CN108884207B - 双组分无溶剂粘合剂组合物和其制备方法 - Google Patents

双组分无溶剂粘合剂组合物和其制备方法 Download PDF

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Publication number
CN108884207B
CN108884207B CN201680084054.8A CN201680084054A CN108884207B CN 108884207 B CN108884207 B CN 108884207B CN 201680084054 A CN201680084054 A CN 201680084054A CN 108884207 B CN108884207 B CN 108884207B
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polyol
component
adhesive composition
composition
isocyanate
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CN108884207A (zh
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白晨艳
陆强
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Dow Global Technologies LLC
Rohm and Haas Co
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Dow Global Technologies LLC
Rohm and Haas Co
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  • Chemical & Material Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Adhesives Or Adhesive Processes (AREA)
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Abstract

公开了一种双组分无溶剂粘合剂组合物，所述组合物包含异氰酸酯组分，所述异氰酸酯组分包含异氰酸酯预聚物，所述异氰酸酯预聚物是包含至少一种聚异氰酸酯、至少一种聚酯多元醇、至少一种聚醚多元醇和至少一种包含羟基和COOH酸官能度的多元醇的反应物的反应产物。所述粘合剂组合物还包含多元醇组分，其包含至少一种聚酯多元醇、至少一种聚醚多元醇或其组合。还公开了使用所述粘合剂组合物形成层压材料的方法和层压材料本身。所述方法包含形成无溶剂粘合剂组合物，向膜的表面上涂覆一层所述粘合剂组合物，使所述层与另一张膜的表面接触以形成层压材料，并固化所述粘合剂组合物。还公开了根据所述方法制备的层压材料。

Description

双组分无溶剂粘合剂组合物和其制备方法
技术领域
本公开涉及无溶剂粘合剂组合物。更具体地，本公开涉及与层压膜一起使用的双组分无溶剂粘合剂组合物，所述组合物具有改进的粘合强度、耐化学性和热封强度，以及制备所述组合物的方法。
背景技术
粘合剂组合物适用于广泛多种目的。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、纸或玻璃纸等基材粘合在一起，形成复合膜，即层压材料。粘合剂在不同的层压最终用途应用中的使用大体上是已知的。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”通常可分为三类：溶剂型、水基型和无溶剂型。粘合剂的性能随着类别和涂覆粘合剂的应用而变化。
无溶剂层压粘合剂可以涂覆高达100％的固体，不含有机溶剂或水性载体。因为在应用时不必从粘合剂干燥有机溶剂或水，所以这些粘合剂可以按高线速度运行并且在需要快速粘合剂应用的应用中是优选的。溶剂型和水基型层压粘合剂受到溶剂或水载体在应用时可被有效干燥和除去的速率的限制。出于环境、健康和安全的原因，层压粘合剂优选是水性或无溶剂的。
在无溶剂层压粘合剂的类别内，有许多变体。一种特殊的变体包括基于聚氨基甲酸酯的双组分层压粘合剂。通常，基于聚氨基甲酸酯的双组分层压粘合剂包括第一组分和第二组分，第一组分包含含异氰酸酯的预聚物，第二组分包含一种或多种多元醇。第一组分通过聚异氰酸酯与聚醚多元醇和/或聚酯多元醇的反应获得。第二组分是聚醚多元醇和/或聚酯多元醇。每种组分可任选地包括一种或多种添加剂。将两种组分以预定比例组合并涂覆在膜/箔基材上，然后将其层压到另一个膜/箔基材上。
与传统的含溶剂粘合剂相比，基于聚氨基甲酸酯的双组分无溶剂层压粘合剂在加工层压材料之前的初始粘合弱并且粘合进展缓慢。另外，这些粘合剂往往显示出相对较差的耐化学性，特别是在酸性条件下，以及差的热封强度。在一些情况下，将硅烷助粘剂掺入粘合剂组合物中以改进初始粘合强度。然而，硅烷助粘剂无法耐热和耐酸，并且在热和/或酸处理后粘合剂组合物的粘合强度受损。此外，掺入硅烷助粘剂的层压材料需要干燥的储存环境，因为硅烷对水分敏感。
因此，期望存在具有改进的粘合强度、耐化学性和热封强度的基于聚氨基甲酸酯的双组分无溶剂层压粘合剂组合物和其制备方法。
发明内容
公开了一种双组分无溶剂粘合剂组合物。所述粘合剂组合物包含异氰酸酯组分，所述异氰酸酯组分包含异氰酸酯预聚物，所述异氰酸酯预聚物是包含以下的反应物的反应产物：至少一种聚异氰酸酯；至少一种选自由聚酯多元醇、聚醚多元醇和其组合组成的组的多元醇；以及至少一种具有两个或更多个羟基(“OH”)基团和选自O＝C-O-、O＝C-C-O-、O＝C-C＝C-O-或其质子化形式的氢桥连基团的多元醇。所述粘合剂组合物还包含多元醇组分，其包含至少一种选自由聚酯多元醇、聚醚多元醇和其组合组成的组的多元醇。相对于现有的双组分无溶剂粘合剂组合物，在异氰酸酯预聚物反应物中混入具有两个或更多个OH基团和氢桥连基团的多元醇改进了所公开的粘合剂组合物的粘合强度和耐化学性。
还公开了一种形成层压材料的方法。所述方法包含形成无溶剂粘合剂组合物，所述组合物包含至少一种包含两个或更多个OH基团和氢桥连基团的多元醇，向膜的表面上涂覆一层所述粘合剂组合物，使所述层与另一张膜的表面接触以形成层压材料，以及固化所述粘合剂组合物。还公开了通过所述方法形成的层压材料。
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含异氰酸酯组分和多元醇组分。
异氰酸酯组分
异氰酸酯组分包含至少一种异氰酸酯预聚物，所述异氰酸酯预聚物是包含以下的反应物(“预聚物反应物”)的反应产物：至少一种聚异氰酸酯；至少一种选自由聚酯多元醇、聚醚多元醇和其组合组成的组的多元醇；以及至少一种具有两个或更多个与异氰酸酯基团(即R-N＝C＝O)反应的OH基团并含有氢桥连基团的多元醇，所述氢桥连基团选自O＝C-O-、O＝C-C-O-、O＝C-C＝C-O-或其质子化形式。在下文详细论述每种预聚物反应物。
如本文所用，“聚异氰酸酯”为任何含有两个或更多个异氰酸酯基团的化合物。“芳香族聚异氰酸酯”是含有一个或多个芳香环的聚异氰酸酯。“脂肪族聚异氰酸酯”不含芳香环。
适合根据本公开使用的聚异氰酸酯可选自由芳香族聚异氰酸酯、脂肪族聚异氰酸酯和其组合组成的组。适合根据本公开使用的芳香族聚异氰酸酯的实例包括但不限于亚甲基二苯基二聚异氰酸酯(“MDI”)的异构体，如4,4-MDI、2,4-MDI和2,2'-MDI；甲苯-二聚异氰酸酯(“TDI”)的异构体，如2,4-TDI、2,6-TDI；萘-二聚异氰酸酯(“NDI”)的异构体，如1,5-NDI，以及其组合。适合根据本公开使用的脂肪族聚异氰酸酯的实例包括但不限于六亚甲基二聚异氰酸酯(“HDI”)的异构体、异佛尔酮二聚异氰酸酯(“IPDI”)的异构体、二甲苯二聚异氰酸酯(“XDI”)的异构体以及其组合。
以异氰酸酯组分的重量计，异氰酸酯组分中聚异氰酸酯的量按重量计为至少10重量％，或至少20重量％，或至少30重量％。以异氰酸酯组分的重量计，异氰酸酯组分中至少一种聚异氰酸酯的量按重量计为不超过80重量％，或70重量％，或65重量％。
具有两个或更多个羟基的化合物是“多元醇”。具有恰好两个羟基的多元醇为“二醇”。具有恰好三个羟基的多元醇为“三醇”。在同一条直链原子链中含有两个或更多个酯键的化合物在本文中称为“聚酯”。既是聚酯又是多元醇的化合物在本文中称为“聚酯多元醇”。所公开的聚酯多元醇具有不超过4,000g/mol的分子量。此外，所公开的聚酯多元醇具有至少1.5且不超过3的羟基官能度(即，1.5≤f≤3)。
适合根据本公开使用的聚酯多元醇是二醇并且任选地也是多元醇(例如，三醇、四醇)与二羧酸并且任选地也是与聚羧酸(例如，三羧酸、四羧酸)或羟基羧酸或内酯的已知缩聚物。聚酯多元醇也可以衍生自相应的聚羧酸酐或相应的低级醇的聚羧酸酯，而不是游离的聚羧酸。
合适的二醇包括但不限于乙二醇、丁二醇、二乙二醇、三乙二醇、聚亚烷基二醇，例如聚乙二醇，以及1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇和新戊二醇。为了获得大于2的聚酯多元醇官能度，可任选地在粘合剂组合物中包括官能度为3的多元醇(例如，三羟甲基丙烷、丙三醇、赤藻糖醇、季戊四醇、三羟甲基苯或三羟乙基异氰脲酸酯)。
合适的二羧酸包括但不限于脂肪族酸、芳香族酸和其组合。合适的芳香族酸的实例包括邻苯二甲酸、间苯二甲酸、对苯二甲酸和四氢邻苯二甲酸。合适的脂肪族酸的实例包括六氢邻苯二甲酸、环己烷二羧酸、己二酸、壬二酸、癸二酸、戊二酸、四氯邻苯二甲酸、马来酸、富马酸、衣康酸、丙二酸、辛二酸、2-甲基琥珀酸、3,3-二乙基戊二酸、2,2-二甲基琥珀酸和偏苯三酸。如本文所用，术语“酸”还包括所述酸的任何酸酐。此外，应当从所公开的组合物中最小化或排除一元羧酸，例如苯甲酸和己烷羧酸。优选饱和脂肪族或芳香族酸，例如己二酸或间苯二甲酸。
以异氰酸酯组分的重量计，异氰酸酯组分中聚酯多元醇的量按重量计为至少2重量％，或至少5重量％，或至少8重量％。以异氰酸酯组分的重量计，异氰酸酯组分中聚酯多元醇的量按重量计为不超过45重量％，或40重量％，或35重量％。
在同一条直链原子链中含有两个或更多个醚键的化合物在本文中称为“聚醚”。既是聚醚又是多元醇的化合物是“聚醚多元醇”。所公开的聚醚多元醇具有不超过5,000g/mol的分子量。此外，所公开的聚醚多元醇具有至少1.5且不超过4的羟基官能度(即，1.5≤f≤4)。
适合根据本公开使用的聚醚多元醇是环氧乙烷、环氧丙烷、四氢呋喃、环氧丁烷的加聚产物，及其共加成和接枝产物，以及通过多元醇的缩合得到的聚醚多元醇或其混合物。适用的聚醚多元醇的实例包括但不限于聚丙二醇(“PPG”)、聚乙二醇(“PEG”)、聚丁二醇和聚四亚甲基醚二醇(“PTMEG”)。
以异氰酸酯组分的重量计，异氰酸酯组分中聚醚多元醇的量按重量计为至少5重量％，或至少10重量％，或至少15重量％。以异氰酸酯组分的重量计，异氰酸酯组分中聚醚多元醇的量按重量计为不超过45重量％，或40重量％，或35重量％。
异氰酸酯组分还包含在多元醇分子链的末端具有两个或更多个OH基团并且在侧链分子链中具有至少一个氢桥连基团的多元醇。合适的氢桥连基团的实例包括但不限于O＝C-Oˉ、O＝C-C-Oˉ、和O＝C-C＝C-Oˉ以及其旋前形式。所公开的具有两个或更多个OH基团和氢桥连基团的多元醇还具有至少50mg KOH/g且不超过200mg KOH/g的酸值。此外，所公开的多元醇具有至少600g/mol且不超过3,000g/mol的分子量。更进一步地，所公开的多元醇具有至少1.8且不超过3的羟基官能度(即，1.8≤f≤3)。
以异氰酸酯组分的重量计，在异氰酸酯组分中具有两个或更多个OH基团和氢桥连基团的多元醇的量按重量计为至少0.01重量％，或至少0.1重量％，或至少1重量％。以异氰酸酯组分的重量计，在异氰酸酯组分中具有两个或更多个OH基团和氢桥连基团的多元醇的量按重量计为不超过25重量％，或20重量％，或15重量％。
所公开的异氰酸酯组分可任选地进一步包含生物基多元醇，例如蓖麻油或其它已知的生物基多元醇。所公开的生物基多元醇具有至少1.5且不超过4的羟基官能度(即，1.5≤f≤4)。
当任选地包含在异氰酸酯组分中时，以异氰酸酯组分的重量计，异氰酸酯组分中生物基多元醇的量按重量计为至少0.01重量％，或至少0.1重量％，或至少3重量％。以异氰酸酯组分的重量计，异氰酸酯组分中生物基多元醇的量按重量计为不超过15重量％，或10重量％，或5重量％。
具有聚异氰酸酯基团的化合物，如异氰酸酯组分的异氰酸酯预聚物，可以用参数“％NCO”表征，该参数是以化合物的重量计，聚异氰酸酯基团的按重量计的量。参数％NCO通过ASTM D 2572-97(2010)的方法测量。所公开的异氰酸酯组分具有至少3重量％，或至少5重量％，或至少7重量％的％NCO。在一些实施例中，异氰酸酯组分具有不超过30重量％，或25重量％，或22重量％，或19重量％的％NCO。
在一些实施例中，异氰酸酯组分在25℃下具有300mPa-s至20,000mPa-s的粘度，如根据ASTM D2196的方法所测量。
异氰酸酯组分可任选地包含一种或多种催化剂。适合根据本公开使用的至少一种催化剂的实例包括但不限于二月桂酸二丁基锡、乙酸锌、2,2-二吗啉基二乙醚以及其组合。
多元醇组分
无溶剂粘合剂组合物还包含多元醇组分，其包含至少一种选自由聚酯多元醇、聚醚多元醇和其组合组成的组的多元醇。多元醇组分可任选地包括具有两个或更多个OH基团和氢桥连基团的多元醇、助粘剂以及二醇或三醇单体。
适用于多元醇组分的聚酯多元醇具有不超过4,000g/mol的分子量。此外，所公开的聚酯多元醇具有至少1.5且不超过3的羟基官能度(即，1.5≤f≤3)。
适合根据本公开使用的聚酯多元醇是二醇并且任选地也是多元醇(例如，三醇、四醇)与二羧酸并且任选地也是与聚羧酸(例如，三羧酸、四羧酸)或羟基羧酸或内酯的已知缩聚物。聚酯多元醇也可以衍生自相应的聚羧酸酐或相应的低级醇的聚羧酸酯，而不是游离的聚羧酸。
合适的二醇包括但不限于乙二醇、丁二醇、二乙二醇、三乙二醇、聚亚烷基二醇，例如聚乙二醇，以及1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇和新戊二醇。为了获得大于2的聚酯多元醇官能度，可任选地在粘合剂组合物中包括官能度为3的多元醇(例如，三羟甲基丙烷、丙三醇、赤藻糖醇、季戊四醇、三羟甲基苯或三羟乙基异氰脲酸酯)。
合适的二羧酸包括但不限于脂肪族酸、芳香族酸和其组合。合适的芳香族酸的实例包括邻苯二甲酸、间苯二甲酸、对苯二甲酸和四氢邻苯二甲酸。合适的脂肪族酸的实例包括六氢邻苯二甲酸、环己烷二羧酸、己二酸、壬二酸、癸二酸、戊二酸、四氯邻苯二甲酸、马来酸、富马酸、衣康酸、丙二酸、辛二酸、2-甲基琥珀酸、3,3-二乙基戊二酸、2,2-二甲基琥珀酸和偏苯三酸。如本文所用，术语“酸”还包括所述酸的任何酸酐。此外，应当从所公开的组合物中最小化或排除一元羧酸，例如苯甲酸和己烷羧酸。优选饱和脂肪族或芳香族酸，例如己二酸或间苯二甲酸。
以多元醇组分的重量计，多元醇组分中聚酯多元醇的量按重量计为至少0重量％，或至少5重量％，或至少8重量％。以多元醇组分的重量计，多元醇组分中聚酯多元醇的量按重量计为不超过100重量％，或90重量％，或80重量％。
适用于多元醇组分的聚醚多元醇具有不超过5,000g/mol的分子量。此外，所公开的聚醚多元醇具有至少1.5且不超过3的羟基官能度(即，1.5≤f≤4)。
适合根据本公开使用的聚醚多元醇是环氧乙烷、环氧丙烷、四氢呋喃、环氧丁烷的加聚产物，及其共加成和接枝产物，以及通过多元醇的缩合得到的聚醚多元醇或其混合物。适用的聚醚多元醇的实例包括但不限于聚丙二醇(“PPG”)、聚乙二醇(“PEG”)、聚丁二醇和聚四亚甲基醚二醇(“PTMEG”)。
以多元醇组分的重量计，多元醇组分中聚醚多元醇的量按重量计为至少0重量％，或至少10重量％，或至少20重量％。以异氰酸酯组分的重量计，多元醇组分中聚醚多元醇的量按重量计为不超过100重量％，或90重量％，或80重量％。
在一些实施例中，异氰酸酯组分与多元醇组分的重量比为1:1或更高，或1.5:1或更高；或1.8:1或更高。在一些实施例中，异氰酸酯组分与多元醇组分的重量比为5:1或更低，或4.5:1或更低，或4:1或更低。
预期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以单独制备，并且必要时，将其储存直至需要使用粘合剂组合物。在一些实施例中，异氰酸酯组分与多元醇组分在25℃下各自是液体。当需要使用粘合剂组合物时，使异氰酸酯组分和多元醇组分彼此接触并混合在一起。预期当使这两种组分接触时，固化反应开始，其中异氰酸酯基团与羟基反应而形成氨基甲酸酯键。通过使两种组分接触而形成的粘合剂组合物可称为“可固化混合物”。
还公开了使用粘合剂组合物形成层压材料的方法。在一些实施例中，粘合剂组合物，例如上文所论述的粘合剂组合物，处于液态。在一些实施例中，所述组合物在25℃下是液体。即使所述组合物在25℃下是固体，需要加热所述组合物以使其处于液态也是可以接受的。向膜表面上涂覆一层组合物。“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。聚合物膜是一种由聚合物或聚合物混合物制成的膜。聚合物膜的组成通常为80重量％或更多的一种或多种聚合物。在一些实施例中，可固化混合物层的厚度是1至5μm。
在一些实施例中，使另一张膜的表面与可固化混合物层接触以形成未固化的层压材料。在一些实施例中，当存在于粘合剂组合物中的未反应的聚异氰酸酯基团的量以摩尔计相较于在与多元醇组分接触之前存在于异氰酸酯组分中的聚异氰酸酯基团的量为至少50％，或至少75％或，或至少90％时，制备未固化的层压材料。当存在于可固化混合物中的未反应的聚异氰酸酯基团的量小于100％，或小于97％，或小于95％时，进一步制备未固化的层压材料。
然后将可固化混合物固化或允许其固化。可以使未固化的层压材料受到压力，例如通过穿过轧辊而受到压力，轧辊可以经过加热或可以不经过加热。可以加热未固化的层压材料以加速固化反应。
合适的膜包括纸、编织和非编织纤维、金属箔、聚合物和镀金属聚合物。膜任选地具有可用油墨打印上图像的表面；油墨可以与粘合剂组合物接触。在一些实施例中，所述膜是聚合物膜和镀金属聚合物膜；更优选为聚合物膜。
本公开的实例
现在将通过说明性实例和比较实例(统称为“实例”)进一步详细解释本公开。然而，本公开的范围当然不限于实例中所述的制剂。实际上，实例仅是本公开的说明。
组合物制备
用于制备实例的原料在下表1中通过商业名称和供应商确定。
表1：原料
Figure BDA0001811880490000091
根据表2中列出的制剂，在合成过程中通过将HA-0135加入商业级MOR-FREETM698A制剂中来合成实例(A1至A4)的异氰酸酯组分。表2中的制剂显示以异氰酸酯组分的总重量计的重量百分比。
表2：异氰酸酯组分组合物A1至A4
组分 A<sub>1</sub> A<sub>2</sub> A<sub>3</sub> A<sub>4</sub>
MOR-FREE<sup>TM</sup>698A 100 94.5 97 98.5
多元醇HA-0135 4.5 3 1.5
总计 100 100 100 100
根据表3中列出的制剂合成实例(B1至B4)的多元醇组分。表3中的原料制剂显示以多元醇组分的总重量计的重量百分比。
表3：多元醇组分组合物B1至B4
原料 B<sub>1</sub> B<sub>2</sub> B<sub>3</sub> B<sub>4</sub>
MOR-FREE<sup>TM</sup>C-83 100 99 95
MOR-FREE<sup>TM</sup>C-411 100
DMPA<sup>TM</sup>多元醇HA-0135 5
SILQUEST<sup>TM</sup>A-187 1
总计 100 100 100 100
对于说明性实例和比较实例，根据典型的聚氨基甲酸酯预聚物制备方法，在1,000ml玻璃反应器中合成异氰酸酯组分。将聚异氰酸酯引入反应器中并在氮气保护下保持在60℃下。接下来，根据表2中的组合物将各种多元醇引入反应器中。将温度缓慢升至80℃并保持2至3小时。最后，将产生的异氰酸酯预聚物，即异氰酸酯组分装入具有氮气保护的密封容器中用于进一步应用。
多元醇组分包括多元醇的混合物，如表3所示。在将多元醇组分的原料引入反应器之前，原料的水分含量应小于500ppm。在搅拌和混合多元醇组分中的原料的同时，供应氮气以避免混合物被水分污染。
为了制备说明性实例和比较实例，然后根据表4中所示的配对，混合异氰酸酯组分和多元醇组分以形成实例的粘合剂组合物。
表4：IE和CE的聚异氰酸酯/多元醇配对
实例 聚异氰酸酯和多元醇组分配对
比较实例1 A<sub>1</sub>/B<sub>1</sub>
比较实例2 A<sub>1</sub>/B<sub>2</sub>
说明性实例1 A<sub>2</sub>/B<sub>1</sub>
说明性实例2 A<sub>3</sub>/B<sub>3</sub>
说明性实例3 A<sub>4</sub>/B<sub>4</sub>
然后使用实例的粘合剂组合物形成包含聚乙烯和铝膜的层压材料。将粘合剂组合物以2.0gsm涂层重量涂覆到聚乙烯上，与铝膜结合在一起，然后在50℃下固化24小时以形成层压材料。一旦形成层压材料，就进行测试以分析粘合强度、热封强度，并用水和苹果汁分析煮沸袋耐受性。
层压材料性能测试
对由实例的粘合剂组合物制备的层压材料进行粘合强度测试。将层压材料切割成15mm宽的带材以用于在250mm/min十字头速度下使用可购自英斯特朗公司(InstronCorporation)的5940系列单立柱台式试验系统(5940 Series Single Column Table TopSystem)进行T-剥离测试。在测试过程中，用手轻轻拉动每个带材的尾部，以确保尾部与剥离方向保持90°角。每个样品测试三条带材并计算平均值。结果以N/15mm为单位。相对较高的值表明较好的粘合强度。
对由实例的粘合剂组合物制备的层压材料进行热封强度测试。将层压材料在购自Brugger Feinmechanik GmbH的HSG-C热封机(HSG-C Heat-Sealing Machine)中在140℃密封温度和300N压力下热封1秒。然后将层压材料冷却并切成15mm宽的带材，以用于在250mm/min的十字头速度下使用购自英斯特朗公司的5940系列单立柱台式试验系统进行热封强度测试。每个样品测试三条带材并计算平均值。结果以N/15mm为单位。相对较高的值表明较好的热封强度。
对由实例的粘合剂组合物制备的层压材料进行煮沸袋耐受性测试。将层压材料切成8cm×12cm的片，并通过热封制成袋，袋内有水。然后将袋子放入沸水中并持续30分钟，确保袋子在整个煮沸过程中始终浸入水中。在完成煮沸过程后记录袋子的隧穿、分层和/或泄漏的程度。对于通过煮沸袋耐受性测试的样品，其必须没有显示出隧穿、分层或泄漏的迹象。然后将袋子打开，倒空并冷却，然后切成15mm宽的带材以在Instron 5943机器中测试T-剥离粘合强度。测试三条带材，取平均值。
表5：性能测试结果
Figure BDA0001811880490000111
实例在室温下表现出良好的粘合强度和热封强度。然而，比较实例在煮沸袋测试完成后表现出降低的粘合强度。另一方面，本发明实例在完成煮沸袋测试后表现出相同或甚至增加的粘合强度。此外，与比较实例相比，本发明实例表现出增加的热封强度。
如上文所论述并在表2至4中所指出，除了包含含有氢桥连基团的多元醇的多元醇之外，对比实例与说明性实例的组成相似。因此，至少在粘合剂组合物的异氰酸酯组分中包括这种多元醇使得层压材料在经过煮沸袋处理后具有更好的粘合强度。

Claims (9)

1.一种双组分无溶剂粘合剂组合物，其包含：
包含异氰酸酯预聚物的异氰酸酯组分，所述异氰酸酯预聚物是包含以下的反应物的反应产物：
至少一种聚异氰酸酯；
至少一种聚酯多元醇；以及
至少一种具有两个或更多个OH基团和选自O＝C-O-、O＝C-C-O-、O＝C-C＝C-O-或其质子化形式的氢桥连基团的多元醇，所述多元醇具有600g/mol至3000g/mol的分子量，以及
多元醇组分，其包含至少一种选自由聚酯多元醇、聚醚多元醇和其组合组成的组的多元醇。
2.根据权利要求1所述的组合物，其中所述异氰酸酯组分还包含生物基多元醇。
3.根据权利要求2所述的组合物，其中所述生物基多元醇是蓖麻油。
4.根据权利要求1所述的组合物，其中异氰酸酯组分与多元醇组分的重量比为5:1至1:1。
5.根据权利要求1所述的组合物，其中所述多元醇组分还包含选自由氨基硅烷、环氧硅烷和其组合组成的组的助粘剂。
6.根据权利要求1所述的组合物，其中所述多元醇组分还包含具有两个或更多个OH基团和选自O＝C-O-、O＝C-C-O-、O＝C-C＝C-O-或其质子化形式的氢桥连基团的多元醇。
7.根据权利要求1所述的组合物，其中具有所述OH基团和氢桥连基团的所述多元醇包含羟基和COOH酸官能度。
8.一种形成层压材料的方法，其包含：
通过使反应物接触形成无溶剂粘合剂组合物，所述反应物包含：
包含异氰酸酯预聚物的异氰酸酯组分，所述异氰酸酯预聚物是包含以下的反应物的反应产物：
至少一种聚异氰酸酯；
至少一种聚酯多元醇；以及
至少一种具有两个或更多个OH基团和选自O＝C-O-、O＝C-C-O-、O＝C-C＝C-O-或其质子化形式的氢桥连基团的多元醇，所述多元醇具有600g/mol至3000g/mol的分子量；以及
多元醇组分，其包含选自由聚酯多元醇、聚醚多元醇和其组合组成的组的多元醇；
向膜的表面上涂覆一层所述粘合剂组合物；
使所述层与另一张膜的表面接触以形成层压材料；以及
固化所述粘合剂组合物。
9.一种层压材料，其通过根据权利要求8所述的方法形成。
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