CN109476929B - 辐射可固化的底漆粘合剂 - Google Patents

辐射可固化的底漆粘合剂 Download PDF

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CN109476929B
CN109476929B CN201780041776.XA CN201780041776A CN109476929B CN 109476929 B CN109476929 B CN 109476929B CN 201780041776 A CN201780041776 A CN 201780041776A CN 109476929 B CN109476929 B CN 109476929B
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V·施瓦利尔
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Abstract

本发明涉及用于粘合至EVA的100％固体、辐射可固化的粘合剂制剂。该制剂可具有如本文详细讨论的不同的组成。然而，组合物可主要地包含至少一种单体和氯化添加剂。光引发剂可用于允许低温UV或其他辐射固化。其他添加剂可用于以各种方式增强功能特征。在使用中，本发明可以涂覆在EVA的表面上，并且然后固化，并且可以仅使用基底上的粘合剂层粘附到基底上，这与现有技术的结构相反，现有技术的结构需要至少双面粘合剂施加，以及其他复杂性。

Description

辐射可固化的底漆粘合剂
技术领域
本发明一般涉及用于乙烯-乙酸乙烯酯(EVA)的底漆和粘合剂。更具体地，本发明涉及100％固体组合物，其在EVA表面上起到粘合剂和底漆中的一种或两者的作用。
背景技术
EVA的工作底漆传统上是溶剂型的。存在一些“水性”形式和辐射可固化形式，但实际上都包含一定程度的溶剂。另外，传统的工作底漆需要在底漆之上直接涂覆粘合剂，从而起作用。热熔施加需要高水平的热量，并且在冷却时导致额外的加工时间。
因此，需要的是100％固体制剂，其可以消除对溶剂使用的需要，其也可以在没有额外底漆层的情况下起到粘合剂的作用。
发明内容
在一些情况下，本申请的主题可涉及相互关联的产品、具体问题的可选解决方案，和/或单个***或制品的多种不同的用途。
在本发明的一个方面，提供了在室温下可操作并且能够辐射固化的100％固体组合物。该组合物和在本文公开的其各种实施方式特别适用于将EVA粘结到基底上。该组合物具有单体、氯化化合物和允许辐射固化的光引发剂。在该方面的一个实施方式中，单体选自(甲基)丙烯酸酯单体和(甲基)丙烯酸酯官能氨基甲酸酯低聚物中的至少一种。在该方面的一个实施方式中，氯化化合物选自氯化聚酯、氯化橡胶和氯化聚烯烃中的至少一种。
在该方面的一个具体实施方式中，该组合物可以具有10-50％的二丙烯酸己二醇酯作为单体；10-40％的氯化聚酯作为氯化化合物；10-30％的环状脂肪族二丙烯酸酯；1-5％的酸性甲基丙烯酸酯；和1-5％的光引发剂。
在该方面的另一个实施方式中，该组合物可以具有10-50％的二丙烯酸己二醇酯作为单体；10-40％的氯化聚酯作为氯化化合物；10-30％的环状脂肪族二丙烯酸酯；1-5％的酸性甲基丙烯酸酯；5-35％的改性的环氧二丙烯酸酯；和1-5％的光引发剂。
在该方面的又另一个实施方式中，该组合物可以具有60-99％的甲基丙烯酸甲酯作为单体；0-20％的二丙烯酸己二醇酯；10-20％的氯化聚烯烃作为氯化化合物；1-20％的酸性甲基丙烯酸酯；1-5％的NVC；和1-5％的光引发剂。
在该方面的一个具体实施方式中，该组合物可具有10-30％的二丙烯酸己二醇酯作为单体；10-70％的丙烯酸聚合物；10-20％的氯化聚酯作为氯化化合物；1-5％的酸性甲基丙烯酸酯；和1-5％的光引发剂。
在该方面的又另一个实施方式中，该组合物可以具有10-40％的二丙烯酸己二醇酯作为单体；10-40％的氯化聚酯作为氯化化合物；10-20％的环状脂肪族二丙烯酸酯；10-20％的βCEA；1-10％的NVC；和1-5％的光引发剂。
在该方面的仍另一个实施方式中，该组合物可以具有10-40％的二丙烯酸己二醇酯作为单体；10-40％的氯化聚酯树脂作为氯化化合物；1-5％的酸性甲基丙烯酸酯；10-20％的βCEA；1-10％的NVC；和1-5％的光引发剂。
在该方面的另一个实施方式中，该组合物可包含10-50％的单体，单体为二丙烯酸己二醇酯和甲基丙烯酸甲酯中的至少一种。在该实施方式的进一步的具体实例中，该组合物可具有多种不同的(甲基)丙烯酸酯官能氨基甲酸酯低聚物，多种不同的(甲基)丙烯酸酯官能氨基甲酸酯低聚物的组合占组合物的11-75％。在该实施方式的又另一个具体实例中，该组合物可包含10-30％的环状脂肪族二丙烯酸酯。在该实施方式的另一个具体实例中，该组合物可包含组合物中的10-40％的氯化化合物。该实施方式还可具有多种不同的(甲基)丙烯酸酯官能氨基甲酸酯低聚物，其可包含环状脂肪族二丙烯酸酯和酸性甲基丙烯酸酯。该实施方式还可具有多种低聚物，其包含环状脂肪族二丙烯酸酯、酸性甲基丙烯酸酯和改性环氧二丙烯酸酯。
在使用该组合物方面的实施方式中，其包括但不限于使用本发明组合物的方面的任何上述组合物实施方式，该组合物可以用于将EVA粘附到基底的方法中。该使用实施方式可以具有以下步骤：获得基底；获得乙烯-乙酸乙烯酯；在室温下将本发明的组合物施加到乙烯-乙酸乙烯酯上；使用辐射固化权利要求1的组合物；将施加有权利要求1的组合物的乙烯-乙酸乙烯酯与基底接触，通过施加到基底上的粘合剂将基底和涂覆组合物的乙烯-乙酸乙烯酯粘结在一起。如上所述，用于该使用方法实施方式的组合物可以是任何上述实施方式，和/或在以下详细说明书、权利要求书、摘要和附图中公开或描述的任何组合物。
附图说明
图1提供了使用本发明组合物的实施方式的流程图。
具体实施方式
以下结合附图阐述的详细描述旨在作为本发明的当前优选实施方式的描述，并不代表可以构造和/或利用本发明的唯一形式。该描述阐述了结合图解的实施方式构造和操作本发明的功能和步骤顺序。
本发明包括与EVA一起使用的粘合剂/底漆组合物，其具有100％固体组合物和0％溶剂添加，并且本身可以起到粘合剂的作用，因此仅接触基底需要粘合剂涂层。本发明的组合物从劳动者和环境中除去不必要的和潜在有害的VOC，消除了对热熔粘合剂所需的高温的需要及其产生的困难，并且还消除了鞋类制造的粘合过程中的步骤。本发明可在环境室温下使用，在使用期间无需任何附加的温度调节步骤。
通常，本发明涉及用于粘合到EVA的100％固体、辐射可固化的粘合剂制剂。进一步，在一些实施方式中，本发明可以用作底漆以及或可选地粘合剂。该制剂可具有不同的组成，如下面详细讨论的。然而，主要地，组合物可包含至少单体和氯化添加剂。光引发剂可用于允许低温UV或其他辐射固化。其他添加剂可用于以各种方式增强功能特征。
该100％固体制剂不需要现有技术所必需的任何溶剂。本文考虑的制剂提供了优于现有解决方案的许多优点。例如，本发明提供了改进的产品和制造中的改进两者。100％固体组合物不使用挥发性有机化合物(VOC)，从而使其成为“更环保(greener)”的技术。消除VOC还会产生危害较小且成本较低的实施。进一步，本发明通过允许室温、无溶剂固化和通过消除了对直接施加到固化的粘合剂/底漆上的粘合剂的需要，而从制造中消除了步骤。相反，仅在待施加至涂覆有本发明的粘合剂/底漆的EVA的基底上需要粘合剂。该粘合剂可以是本发明的组合物，或可以是另一种粘合剂。在许多实施方式中，不需要第二粘合剂，并且本发明的组合物足以将EVA粘结到基底上。这些消除的步骤可以导致成本节约以及又能量节约(例如移除烤箱或为焚烧炉提供更少的能量)，这又导致“更环保”的技术，其提供更安全的工作环境和成本节约。
一般而言，在本发明的许多但非全部实施方式中，该组合物可包括丙烯酸酯或甲基丙烯酸酯、稀释剂和光引发剂。为了促进EVA的粘合，还可能需要氯化化合物，例如氯化聚酯或氯化聚烯烃。
通常，本发明组合物需要单体，例如(甲基)丙烯酸酯单体或(甲基)丙烯酸酯官能氨基甲酸酯低聚物。进一步，该组合物需要氯化化合物，例如氯化聚酯、氯化橡胶和/或氯化聚烯烃。另外，光引发剂允许通过例如UV辐射进行固化。
如上所述，本发明组合物的主要特征是选自(甲基)丙烯酸酯单体和(甲基)丙烯酸酯官能氨基甲酸酯低聚物中的至少一种的单体；选自氯化聚酯、氯化橡胶和氯化聚烯烃中的至少一种的氯化化合物；和光引发剂。在许多情况下，本文公开的具体组合物可以具有不同的添加剂，其在其他实施方式中互换或使用，而不偏离本发明的范围。以下非限制性实施例提供了已经用于成功地将EVA粘结到接触基底的本发明的100％固体组合物的近似范围：
实施例1
HDDA(二丙烯酸己二醇酯)-单体 10-50％
Ebecryl 438-氯化聚酯 10-40％
Ebecryl 130-环状脂肪族二丙烯酸酯 10-30％
Ebecryl 168-酸性甲基丙烯酸酯 1-5％
Irgacure 500 1-5％
实施例2
HDDA(二丙烯酸己二醇酯)-单体 10-50％
Ebecryl 436-氯化聚酯 10-40％
Ebecryl 130-环状脂肪族二丙烯酸酯 10-30％
Ebecryl 168-酸性甲基丙烯酸酯 1-5％
Ebecryl 3418-改性环氧二丙烯酸酯 5-35％
Irgacure 500 1-5％
实施例3
MMA(甲基丙烯酸甲酯)-单体 60-99％
HDDA(二丙烯酸己二醇酯)-单体 0-20％
DX-530p-氯化聚烯烃 1-20％
Ebecryl 168-酸性甲基丙烯酸酯 0-20％
NVC 1-5％
Irgacure 500 1-5％
实施例4
Figure BDA0001935502180000041
Figure BDA0001935502180000051
实施例5
HDDA(二丙烯酸己二醇酯)-单体 10-40％
Ebecryl 438-氯化聚酯 10-40％
Ebecryl 130-环状脂肪族二丙烯酸酯 10-20％
βCEA 10-20％
NVC 1-10％
Irgacure 500 1-5％
实施例6
HDDA(二丙烯酸己二醇酯)-单体 10-40％
Genomer 6050-氯化聚酯树脂 10-40％
Ebecryl 168-酸性甲基丙烯酸酯 1-5％
βCEA 10-20％
NVC 1-10％
Irgacure 500 1-5％
实施例7
Genomer 1120(环状单官能丙烯酸酯) 75-90％
Pergut S20(氯化橡胶) 8-20％
Irgacure 500 0-5％
βCEA 0-5％％
CN 780 0-5％
通常，本领域已知氯化材料如氯化聚酯或氯化聚烯烃被设计成促进与具体物质的粘合。这些物质包括聚酯、聚丙烯和其他热塑性烯烃(TPO)。EVA与这些类别的材料不同且不相关。因此，本发明的组合物显示出作为底漆和粘合剂用在EVA上时非常有效的意想不到的结果。
据信这些制剂与现有的商业制剂的不同之处在于省略了三官能丙烯酸酯，而是使用单官能和双官能丙烯酸酯单体。与现有技术的组合物相比，这使得底漆保持热塑性，其允许固化的底漆在热活化后更多地流动并润湿PU/粘合剂涂覆的基底。三官能丙烯酸酯交联多于单官能和双官能丙烯酸酯，因此当试图粘结到热活化的粘合剂表面时不是非常可流动的。值得注意的是，现有技术中的EVA底漆使用溶剂基质，并且不是100％固体组合物。
另外，与现有的溶剂型制剂相比，本发明也更厚，因为溶剂型制剂在溶剂被驱除时倾向于仅铺设单层，仅留下固体。使用100％固体制剂，EVA材料上的所有物品都会保留。这允许在涂底漆的表面/粘合剂界面处更好的表面浸湿和渗透。总之，与具有现有技术溶剂基组合物的薄单层相比，层之间存在更多的接触。
在使用的一个实施方式中，如图1所图解，可将组合物施加于EVA表面，例如鞋底。该施加可以通过例如喷涂、刷涂、辊涂等。然后可以将本发明的组合物辐射固化——通常UV固化。一旦固化，表面就准备好与粘合剂粘结，例如涂覆聚氨酯粘合剂的鞋帮部分。然后使用该粘合剂将EVA与配合表面连接。任选地，可以在本发明的固化粘合剂/底漆上涂覆粘合剂，但不需要这种额外的粘合剂。与现有技术方法相比，不包括该第二粘合剂施加减少一个步骤。应当理解，该使用实施方式可以使用本文公开的本发明组合物的任何变型而不偏离本发明的范围。
虽然已经在优选或具体实施方式中以举例的方式说明了本发明的若干变型，但显然可以在本发明的精神和范围或其发明构思内开发进一步的实例。然而，应该清楚地理解，这些修改和调整在本发明的精神和范围内，并且包括在内但不限于所提出的所附权利要求。进一步应理解，各个方面和实施方式可包括类似且同等地适用于其他方面和实施方式的元件和/或组件，而不限于所描述的具体方面或实施方式。

Claims (21)

1.一种可与乙烯-乙酸乙烯酯粘结并用作施加到所述乙烯-乙酸乙烯酯表面的底漆的100%固体组合物，其在室温下可施加并且能够辐射固化，其包括：
单体，其选自(甲基)丙烯酸酯单体和(甲基)丙烯酸酯官能氨基甲酸酯低聚物中的至少一种；
氯化化合物，其选自氯化聚酯、氯化橡胶和氯化聚烯烃中的至少一种；和
光引发剂，其占所述100%固体组合物的5%；
所述100%固体组合物不具有三官能丙烯酸酯，并且所述(甲基)丙烯酸酯单体仅包括单官能单体和双官能单体。
2.权利要求1所述的100%固体组合物，其包含：
10-50%的二丙烯酸己二醇酯作为所述单体；
10-40%的氯化聚酯作为所述氯化化合物；
10-30%的环状脂肪族二丙烯酸酯；
1-5%的酸性甲基丙烯酸酯；和
1-5%的光引发剂。
3.权利要求1所述的100%固体组合物，其包含：
10-50%的二丙烯酸己二醇酯作为所述单体；
10-40%的氯化聚酯作为所述氯化化合物；
10-30%的环状脂肪族二丙烯酸酯；
1-5%的酸性甲基丙烯酸酯；
5-35%的改性环氧二丙烯酸酯；和
1-5%的光引发剂。
4.权利要求1所述的100%固体组合物，其包含：
60-99%的甲基丙烯酸甲酯作为所述单体；
0-20%的二丙烯酸己二醇酯，其中所述二丙烯酸己二醇酯的量不为0；
10-20%的氯化聚烯烃作为所述氯化化合物；
1-20%的酸性甲基丙烯酸酯；
1-5%的NVC；和
1-5%的光引发剂。
5.权利要求1所述的100%固体组合物，其包含：
10-30%的二丙烯酸己二醇酯作为所述单体；
10-70%的丙烯酸聚合物；
10-20%的氯化聚酯作为所述氯化化合物；
1-5%的酸性甲基丙烯酸酯；和
1-5%的光引发剂。
6.权利要求1所述的100%固体组合物，其包含：
10-40%的二丙烯酸己二醇酯作为所述单体；
10-40%的氯化聚酯作为所述氯化化合物；
10-20%的环状脂肪族二丙烯酸酯；
10-20%的ßCEA；
1-10%的NVC；和
1-5%的光引发剂。
7.权利要求1所述的100%固体组合物，其包含：
10-40%的二丙烯酸己二醇酯作为所述单体；
10-40%的氯化聚酯树脂作为所述氯化化合物；
1-5%的酸性甲基丙烯酸酯；
10-20%的ßCEA；
1-10%的NVC；和
1-5%的光引发剂。
8.权利要求1所述的100%固体组合物，进一步包含10-50%的所述单体，所述单体是二丙烯酸己二醇酯和甲基丙烯酸甲酯。
9.权利要求8所述的100%固体组合物，进一步包含多种不同的所述(甲基)丙烯酸酯官能氨基甲酸酯低聚物，所述多种不同的所述(甲基)丙烯酸酯官能氨基甲酸酯低聚物的组合占所述100%固体组合物的11-75%。
10.权利要求8所述的100%固体组合物，进一步包含所述100%固体组合物中的10-40%的所述氯化化合物。
11.权利要求10所述的100%固体组合物，进一步包含多种不同的所述(甲基)丙烯酸酯官能氨基甲酸酯低聚物。
12.权利要求11所述的100%固体组合物，其中所述多种低聚物包括环状脂肪族二丙烯酸酯和酸性甲基丙烯酸酯。
13.权利要求11所述的100%固体组合物，其中所述多种低聚物包括环状脂肪族二丙烯酸酯、酸性甲基丙烯酸酯和改性环氧二丙烯酸酯。
14.权利要求8所述的100%固体组合物，进一步包含10-30%的环状脂肪族二丙烯酸酯。
15.权利要求1所述的100%固体组合物，其中所述100%固体组合物被施加至乙烯-乙酸乙烯酯表面。
16.一种将乙烯-乙酸乙烯酯粘附到基底上的方法，其包括以下步骤：
获得所述基底；
获得所述乙烯-乙酸乙烯酯；
在室温下将下述100%固体组合物施加到所述乙烯-乙酸乙烯酯上，所述100%固体组合物包括：
单体，其选自(甲基)丙烯酸酯单体和(甲基)丙烯酸酯官能氨基甲酸酯低聚物中的至少一种；
氯化化合物，其选自氯化聚酯、氯化橡胶和氯化聚烯烃中的至少一种；和
光引发剂，其占所述100%固体组合物的5%；
将施加有所述100%固体组合物的所述乙烯-乙酸乙烯酯与所述基底接触；和
使用辐射固化所述100%固体组合物，
其中所述100%固体组合物不包括三官能丙烯酸酯，并且所述(甲基)丙烯酸酯单体仅包括单官能单体和双官能单体。
17.权利要求16所述的方法，其中所述100%固体组合物进一步包含10-50%的所述单体，所述单体是二丙烯酸己二醇酯和甲基丙烯酸甲酯。
18.根据权利要求17所述的方法，其中所述100%固体组合物进一步包含多种不同的所述(甲基)丙烯酸酯官能氨基甲酸酯低聚物，所述多种不同的所述(甲基)丙烯酸酯官能氨基甲酸酯低聚物的组合占所述100%固体组合物的11-75%。
19.权利要求17所述的方法，其中所述100%固体组合物进一步包含100%固体组合物中的10-40%的所述氯化化合物。
20.权利要求19所述的方法，其中所述100%固体组合物进一步包含多种不同的所述(甲基)丙烯酸酯官能氨基甲酸酯低聚物。
21.权利要求17所述的方法，其中所述100%固体组合物进一步包含10-30%的环状脂肪族二丙烯酸酯。
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EP1686155A1 (en) * 2003-11-06 2006-08-02 Toyo Kasei Kogyo Company Limited Ultraviolet curing resin composition, paint, ink, adhesive, sealing agent and primer

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