CN103443235A - 包覆的psa颗粒 - Google Patents
包覆的psa颗粒 Download PDFInfo
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Abstract
颗粒状热熔压敏粘合剂(PSA),所述颗粒包含由热熔压敏粘合剂形成的核以及包围所述核的外层,所述外层由不是压敏粘合剂的组合物形成,其中所述外层包含:5-35重量%的氢化苯乙烯嵌段共聚物,20-65重量%的至少一种油,以及0-15重量%的添加剂。
Description
本发明涉及颗粒状抗粘连热熔粘合剂,其中所述颗粒分别被壳(casing)包围。优选该壳与热熔粘合剂相容,并且在熔化在一起时将形成均一的粘合剂。
EP1812297描述了一种包覆热熔粘合剂的方法,其中通过一种包含至少25重量%蜡的壳包覆粘合剂。特定的聚乙烯,以及弹性嵌段共聚物被描述为进一步的组分。
EP0469564描述了包覆热熔粘合剂的方法。据称此处的包覆材料与粘合剂相容。所述粘合剂单元的量为100g-4kg。因此粘合剂中壳材料的比例较小。聚烯烃被进一步描述为优选的壳材料。
EP1196509描述了颗粒状热熔粘合剂。此处提供了一种在冷却后具有特定涂层的颗粒。所述涂层以液体形式施加到各粒子上,进而在颗粒上形成涂层。所述涂层的组分被描述为非粘合剂。
已知的壳材料的缺点在于加工和组成。当制备大块粘合剂时,所述粘合剂通常只能手动计量。进而不能进行自动加工。如果生成较小的颗粒,壳材料相对于核的比例是相当大的。因此壳材料不仅必须在粘合剂中可溶,同时还必须不劣化作为PSA的性能。这是很困难的,特别是当本身不具有粘性的组分,例如蜡用作壳材料时尤其如此。如果选择的涂层较薄,则由于在破损或贮存时这些层会失去抗粘连性,因此其运输成为问题。在此情况下已知的是,粘性物质会从核向外扩散进入壳中,因此降低抗粘连性。
因此本发明的目的是提供一种颗粒状热熔粘合剂,以便所述颗粒能够在自动传输系统中输送。为了达到该目的,其在贮存时显示出抗粘连性,同时选择壳材料以便在颗粒均匀融化时不会损害粘合性。也优选壳材料与粘合剂混溶。
本发明的目的通过颗粒状热熔粘合剂来实现,所述颗粒包含由热熔压敏粘合剂形成的核,并且具有包围所述核的外层(outer layer),该外层由不是压敏粘合剂的组合物形成,其中所述外层包含5-30重量%的氢化苯乙烯嵌段共聚物,20-65重量%的至少一种油,以及0-15重量%的添加剂。
根据本发明的热熔粘合剂必须以颗粒形式存在。“颗粒”理解为尺寸小且可以流动的粒子。由固体材料形成的这些颗粒原则上是已知的。其尺寸可以为1-20mm;优选2-10mm。根据本发明,颗粒的重量为例如小于20g,特别地为小于10g。形状可以在宽范围内变化,并且受制备工艺的影响。所述颗粒优选像垫状(cushion-like),柱状或像球状;该形状也可以偏离理想形状,并可以变形。根据本发明,所述粒子必需具有非粘性表面以确保颗粒具有流动性能。
在本发明中,“可流动”指的是从-10℃到+40℃,在50cm填充高度的固有压力下,颗粒在自身重量下仍然可以流经直径5cm的开口。如果颗粒在此情况下没有互相粘附,其表面是抗粘连的。
根据各个组分的性质和用量,颗粒的核的材料相应于通常的热熔粘合剂组合物,特别是热熔压敏粘合剂(PSA)。热熔粘合剂包括多种基础聚合物(base polymers),所述基础聚合物与其他组分例如增塑剂、树脂(增粘剂)、和添加剂混合,从而构成所述粘合剂。基础聚合物基本上决定了粘合剂在粘合性、强度和温度特性方面的性能。也可以使用混合物,前提是它们彼此相容。
合适的基础聚合物,例如是弹性嵌段共聚物如苯乙烯-丁二烯、苯乙烯-丁二烯-苯乙烯、苯乙烯-异戊二烯-苯乙烯、苯乙烯-乙烯-丁烯-苯乙烯、苯乙烯-乙烯-丙烯-苯乙烯;烯烃共聚物如乙烯-醋酸乙烯聚合物、乙烯-甲基丙烯酸酯、乙烯-丙烯酸正丁酯、或乙烯-丙烯酸聚合物;聚烯烃如聚乙烯、聚丙烯、及共聚物;聚丙烯酸酯;聚酰胺;聚酯;聚乙烯醇及共聚物;聚氨酯。
特别合适的,例如是乙烯-醋酸乙烯共聚物(EVA)、(部分)结晶的聚丙烯(共)聚合物、非晶态聚烯烃(APAO)、聚乙烯及共聚物、聚烯烃如统计或嵌段共聚物或星型聚合物、苯乙烯嵌段共聚物如苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-异戊二烯-苯乙烯(SIS)、聚丁烯、聚(甲基)丙烯酸酯如包含C4-C16烷基的(甲基)丙烯酸酯。通过缩合制得的聚合物也是适合的,例如特别是由二异氰酸酯和多元醇制成的热塑性非反应性聚氨酯。本发明的一个具体实施方式中使用了惰性的基础聚合物,另一个具体实施方式使用了包含可交联官能团的聚合物,其在施用后可以进行交联反应。
前述基础聚合物以及能够影响粘合剂特定性能,例如粘结强度、粘合性、软化点或加工粘度的添加剂,可作为进一步的组分包含在核的合适的热熔粘合剂中。这些添加剂例如可以是增塑剂、稳定剂、蜡、粘合促进剂、抗氧剂、光防护剂(light protection agents)、颜料、填料或类似的添加物。其用量最多可为70重量%。多种添加剂也可作为混合物使用。
作为进一步的组分,根据本发明所述的合适的热熔粘合剂包含至少一种增粘树脂。所述树脂使得粘合剂更加粘稠。其用量为5-50重量%,优选10-40重量%。本发明的上下文中的树脂可以选自芳族、脂肪族、或脂环族烃树脂、及其改性的或氢化的衍生物。本发明的上下文中可用的其他树脂是聚萜烯树脂、苯酚或芳香改性的聚萜烯树脂、改性的天然树脂,例如得自香脂树脂(balsam resin),塔尔树脂(tall resin)或木松香的树脂酸、也可以任选氢化松香醇及其酯、丙烯酸共聚物例如苯乙烯-丙烯酸共聚物、和基于官能烃树脂的树脂。根据本发明,优选这些树脂的软化点为50-130℃(环球法)
优选使用增塑剂来调整粘度或柔性,通常增塑剂的浓度为0-30重量%,优选2-20重量%。合适的增塑剂,例如是药用白油、环烷基矿物油、聚丙烯、聚丁烯、聚异戊二烯低聚物、氢化聚异戊二烯和/或聚丁二烯低聚物、石蜡烃油、苯甲酸酯、苯二甲酸酯、己二酸酯、甘油酯、植物油或动物油及它们的衍生物、聚丙二醇、聚丁二醇、聚亚甲基二醇(polymethyleneglycol)。增塑剂也可以增加粘合剂组合物的粘性。
所述热熔粘合剂可以任选地包含0-20重量%的蜡。调节蜡的用量,从而方面将粘度降低到所需的范围内,而另一方面对粘合性没有负面影响。蜡可以是天然的或合成的来源。植物蜡、动物蜡、天然石蜡或石化蜡可作为天然蜡使用。硬质蜡例如褐煤酯蜡(montan ester wax)、沙索蜡等可作用化学改性蜡使用。聚烯烃蜡以及聚乙二醇蜡可以作为合成蜡使用。优选使用石化蜡例如凡士林、微蜡,以及合成蜡,特别是聚乙烯蜡、聚丙烯蜡、费托蜡、石蜡、或微晶蜡。
稳定剂是另一组添加剂。其目的是防止聚合物在加工过程中分解。此处特别提及抗氧剂。其在热熔压敏粘合剂中的添加量通常最高为3重量%,优选约0.1-1.0重量%。
这些类型的添加剂和热熔粘合剂原则上是本领域技术人员已知的,本领域技术人员可以基于热熔粘合剂需要的性能进行选择。
特别地,选择为高度压敏粘合剂的热熔粘合剂,例如压敏粘合剂(PSA),作为核材料的热熔粘合剂。这些PSA可以理解为,作为层施加到表面上,通过轻压可以粘合到各种基材上的那些粘合剂。但是,也可以相应地包覆其它的热熔粘合剂。本发明的一个具体实施方式使用惰性热熔压敏粘合剂作为核。另一个具体实施方式使用反应性热熔压敏粘合剂,其在施加后可以进一步交联。其实例为还包含可辐射交联基团的热熔粘合剂、能够通过自由基聚合进行进一步交联的热熔粘合剂、或通过缩聚反应可以交联的热熔粘合剂。
特别合适的热熔粘合剂是具有低软化点例如60-130℃,特别是70-120℃(软化温度通过环球法测定,ISO4625-1)的那些。
与之相反,包围例如由热熔压敏粘合剂形成的核的层必须显示为非粘性的。外部包覆层的组分优选与核的热熔粘合剂相容。这可以理解为,当两种组分熔化时,能够得到均匀的熔融组合物。在本文所述的制备和加工中,均匀的熔融组合物在熔融状态将不会引起相分离。这可以通过使用原则上常规和已知的,并且与核的热熔粘合剂相容的组分来实现。
本发明的包覆层(encasing layer)包含苯乙烯嵌段共聚物。其为基于烯烃和苯乙烯的共聚物。它们是二嵌段或多嵌段聚合物,且具有弹性。也可以使用氢化嵌段共聚物。氢化嵌段共聚物是本领域技术人员已知的,并且能够商购得到。例如,可以是SIS,SBS,SIBS,SIPS,SEBS,SEPS。基于壳(casing)组合物,苯乙烯嵌段共聚物的量为5-35重量%,优选10-25重量%。
本发明的包覆层必须进一步包含20-65重量%的至少一种油。上述增塑油原则上可用作油。氢化增塑剂是特别适合的,例如矿物油、烃类、或烯烃低聚物。油优选自烃油、石蜡油、环烷油、或药用白油。这些油与苯乙烯嵌段共聚物高度相容。没有观察到“渗出(sweating)”(即油聚集在相应层的表面)。
特别地,包覆层中油的用量优选为30-50重量%。包覆层中油的用量优选不大于热熔压敏粘合剂组合物中增塑剂或油的用量。
外层可进一步包含0-15重量%的添加剂,特别地为不大于5重量%。“添加剂”例如可以理解为增塑剂、光防护剂、氧化剂、以及类似的物质。
在本发明一个具体实施方式中,包覆层也可以包含5-30重量%的聚烯烃共聚物。这指的是软化点为90-130℃的那些聚合物。这些聚烯烃是已知的;特别地,它们选自聚乙烯或聚丙烯或共聚物,特别优选LDPE或EVA。共聚物与蜡不同的地方在于其通常具有较高的分子量,例如15,000-150,000g/mol。根据本发明,包覆层的组合物可进一步包含0-25重量%的蜡。这里的蜡可以使用上述用作粘合剂组分的蜡。特别地,用量为5-20重量%。选择蜡的用量以便基本上不损害核和壳的全部熔融混合物的压敏粘合性。可以在前述用量范围内独立选择壳组合物的各个组分的用量,前提是混合物具有所需的性能。壳的组分之和为100%。
在一个具体实施方式中,外层由以下混合物组成:5-30重量%的苯乙烯嵌段共聚物,5-30重量%的聚烯烃共聚物,0-20重量%的蜡,0-15重量%的添加剂,和20-65重量%的至少一种选自石蜡油或环烷油或药用白油的油。
包覆层的软化点小于135℃,优选小于125℃,特别优选小于115℃。然而,其通常大于80℃,优选大于90℃,特别优选大于100℃。包覆层是抗粘连的,即作为颗粒,在不超过40℃的温度下,其在自身重量下不发生粘连。在贮存期间同样存在抗粘连性。特别是,根据本发明的颗粒在贮存2个月,特别是4个月之后仍然可以流动。
基于粘合剂的总重量,外部包覆层的重量比例为5-20重量%,特别地为7-12重量%。颗粒的外层厚度为10-300μm,特别地为30-150μm。核因此足够稳定,在对颗粒进行常规操作,例如运输、贮存、以及倾倒的情况下具有稳定的表面,并且不发生相互粘连。
本发明的进一步的目的是提供一种由完全被包覆的热熔压敏粘合剂粒子制备颗粒的方法。制备热熔粘合剂组合物以及颗粒的壳组合物的方法是已知的。通常熔化所述组分,并在熔融状态下将它们混合。可以在容器中间歇进行,也可以在挤出机中进行连续制备。核材料和壳材料的混合物在室温下各自为固体。它们通常不含有机溶剂。
在一个优选的制备方式中,通过共挤出来加工颗粒的熔融组分(核、壳)。此处热熔粘合剂以股(strand)状从中央喷嘴挤出,与此同时,壳材料通过另一个环形喷嘴挤出,并置于所述股状物的周围。已知挤出操作在水中进行,或在基础之后立即在水中或其它液体中冷却挤出的股。
为了制备颗粒,需要将股状物分成单独的粒子。原则上可以使用已知的方法例如切割或挤压(pinching)来进行,由核和壳组成的股状物一起分开。分离发生在材料仍然是塑性的时候,即核和壳仍然可以发生变形。从而此时的柔性足以使得包覆层全部包覆住核材料的切割末端。对切割的末端进行密封,例如粘合连接,熔合,或焊接,不需要进一步的加工步骤。这确保各颗粒完全被外壳材料的层覆盖。因此各颗粒在壳中仅仅有两个细的接缝。
根据本发明得到的粘合剂颗粒较小。尺寸可以是,例如,10×10×15mm;粒子的重量小于20g,优选为0.1-10g,特别地为0.3-5g。
根据本发明的颗粒在制备后进行冷却。因此它们是尺寸稳定的,不再互相粘附。然后这些颗粒可以倒入已知的包装装置中,例如桶,罐,硬纸盒,袋或容器中。根据本发明的颗粒可以贮存在这些包装装置中。已经发现这些颗粒在不超过40℃的温度下不会发生粘连,即甚至在相应的温度下长期贮存或运输后,颗粒仍可以自由流动,并且可以从容器中取出。根据本发明的热熔粘合剂颗粒将在应用前进行熔化。为了达到该目的,将颗粒从容器中取出,并例如通过机械传输设备输送到熔融罐中。在那里这些颗粒熔融并且被输送到施加位置,任选同时进行混合。
由于颗粒重量非常轻,可以仅仅熔融和施加少量的热熔粘合剂。根据本发明的热熔粘合剂颗粒上的热应力在本文中是减少的。另外可以使用自动传输设备运输这些颗粒,例如压缩空气或真空传输设备。因此可以增加粘合剂应用工艺的自动化。另外,消费者可以购买较大量的粘合剂,但相对于实际的需求可能仅仅使用少量的粘合剂。这改善了粘合剂的贮存管理和物流。
本发明的热熔粘合剂的进一步的优点在于改善的贮存稳定性。避免了增加表面粘性的物质迁移到外部包覆层,并因此改善了颗粒的抗粘连性进。
实施例旨在解释本发明。
热熔压敏粘合剂的制备方法
于180℃在实验室搅拌器中熔化和混合聚合物。然后加入进一步的配方组分,使其充分混合均匀,并任选脱气。倒出熔融混合物并冷却,由此固化。
表1:热熔粘合剂的组成
列举的组分是常见的市售产品。
表2:热熔粘合剂的性能
性能 | 实施例1 | 实施例2 | 实施例3 |
在150℃的熔融粘度(mPas) | 1150 | 3500 | |
软化点(℃) | 80-90 | 76 | 75 |
热熔粘合剂4:
由以下物质构成的辐射固化热熔粘合剂:
将80g基于丙烯酸酯与反应性(reacted-on)引发剂的共聚物(AC树脂A204UV)与20g树脂(Kristalex)于约130℃-150℃在搅拌下熔化,均匀混合,然后冷却,由此粘合剂成为固体。
壳组合物1:
将15g SEBS共聚物(Kraton G1652)、5g树脂(Escorez5320)、15g蜡(Sasolwax H1)、20g聚乙烯(Escorene LD655)、0.05g稳定剂(Irganox1010)、以及44.5g油(Primol352)于约190℃在搅拌下熔化,并且均匀混合。
软化点:112℃。
壳组合物2:
将20g SEBS共聚物(Kraton G1652)、10g树脂(Escorez5400)、15g蜡(SasolwaxH1)、15g聚乙烯(Escorene LD655)、0.05g稳定剂(Irganox1010)、以及39.5g油(Primol352)于约190℃在搅拌下熔化,并且均匀混合。
软化点:102℃。
制备颗粒:
熔化实施例1-4的热熔粘合剂。与此同时,熔化壳混合物1或2。
在挤出机中,于水中将粘合剂通过中央喷嘴挤出,并且将壳材料通过环形喷嘴挤出。形成了一个被包覆的管(直径约5mm),并立即对其进行冷却。进一步传输股状物,然后将其夹断,分离成短的枕形片。将其在冷却浴中冷却至室温。随后它们不再具有粘性,具有储存稳定性,并且能够干燥。
单个颗粒的尺寸约为8×8×5mm,重量约为1.5g。
壳的量由挤出的熔体来确定,约为12重量%。
核1+壳1 核2+壳1
核3+壳2 核4+壳2
颗粒均能自由流动。混合物即使在95%的相对湿度,50cm的散装高度(bulk height),以及35℃贮存一个月后也能自由流动。
由颗粒(1-3)通过熔化来制备可流动压敏粘合剂。使用常规的泵和分配设备来施加粘合剂,冷却后得到压敏粘合剂层。
Claims (14)
1.颗粒状热熔压敏粘合剂(PSA),所述颗粒包含由热熔压敏粘合剂形成的核以及包围所述核的外层,所述外层由不是压敏粘合剂的组合物形成,其中所述外层包含:
-5-35重量%的苯乙烯嵌段共聚物,
-20-65重量%的至少一种油,以及
-0-15重量%的添加剂。
2.根据权利要求1所述的热熔压敏粘合剂,其中所述组合物进一步包含5-30重量%的聚烯烃共聚物,特别是进一步包含LDPE或EVA作为所述聚烯烃共聚物。
3.根据权利要求1或2所述的热熔压敏粘合剂,其中所述油选自烃油、石蜡油、环烷油、或药用白油。
4.根据权利要求3所述的热熔压敏粘合剂,其中所述外层中油的量大于所述核中热熔压敏粘合剂所含的油和增塑剂的比例。
5.根据权利要求1-4所述的热熔压敏粘合剂,其中所述外层占所述颗粒的5-20重量%。
6.根据权利要求1-5所述的热熔压敏粘合剂,其中所述外层的混合物的软化点为80-135℃。
7.根据权利要求1-6所述的热熔压敏粘合剂,其中所述颗粒是自由流动的。
8.根据权利要求1-7所述的热熔压敏粘合剂,其中壳组合物由以下物质构成:
-5-30重量%的苯乙烯嵌段共聚物,
-5-30重量%的聚烯烃共聚物,
-20-65重量%的至少一种油,
-0-20重量%的蜡,以及
-0-15重量%的添加剂。
9.根据权利要求1-8所述的热熔压敏粘合剂,其中所述颗粒的重量小于20g,特别是小于10g。
10.根据权利要求1-9所述的热熔压敏粘合剂,其中所述颗粒完全被非压敏粘合剂的外层包围,并且所述壳包括两个实质上封闭的分隔接缝。
11.制备前述权利要求中任一项所述的颗粒的方法,其中通过共挤出将核组合物和壳组合物以熔融形式的股状物挤出,随后分离所述颗粒的被包覆的股状物,由此制备所述颗粒。
12.根据权利要求11所述的方法,其中分离时,通过熔化、密封或焊接来封闭外层的封闭接缝。
13.根据权利要求11或12所述的方法,其中通过挤压或切割来分离所述股状物。
14.根据权利要求1-10中任一项的热熔粘合剂用于压缩空气传输或真空传输粘合剂颗粒的用途。
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EP4013910B1 (en) * | 2019-08-15 | 2023-04-05 | 3M Innovative Properties Company | Core-sheath filament with a silicone-containing block copolymer core |
WO2021033084A1 (en) | 2019-08-19 | 2021-02-25 | 3M Innovative Properties Company | Core-sheath filaments including crosslinkable and crosslinked adhesive compositions and methods of making the same |
EP4118351A4 (en) * | 2020-03-13 | 2024-03-27 | Nautilus Solutions, LLC | BEARINGS AND BEARING COMPONENTS COMPRISING A HOT-MELT PRESSURE-SENSITIVE ADHESIVE AND ASSOCIATED MANUFACTURING METHODS |
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- 2012-03-06 CA CA2829846A patent/CA2829846A1/en not_active Abandoned
- 2012-03-06 RU RU2013146244/05A patent/RU2013146244A/ru not_active Application Discontinuation
- 2012-03-06 JP JP2013558359A patent/JP2014512427A/ja active Pending
- 2012-03-06 BR BR112013023488A patent/BR112013023488A2/pt not_active IP Right Cessation
- 2012-03-06 CN CN2012800133888A patent/CN103443235A/zh active Pending
- 2012-03-06 EP EP12708296.4A patent/EP2686398A1/de not_active Withdrawn
- 2012-03-06 MX MX2013010491A patent/MX2013010491A/es unknown
- 2012-03-06 KR KR1020137024257A patent/KR20140012666A/ko not_active Application Discontinuation
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2013
- 2013-09-17 US US14/028,580 patent/US20140011912A1/en not_active Abandoned
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EP0957029A1 (en) * | 1998-05-14 | 1999-11-17 | Nordson Corporation | A method and installation for packaging an adhesive product or similar product |
US6716527B1 (en) * | 1999-07-09 | 2004-04-06 | Henkel Kommanditgesellschaft Auf Aktien | Hot-melt-type adhesive in the form of a granulate |
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TWI673316B (zh) * | 2014-05-30 | 2019-10-01 | Kuraray Co., Ltd. | 熱塑性彈性體丸粒及由該丸粒所成形之成形品 |
Also Published As
Publication number | Publication date |
---|---|
BR112013023488A2 (pt) | 2016-12-06 |
EP2686398A1 (de) | 2014-01-22 |
KR20140012666A (ko) | 2014-02-03 |
WO2012123282A1 (de) | 2012-09-20 |
CA2829846A1 (en) | 2012-09-20 |
JP2014512427A (ja) | 2014-05-22 |
US20140011912A1 (en) | 2014-01-09 |
RU2013146244A (ru) | 2015-04-27 |
MX2013010491A (es) | 2013-10-01 |
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