/聚乙烯、聚氨酯/聚烯烃、聚氨酯/聚碳酸酯、聚氨酯/聚酯。
在一些实施方案中,芯为或包括复合泡沫,该复合泡沫包括柔性聚合物泡沫层、层压到泡沫层的第一主表面的第一膜,以及层压到泡沫层的第二相对的主表面的第二膜。粘合剂可附接到膜以形成粘合剂-膜-泡沫-膜-粘合剂的结构。可选择柔性聚合物泡沫层以优化适形能力和回弹力特性,当粘合剂制品粘附到具有表面不平度的表面时该适形能力和回弹力特性是有帮助的。典型的壁表面就属于这种情况。示例性柔性聚合物泡沫层可商品名“Command(命令)”从明尼苏达州圣保罗市的明尼苏达矿业及制造公司(“3M”)(MinnesotaMining and Manufacturing Company(“3M”)of St.Paul,Minn.)商购获得。在一些实施方案中,芯的柔性聚合物泡沫层可包括聚烯烃泡沫,该聚烯烃泡沫可以商品名“Volextra”和“Volara”从马萨诸塞州劳伦斯市积水美国分公司Voltek(Voltek,Division of SekisuiAmerica Corporation,Lawrence,Mass)获得。在一些实施方案中,芯为金属或包括金属,或者为金属类似物。在一些实施方案中,芯为木材或包括木材,或者为木材类似物。
芯可为或可包括以下专利申请中任一项所述的材料或背衬中的任一者,所有这些专利申请均全文并入本文:PCT申请US2018/024347和WO公布2015/195344、2017/136432和2018/039584。
在各种实施方案中,芯可由例如授予Bartusiak等人的美国专利8,530,021中所述的微结构带材料制造或生产。
在一些实施方案中,芯可包括在与此同时提交的题为“允许无损移除的粘合剂制品”的3M代理人案件79768WO004中描述的图案化芯。
芯可为任何期望的形状,该形状包括例如正方形、矩形、三角形、多边形、圆形、四边形、梯形、圆柱形、半圆形、星形、半月形、四面体等。
芯可为基本上不可拉伸的或弹性的。在一些实施方案中,芯材料在25摄氏度下的储能模量介于约15×103Pa和约2.5×106Pa之间。在一些实施方案中,芯在25摄氏度下的tanδ(其中tanδ为损耗模量除以储能模量)介于约0.4和约1.2之间。在一些实施方案中,芯具有介于约-125摄氏度和约40摄氏度之间的玻璃化转变温度。在其它实施方案中,芯材料在10秒后的应力弛豫介于10%和100%之间。
在一些实施方案中,芯在10%应变下表现出1%至99%的弹性恢复率。在一些实施方案中,芯在20%应变下表现出1%至99%的弹性恢复率。本公开的一些实施方案中,芯材料在至少一个方向上的断裂伸长率大于50%。本公开的一些实施方案中,芯材料在至少一个方向上的断裂伸长率介于约50%和约1200%之间。
在一些实施方案中,芯的杨氏模量介于约100psi和约100,000psi之间。在一些实施方案中,如通过ASTM d5459 95所测量的,芯在10%应变下表现出1%至100%的弹性恢复率。在一些实施方案中,芯在20%应变下表现出1%至100%的弹性恢复率。
在一些实施方案中,如通过ASTM D638-14和ASTM D412-06a中的至少一者测量的,芯的弹性模量和/或割线模量介于约100psi和约15,000psi之间。在一些实施方案中,芯的模量范围介于100psi和15000psi之间。在一些实施方案中,模量大于100psi、大于500psi、大于1000psi。在一些实施方案中,芯模量小于15000psi、小于10000psi、小于8,000psi、小于5,000psi、小于3,500psi、小于2000psi和小于1500psi。
在一些实施方案中,芯的厚度介于约0.1密耳和约100密耳之间。在一些实施方案中,芯的厚度大于1密耳、大于5密耳、大于8密耳、大于10密耳、大于12密耳、大于15密耳、大于20密耳、大于22密耳或大于24密耳。在一些实施方案中,芯的厚度小于100密耳、小于90密耳、小于80密耳、小于75密耳、小于70密耳、小于65密耳、小于60密耳、小于55密耳、小于50密耳、小于45密耳、小于40密耳、小于38密耳、小于35密耳、小于32密耳、小于30密耳、小于28密耳或小于25密耳。
非织造织物
在一些目前优选实施方案中,芯包括非织造基底。该非织造基底可为通过生产非织造幅材的任何通常已知工艺制造的非织造织物或幅材。如本文所用,术语“非织造”是指具有单根纤维或细丝的结构的织物,这些纤维或细丝以毡状方式随机和/或单向交织,但不像针织物那样以可识别的方式交织。非织造织物或幅材可由各种工艺(诸如熔喷工艺、纺粘法处理、水刺工艺和粘结梳理成网幅材工艺、气流成网工艺和湿法成网工艺)形成。在一些实施方案中,芯包含多层非织造材料,其中具有例如至少一层熔喷非织造材料和至少一层纺粘非织造材料,或非织造材料的任何其它合适组合。例如,芯可为纺粘-熔粘-纺粘、纺粘-纺粘或纺粘-纺粘-纺粘多层材料。或者,芯可为包括非织造织物层和膜层的复合幅材。
如本文所用,“熔喷”意指用于通过如下方式形成非织造纤维幅材的方法:将熔融的成纤材料挤出通过在模具中的多个喷丝孔以形成纤维,同时使所述纤维与空气或其它细化用流体接触以将所述纤维细化成纤维,并随后收集经细化的纤维。示例性熔喷工艺在例如美国专利6,607,624(Berrigan等人)中教导。“熔喷纤维”意指通过熔喷或熔喷工艺制备的纤维。“纺粘法”和“纺粘工艺”意指用于通过将熔化的成纤材料从喷丝头的多个细毛细管挤出成连续或半连续纤维,并随后收集经细化的纤维而形成非织造纤维幅材的方法。示例性纺粘工艺在例如授予Matsuki等人的美国专利3,802,817中有所公开。“纺粘纤维”和“经纺粘的纤维”意指使用纺粘或纺粘工艺制备的纤维。此类纤维通常为连续纤维,并且充分缠结或点粘结以形成内聚非织造纤维幅材,由此使得通常不能从此类纤维的整体中取出一根完整的纺粘纤维。所述纤维也可具有例如在授予Hogle等人的美国专利5,277,976中描述的那些形状,该专利描述了具有非常规形状的纤维。“粗梳法”和“粗梳工艺”指通过将短纤维通过梳理或粗梳单元加工而形成非织造纤维幅材的方法,所述梳理或粗梳单元分离或拆分短纤维并沿着纵向对齐短纤维,从而形成总体上纵向取向的非织造纤维幅材。示例性梳理工艺和梳理机在例如授予Chaplin等人的美国专利5,114,787和5,643,397中教导。“粘结梳理成网幅材”是指通过梳理工艺形成的非织造纤维幅材,其中至少一部分纤维通过包括例如热点粘结、自生粘结、热空气粘结、超声波粘结、针刺法、压延法、施用喷雾粘合剂等的方法粘结在一起。关于非织造幅材和包括非织造幅材的层压体的生产和特性的更多细节可见于例如美国专利9,469,091(Henke等人)中,该专利全文以引用方式并入本文。“气流成网”是指这样一种工艺,其中典型长度为在约3毫米(mm)至约52毫米范围内的小纤维束被分离并被夹带在气源中,并且然后通常借助于真空源而沉积到形成筛网上。无规取向纤维然后可使用例如热点粘结、自生粘结、热空气粘结、针刺、压延、喷雾粘合剂等等而彼此粘结。示例性气流成网法工艺在例如授予Laursen等人的美国专利No.4,640,810中教导。“湿法成网”是指这样一种工艺,其中典型长度为在约3至约52毫米(mm)范围内的小纤维束分离并被夹带在液体源中,并且随后通常借助于真空源而沉积到形成筛网上。水通常是优选的液体。无规沉积的纤维还可通过进一步缠结(例如水力缠结),或可利用例如热点粘结、自生粘结、热空气粘结、超声波粘结、针刺、压延、施加喷雾粘合剂等等而彼此粘结。在例如美国专利5,167,765(Nielsen等人)中提出了示例性湿法成网和粘结工艺。在例如授予Berrigan等人的美国专利9,139,940中也公开了示例性粘合工艺。
提供可用的非织造芯的纤维材料可由天然纤维(例如,木材或棉纤维)、合成纤维(例如,热塑性纤维),或者天然纤维和合成纤维的组合制成。用于形成热塑性纤维的示例性材料包括聚烯烃(例如,聚乙烯、聚丙烯、聚丁烯、乙烯共聚物、丙烯共聚物、丁烯共聚物,以及这些聚合物的共聚物和共混物)、聚酯和聚酰胺。非织造基底可由任何合适的热塑性聚合物材料制成的纤维或细丝形成。合适的聚合物材料包括但不限于聚烯烃、聚(异戊二烯)、聚(丁二烯)、氟化聚合物、氯化聚合物、聚酰胺、聚酰亚胺、聚醚、聚(醚砜)、聚(砜)、聚(乙酸乙烯酯)、乙酸乙烯酯的共聚物如聚(乙烯)-共-聚(乙烯醇)、聚(磷腈)、聚(乙烯基酯)、聚(乙烯基醚)、聚(乙烯醇)以及聚(碳酸酯)。合适的聚烯烃包括但不限于聚(乙烯)、聚(丙烯)、聚(1-丁烯)、乙烯和丙烯的共聚物、α-烯烃共聚物(诸如乙烯或丙烯与1-丁烯、1-己烯、1-辛烯和1-癸烯的共聚物)、聚(乙烯-共-1-丁烯)以及聚(乙烯-共-1-丁烯-共-1-己烯)。合适的氟化聚合物包括但不限于聚(氟乙烯)、聚(偏二氟乙烯)、偏二氟乙烯的共聚物(诸如聚(偏二氟乙烯-共-六氟丙烯))以及三氟氯乙烯的共聚物(诸如聚(乙烯-共-三氟氯乙烯))。合适的聚酰胺包括但不限于:聚(亚胺基己二酰亚胺基六亚甲基)、聚(亚胺基己二酰亚胺基十亚甲基)以及聚己内酰胺。合适的聚酰亚胺包括聚(均苯四酰亚胺)。合适的聚(醚砜)包括但不限于聚(二苯醚砜)和聚(二苯砜-共-氧化二亚苯砜)。合适的乙酸乙烯酯的共聚物包括(但不限于)聚(乙烯-共-乙酸乙烯酯)和其中乙酸酯基团中的至少一部分已经水解以提供各种聚(乙烯醇)的此类聚合物,包括聚(乙烯-共-乙烯醇)。
该纤维也可为多组分纤维,例如,具有一种热塑性材料的芯部和另一种热塑性材料的外皮。外皮可在比芯低的温度下熔融,从而当纤维垫暴露于外皮熔融物时,在纤维之间提供部分的无规粘结。具有不同熔点的单组分纤维的组合也可用于此目的。在一些实施方案中,可用于根据本公开的芯中的非织造织物或幅材为至少部分弹性的。用于制造弹性纤维的聚合物的示例包括热塑性弹性体诸如ABA嵌段共聚物、聚氨酯弹性体、聚烯烃弹性体(例如,金属茂聚烯烃弹性体)、烯烃嵌段共聚物、聚酰胺弹性体、乙烯乙酸乙烯酯弹性体、和聚酯弹性体。ABA嵌段共聚物弹性体通常为如下弹性体,其中A嵌段为聚苯乙烯系,并且B嵌段由共轭双烯(例如,低级亚烷基双烯)制备而成。A嵌段通常主要由取代(例如,烷基化)或未取代的苯乙烯系部分(例如,聚苯乙烯、聚(α-甲基苯乙烯)或者聚(叔丁基苯乙烯))形成,其平均分子量为约4,000克/摩尔至50,000克/摩尔。(一个或多个)B嵌段通常主要由共轭双烯(例如,异戊二烯、1,3-丁二烯或乙烯-丁烯单体)形成,所述共轭双烯可为被取代或未取代的,并且平均分子量为约5,000克/摩尔至500,000克/摩尔。例如,A嵌段和B嵌段可以线性、放射状或者星状构型来构造。ABA嵌段共聚物可包含多个A嵌段和/或B嵌段,这些嵌段可由相同或不同的单体制成。典型的嵌段共聚物为线性ABA嵌段共聚物,其中A嵌段可相同或不同,或者为具有多于三个嵌段且主要由A嵌段封端的嵌段共聚物。例如,多嵌段共聚物可包括一定比例的AB双嵌段共聚物,该AB双嵌段共聚物趋于形成更发粘的弹性体膜链段。其它弹性聚合物可与嵌段共聚物弹性体共混,并且各种弹性聚合物可进行共混,以使其具有不同程度的弹性特性。多种类型的热塑性弹性体可商购获得,包括以商品名“STYROFLEX”得自美国新泽西州弗洛勒姆帕克的巴斯夫公司(BASF,Florham Park,N.J.)、以商品名“KRATON”得自美国德克萨斯州休斯敦的科腾聚合物公司(Kraton Polymers,Houston,Tex.)、以商品名“PELLETHANE”、“INFUSE”、“VERSIFY”或“NORDEL”得自美国密歇根州米德兰的陶氏化学公司(Dow Chemical,Midland,Mich.),以商品名“ARNITEL”得自荷兰海尔伦的帝斯曼公司(DSM,Heerlen,Netherlands)、以商品名“HYTREL”得自美国特拉华州威明顿的杜邦公司(E.I.duPont de Nemours and Company,Wilmington,Del)、以商品名“VISTAMAXX”得自美国德克萨斯州欧文的埃克森美孚公司(ExxonMobil,Irving,Tex)的热塑性弹体等。
例如,纤维非织造网可通过以下方法制成:梳理成网法、气纺法、湿法成网法、射流喷网法、纺粘法、静电纺纱法或熔喷法技术(例如熔纺法或熔喷法)、或它们的组合。非织造幅材中的任何一种均可由单一类型的纤维或在热塑性聚合物的类型、形状和/或厚度方面不同的两种或多种纤维制成;单纤维类型或多种纤维类型中的至少一种可各自为如上所述的多组分纤维。
短纤维也可存在于料片中。短纤维的存在通常提供比仅仅熔喷的微纤维网更为蓬松、不太致密的网。较蓬松的幅材可在芯界面处或芯自身的大部分处具有减小的内聚强度,从而导致更容易地与一个或多个粘合剂层分离。
非织造芯还可任选包含一层或多层稀松布。例如,一个或全部两个主表面还可以任选各包括稀松布层。将稀松布(其通常为由纤维制成的织造或非织造的增强层)包括在内,以向非织造制品提供强度。合适的稀松布材料包括但不限于尼龙、聚酯、玻璃纤维、聚乙烯、聚丙烯等等。稀松布的平均厚度可以是变化的。稀松布的层可任选地粘结到非织造基底。多种粘合剂材料可用于将稀松布粘结到基底。或者,稀松布可以热粘结到非织造物。
可用的非织造芯可具有特定应用所需的任何合适的EFD、基重或厚度。“有效纤维直径”或“EFD”是基于空气渗透试验的纤维幅材中纤维的表观直径,在空气渗透试验中,空气在1个大气压和室温下以规定的浓度和面速度(通常5.3cm/sec)穿过幅材样品,并测量对应的压降。基于测量的压降,有效纤维直径如以下中所示出的计算:Davies,C.N.,“气载尘埃和颗粒的分离(The Separation of Airborne Dust and Particles)”,伦敦机械工程研究所(Institution of Mechanical Engineers,London),程序1B(Proceedings 1B),1952年)。非织造基底的纤维的有效纤维直径通常为至少0.1微米、1微米、2微米或甚至4微米并且至多125微米、75微米、50微米、35微米、25微米、20微米、15微米、10微米、8微米或甚至6微米。纺粘芯的EFD通常不大于35,而气流成网芯的EFD可为大约100微米或更大。非织造基底的基重优选在至少5g/m2、10g/m2、20g/m2或甚至50g/m2范围内;并且最多800g/m2、600g/m2、400g/m2、200g/m2或者甚至100g/m2范围内的基重。根据10cm×10cm的样品的重量计算基重。非织造幅材在纵向上的最小拉伸强度为约4.0牛顿。
芯非织造织物的蓬松度也可用密实度(如本文中所定义并通过本文中报告的方法所测量)来表征。
密实度通过将非织造纤维幅材的所测量的堆密度除以构成幅材的固体部分的材料的密度来确定。幅材的堆密度可通过首先测量幅材的重量(例如,10cm×10cm的区段)来确定。将测量的纤维网的重量除以纤维网面积,得到纤维网的基重,以g/m2为单位记录。幅材的厚度可通过获得(例如,通过模切)135mm直径的幅材盘并在幅材顶部居中放置100mm直径的230g重物的情况下测量幅材厚度而测得。纤维网的堆密度是通过将纤维网的基重除以纤维网的厚度来确定,以g/m3为单位记录。然后密实度通过将非织造纤维幅材的堆密度除以包含幅材的固体细丝的材料(例如,聚合物)的密度来确定。如果供应商没有指定材料的密度,则可以通过标准方法来测量堆聚合物的密度。蓬松度通常报告为100%减去密实度(例如,7%的密实度相当于93%的蓬松度)。
如本文所公开的,可生成密实度从约2.0%至小于12.0%(即,蓬松度从约98.0%至大于88.0%)的幅材。在各种实施方案中,如本文所公开的幅材具有至多约7.5%、至多约7.0%或至多约6.5%的密实度。在特定实施方案中,如本文所公开的幅材具有至少约5.0%、至少约5.5%或至少约6.0%的密实度。
聚合物膜
在本公开的许多实施方案中,芯可包括聚合物膜或由聚合物膜组成。聚合物膜芯层可有多种形式,包括例如单层或多层膜、多孔膜以及它们的组合。聚合物膜可包含一种或多种填料(例如,碳酸钙)。聚合物膜可以是连续的层或不连续的层。多层聚合物膜优选以复合膜、层合膜以及它们的组合的形式彼此一体地粘结。可以采用任意合适的方法制备多层聚合物膜,这些方法包括例如共成型、共挤出、挤压涂布、通过粘合剂结合、在压力下结合、在受热的情况下结合以及它们的组合。
所述膜可包含单一聚合物材料或可以由聚合物材料的混合物制备。合适的材料的例子包括聚酯,诸如聚对苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、基于萘二甲酸的共聚酯或聚酯共混物;聚碳酸酯;聚苯乙烯类;苯乙烯-丙烯腈;乙酸纤维素;聚醚砜;聚(甲基)丙烯酸酯,诸如聚甲基丙烯酸甲酯;聚氨酯;聚氯乙烯;聚环烯烃;聚酰亚胺;或它们的组合物或共混物。
可包括在芯中的材料的示例包括聚烯烃诸如聚乙烯、聚丙烯(包括全同立构聚丙烯)、聚苯乙烯、聚酯、聚乙烯醇、聚(对苯二甲酸乙二醇酯)、聚(对苯二甲酸丁二醇酯)、聚酰亚胺、聚(己内酰胺)、聚(偏二氟乙烯)、聚交酯、乙酸纤维素和乙基纤维素等。
聚合物膜层可以是单层或者多层构造。可存在多于一个聚合物膜层。聚合物膜层可由任何成膜性聚合物组成。
在一些实施方案中,聚合物膜层包含下列物质中的至少一者:乙烯基芳族共聚物、线型低密度聚乙烯、低密度聚乙烯、高密度聚乙烯、乙烯与(甲基)丙烯酸酯单体的共聚物、乙烯与经过酸改性的(甲基)丙烯酸酯单体的共聚物、乙烯与乙酸乙烯酯的共聚物、乙烯与含有丙烯酸酯和/或经过酸改性的乙酸乙烯酯的共聚物。在一些实施方案中,该膜包含具有2至16个碳的烯烃单体的聚合物。在一些实施方案中,该膜为两种或更多种烯烃单体的共聚物。在一些实施方案中,该膜包含具有无规立构、间同立构或全同立构立体化学的烯烃单体的聚合物。在一些实施方案中,该膜为一种或多种使用茂金属催化剂聚合的烯烃单体的共聚物。在一些实施方案中,该膜由乙烯基共聚物诸如聚(氯乙烯)、聚(乙酸乙烯酯)等组成。在一些实施方案中,该膜为由上面列出的任何聚合物组成的共混物。
示例性合适的膜材料可包括SEBS、SEPS、SIS、SBS、聚氨酯、乙酸乙烯酯(EVA)、超低线性密度聚乙烯(ULLDPE)、氢化聚丙烯、丙烯酸乙酯(EMA)、超低线性密度聚乙烯(ULLDPE)、氢化聚丙烯、高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、包括聚对苯二甲酸乙二酯(PET)的聚合物,以及它们的组合或共混物。在一些实施方案中,聚合物膜由多层上文所列的任何聚合物组成。在特定实施方案中,该多个层包括芯层和一个或多个表层,如以引用的方式整体并入本文的PCT专利号US2017/016039(Runge等人)中所述。
可使用本领域已知的任何方法制备本文所述的聚合物膜。
颗粒
在一些实施方案中,芯层由各种颗粒的混合物组成。颗粒可分布在一个或多个芯层中。一般来讲,颗粒可为实心的、中空的或多孔的以及刚性的或非刚性的。颗粒可由任何合适的材料制成,包括木材、玻璃、陶瓷、聚合物、金属、金属氧化物和碳材料。芯层的颗粒通常在约1微米至约100密耳的大小范围内。不同的颗粒可分布在不同的芯层中。一个芯层也可包括多种组成、类型或大小的颗粒。一个芯层中的颗粒可具有相同或不同的组成和表面处理。颗粒可以特定的形状排列或者可不均匀地分布。颗粒的表面可被处理或官能化为疏水的或为亲水的。颗粒可为团聚的或非团聚的和聚集的或非聚集的。“团聚体”是指一次颗粒之间的弱缔合,其可由电荷或极性固持在一起并可被分解成较小的实体。“聚集体”是指强粘结或熔合的颗粒,其中所得外表面积可能显著小于单独的组分的表面积计算值之和。将聚集体保持在一起的力可包括很强的力,例如共价键,或通过烧结或复杂物理缠结产生的力。聚集体也可通过可逆或温度依赖性粘结(例如,离子键)保持在一起。
在一些实施方案中,芯包括无机颗粒。无机颗粒可为天然的或合成的。如本文所使用,术语“合成无机颗粒”包括通过化学合成工艺(例如,从溶液沉淀、通过火焰处理水解产生等),或通过物理合成工艺(例如,从气相沉淀、通过溶胶凝胶工艺硬化等),从初始状态(可为其天然存在的开采状态)转化、再生、重结晶、重构(等)为其当前状态的任何颗粒。如本文所用,术语“合成无机填料”也包括通过使其达到至少部分软化或熔化状态,然后通过冷却硬化的物理合成方法,从初始状态(可为其天然存在的开采状态)大致转化为其当前状态,使得大致消除了天然状态下可能已存在的任何大致晶体结构,使得材料现在处于大致非晶态的形式(例如,具有小于约0.5重量%的结晶度)的任何填料。此类工艺可包括(例如)熔融处理、焰熔法等等。反之,“天然无机颗粒”被定义为以其天然存在的形式从地球中提取的矿物,并且虽然可经受纯化和/或改性工艺,但仍大致以其天然存在形式使用。
使用上文提供的定义,合成无机颗粒包括(例如)所谓的玻璃泡或微球(诸如以商品名3M Glass Bubbles购自明尼苏达州圣保罗的3M公司(3M Company of St.Paul,MN)的那些)、陶瓷微球(诸如以商品名3M Ceramic Microspheres购自3M公司(3M Company)的那些)、合成粘土(例如,合成硅酸盐粘土,诸如以商品名Laponite购自得克萨斯州冈萨雷斯的南方粘土产品(Southern Clay Products of Gonzales,TX)的那些)、沉淀二氧化硅、热解法二氧化硅、玻璃质二氧化硅、合成二氧化钛(例如,通过硫酸盐法或氯化物法所制备的)、合成(沉淀)碳酸钙(例如,通过将二氧化碳通过氢氧化钙溶液所制备的)等等。
合适的天然无机颗粒包括方解石、毒重石、金红石、锐钛矿、钛铁矿、云母、绢云母、珍珠岩、滑石、石灰岩、二氧化硅、重晶石、石膏、烧石膏、高岭石、蒙脱石、绿坡缕石、伊利石、滑石粉、锂蒙脱石、贝得石、硅镁石、海泡石、膨润土、叶蜡石、硅藻土等等,以及它们的混合物。
如果用于芯中,则聚合物颗粒可由任何合适的聚合物材料制成。聚合物颗粒可由刚性材料或弹性体材料制成。合适的刚性聚合材料包括热固性聚合物,例如酚醛聚合物,或热塑性聚合物,例如聚偏二氯乙烯丙烯腈共聚物(PVDC共聚物)。示例性弹性体微球体描述于授予Baker等人的美国专利3,691,140、授予Baker等人的3,857,731和4,166,152。在另一方面,流体填充微球包含由具有碳酸钙涂层的丙烯腈共聚物或聚偏二氯乙烯共聚物组成的聚合物壳,诸如由Henkel以商品名DUALITE聚合物微球出售的那些。
其它示例性颗粒包括熔融氧化铝、经热处理的氧化铝、白色熔融氧化铝、黑碳化硅、绿碳化硅、二硼化钛、碳化硼、碳化钨、碳化钛、金刚石(天然的和合成的)、二氧化硅、氧化铁、氧化铬、二氧化铈、氧化锆、二氧化钛、硅酸盐、氧化锡、立方氮化硼、石榴石、熔融氧化铝-氧化锆、溶胶-凝胶颗粒等以及它们的混合物。
通常,用于芯中的颗粒的平均一次(在一些实施方案中,平均一次和团聚体)粒度(例如,直径)不大于1微米。“一次粒度”是指单个(非聚集、非团聚)颗粒的最大维度(例如,球形颗粒的直径)。在一些实施方案中,颗粒的平均一次(在一些实施方案中,平均一次和团聚体)粒度不大于0.1微米。
颗粒的形状可为大致球形。然而,作为另外一种选择,可采用其它形状如细长形状。此类形状的示例包括杆形、三角形、片状、棱锥形、圆锥形、实心球形、空心球形等。另外,颗粒可为无规形状的。
凝胶
如果用于芯中,则当在23℃下使用布氏LVT粘度计测量时,凝胶的粘度(在可测量的程度上)通常为至少100,000厘泊(cps)、至少500,000cps、至少600,000cps并且在又一其它实施方案中至少700,000cps。在一些实施方案中,当通过可溶性聚合物在合适的溶剂(例如,加热的四氢呋喃或甲苯)中提取进行测量时,芯的凝胶含量(即,凝胶分数)可大于25%、或大于50%、或大于80%。在一些实施方案中,凝胶为如下所述的粘合剂。某些凝胶中的键或其它吸引力在分离之后可为可重构的,使得即使在粘合剂制品已从粘附体移除之后,也可重复使用凝胶芯。
触变凝胶对于包括在芯中特别有用,因为它们在使用本公开的粘合剂制品期间通常受到的力下不太可能流动。合适的凝胶包括含有甘油的凝胶(参见例如美国专利3,780,537(Spencer)和美国专利申请公布US 2010/0274333(Dunshee等人));含有硅氧烷和甲硅烷氧基化合物的凝胶(参见例如美国专利7,795,326(Salamone等人));含有丙二醇的凝胶(参见例如美国专利5,843,145(Brink));含有交联的吸水聚合物例如交联的聚丙烯酰胺和聚丙烯酸钠的凝胶(参见例如美国专利5,697,961(Kiamil);以及从诸如聚环氧乙烷、聚乙烯吡咯烷酮、聚丙烯酰胺、阴离子聚丙烯酰胺、聚乙烯醇、马来酸酐-乙烯基醚共聚物、聚丙烯酸、乙烯-马来酸酐共聚物、聚乙烯醚、葡聚糖、明胶、羟丙基纤维素、甲基纤维素、羧甲基纤维素、羟乙基-羧甲基纤维素、羟乙基纤维素、丙二醇藻酸盐、藻酸钠、聚乙烯亚胺、卤代聚乙烯烷基吡啶鎓、聚脯氨酸、天然淀粉、酪蛋白、蛋白、聚甲基丙烯酸、聚乙烯磺酸、聚苯乙烯磺酸、聚乙烯胺、聚4-乙烯基吡啶、烯属酸的聚合单酯、烯属酸的聚合二酯、丙烯酰胺以及双官能可聚合材料(例如,二酸、二酯或二酰胺)等的起始物质制备的亲水凝胶。
示例性的合适凝胶可作为NICKOLODEON GAK(来自NSI国际)商购获得。
粘合剂
在一些实施方案中,芯包括粘合剂。在一些实施方案中,芯为压敏粘合剂。可用的压敏粘合剂的一般性描述可在如下文献中找到:《聚合物科学和工程百科全书》,第13卷,威利国际科学出版社(纽约,1988年)(Encyclopedia of Polymer Science andEngineering,Vol.13,Wiley-Interscience Publishers(New York,1988))。可用的压敏粘合剂的附加描述可在如下文献中找到:《聚合物科学和技术百科全书》,第1卷,国际科学出版社(纽约,1964年)(Encyclopedia of Polymer Science and Technology,Vol.1,Interscience Publishers(New York,1964))。本领域的普通技术人员熟知压敏粘合剂组合物具有包括如下在内的性质:(1)粘着性,(2)用手指按压就能进行粘附,(3)足够的保持在粘附体上的能力,以及(4)足够的内聚强度,以从粘附体上干净地移除。经发现良好地用作压敏粘合剂的材料为经设计和配制而表现出所需粘弹特性,从而使得粘性、剥离粘附力和剪切保持力达到期望平衡的聚合物。合适的PSA可基于交联或非交联(甲基)丙烯酸类、橡胶、热塑性弹性体、硅氧烷、聚氨酯等,并且可包括增粘剂以提供期望的粘着性以及其它添加剂。在一些实施方案中,PSA基于(甲基)丙烯酸类PSA或至少一种聚(甲基)丙烯酸酯,其中(甲基)丙烯酸酯是指丙烯酸酯基团和甲基丙烯酸酯基团两者。在一些实施方案中,PSA为基于烯烃嵌段共聚物的粘合剂。丙烯酸基压敏粘合剂描述于例如,美国专利4,726,982(Traynor等人)和美国专利5,965,256(Barrera)中。硅氧烷基粘合剂压敏粘合剂描述于例如,美国专利6,730,397(Melancon等人)和美国专利5,082,706(Tangney)中。聚氨酯基压敏粘合剂描述于例如,美国专利申请公布2005/0137375(Hansen等人)中。烯烃嵌段共聚物基压敏粘合剂描述于美国专利申请公布2014/0335299(Wang等人)中。
芯可包括多个粘合剂层。例如,芯可包括相对较硬的橡胶基粘合剂作为内层,其中较软的丙烯酸基PSA设置在内芯层和(一个或多个)可剥离粘合剂层之间。作为另一个示例,芯可包括相对软的丙烯酸基粘合剂作为内层,其中相对较硬的橡胶基粘合剂设置在内芯层和(一个或多个)可剥离粘合剂层之间。芯中粘合剂的特性可被选择或改性,以获得期望的属性。
如果用于芯中,粘合剂可具有与(一个或多个)可剥离粘合剂层不同的组成,以避免任何芯-粘合剂界面处的内聚强度的增加。另选地,如上所述,粘合剂的表面可通过释放材料或(一个或多个)消音层进行改性。
可剥离粘合剂层
用于本文所述的粘合剂制品中的粘合剂可包括具有期望特性的任何粘合剂。在一些实施方案中,粘合剂为可剥离的。在一些实施方案中,当粘合剂制品以约35°或更小的角度从粘附体的表面剥离时,粘合剂从粘附体的表面干净地释放。在一些实施方案中,当多层载体以约35°或更大的角度从粘附体表面剥离时,可剥离粘合剂从粘附体的表面释放,使得在粘附体的表面上基本上不留下粘合剂的痕迹。
粘合剂可为例如以下专利申请中任一项所述的任何粘合剂,所有这些均以引用方式并入本文:国际公布WO/2015/035556、WO/2015/035960、WO/2017/136219、WO/2017/136188和美国专利申请2015/034104,所有这些专利申请均全文并入本文。
在一些实施方案中,可剥离的粘合剂为压敏粘合剂。任何合适的组合物、材料或成分均可用于压敏粘合剂中。示例性压敏粘合剂利用例如与一种或多种增粘树脂结合的一种或多种热塑性弹性体。在一些实施方案中,粘合剂不是压敏粘合剂。
在一些实施方案中,可剥离的粘合剂层可包含橡胶、有机硅或丙烯酸类粘合剂中的至少一种。在一些实施方案中,可剥离的粘合剂层可包含压敏粘合剂(PSA)。在一些实施方案中,可剥离的粘合剂可包含增粘橡胶粘合剂诸如天然橡胶;烯烃;有机硅诸如有机硅聚脲或有机硅嵌段共聚物;合成橡胶粘合剂,诸如聚异戊二烯、聚丁二烯和苯乙烯-异戊二烯-苯乙烯、苯乙烯-乙烯-丁烯-苯乙烯和苯乙烯-丁二烯-苯乙烯嵌段共聚物以及其它合成弹性体;以及增粘的或未增粘的丙烯酸类粘合剂,诸如丙烯酸异辛酯和丙烯酸的共聚物,其能够通过辐射、溶解、悬浮或乳化技术聚合;聚氨酯;有机硅嵌段共聚物;以及上述的组合。
一般来讲,也可包括任何已知的可用于配制粘合剂的添加剂。添加剂包括增塑剂、抗老化剂、紫外线稳定剂、着色剂、热稳定剂、抗感染剂、填料、交联剂以及它们的混合物和组合。在某些实施方案中,粘合剂可用纤维或纤维稀松布来增强,该纤维或稀松布可包含无机纤维和/或有机纤维。合适的纤维稀松布可包括织造辐材、非织造幅材或针织辐材或稀松布。例如,稀松布中的纤维可包括线材、陶瓷纤维、玻璃纤维(例如纤维玻璃)和有机纤维(例如天然有机纤维和/或合成有机纤维)。
在一些实施方案中,粘合剂包括增粘剂。一些示例性增粘剂包含聚萜烯、萜烯苯酚、松香酯和/或松香酸中的至少一种。
在一些实施方案中,可剥离的粘合剂是可被涂覆到背衬上的可流动粘合剂。在一些实施方案中,可剥离的粘合剂是更固体的粘合剂,如例如德国专利33 31 016中一般性描述的。
在一些实施方案中,可剥离粘合剂的Tg介于约-125摄氏度和约20摄氏度之间,如通过tanδ峰值的动态机械分析所确定的。在一些实施方案中,可剥离的粘合剂具有介于约-70℃和约0℃之间的Tg。在一些实施方案中,可剥离的粘合剂具有介于约-60℃和约-20℃之间的Tg。在一些实施方案中,可剥离的粘合剂的Tg大于-80℃、大于-70℃、大于-60℃、大于-50℃、大于-40℃或大于-30℃。在一些实施方案中,可剥离的粘合剂的Tg小于20℃、10℃、0℃、-10℃、-20℃或-30℃。
可用于本公开的粘合剂制品中的一些可剥离粘合剂在25℃下的储能模量为约300,000Pa或更大、约400,000Pa或更大、约500,000Pa或更大或者约1,000,000Pa或更大,如通过动态力学分析所确定的。在其它实施方案中,粘合剂在25℃下的储能模量为1,50,000Pa或更小、7550,000Pa或更小、500,00Pa或更小、400,000Pa或更小、300,000Pa或更小、或250,000Pa或更小,如通过动态机械分析所确定的。
在一些实施方案中,芯的第一主表面或第二主表面中的至少一者上的可剥离粘合剂的厚度为约1μm至约1mm。
在一些实施方案中,粘合剂的粘合特性可在0.1N/dm至25N/dm的范围内。在一些实施方案中,粘合剂的粘合属性可在0.5N/dm至10N/dm的范围内。在一些实施方案中,粘合剂的粘合属性可在1N/dm至5N/dm的范围内。
在一些实施方案中,通过ASTM测试方法D3654M-06测量,可剥离的粘合剂可提供例如1-20磅每平方英寸的剪切强度。
在一些实施方案中,可剥离的粘合剂被设计成在无损坏或损坏最小的情况下实现剥离。用于这样做的示例性方法和制品在例如美国专利6,835,452、国际公布WO/2018/039584和WO/2017/136188中有所描述,每个申请引用的方式整体并入本文。
粘合剂制品
在一些实施方案中,粘合剂制品还包括突片。突片是使用者可容易触及以有助于或开始从粘附体释放粘合剂制品的区域。移除突片可从最外侧粘合剂层发粘,或通过覆盖拉伸膜、非拉伸膜、剥离衬垫或由于防粘粘合剂而不发粘。
在一些实施方案中,粘合剂制品还包括一个或多个剥离衬垫。剥离衬垫可例如位于粘合剂层的主表面的任一者或两者上。释放衬垫在制造、运输期间和在使用之前保护粘合剂。当用户期望使用粘合剂制品时,用户可剥离或移除释放衬垫以暴露粘合剂。合适的衬垫的示例包括纸材,例如牛皮纸,或聚合物膜,例如聚乙烯、聚丙烯或聚酯。可将衬垫的至少一个表面用释放剂(诸如有机硅、含氟化合物或其它基于低表面能的释放材料)处理以提供释放衬垫。合适的释放衬垫和用于处理衬垫的方法在例如美国专利4,472,480、4,980,443和4,736,048中有所描述。优选的剥离衬垫为氟代烷基有机硅聚合物涂覆的纸材。这些剥离衬垫可印刷有线条、商标标记或其它信息。
在一些实施方案中,本公开的粘合剂制品可从基底或表面移除而不会损坏。在特别有利的实施方案中,可将粘合剂制品从涂漆的干式墙和墙纸中的至少一者移除而不会损坏。
本公开的一些粘合剂制品具有优异的剪切强度。本公开的一些实施方案具有大于1600分钟的剪切强度,如根据ASTM D3654-82所测量。本公开的一些实施方案具有大于10,000分钟的剪切强度,如根据ASTM D3654-82所测量。本公开的一些其它实施方案具有大于100,000分钟的剪切强度,如根据ASTM D3654-82所测量。
本公开的一些粘合剂制品展示出较低的90°剥离粘合强度,以使得粘合剂制品更易于移除。其它实施方案展示出较高的90°剥离粘合强度,但仍提供无损移除。本公开的一些粘合剂制品可具有更高的90°剥离粘合强度,以便允许使用者在没有意外分离的情况下处理粘合剂制品。本公开的一些实施方案具有介于约10oz/in2至300oz/in2之间的90°剥离粘合强度。本公开的一些实施方案具有介于约50oz/in2至200oz/in2之间的90°剥离粘合强度。
根据重量悬挂测试,本公开的一些粘合剂制品展示出改善的重量承载能力,保持0.5磅的重量至少24小时。在其它实施方式中,根据重量悬挂测试,本公开的粘合剂制品展示出保持0.5磅的重量至少24小时。在目前优选实施方案中,根据重量悬挂测试,本公开的粘合剂制品展示出增强的重量承载能力,保持0.5磅的重量至少72小时。
本公开的一些粘合剂制品在至少一个方向上具有大于50%的断裂伸长率。本公开的一些粘合剂制品在至少一个方向上具有介于约50%和约1200%之间的断裂伸长率。
本公开的一些粘合剂制品具有足够高的断裂拉伸强度,使得粘合剂制品在以35°或更大的角度从粘附体移除之前不破裂。
在一些实施方案中,本公开的粘合剂制品表现出比现有技术粘合剂安装制品更强的对基底或表面的适形性。在一些实施方案中,本公开的粘合剂制品当粘附或附接到基底或表面时比现有技术粘合剂安装制品保持更大的重量。在一些实施方案中,本公开的粘合剂制品当粘附或附接到基底或表面时比现有技术粘合剂安装制品保持更大的重量,且保持更长一段时间。在一些实施方案中,本公开的粘合剂制品保持粘附到纹理化、粗糙或不规则的表面,比现有技术粘合剂安装制品保持更长的一段时间。在一些实施方案中,本公开的粘合剂制品当粘附到纹理化、粗糙或不规则表面时比现有技术粘合剂安装制品保持更大的重量。
在一些实施方案中,粘合剂制品是基本上光学透明的。一些实施方案具有至少约50%的透光率。一些实施方案的透光率为至少约75%。一些实施方案具有不大于40%的雾度。一些实施方案具有不大于20%的雾度。可采用例如ASTM D1003-95来测定粘合剂制品的透光率和雾度两者。
在一些实施方案中,粘合剂制品在10%应变下表现出大于70%或大于80%或大于95%的弹性恢复率。在一些实施方案中,粘合制品在25%应变下表现出大于70%或大于80%或大于90%的弹性恢复率。在一些实施方案中,粘合剂制品在50%应变下表现出大于70%或大于80%或大于90%或大于95%的弹性恢复。在一些实施方案中,粘合剂制品在100%应变下表现出大于50%或大于70%或大于95%的弹性恢复率。
在一些实施方案中,芯可通过减少、最小化或消除芯材料对剥离力的贡献来防止或最小化基底损坏,这有助于无损粘合剂移除。在一些实施方案中,这可在0-180度的剥离角度下发生。在一些实施方案中,当最终粘合剂制品构造以90度至180度从粘附体上剥离时,芯在剥离期间伸长小于1%。在一些实施方案中,当最终粘合剂制品构造以90度至180度从粘附体上剥离时,芯在剥离期间伸长小于5%。在一些实施方案中,当最终粘合剂制品构造以90度至180度从粘附体上剥离时,芯在剥离期间伸长小于10%。在一些实施方案中,当最终粘合剂制品构造以90度至180度从粘附体上剥离时,芯伸长超过10%的应变,并且弹性恢复超过80%的变形。在一些实施方案中,当最终粘合剂制品构造以90度至180度从粘附体上剥离时,芯伸长超过10%的应变,并且弹性恢复超过90%的变形。在一些实施方案中,当最终粘合剂制品构造以90度至180度从粘附体上剥离时,芯伸长超过10%的应变,并且弹性恢复超过95%的变形。在一些实施方案中,当最终粘合剂制品构造以90度至180度从粘附体上剥离时,芯伸长超过10%的应变,并且弹性恢复超过99%的变形。
本公开的粘合剂制品可有利地提供增强的重量承载能力,同时在移除时减少或消除基底损坏。因此,本公开的当前优选实施方案展示出有效的重量承载能力、每平方英寸可用粘合剂区域的更强粘附力以及从涂漆的干式墙基底上剥离而不损坏的可移除性。
耐用件
一些实施方案还包括耐用件或安装装置。示例性安装装置包括例如钩、旋钮、夹和环。在一些实施方案中,耐用件类似于钉。在一些实施方案中,耐用件具有充当悬挂表面的单个向外突起部。在一些实施方案中,耐用件具有充当悬挂表面的多个向外突起部。在一些实施方案中,耐用件被模制成可将一个或多个物品保持在诸如但不限于盒或箱内的形状。在一些实施方案中,耐用件是搁架、凸缘或齿条。在一些实施方案中,耐用件是杆,其中杆可以是直的或弯曲的或基本上为环形的,其中杆可平行或正交于基底表面安装。在一些实施方案中,耐用件使用多种方法来安装或悬挂物品。以下安装装置中的任一种可与本公开的粘合剂制品一起使用:申请案件号77486US002(转让给本受让人)、美国专利5,409,189(Luhmann)、美国专利5,989,708(Kreckel)、8,708,305(McGreevy)、美国专利5,507,464(Hamerski等人)、美国专利5,967,474(doCanto等人)、美国专利6,082,686(Schumann)、美国专利6,131,864(Schumann)、美国专利6,811,126(Johansson等人)、美国专利D665,653以及美国专利7,028,958(Pitzen等人),所有这些专利全文以引用方式并入本文。耐用件可以是要安装到基底的任何物体。
在一些实施方案中,耐用件在一个或多个位置安装到基底,其中安装位置中的一个或多个含有本发明所述的粘合剂制品。在一些实施方案中,耐用件是使用可移除制品(一个或多个)和常规机械紧固件的组合来安装的,该常规机械紧固件包括但不限于钉、螺钉、螺栓和铆钉。
在一些实施方案中,耐用件是由热塑性聚合物制成的。在一些实施方案中,耐用件是由热固性聚合物制成的。在一些实施方案中,耐用件是使用聚烯烃材料制成的。在一些实施方案中,耐用件是使用聚碳酸酯材料制成的。在一些实施方案中,耐用件是使用高抗冲聚苯乙烯制成的。在一些实施方案中,耐用件是使用丙烯腈丁二烯苯乙烯(ABS)三元共聚物制成的。在一些实施方案中,耐用件使用两种或更多种聚合物材料制成的。在一些实施方案中,耐用件是由金属制成的。在一些实施方案中,耐用件是由不锈钢制成的。在一些实施方案中,对金属进行涂漆、上釉、染色、刷涂或涂覆以改变其外观。在一些实施方案中,耐用件是由陶瓷制成的。在一些实施方案中,耐用件是由上釉陶瓷制成的。在一些实施方案中,耐用件是由未上釉陶瓷制成的。在一些实施方案中,耐用件由诸如木材、竹子、刨花板、布料、帆布或衍生自生物来源等天然基材料构成。在一些实施方案中,天然基材料可被涂漆、上釉、染色或涂覆以改变其外观。在一些实施方案中,耐用件是使用上文列表中的两种或更多种材料制成的。在一些实施方案中,耐用件是由可逆或不可逆地附接、结合或焊接在一起的两个零件制成的。
在一些实施方案中,耐用件包含两个零件,其中第一零件充当用于将粘合剂制品附接到基底的安装表面,并且第二零件充当可用于将物体悬挂或安装到基底的悬挂构件。这两个零件可使用机械紧固件、钩-环材料或另外的粘合剂层可逆地附接。
耐用件可使用本领域中已知的任何方法来制成。
在一些实施方案中,(一个或多个)可剥离粘合剂层和芯可使用层压工艺附接到耐用件。在一些实施方案中,(一个或多个)可剥离粘合剂层和芯可使用多个层压工艺附接到耐用件。
在一些实施方案中,芯可在使用一个或多个模具时使用两个或更多个注塑步骤来附接到耐用件。在一些实施方案中,芯和/或(一个或多个)可剥离粘合剂层可由最终使用者手动地附接。
制备本文所述的粘合剂制品的方法
本文所述的粘合剂制品可以各种方式制备。一个实施方案涉及将粘合剂设置到芯的主表面上或邻近芯的主表面设置。在一些实施方案中,将第二粘合剂设置到芯的另一主表面上。
粘合剂可以任何已知的方式设置在芯上,这些方式包括例如可将压敏粘合剂组合物涂布到释放衬垫上,直接涂布到载体上,或作为单独层形成(例如,涂布到释放衬垫上),并且然后层压到载体上。粘合剂可用已知的沉积方法沉积到芯上,该沉积方法包括例如溶剂涂布方法、水性涂布方法或热熔涂布方法,例如刮涂、辊涂、逆转辊涂、凹版印刷涂布、绕线棒涂、狭缝喷嘴式涂布、狭缝式涂布、挤出涂布等等。
粘合剂界面可通过上述方法中的任一种或下文实施例中所述的那些方法在芯内或沿芯的一个或多个边缘形成。
使用本文所述的粘合剂制品的方法
本公开的可剥离制品可以各种方式使用。在一些实施方案中,将粘合剂制品施加、附接或按压到粘附体中。以这种方式,粘合剂制品接触粘附体。在存在剥离衬垫的情况下,在将粘合剂制品施加、附接或按压到粘附体中之前将剥离衬垫移除。在一些实施方案中,在将粘合剂制品施加、附接或按压到粘附体中之前将粘附体的至少一部分用醇擦拭。
为了从粘附体中移除粘合剂制品,将粘合剂制品的至少一部分从粘附体剥离或拉伸拉伸远离该粘附体。在一些实施方案中,拉伸角度是35°或更小。在存在突片的实施方案中,使用者可握持突片并使用它从粘附体释放或移除粘合剂制品。
粘合剂制品可单独使用,作为附接到表面的许多制品中的一种,或者作为粘合剂制品的叠堆的一部分。在后一个实施方式中,所得构造将包括彼此垂直设置的多个粘合剂制品。
用途
该粘合剂制品可用于潮湿或高湿度的环境中,如存在于浴室中的那些。例如,可将它们粘附到马桶(例如,马桶水箱)、浴缸、水槽和墙壁。粘合剂制品可用于淋浴间、衣帽间、蒸汽房、水池、热水澡桶和厨房(例如,厨房水槽、洗碗机和后挡板区、冰箱和冷藏箱)。粘合剂制品还可用于包括户外应用及冰箱在内的低温应用当中。可用的户外应用包括将诸如标牌之类的制品粘结到诸如窗、门及车辆之类的户外表面。
粘合剂制品可用于将各种物品及物体安装于诸如涂漆预制墙、石膏、水泥、玻璃、陶瓷、玻璃纤维、金属或塑料之类的表面上。可安装的物品包括但不限于壁挂、记事本、夹持器、篮子、容器、装饰品(例如,节日装饰品)、日历、海报、自动售货机、线夹、车辆上的车身防擦条、提把手、诸如道路标志等标牌应用、车辆标志、运输标志和反光挡板。
粘合剂制品可用于将诸如防滑垫或抗疲劳垫之类的物品和材料安装于地板表面或洗澡桶或淋浴下面,或者可用于将诸如小地毯的物品固定到地板。粘合剂制品可用于包括诸如粘附稍后要分开的至少两个容器(例如,箱)的各种结合和组装应用中。粘合剂制品可用于各种缓冲和消音应用中,例如置于物体下面的缓冲材料、隔音薄片材料、减震以及它们的组合。粘合剂制品可用于各种开闭装置应用,包括容器开闭装置(例如,箱开闭装置、食物容器的开闭装置和饮料容器的封闭装置)、尿布开闭装置和手术盖布开闭装置。粘合剂制品可用于各种隔热应用。粘合剂制品可用于各种密封应用,例如用于密封液体、蒸气体(例如,水气)和灰尘的垫圈。粘合剂制品可用于各种标签,诸如可移除标签(例如,便条、价签和容器上的识别标签),以及用于标牌中。粘合剂制品可用于各种医疗应用中(例如,绷带、伤口护理和医院环境中的医疗装置贴标签)。粘合剂制品可用于各种紧固应用中,诸如将一个物体(例如,花瓶或其它易碎物体)紧固到另一物体(例如,桌子或书架)。粘合剂制品可用于各种进行固定的应用中,诸如将锁定机构的一个或多个部件紧固到基底(例如,可将儿童安全锁粘附到橱柜或碗橱)。粘合剂制品可用于各种防篡改指示应用(例如,防篡改指示条)中。还可将粘合剂制品结合到多种其它构造中,这些构造包括但不限于磨料制品(例如,用于磨砂)、用于砂磨和抛光应用的制品(例如,磨光垫、刹车片、手工研磨垫和抛光垫)、道路标记制品、地毯(例如,地毯背衬)和电子器件(例如,把电池固定在移动电话或PDA(个人数字助理)的壳体内以防不需要的移动)。
可以任何适用的形式设置粘合剂制品(即,在粘合带中的那些制品或单个制品),这些适用的形式包括例如带、条、片(例如,穿孔片)、标签、卷筒、幅材、盘和套件(例如,要安装的物体和用于安装该物体的粘合带)。同样地,可在任何合适的包装件(例如,自动售货机、包、箱和纸板盒)中以任何适用的形式(包括例如带、条、片(例如,穿孔片)、标签、卷筒、幅材、盘、套件、层叠件、料片以及它们的组合)设置多个粘合剂制品。
还存在对一种具有期望的光学属性的粘合剂制品的需要,这些光学属性允许将粘合剂制品用于将诸如光学透镜或罩的基底附连到诸如蜂窝电话或便携式音乐播放器(例如,MP3播放器)的光学显示设备。在此类最终用途应用中,期望粘合剂制品为光学透明的。
粘合剂制品也可最初为可重新定位的,并且甚至可在一些芯迭代中重复使用,直到粘合剂层中的一个失去粘性为止。如本文所用,“可重新定位的”意指可施加到基底上,并且然后在不扭曲、污损或破坏粘合剂制品或基底的情况下移除和重新施加的粘合剂制品。
实施方案
1.一种粘合剂制品,包括:第一可剥离粘合剂层;第二可剥离粘合剂层;离散芯,所述离散芯设置在所述第一可剥离粘合剂和所述第二可剥离粘合剂之间,并具有第一主表面和第二主表面,其中所述芯限定与所述第一主表面重合的芯平面;以及多个粘合剂接触区域,所述多个粘合剂接触区域各自包括所述第一粘合剂层和所述第二粘合剂层之间的界面。
2.根据实施方案1所述的粘合剂制品,其中每个界面均存在于所述芯平面之外。
3.根据实施方案1或2所述的粘合剂制品,其中所述芯包括多层膜。
4.根据实施方案3所述的粘合剂制品,其中所述多层膜包括膜芯和至少一个表层。
5.根据实施方案1至4所述的粘合剂制品,其中所述芯包括不连续材料层。
6.根据实施方案1至4所述的粘合剂制品,其中所述芯包括连续材料层。
7.根据实施方案1至6所述的粘合剂制品,其中所述第一粘合剂层以粘合方式粘结到所述芯。
8.根据实施方案1至7所述的粘合剂制品,其中所述芯包含非织造材料。
9.根据实施方案1至8所述的粘合剂制品,其中所述芯限定一系列孔,并且其中每个界面位于孔内。
10.根据实施方案1所述的粘合剂制品,其中所述芯包括与所述第一粘合剂接触的第三粘合剂,并且其中每个界面处的所述剥离强度大于所述第一粘合剂和所述第三粘合剂之间的所述剥离强度。
11.根据实施方案1至2所述的粘合剂制品,其中所述芯由多个颗粒组成,所述颗粒的大小足以防止所述第一粘合剂层和所述第二粘合剂层之间的接触。
12.根据实施方案11所述的粘合剂制品,其中所述颗粒选自由木材、金属、金属氧化物、陶瓷以及它们的组合组成的组。
13.根据实施方案1所述的粘合剂制品,其中所述制品包括在所述第一粘合剂层和所述芯之间的芯界面,并且其中粘合剂界面处的粘合剂粘结强度大于所述芯界面处的粘合剂粘结强度。
14.根据前述实施方案中任一项所述的粘合剂制品,其中在垂直于所述芯平面的方向上施加力导致所述芯内的结构完整性损失。
15.根据前述实施方案中任一项所述的粘合剂制品,其中所述芯限定周边,并且其中所述粘合剂接触区域围绕周边。
16.根据实施方案15所述的粘合剂制品,其中所述粘合剂接触区域包括沿所述周边的一部分延伸的至少一个连续接缝。
17.根据实施方案1至16所述的粘合剂制品,其中所述芯限定周边边界,并且其中所述粘合剂接触区域设置在所述边界内。
18.一种用于安装物体的粘合剂制品,所述制品包括:第一剥离释放粘合剂层;第二剥离释放粘合剂层;芯,所述芯限定周边边界,并设置在所述第一粘合剂层和所述第二粘合剂层之间;以及多个接缝,所述多个接缝沿所述周边边界的至少一部分延伸,其中所述接缝包括所述第一粘合剂层和所述第二粘合剂层之间的界面。
19.根据实施方案18所述的粘合剂制品,其中所述多个接缝包括沿所述边界的至少两侧延伸的接缝。
20.根据实施方案18至19所述的粘合剂制品,其中所述多个接缝围绕所述边界。
21.根据实施方案18至20所述的粘合剂制品,其中所述边界的形状为正方形、矩形、圆形、卵形和四面体中的一种。
22.根据实施方案18至21所述的粘合剂制品,其中所述芯包括非织造材料层。
23.根据实施方案22所述的粘合剂制品,其中所述芯包括设置在所述非织造材料和所述第一粘合剂层之间的释放层。
24.根据实施方案18至23所述的粘合剂制品,其中所述芯限定平面,所述平面基本上平行于所述第一粘合剂层和所述芯之间的界面。
25.根据实施方案24所述的粘合剂制品,其中所述制品的90°度粘合强度为至少40oz/in2
26.根据实施方案18至25所述的粘合剂制品,其中所述制品粘附到表面并且所述第一粘合剂层以至少35度的剥离角度从所述表面移除,所述芯基本上不有助于所述剥离力。
27.根据实施方案26所述的粘合剂制品,其中所述第一粘合剂层粘结到所述芯,并且其中从所述安装表面移除所述第一粘合剂层导致所述第一粘合剂与所述芯脱粘。
28.根据实施方案18至27所述的粘合剂制品,其中从所述安装表面移除所述第一粘合剂层不会导致所述接缝中的至少一者中的脱粘。
29.根据实施方案18所述的粘合剂制品,并且还包括在与所述芯相对的所述第一粘合剂层的表面上的释放衬垫。
30.根据实施方案18至29所述的粘合剂制品,并且还包括在与所述芯相对的所述第一粘合剂层的表面上的耐用件。
31.根据实施方案18至29所述的粘合剂制品,并且还包括在与所述芯相对的所述第一粘合剂层的表面上的框架或海报。
32.根据实施方案18至29所述的粘合剂制品,其中如根据ASTMD638测量的,所述芯的拉伸和/或弹性模量介于约50psi和约5000psi之间。
33.根据实施方案18所述的粘合剂制品,其中所述芯为光学透明的。
34.根据实施方案18所述的粘合剂制品,其中芯包括多层膜,所述多层膜包括:芯层,所述芯层包含弹性体材料、弹性体聚合物、SEBS、SEPS、SIS、SBS、聚氨酯、乙酸乙酯(EVA)、丙烯酸甲酯(EMA)超低线性密度聚乙烯(ULLDPE)、氢化聚丙烯以及它们的组合或共混物中的至少一种;以及第一表层,所述第一表层包含聚丙烯、聚乙烯、高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LDPE)、聚氨酯、EVA、EMA、粘合剂以及它们的组合或共混物中的至少一种。
35.一种用于将物体安装到表面的粘合剂制品,所述制品包括:第一粘合剂层;第二粘合剂层;芯,所述芯限定周边,所述芯设置在所述第一粘合剂层和所述第二粘合剂层之间;以及多个粘合剂接触区域,其中所述粘合剂接触区域包括所述第一粘合剂层和所述第二粘合剂层之间的界面,并且其中所述粘合剂接触区域位于所述芯的所述周边内。
36.根据实施方案35所述的粘合剂制品,其中所述芯包含非织造材料。
37.根据实施方案35所述的粘合剂制品,其中所述芯包含多个颗粒,所述颗粒的大小足以防止所述第一粘合剂层和所述第二粘合剂层的一部分建立界面。
38.根据实施方案35所述的粘合剂制品,其中所述芯包括孔,并且其中所述粘合剂接触区域中的至少一者位于所述孔内。
39.根据前述实施方案中任一项所述的粘合剂制品,其中当所述制品以约35°或更大的角度从所述粘附体的表面释放时,所述粘合剂制品从所述粘附体表面释放。
40.根据前述实施方案中任一项所述的粘合剂制品,其中所述粘合剂制品从粘附体无损坏地移除。
41.根据实施方案35所述的粘合剂制品,其中当所述粘合剂制品以大于35度的角度移除时,至少所述第一粘合剂层与所述芯脱粘,并且其中当所述粘合剂制品以大于35度的角度移除时,所述第一粘合剂层在所述界面中的每个处不与所述第二粘合剂层脱粘。
42.根据前述实施方案中任一项所述的粘合剂制品,其中所述可剥离粘合剂包括SBS、SBR、SIS、SEBS、丙烯酸酯和/或聚氨酯中的至少一种。
43.根据前述实施方案中任一项所述的粘合剂制品,其中所述可剥离粘合剂包括以下增粘剂中的至少一种:聚萜烯、萜烯苯酚、松香酯、烃、C5树脂、C9树脂和/或松香酸。
44.根据前述实施方案中任一项所述的粘合剂制品,其中所述可剥离粘合剂包括以下中的至少一种:丙烯酸酯、聚氨酯、增粘橡胶粘合剂(诸如天然橡胶);烯烃;硅氧烷,诸如硅氧烷聚脲;合成橡胶粘合剂,诸如聚异戊二烯、聚丁二烯和苯乙烯-异戊二烯-苯乙烯、苯乙烯-乙烯-丁烯-苯乙烯和苯乙烯-丁二烯-苯乙烯嵌段共聚物、SBR、SEBS以及其它合成弹性体;以及增粘的或未增粘的丙烯酸类粘合剂,诸如丙烯酸异辛酯和丙烯酸的共聚物,其能够通过辐射、溶解、悬浮或乳化技术聚合;聚氨酯;有机硅嵌段共聚物;以及它们的组合。
45.一种用于安装到表面的物体,所述物体包括:耐用件,所述耐用件具有第一主表面;离散芯,所述离散芯限定与所述耐用件接触的第一表面和与所述第一表面相对的第二表面;粘合剂层,所述粘合剂层粘结到所述耐用件的所述第一主表面和所述芯的所述第二表面两者,其中从所述耐用件移除粘合剂所需的剥离释放力大于将所述粘合剂与所述芯脱粘或致使所述芯分层中的至少一种所需的剥离释放力。
46.根据实施方案45所述的安装物体,其中所述耐用件包括钩、旋钮、夹、箱、盒和/或环中的至少一种。
47.一种使用粘合剂制品的方法,包括:使根据实施方案1至46中任一项所述的粘合剂制品与粘附体表面接触。
48.根据实施方案47所述的方法,还包括:从所述粘附体表面剥离所述粘合剂制品,以从所述粘附体表面移除所述粘合剂制品的至少一部分,其中所述粘合剂制品以35°或更大的角度剥离。
49.根据实施方案48所述的方法,其中在从所述粘附表面剥离所述粘合剂制品的步骤期间,所述芯的结构完整性受损。
50.根据实施方案48或49所述的方法,其中从所述粘附表面剥离所述粘合剂制品致使所述第一粘合剂层与所述芯脱粘。
51.根据以上实施方案48至50所述的方法,其中在剥离所述粘合剂制品期间,第一粘合剂层在粘合剂接触区域处保持粘结到所述第二粘合剂层。
以下实施例描述了一些示例性构造以及在本申请的范围内构造各种实施方案的方法。以下实施例旨在说明性的,但这些实施例中所提到的具体材料及其量以及其它条件和细节,均不应被解释为对本公开的不当限制。
实施例
表1:材料和供应商信息
Figure BDA0002390038780000521
Figure BDA0002390038780000531
测试方法
搭接剪切(0°剥离)粘合强度测试
采用以下方法来评估剥离粘附强度和可移除性。用手在中等压力(大约5磅)下将测试构造施加到粘附体5秒。在测试之前,将粘附的样品在72℉(22℃)、50%相对湿度下老化3天。在测试之前,立即移除粘合剂构造的剩余衬垫,并将不锈钢垫片(6"×2"×0.031",得自俄亥俄州西切斯特镇化学仪器公司(ChemInstruments,West Chester Township,OH))以中等压力(大约5磅)施加到顶部粘合剂表面5秒。将粘附体和不锈钢的暴露边缘置于INSTRON通用测试机上的相对夹钳中。用具有12in/min(30.5cm/min)夹头速度的INSTRON通用测试机进行剪切测试,直到构造从粘附体表面移除。根据夹头位移记录负荷传感器力。对每个样品测试四个平行样。
90°剥离粘合强度测试
采用以下方法来评估剥离粘附强度和可移除性。用手在中等压力(大约5磅)下将测试构造施加到粘附体5秒。在测试之前,将粘附的样品在72℉(22℃)、50%相对湿度下老化3天。在测试之前,立即移除粘合剂构造的剩余衬垫,并且将铝t形杆(铝6061-T6裸t形杆1.5"×1.5"×0.25"切割成1.5",华盛顿州西雅图在线金属公司(OnlineMetals,SeattleWA))以中等压力(大约1.5磅)下施加到顶部粘合剂表面5秒。将粘附体夹紧到平坦表面上,并且将铝t形杆置于INSTRON通用测试机的顶部夹钳中。用具有12in/min(30.5cm/min)夹头速度的INSTRON通用测试机进行剥离测试,直到构造从粘附体表面移除为止。根据夹头位移记录负荷传感器力。如果任何粘合剂保留在粘附体上,则用手将其移除以更好地观察损坏程度。对每个样品测试四个平行样。损坏视觉评估如下:0-无损坏;1-小油漆气泡(小于表面积的10%);2-大油漆气泡(大于表面积的10%);3-小纸撕裂;4-纸材撕裂/损坏(<50%),5-纸材撕裂损坏(>50%)。对每个样品测试两个平行样。
挂重测试
首先在中等压力(大约5磅)下用手将测试构造施加到1.25英寸乘1.35英寸的注塑聚碳酸酯钩5秒,每个钩的厚度为30密耳并且其类型如图11所示。然后在中等压力(大约5磅5秒)下用手将钩和粘合剂构造施加到粘附体,使得钩定位在构造的底部,允许悬挂重物。将含有钢丸(0.5磅)的塑料袋施加到墙板粘附体之后,立即从钩上悬挂下来。在悬挂1小时、24小时、48小时和72小时之后观察样品,并且在每个时间点记录失效。除实施例9(其具有2次重复)之外,所有样品均在3次重复中测试。性能值为给定实施例的所有重复的悬挂时间的平均值,使得最大性能值为72小时,并且最小性能值为0小时。
峰值力的确定
根据记录夹头位移和力(oz)的INSTRON Bluehill 3软件输出的原始数据确定每个粘合强度测试的峰值力。然后将峰值力除以有效粘合剂区域,以获得每单位面积(平方英寸)的力(盎司)。
测试粘附体
将干式墙(得自明尼苏达州圣保罗市梅兹格建筑材料公司(Materials Company,Metzger Building,St.Paul,MN))涂上舍温-威廉姆斯持续时间内丙烯酸乳胶公司本骨白漆(Sherwin-Williams DURATION Interior Acrylic Latex Ben Bone White Paint)(俄亥俄州克利夫兰市舍温-威廉姆斯公司(Sherwin-Williams Company,Cleveland,OH))进行剥离测试,并且涂上Behr Premium Plus超平埃及尼罗河漆和底漆于一体内漆(BehrPremium Plus Ultra Flat Egyptian Nile Paint&Primer in One Interior Paint)(加利福尼亚州圣安娜贝赫尔工艺公司(Behr Process Corporation,Santa Ana,CA))进行悬挂测试。
涂漆规程:通过漆滚筒将第一涂层油漆施涂到面板上,随后在环境条件下风干大约1小时。在使用之前的环境条件下,施涂油漆的第二涂层,并且在环境条件下干燥至少7天。
实施例1至9和比较例1至4以及对照1至2
表2:实施例构造
Figure BDA0002390038780000551
Figure BDA0002390038780000561
多层膜
在实施例中使用的多层膜通过使用如美国专利5,501,679中实施例3所述的连续共挤出工艺将弹性体芯材料片与两个表层(一个在弹性体芯层的任一侧上)共挤出来制备。多层膜构造的细节提供于表3中。该膜类似于来自PCT公布WO2017/136432的实施例16。
表3:多层膜构造
Figure BDA0002390038780000562
非织造幅材
非织造幅材可购自美国专利8,162,153中所述的一般类型的明尼苏达州圣保罗的3M公司(3M Company,St.Paul MN)。该幅材为纺粘幅材,该纺粘幅材的基重为65克/平方米并且有效纤维直径(如‘153专利中定义和描述的)为18.40μm。
压敏粘合剂组合物
粘合剂1:制备压敏粘合剂组合物,其具有作为弹性体组分的KRATON D1184与SOLPRENE 1205的15∶85的比率和基于100份总弹性体的35份总增粘剂组分。将所有组分连同甲苯一起加入到玻璃广口瓶中,以制备大约30%固体的溶液。在涂布之前,将广口瓶密封,并且通过将广口瓶置于约2rpm至6rpm下的滚筒上至少24小时,使内容物充分混合。
粘合剂2:根据美国专利6,569,521中实施例28所述的方法制备硅氧烷聚脲嵌段共聚物基压敏粘合剂组合物,不同之处在于将组合物制备成具有50重量%的MQ树脂量。
转移粘合剂的制备
粘合剂1:将上述压敏粘合剂组合物刮涂到具有硅氧烷释放表面的纸材衬垫幅材上。纸材衬垫幅材速度为2.75米/分钟。涂布之后,使幅材通过具有三个温度区的11米长(总停留时间4分钟)的烘箱。区1(2.75米)中的温度为57℃;区2(2.75米)中的温度为71℃;区3(约5.5米)中的温度为82℃。干燥粘合剂的厚度为大约2.0密耳。然后将转移粘合剂储存在环境条件下。
粘合剂2:将压敏粘合剂组合物刮涂到具有硅氧烷释放表面的纸材衬垫幅材上。纸材衬垫幅材速度为2.75米/分钟。涂布之后,使幅材通过具有三个温度区的11米长(总停留时间4分钟)的烘箱。区1(2.75米)中的温度为57℃;区2(2.75米)中的温度为80℃;区3(约5.5米)中的温度为93℃。干燥粘合剂的厚度为大约2.5密耳至3.0密耳。然后将转移粘合剂储存在环境条件下。
粘合剂制品构造的制备
对照物1:对非织造幅材(大约6"×12")的一侧进行电晕处理。将衬垫上的粘合剂手动层压到表面上,并且然后在40PSI的压力下以大约12英寸/分钟的速度通过辊层压机。然后对非织造幅材的第二(暴露)侧进行电晕处理,并且在相同条件下手动层压衬垫上的粘合剂并使其通过辊层压机。最后,以12英寸/分钟的速率在100PSI下通过辊层压机发送整个构造。从组装的层压体模切出1"×1"正方形粘合剂构造。
对照2:将粘合剂置于衬垫之间并模切成1"×1"正方形。移除一个衬垫,使得将粘合剂正方形的一侧暴露出来,并且将两个正方形手动层压在一起。
实施例1至6:将粘合剂置于衬垫之间并且模切至1.25"×1.25"正方形。移除一个衬垫,使得粘合剂正方形的一侧暴露出来。芯材料(参见下文)以暴露的粘合剂为中心,以便在构造的周边周围留下0.125"的暴露粘合剂边界。然后将第二个粘合剂正方形层压在顶部并用手密封,使得0.125"的边界在芯周围形成接缝。
■实施例1和2:1"×1"模切非织造正方形
■实施例3:涂布有平滑释放喷雾的多层膜(根据制造商规格施涂)
■实施例4:将1.0克的gak在冷冻机(~10℉)中冷却,并且然后在粘合剂之间密封之前将其成形为大约1"×1"正方形。
■实施例5:将0.05克玻璃泡置于粘合剂正方形的中心,并在粘合剂之间密封之前展开以覆盖大约1"×1"正方形。
■实施例6:从释放衬垫材料模切出1"×1"正方形。堆叠两片释放衬垫,使得释放涂布的侧面彼此相对并面向粘合剂表面。
实施例7至8:将粘合剂置于衬垫之间并模切成1"×1"正方形。用1/16"中空冲头手动冲切非织造芯材料,使得芯材料中形成1/16"间隙。间隙以每芯9孔的密度间隔开3/8"中心-中心。移除一个衬垫,使得粘合剂正方形的一侧暴露出来。用手将芯材料层压在粘合剂层之间,使得模切孔形成接缝。
实施例9:将粘合剂置于衬垫之间并且模切成1.25"×1.25"正方形和1"×1"正方形。芯材料通过将1"×1"正方形从3M二次释放衬垫5002模切,并且然后层压1"×1"衬垫—1"×1"粘合剂—1"×1"衬垫的叠堆来构造,使得非释放部分面向内朝向1"×1"粘合剂正方形,并且释放表面面向外。用1/16"中空冲头手动冲切3层芯,使得芯材料中形成1/16"间隙。间隙以每芯9孔的密度间隔开3/8"中心-中心。移除一个衬垫,使得1.25"×1.25"粘合剂正方形的一侧暴露出来。用手将芯材料层压在1.25"×1.25"粘合剂层之间,使得模切孔形成接缝。
比较例1至4:将样品以最接近1"×1"正方形占有面积的格式施加到所接收的粘附体。
表4:搭接剪切(0°剥离)粘合强度测试数据
Figure BDA0002390038780000591
Figure BDA0002390038780000601
表5:90°剥离粘合强度测试数据
Figure BDA0002390038780000602
表6:挂重测试数据
Figure BDA0002390038780000603
Figure BDA0002390038780000611
搭接剪切给出制品在剪切时失效所需的力的指示。数据示出,对于给定的粘合剂组合物,固体粘合剂板(对照2)给出最高值,但会造成损坏。如本发明所述的芯的存在提供无损释放,但以剪切强度为代价。芯和接缝的存在(实施例1至9)改善剪切性能,同时维持两个刚性表面之间的无损剥离移除。相比之下,比较例各自造成损坏,同时显示不同程度的剪切性能。重量悬挂测试数据示出,芯的组成和接缝的格式均可被调整,以影响重量悬挂性能。
通过端点的所有数值范围的表述旨在包括归入该范围内的所有数字(即,1至10的范围包括例如1、1.5、3.33、和10)。
将本文所引用的专利、专利文献和专利申请中以引用方式全文并入本文,就如同将它们每个单独引入本文一样。本领域普通技术人员将显而易见,可在不脱离上文设定的本发明概念下作出各种变化和修改。因此,本公开的范围不应限于本文中所描述的结构。本领域中的技术人员将会知道,可在不脱离本公开基本原理的前提下对上述实施方案和具体实施的细节做出许多改变。此外,在不脱离本发明的实质和范围的前提下,对本发明的各种修改和更改对本领域技术人员将是显而易见的。因此,本申请的范围应当仅由以下权利要求书以及其等同物所确定。

Claims (20)

1.一种粘合剂制品,包括:
第一可剥离粘合剂层;
第二可剥离粘合剂层;
离散芯,所述离散芯设置在所述第一可剥离粘合剂和所述第二可剥离粘合剂之间,并具有第一主表面和第二主表面,其中所述芯限定与所述第一主表面重合的芯平面;以及
多个粘合剂接触区域,所述多个粘合剂接触区域各自包括所述第一粘合剂层和所述第二粘合剂层之间的界面。
2.根据权利要求1所述的粘合剂制品,其中每个界面均存在于所述芯平面之外。
3.根据权利要求1所述的粘合剂制品,其中所述第一粘合剂层以粘合方式粘结到所述芯。
4.根据权利要求1所述的粘合剂制品,其中所述芯包含非织造材料。
5.根据权利要求1所述的粘合剂制品,其中所述芯限定一系列孔,并且其中每个界面位于孔内。
6.根据权利要求1或2所述的粘合剂制品,其中所述芯由多个颗粒组成,所述颗粒的大小足以防止所述第一粘合剂层和所述第二粘合剂层之间的接触,并且其中所述颗粒选自由木材、金属、金属氧化物、陶瓷以及它们的组合组成的组。
7.根据权利要求1至5所述的粘合剂制品,其中制品包括在所述第一粘合剂层和所述芯之间的芯界面,并且其中粘合剂界面处的粘合剂粘结强度大于所述芯界面处的粘合剂粘结强度。
8.根据权利要求1至5所述的粘合剂制品,其中在垂直于所述芯平面的方向上施加力导致所述芯内的结构完整性损失。
9.根据权利要求1至5所述的粘合剂制品,其中所述芯限定周边,并且其中所述粘合剂接触区域围绕所述周边。
10.根据权利要求9所述的粘合剂制品,其中所述粘合剂接触区域包括沿所述周边的一部分延伸的至少一个连续接缝。
11.根据权利要求1或2所述的粘合剂制品,其中所述芯限定周边边界,并且其中所述粘合剂接触区域设置在所述边界内。
12.一种用于安装物体的粘合剂制品,所述制品包括:
第一剥离释放粘合剂层;
第二剥离释放粘合剂层;
芯,所述芯限定周边边界,并设置在所述第一粘合剂层和所述第二粘合剂层之间;以及
多个接缝,所述多个接缝沿所述周边边界的至少一部分延伸,其中所述接缝包括所述第一粘合剂层和所述第二粘合剂层之间的界面。
13.根据权利要求12所述的粘合剂制品,其中所述多个接缝包括沿所述边界的至少两侧延伸的接缝。
14.根据权利要求12所述的粘合剂制品,其中所述芯包括非织造材料层,并且其中所述芯包括设置在所述非织造材料和所述第一粘合剂层之间的释放层。
15.根据权利要求12所述的粘合剂制品,其中所述芯限定平面,所述平面基本上平行于所述第一粘合剂层和所述芯之间的界面。
16.根据权利要求12所述的粘合剂制品,其中所述第一粘合剂层粘结到所述芯,并且其中以下至少一者:从安装表面移除所述第一粘合剂层导致所述第一粘合剂与所述芯脱粘;以及从所述安装表面移除所述第一粘合剂层不会导致所述接缝中的至少一者中的脱粘。
17.一种用于将物体安装到表面的粘合剂制品,所述制品包括:
第一粘合剂层;
第二粘合剂层;
芯,所述芯限定周边,所述芯设置在所述第一粘合剂层和所述第二粘合剂层之间;以及
多个粘合剂接触区域,其中所述粘合剂接触区域包括所述第一粘合剂层和所述第二粘合剂层之间的界面,并且其中所述粘合剂接触区域位于所述芯的所述周边内。
18.根据权利要求17所述的粘合剂制品,其中所述芯包括孔,并且其中所述粘合剂接触区域中的至少一者位于所述孔内。
19.根据权利要求17所述的粘合剂制品,其中当以大于35度的角度移除所述粘合剂制品时,至少所述第一粘合剂层与所述芯脱粘,并且
其中当以大于35度的角度移除所述粘合剂制品时,所述第一粘合剂层在所述界面中的每个处不与所述第二粘合剂层脱粘。
20.一种使用粘合剂制品的方法,包括:
将根据权利要求1、12和17中任一项所述的粘合剂制品与粘附体表面接触;以及
从所述粘附体表面剥离所述粘合剂制品,以从所述粘附体表面移除所述粘合剂制品的至少一部分,其中所述粘合剂制品以35°或更大的角度剥离,其中在从所述粘附体表面剥离所述粘合剂制品的步骤期间,所述芯的结构完整性受损。
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