CN109071759B - 包括胺引发多元醇的双组分无溶剂粘合剂组合物 - Google Patents

包括胺引发多元醇的双组分无溶剂粘合剂组合物 Download PDF

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CN109071759B
CN109071759B CN201780027837.7A CN201780027837A CN109071759B CN 109071759 B CN109071759 B CN 109071759B CN 201780027837 A CN201780027837 A CN 201780027837A CN 109071759 B CN109071759 B CN 109071759B
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D·文西
T·施密特
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Abstract

公开了双组分无溶剂聚氨基甲酸酯粘合剂组合物,所述粘合剂组合物包括异氰酸酯组分和多元醇组分,所述多元醇组分包括至少一种高反应性胺引发多元醇。所述至少一种胺引发多元醇包括伯羟基和结合一个或多个叔胺的主链。所述胺引发多元醇进一步包括2到12的官能度、5到1,830的羟基数,和在40℃下500到20,000mPa‑s的粘度。所述多元醇组分可进一步包括非胺引发多元醇。所述粘合剂组合物被配制成使得所述异氰酸酯和多元醇组分可在混合之前涂覆到单独的基材。更进一步,公开了一种包括所述粘合剂组合物的层压材料。

Description

包括胺引发多元醇的双组分无溶剂粘合剂组合物
相关申请的引用
本申请要求2016年5月10日提交的意大利申请第102016000047936号的权益。
技术领域
本公开涉及无溶剂粘合剂组合物。更具体地说,本公开涉及用于层压结构的双组分无溶剂聚氨基甲酸酯粘合剂组合物。所公开的粘合剂组合物包括胺引发多元醇,其提供具有改进的转化效率的层压结构。
在一些实施例中,粘合剂组合物展现高反应性,并且因此被配制成独立地涂覆到两个基材,然后将两个基材放在一起以使粘合剂组合物混合和反应。具体地说,粘合剂组合物的一种组分被配置成均匀地涂覆到第一基材的表面,并且粘合剂组合物的另一种组分被配置成涂覆到第二基材的表面。随后将第一和第二基材放在一起,由此使两种组分混合和反应,以在第一和第二基材之间形成粘合剂。以此方式,然后可使粘合剂固化,由此粘结第一和第二基材。
背景技术
粘合剂组合物适用于各种各样的目的。例如,粘合剂组合物用于将例如聚乙烯、聚丙烯、聚酯、聚酰胺、金属、纸或玻璃纸的基材粘结在一起,以形成复合膜,即,层压材料。粘合剂在不同的最终用途应用中的使用通常是已知的。例如,粘合剂可用于制造包装工业、特别是食品包装中所使用的膜/膜和膜/箔层压材料。用于层压应用的粘合剂或“层压粘合剂”通常可分为三种类别:溶剂型、水基型和无溶剂型。粘合剂的性能随着类别和粘合剂被涂覆的应用而变化。
无溶剂层压粘合剂可被涂覆高达百分之百的固体,不含有机溶剂或水性载体。因为在涂覆后就不必从粘合剂干燥有机溶剂或水,所以这些粘合剂可以高线速度运行并且在需要快速粘合剂涂覆的应用中是优选的。溶剂型和水基型层压粘合剂受到溶剂或水在粘合剂涂覆之后可从层压结构被有效地干燥和移除的速率限制。出于环境、健康和安全的原因,层压粘合剂优选地是水性或无溶剂的。
在无溶剂层压粘合剂的类别内,有许多变体。一种特定变体包含预混合的双组分聚氨基甲酸酯基层压粘合剂。通常,双组分聚氨基甲酸酯基层压粘合剂包含包括含异氰酸酯预聚物和/或聚异氰酸酯的第一组分,以及包括多元醇的第二组分。预聚物可通过过量异氰酸酯与每分子含有两个或更多个羟基的聚醚和/或聚酯的反应来获得。第二组分包括每分子经两个或更多个羟基引发的聚醚和/或聚酯。将两种组分以预定比率组合,或“预混合”,并且然后涂覆在第一基材(“载体腹板”)上。然后将第一基材与第二基材放在一起以形成层压结构。
可将额外基材层添加到所述结构,其中额外粘合剂组合物层位于每个连续基材之间。然后在室温或高温下使粘合剂固化,由此将基材粘结在一起。
层压结构的进一步处理取决于粘合剂的固化速度。粘合剂的固化速度是由层压基材之间的机械粘结变得足以允许进一步处理所花费的时间表示,并且层压材料符合适用的法规(例如,食品接触法规)。缓慢的固化速度会导致较低的转化效率。与传统的含溶剂粘合剂相比,预混合的双组分无溶剂层压粘合剂展现弱的初始粘结和缓慢的固化速度。转化工业中的一般趋势是使层压粘合剂较快地固化。较快的固化会改进转化器的操作效率。具体地说,将成品快速地移出仓库会提高生产能力和用于处置最后一分钟订单(例如,零售商促销活动)的灵活性。为了提高操作效率,应使用相比于现有粘合剂组合物具有高得多的反应性的粘合剂组合物来形成层压材料。然而,此类粘合剂组合物将对传统的粘合剂涂覆技术提出挑战。
因此,需要具有改进的粘结强度和较快的固化速度的双组分无溶剂聚氨基甲酸酯基层压粘合剂组合物。
发明内容
公开了双组分无溶剂聚氨基甲酸酯粘合剂组合物。在一些实施例中,无溶剂粘合剂组合物包含异氰酸酯组分,异氰酸酯组分包含至少一种异氰酸酯。无溶剂粘合剂组合物进一步包含多元醇组分,多元醇组分包含至少一种高反应性胺引发多元醇。至少一种异氰酸酯可选自由芳香族异氰酸酯、脂肪族异氰酸酯和其组合组成的组。胺引发多元醇可进一步包括约2到约12的官能度、约5到约1,830的羟基数,和约500到约20,000的分子量。在组合异氰酸酯和多元醇组分,由此形成粘合剂组合物后,粘合剂组合物就可在10分钟内展现大于10,000mPa-s(在40℃下)的粘度。多元醇组分可进一步包含非胺引发多元醇。
所公开的粘合剂组合物相对于现有双组分无溶剂粘合剂组合物展现快速的固化速率。因此,包括粘合剂组合物的层压结构可在层压之后少到两小时内切割,并在两天内递送给客户。包括现有通用粘合剂组合物的层压材料通常需要两到三天的层压用于切割和五到七天用于递送。因此,使用所公开的粘合剂组合物极大地改进了过程效率。另外,与现有通用粘合剂的二十到三十分钟的适用期相比,所公开的粘合剂组合物的适用期是无限期的。这是因为所公开的粘合剂组合物的适用期与固化过程完全无关,如下文将论述。
因为与现有粘合剂组合物相比,所公开的粘合剂组合物被配制成具有较高的反应性并且展现较快的固化速率,所以所公开的粘合剂组合物并不理想地适合与现有粘合剂涂覆设备一起使用。这是因为两种组分反应得非常快,从而造成粘合剂胶凝并且不适合涂覆到基材。为此,所公开的粘合剂组合物被配制成使得异氰酸酯和多元醇组分单独地涂覆在两个不同基材上,而不是预混合和涂覆在载体腹板上。
具体地说,所公开的粘合剂组合物被配制成使得异氰酸酯组分可均匀地涂覆到第一基材的表面并且多元醇组分可涂覆到第二基材的表面。然后使第一基材的表面与第二基材的表面接触,以使两种组分混合和反应,由此形成层压材料。然后可使粘合剂组合物固化。
附图说明
参考附图,其中:
图1是绘示粘合剂组合物的粘度对时间的曲线图。
具体实施方式
根据本公开的双组分无溶剂粘合剂组合物包括异氰酸酯组分和多元醇组分,如上文所叙述。
异氰酸酯组分
异氰酸酯组分包括至少一种异氰酸酯。至少一种异氰酸酯可选自由异氰酸酯预聚物、异氰酸酯单体、聚异氰酸酯(例如,二聚物、三聚物等等)和其两种或更多种的组合组成的组。如本文中所使用,“聚异氰酸酯”是任何含有两种或更多种异氰酸酯基的化合物。异氰酸酯预聚物是包括至少一种异氰酸酯和至少一种多元醇的反应物的反应产物。如本文中所使用,“异氰酸酯预聚物”可以是聚异氰酸酯本身。
至少一种异氰酸酯包括1.5到10,或1.8到5,或2到3的官能度。如关于异氰酸酯组分所使用,“官能度”是指每分子的羟基反应性位点的数目。具有异氰酸酯基的化合物,例如异氰酸酯组分,可以用参数“%NCO”来表征,所述参数是以所述化合物的重量计的异氰酸酯基以重量计的量。参数%NCO是通过ASTM D 2572-97(2010)的方法来测量。所公开的异氰酸酯组分具有至少3%,或至少6%,或至少10%的%NCO。优选地,异氰酸酯组分具有不超过25%,或18%,或14%的%NCO。
此外,至少一种异氰酸酯包括0到50%,或5到40%,或10到30%的游离单体含量。更进一步,至少一种异氰酸酯包括200到3,000g/mol,或300到2,000g/mol,或500到1,000g/mol的分子量。更进一步,异氰酸酯组分具有在25℃下的300到40,000mPa-s,或500到20,000mPa-s,或1,000到10,000mPa-s的粘度,如通过ASTM D2196的方法所测量。
异氰酸酯组分的至少一种异氰酸酯可选自由芳香族异氰酸酯、脂肪族异氰酸酯、环脂族异氰酸酯和其组合组成的组。“芳香族聚异氰酸酯”是含有一个或多个芳香环的异氰酸酯。“脂肪族聚异氰酸酯”不含芳香环。“环脂族聚异氰酸酯”是脂肪族聚异氰酸酯的子集,其中化学链是环状结构的。
根据本公开适用的芳香族异氰酸酯的实例包含但不限于:亚甲基二苯基二异氰酸酯(“MDI”)的异构体,例如4,4-MDI、2,2-MDI和2,4-MDI;甲苯-二异氰酸酯(“TDI”)的异构体,例如2,4-TDI、2,6-TDI;萘-二异氰酸酯(“NDI”)的异构体,例如1,5-NDI;降冰片烷二异氰酸酯(“NBDI”)的异构体;四甲基亚二甲苯基二异氰酸酯(“TMXDI”)的异构体;和其两种或更多种的组合。优选的是MDI的异构体,特别是4,4-MDI和2,4-MDI(即,液体MDI)或4,4-MDI(即,固体MDI)的混合物。
根据本公开适用的脂肪族和环脂族异氰酸酯的实例包含但不限于六亚甲基二异氰酸酯(“HDI”)的异构体、异佛尔酮二异氰酸酯(“IPDI”)的异构体、二甲苯二异氰酸酯(“XDI”)的异构体,和其组合。
以粘合剂组合物的重量(即,异氰酸酯组分和多元醇组分的总重量)计,粘合剂组合物中的至少一种异氰酸酯的量以重量计是至少5重量%,或至少10重量%,或至少20重量%。以粘合剂组合物的重量计,粘合剂组合物中的至少一种异氰酸酯的量以重量计不超过100重量%,或不超过95重量%,或不超过90重量%。
异氰酸酯组分可进一步包括本领域普通技术人员通常已知的其它成分。
多元醇组分
无溶剂粘合剂组合物进一步包括多元醇组分,多元醇组分包括至少一种高反应性胺引发多元醇。与现有双组分无溶剂粘合剂组合物中使用的传统多元醇相比,在多元醇组分中包含至少一种胺引发多元醇会提供较高的反应性和较快的固化。胺引发多元醇包括伯羟基和结合至少一个叔胺的主链。在一些实施例中,多元醇组分还可包括另一种类型的多元醇,其是非胺引发多元醇。每种多元醇类型可包含一种多元醇。替代地,每种多元醇类型可包含不同种多元醇的混合物。在一些实施例中,一种多元醇类型可以是一种多元醇,而另一种多元醇类型可以是不同种多元醇的混合物。
胺引发多元醇包括伯羟基和结合至少一个叔胺的主链。在一些实施例中,胺引发多元醇具有I的化学结构:
Figure BDA0001853924400000061
其中R1、R2和R3各自独立地是直链或支链烷基。例如,可各自独立地是C1-C6直链或支链烷基。在一些实施例中,胺引发多元醇包括叔胺和仲胺。
至少一种胺引发多元醇包括2到12,或3到10,或4到8的官能度。如关于多元醇组分所使用,“官能度”是指每分子的异氰酸酯反应性位点的数目。此外,至少一种胺引发多元醇包括5到1,830,或20到100,或31到40的羟基数。如关于多元醇组分所使用,“羟基数”是可用于反应的反应性羟基的量的度量。此数目是以湿分析方法来测定,并被报告为相当于一克样品中发现的羟基的氢氧化钾的毫克数。ASTM D 4274D中描述了最常用的用于测定羟基数的方法。更进一步,至少一种胺引发多元醇包括在25℃下500到20,000mPa-s,或1,000到15,000mPa-s,或1500到10,000mPa-s的粘度。
根据本公开适用的胺引发多元醇是通过用一种或多种烯化氧使一种或多种胺引发剂烷氧基化而制得。
以粘合剂组合物的重量(即,异氰酸酯组分和多元醇组分的总重量)计,粘合剂组合物中的至少一种胺引发多元醇的量以重量计是至少2重量%,或至少10重量%,或至少20重量%。以粘合剂组合物的重量计,粘合剂组合物中的至少一种胺引发多元醇的量以重量计不超过100重量%,或不超过95重量%,或不超过90重量%。
在一些实施例中,至少一种非胺引发多元醇可任选地包含在粘合剂组合物中,例如在多元醇组分中。非胺引发多元醇的实例包含但不限于聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、聚丙烯酸酯多元醇、聚己内酯多元醇、聚烯烃多元醇、天然油多元醇,和其两种或更多种的组合。优选地,非胺引发多元醇具有在25℃下30到40,000mPa-s,或50到30,000mPa-s,或70到20,000mPa-s的粘度,如通过ASTM D2196的方法所测量。优选地,非胺引发多元醇具有在25℃下100到10,000mPa-s的粘度,如通过ASTM D2196的方法所测量。
粘合剂组合物中的至少一种非胺引发多元醇的量是至少0重量%,或至少5重量%,或至少10重量%。粘合剂组合物中的至少一种非胺引发多元醇的量不超过98重量%,或不超过90重量%,或不超过80重量%。
通过调节每种组分到其相应基材的涂布重量来控制异氰酸酯组分对多元醇组分的以重量计的混合比。在一些实施例中,最终粘合剂组合物中的异氰酸酯组分对多元醇组分的混合比可以是100:100,或100:90,或100:80。与传统的粘合剂相比,所公开的粘合剂组合物是更宽容的,并且可适应一些涂布重量误差(例如,高达约10%的涂布重量误差)。
在一些实施例中,一种或多种添加剂可任选地包含在粘合剂组合物中。此类添加剂的实例包含但不限于增粘剂、增塑剂、流变改性剂、粘合促进剂、抗氧化剂、填充剂、着色剂、表面活性剂、溶剂,和其两种或更多种的组合。
多元醇组分可进一步包括本领域普通技术人员通常已知的其它成分,例如额外的多元醇、异氰酸酯等等。
层压材料形成
预期到,所公开的无溶剂粘合剂组合物的异氰酸酯组分和多元醇组分可被单独地配制和存储,直到需要使用所述无溶剂粘合剂组合物来形成层压结构。优选地,异氰酸酯组分和多元醇组分在25℃下呈液态。即使所述组分在25℃下是固体,必要时加热所述组分以使其处于液态也是可接受的。由于粘合剂组合物的适用期与固化过程无关,故所述组分可被无限期地存储。
包括所公开的粘合剂组合物的层压材料可通过将粘合剂组合物的异氰酸酯和多元醇组分单独地涂覆到例如两个膜的两个不同基材来形成。如本文中所使用,“膜”是在一个维度上为0.5mm或更小且在另外两个维度上均为1cm或更大的任何结构。“聚合物膜”是由聚合物或聚合物的混合物制成的膜。聚合物膜的组成通常是80重量%或更多的一种或多种聚合物。
例如,将异氰酸酯组分层涂覆到第一基材的表面。优选地,第一基材上的异氰酸酯组分层的厚度是0.5到2.5μm。将多元醇组分层涂覆到第二基材的表面。优选地,第二基材上的多元醇组分层的厚度是0.5到2.5μm。通过控制涂覆到每个基材的层的厚度,可控制组分的比率。
然后,使第一和第二基材的表面穿过用于向第一和第二基材施加外部压力的装置,例如轧辊。将异氰酸酯组分和多元醇组分放在一起会形成可固化的粘合剂混合物层。当将第一和第二基材的表面放在一起时,可固化的粘合剂混合物层的厚度是1到5μm。当将第一和第二基材放在一起并且异氰酸酯组分和多元醇组分彼此接触时,所述组分开始混合和反应。这标志着固化过程开始。
随着使第一和第二基材穿过各种其它辊并且最终到达重绕辊,会实现进一步混合和反应。随着第一和第二基材穿过辊,会发生进一步混合和反应,这是因为每个基材相比于另一个基材遍及每个辊采取较长或较短的路径。以此方式,两个基材相对于彼此移动,从而混合相应基材上的组分。此类辊在涂覆设备中的布置在本领域中是通常已知的。然后使可固化的混合物固化或允许其固化。
层压结构中合适的基材包含膜,例如纸、织造和非织造织物、金属箔、聚合物膜和金属涂布聚合物膜。一些膜任选地具有可用油墨印刷上图像的表面,所述油墨可与粘合剂组合物接触。将基材分层以形成层压结构,其中根据本公开的粘合剂组合物将一个或多个基材粘合在一起。
现在转到图1,展示了展示以下各项的反应性分布图的曲线图:根据本公开的粘合剂组合物,即,包括所公开的胺引发多元醇;以及没有胺引发多元醇的粘合剂组合物。在图1中,包括胺引发多元醇的粘合剂组合物最初包括在层压时在40℃下约6,000mPa-s的粘度。令人惊讶的是,在层压之后不到十分钟内,粘度快速地增加到大于10,000mPa-s。相反,没有胺引发多元醇的粘合剂组合物最初包括在层压时在40℃下约1,000mPa-s的粘度。在层压之后直到约五十分钟,粘度不超过10,000mPa-s。此反应性分布图是现有无溶剂粘合剂组合物的典型特征。
因此,在粘合剂组合物的多元醇组分中包含所公开的胺引发多元醇会提供具有显著较快的反应性分布图的粘合剂组合物。此类粘合剂组合物特别适合于根据本文中所公开的方法进行层压。
本公开的实例
现在将通过描述说明所公开的粘合剂组合物和现有粘合剂组合物的实例(统称为“实例”)来进一步详细地阐释本公开。然而,本公开的范围当然不限于所述实例。
在实例中,异氰酸酯组分包括本领域普通技术人员通常已知的芳香族异氰酸酯,例如TDI MDI。根据下表1中列出的配制物制备实例的多元醇组分:
表1:OH组分样品配制物
Figure BDA0001853924400000091
在Nordmeccanica LABO COMBITM层压机上制备包括表1中所描述的多元醇组分的层压结构。然后在LABO COMBITM层压机上测试所制备的层压结构的粘结强度和伯芳香胺衰变。根据ASTM F904测试层压结构的粘结强度。伯芳香胺衰变分析是用于测定水性食品刺激剂(3%乙酸)中的伯芳香胺的测试。所述测试是基于官方BrF方法第L 00-00.6号和委员会法规(EU)第10/2011号。
下表2中展示了性能结果。在层压之后的2小时、4小时、1天和2天根据ASTM F904测量粘结强度。根据BrF方法第L 00-00.6号和委员会法规(EU)第10/2011号在层压之后的24小时、2天和3天测试伯芳香胺衰变。
表2:LABO COMBITM上的性能结果
Figure BDA0001853924400000101
在表2中,“a”表示粘合剂保持完好,并且“t”表示一个层压结构撕裂。基于表2中的数据,包含胺引发多元醇会增加粘合剂组合物的反应性。如表3中所绘示,包括胺引发多元醇的配制物展现较快的粘结发展和较快的PAA衰变。具体地说,会在两天内实现完全粘结发展。当至少一种异氰酸酯和多元醇的所有官能基(例如,NCO和OH基)已经反应并整合成最终聚合物链时会发生完全粘结发展,即,没有进行中的进一步交联反应并且实现了最终的粘结性能、耐热和耐化学性。然而,使用包括高反应性胺引发多元醇的多元醇组分会在层压之后的一小时内实现足以切割层压结构的粘结。当层压结构具有至少1N/15min的粘结强度和无粘性粘合剂时,其具有足以切割的粘结。
还在具有两个涂布头的层压机器上形成层压结构,如根据本公开所设想。然后测试所制备的层压结构的粘结强度和伯芳香胺衰变。
表3:双涂布头层压机上的性能结果
Figure BDA0001853924400000111
如表3中所表示,包含所公开的胺引发多元醇的粘合剂组合物令人惊讶地均在层压两小时内实现超过1.0N/15min的粘结强度。许多实例甚至在层压两小时内展现超过2.0N/15min的粘结强度。

Claims (9)

1.一种形成层压结构的方法,所述层压结构包括双组分无溶剂粘合剂组合物,所述方法包括:
将异氰酸酯组分均匀地涂覆到第一基材的表面,所述异氰酸酯组分适用于涂覆到第一基材并且包括至少一种异氰酸酯,其中第一基材上的所述异氰酸酯组分层的厚度是0.5到2.5μm;
将多元醇组分均匀地涂覆到第二基材的表面,所述多元醇组分适用于涂覆到第二基材并且包括至少一种胺引发多元醇,所述胺引发多元醇包括伯羟基和结合叔胺的主链,其中第二基材上的所述多元醇组分层的厚度是0.5到2.5μm;
使第一基材的表面与第二基材的表面接触,由此使两种组分混合和反应;
并且其中所述异氰酸酯组分和所述多元醇组分的涂布重量各自控制所述粘合剂组合物中的异氰酸酯组分对多元醇组分的混合比为100:100至100:80。
2.根据权利要求1所述的方法,其中所述多元醇组分包括至少一种胺引发多元醇,所述胺引发多元醇包括两个或更多个伯羟基和2到12的官能度、5到1,830的羟基数,和在40℃下500到20,000mPa-s的粘度,通过ASTM D2196的方法所测量。
3.根据权利要求2所述的方法,所述粘合剂组合物包括在将所述异氰酸酯组分和多元醇组分混合的10分钟内在40℃下大于10,000mPa-s的粘度。
4.根据权利要求1所述的方法,其中所述胺引发多元醇具有结构I:
Figure FDA0003494812060000021
其中R1、R2和R3独立地是直链或支链烷基。
5.根据权利要求1所述的方法,其中所述胺引发多元醇包括4的官能度。
6.根据权利要求1所述的方法,其中所述胺引发多元醇包括37的羟基数。
7.根据权利要求1所述的方法,其中所述胺引发多元醇包括在25℃下1,200mPa-s的粘度。
8.根据权利要求1所述的方法,其中所述异氰酸酯组分包括小于50%的单体含量。
9.根据权利要求1所述的方法,其中至少一种聚异氰酸酯是选自由以下组成的组:4,4-亚甲基二苯基二聚异氰酸酯MDI、2,4-MDI、2,2'-MDI、2,4-甲苯-二聚异氰酸酯TDI、2,6-TDI、六亚甲基二异氰酸酯HDI的异构体,和其两种或更多种的组合。
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