CN107406715A - 溶剂型底漆组合物 - Google Patents

溶剂型底漆组合物 Download PDF

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CN107406715A
CN107406715A CN201680013854.0A CN201680013854A CN107406715A CN 107406715 A CN107406715 A CN 107406715A CN 201680013854 A CN201680013854 A CN 201680013854A CN 107406715 A CN107406715 A CN 107406715A
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P·P·古默尔斯舍梅尔
M·J·舒
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Abstract

本发明涉及一种底漆组合物，其包含2,5,7,10‑四氧杂十一烷(TOU)。本发明还提供一种对基底进行表面处理以改善对其的粘合剂粘结的方法。此外，本发明还涉及一种制品，所述制品包括用根据本发明的底漆组合物进行表面处理的基底。

Description

溶剂型底漆组合物
技术领域
本发明涉及一种底漆组合物，其包含2,5,7,10-四氧杂十一烷(2,5,7,10-tetraoxaundecane)(TOU)。本发明还提供一种表面处理基底以改善对其的粘合剂粘结的方法。此外，本发明还涉及一种制品，该制品包括用根据本发明的底漆组合物进行表面处理的基底。
背景技术
底漆组合物或底漆用于本领域中以改善粘合剂或密封剂对不同基底的粘附性。底漆组合物用于改善用底漆组合物进行表面处理的基底与待粘结的基底之间的粘合剂层之间的粘附性。取决于应用领域，已知使用多种不同的粘合剂来粘结多种不同的基底，其中通常将特定的底漆组合物用于特定种类的基底。
一些塑性材料诸如聚氯乙烯(PVC)或丙烯腈-丁二烯-苯乙烯(ABS)难以用粘合剂诸如反应性聚氨酯热熔体(HMMC)粘结。因此，为改善对此类基底的粘附性，必须使用底漆组合物，其制备用于与粘合剂粘结的表面。底漆组合物在待粘结的基底的表面上形成特定粗糙度并因此改善粘合剂的锚定用于最终粘结。
用于处理塑性材料诸如PVC或ABS的底漆组合物在本领域中是已知的这些底漆组合物包含能够在一定程度上溶解或攻击塑性材料的基于腐蚀性N-甲基-吡咯烷酮(NMP)或N-乙基-吡咯烷酮(NEP)的溶剂。因此，目前可在市场上购得的用于底涂基底诸如PVC或ABS的底漆组合物全部均包含NMP或NEP。
然而，腐蚀性溶剂诸如NMP或NEP是有害物质。因此，其使用同时也是不期望的。相反，在2015年，将这些溶剂分类为高度危险的，并将被宣布为致癌的。因此，本领域中强烈需要适用于对难以粘结的材料诸如PVC或ABS进行底涂的底漆组合物，其不含腐蚀性有害物质如NEP或NMP。
发明内容
本发明的目的是满足上述需求。具体地讲，本发明的目的是提供适用于对难以粘结的基底诸如PVC或ABS进行底涂，同时避免使用有害溶剂诸如NMP和NEP的底漆组合物。
本发明提供一种底漆组合物，其包含：(a)2,5,7,10-四氧杂十一烷(TOU)，和(b)聚合物，其选自聚酯(PES)、热塑性聚氨酯(TPU)和氯化的聚氯乙烯(CPVC)。在某些实施方案中，底漆组合物还包含(c)1,3-二氧杂环戊烷。
本发明的发明人已经发现包含TOU和任选地但优选地1,3-二氧杂环戊烷的组合物可有效地底涂基底诸如PVC或ABS，以便即使在不使用有害物质诸如NEP和NMP的情况下也改善粘合剂粘结。因此，根据本发明的底漆组合物通常不含NMP或NEP。在某些实施方案中，底漆组合物不含NMP、NEP，或任何其它N-烷基吡咯烷酮衍生物。在一个优选的实施方案中，本发明的底漆组合物还不含四氢呋喃(THF)和甲苯。
因此，本发明还涉及对基底进行表面处理以改善对其的粘合剂粘结的方法，所述方法包括：将上述根据本发明的底漆组合物的层施加于待处理的基底的表面，以及将所述组合物干燥以形成底漆涂层。
本发明还提供一种制品，所述制品包括：具有至少一个表面的基底，和涂覆或施加于所述基底的至少一个表面上的根据本发明的底漆组合物的层。
本发明的其它实施方案由所附权利要求书或以下具体实施方式显而易见。
具体实施方式
原则上，底漆组合物可分类为溶剂型底漆组合物和水性底漆组合物。本发明涉及溶剂型(solvent borne或solvent based)底漆组合物。
根据本发明的溶剂型底漆组合物包含：(a)2,5,7,10-四氧杂十一烷(TOU)，和溶于其中的(b)聚合物，所述聚合物选自聚酯(PES)、热塑性聚氨酯(TPU)和氯化的聚氯乙烯(CPVC)。任选地但优选地，底漆组合物还包含(c)1,3-二氧杂环戊烷。
2,5,7,10-四氧杂十一烷(分子式C7H16O4)为通常用于清洁产品领域中的乙缩醛型溶剂。在本发明中，所述化合物还称为TOU。TOU的化学结构示于下文。
本发明的发明人已经发现TOU适于替代通常用于常规底漆组合物中的有害物质诸如NMP或NEP。因此，本发明的底漆组合物包含TOU，同时本发明的底漆组合物通常不含NMP、NEP或任何其它N-烷基吡咯烷酮衍生物。此外，本发明的底漆组合物可以并且优选地还不含THF和甲苯。
基于所述组合物的总重量，在某些实施方案中，本发明的底漆组合物包含至少约40重量％的TOU。在一个优选的实施方案中，根据本发明的底漆组合物还包含基于所述组合物的总重量约45重量％至约97重量％的TOU。例如，底漆组合物可包含含量为约50重量％至约93重量％，诸如85重量％至92.9重量％，85重量％至92.5重量％，或85重量％至92重量％的TOU。
本发明的底漆组合物还可包含1,3-二氧杂环戊烷。本发明的发明人已经发现即使在不使用有害溶剂诸如NEP或NMP的情况下，TOU，尤其是与1,3-二氧杂环戊烷的组合对于底涂难以粘结的基底诸如PVC或ABS也是特别有效的。
在某些实施方案中，底漆组合物包含基于所述组合物的总重量至多约25重量％的量的1,3-二氧杂环戊烷。在一些实施方案中，1,3-二氧杂环戊烷以约2重量％至约15重量％的量包含于根据本发明的底漆组合物中。例如，在某些实施方案中，1,3-二氧杂环戊烷以基于所述组合物的总重量约5重量％至约10重量％的量使用。
在其它实施方案中，根据本发明的上述底漆组合物中的TOU，和如果存在，1,3-二氧杂环戊烷的部分由具有低蒸气压的有机溶剂替代。以这种方式，可获得具有低含量的挥发性有机化合物(VOC)的底漆组合物。根据该实施方案可提供符合欧盟指令1999/13/EC的要求的底漆组合物。在此类底漆组合物中，TOU和1,3-二氧杂环戊烷的总量小于约50重量％，优选地约40重量％至约49重量％。TOU与1,3-二氧杂环戊烷的重量比优选地为约30:1至约5:1，更优选地为约20:1至约10:1。根据本发明的低VOC底漆组合物包含其它有机溶剂，其选自：戊二酸二甲酯、琥珀酸二甲酯、己二酸二甲酯、2-甲基戊二酸二甲酯、2-乙基己醛以及它们的组合。在此类低VOC底漆组合物中，TOU、1,3-二氧杂环戊烷和选自戊二酸二甲酯、琥珀酸二甲酯、己二酸二甲酯、2-甲基戊二酸二甲酯、2-乙基己醛以及它们的组合的其它有机溶剂的总量为约89重量％至约99重量％，优选地约90重量％至约98重量％。选自戊二酸二甲酯、琥珀酸二甲酯、己二酸二甲酯、2-甲基戊二酸二甲酯、2-乙基己醛以及它们的组合的低蒸气压溶剂是本领域中已知用于底漆组合物中的，并且包括例如购自Rhodia的Rhodiasolv RPDE和Rhodiasolv IRIS，购自Invista的FlexiSolv DBE-4，或购自Lambiotte的2-乙基己醛。
本发明的底漆组合物还包含选自下列的聚合物：PES、TPU和CPVC。向底漆组合物中加入聚合物诸如PES、TPU或CPVC是常规底漆的领域中已知的。在一些实施方案中，根据本发明的底漆组合物包含基于所述组合物的总重量至多约10重量％的量的PES、TPU和/或CPVC。例如，选自PES、TPU和CPVC的聚合物可以约1重量％至约8重量％，诸如约2重量％至约5重量％的量包含于本发明的底漆组合物中。
在一些实施方案中，包含于根据本发明的底漆组合物中的聚合物优选地为PES。
此外，在此类实施方案中，PES可具有根据DIN ISO 4625所测量的例如约60℃至约160℃的软化点(Ring&Ball)。优选地，PES具有约80℃至约140℃的软化点。
此外，PES可具有根据DIN 53765所测量的约10℃或更低的玻璃化转变温度(DSC)。优选地，PES具有约0℃或更低的玻璃化转变温度。
根据本发明适宜的聚酯在本领域中是已知的。适宜的PES通常是基本线性或线性的。此外，PES通常具有一些结晶度，诸如轻微的结晶度。可用的可商购获得的羟基封端的聚酯材料包括各种饱和的线性、半结晶共聚酯，其购自EVONIK INDUSTRIES，诸如S1272、S 1401或S 1402；或者购自BOSTIK的7400或1405。
在其它实施方案中，另选地或除PES之外，本发明的底漆组合物还包含热塑性聚氨酯(TPU)。根据本发明适宜的热塑性聚氨酯在本领域中是已知的。适宜的热塑性聚氨酯通常是基本线性或线性的。此类热塑性聚氨酯一方面衍生自基本线性或线性的多元醇，例如聚酯多元醇、聚醚多元醇或聚己内酯多元纯，另一方面衍生自基本上线性或线性的多异氰酸酯。
此外，适宜的热塑性聚氨酯通常具有明显或较高的结晶趋势。在一个优选的实施方案中，根据本发明适宜的TPU具有根据DIN 53505所测量的约60分钟或更低，优选地约40分钟或更低，诸如例如约25分钟至约35分钟的结晶速率。
热塑性聚氨酯也称为热塑性聚氨酯弹性体，因为其是高弹性的。热塑性聚氨酯包括以嵌段结构组合的线性或基本上线性的聚合物链。这些嵌段结构包含低极性链段，其相对长并且被称为软链段。软链段与更短的高极性“硬”链段共价键合。可用的热塑性聚氨酯包括至少一种软链段(例如，聚醚、聚酯和聚己内酯)和异氰酸酯，例如亚甲基二苯基二异氰酸酯(MDI)的反应产物。关于热塑性聚氨酯的更多信息可见于“ThermoplasticPolyurethanes:Chemistry Opens Up New Opportunities”，Urethane Technology，第24、26页，1997年12月/1998年1月，其以引用方式并入本文。
可用的热塑性聚氨酯例如以商品名购得，诸如例如，购自位于Barcelona，Spain的MERQUINSA的46-10；购自HUNTSMAN的S 7514；购自COIM的1460或购自LUBRIZOL的Estane T5648。
在另一个实施方案中，另选地或除PES和/或(TPU)之外，本发明的底漆组合物还包含氯化聚氯乙烯(CPVC)作为至少一种聚合物。包括本发明的底漆组合物在内的底漆组合物中适宜的氯化聚氯乙烯(CPVC)在本领域中是已知的。根据本发明，CPVC尤其适用于用于镶边(edge banding)应用的底漆组合物中。通常，CPVC具有约60重量％至约70重量％，诸如例如约63重量％至约69重量％的氯含量。
根据本发明的底漆组合物还可包含微量的常用添加剂。适用于底漆组合物的添加剂在本领域中是已知的。例如，可任选地添加添加剂诸如荧光增白剂或UV示踪剂。通常，如果存在，则此类添加剂以较低量使用，诸如基于所述底漆组合物的总重量小于约1重量％、小于约0.5重量％或小于约0.1重量％。
在一个实施方案中，底漆组合物包含荧光增白剂或光学增白剂(OBA)。荧光增白剂为吸收电磁光谱的紫外线和紫色区域中的光(通常340nm-370nm)并且重新发射蓝色区域中的光(通常420nm-470nm)的化学化合物。适宜的示例是本领域技术人员已知的。在本发明的一些实施方案中，包含基于所述底漆组合物的总重量小于约0.1重量％的量的荧光增白剂。适宜的荧光增白剂的示例性示例包括例如购自Mayzo Inc.的Bentex OB、购自CibaSpecialty Chemicals的Uvitex OB、购自3V Sigma的Optiblanc PL、或Lunabrite OB。
如上所述，本发明还涉及对基底进行表面处理以改善对其的粘合剂粘结的方法。本发明的方法包括：将如上所定义的根据本发明的底漆组合物的层施加于待处理的基底的表面，以及将组合物干燥以形成底漆涂层。
将底漆组合物施用或涂覆到基底上的方法没有特别限制。例如，底漆组合物可如本领域已知进行施加，例如，利用所有种类的辊(诸如钢辊或橡胶辊)，或直列式和反向旋转的辊的组合，通过喷涂或利用辊涂机或涂布刀，通过与具有施加于其上的底漆组合物的垫或毡接触、真空系统等。在一个示例性实施方案中，将底漆组合物滴到旋转毡上，并将其上施加底漆组合物的毡与待处理的基底接触，从而将底漆组合物施加或涂覆到基底上。以这种方式，还可观察到基底的一些清洁。
干燥温度没有特别限制。通常干燥可通过使用例如红外烘箱、热空气枪或电扇将基底的表面温度升高来进行。通常可采用在约35℃至约120℃，诸如50℃至约80℃范围内的升高的表面温度。干燥时间足够长以确保底漆组合物可与基底相互作用以改善粘合剂粘结。取决于采用的机械，包括速度、热空气枪数、红外烘箱长度等，这通常在例如小于约一分钟或小于约40秒，诸如例如约5秒至约20秒内实现。
有利地可根据本发明处理的基底包括但不限于下列基底，其包含：聚氯乙烯(PVC)、丙烯腈-丁二烯-苯乙烯(ABS)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚酯浸渍纸或三聚氰胺浸渍纸。本发明的底漆组合物对底涂PVC或ABS，尤其是PVC特别有利。
在一个实施方案中，底漆组合物可以连续涂层的形式施用。获得的涂层干重优选地为约0.01g/m2至25g/m2。本发明的发明人已经发现，即使在以低于常规底漆组合物的量施加本发明的底漆组合物时，根据本发明的底漆组合物对于底涂诸如PVC的难以粘结的基底也是有效的。因此，在一些实施方案中，将底漆组合物施加于基底上以便获得优选约0.05g/m2至约15g/m2，更优选地约0.1g/m2至约10g/m2，诸如例如0.1g/m2至7g/m2或0.1g/m2至0.5g/m2的干涂层重量。
本发明还涉及一种制品，所述制品包括：具有至少一个表面的基底，和涂覆在所述基底的至少一个表面上的根据本发明的底漆组合物的层。适宜的基底已经在上文讨论，并且包括但不限于以下基底，其包含例如聚氯乙烯(PVC)、丙烯腈-丁二烯-苯乙烯(ABS)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚酯浸渍纸或三聚氰胺浸渍纸，诸如具体地PVC或ABS，尤其是PVC。根据本发明的制品的具体示例包括但不限于镶边、窗型材或PVC-型材。
可有利地与本发明的底漆组合物结合使用的粘合剂没有特别限制，只要实现粘合剂和底漆层之间的良好粘结即可。例如，适宜的粘合剂可包括热熔融粘合剂，诸如热熔融湿固化聚氨酯粘合剂(HMMC)、热熔融乙烯-乙酸乙烯酯粘合剂(HM EVA)或基于无定形聚-α-烯烃的热熔融粘合剂(HM APAO)。在一些实施方案中，粘合剂为HMMC粘合剂。
在一个示例性实施方案中，可将根据发明的底漆组合物用于窗型材包裹物。适宜的窗型材通常包含PVC。在此类实施方案中，可优选底漆组合物除了TOU之外还包含1,3-二氧杂环戊烷。可通过垫或毡或真空系统，将底漆组合物施加于窗型材。干燥可通过热空气枪或风扇直至完全干燥来实现。在此适宜的干涂层重量低至例如约7g/m2或更低，诸如1g/m2或更低，例如约0.1g/m2至约0.5g/m2。在此类实施方案中，可有利地采用HMMC粘合剂。
工作例
通过在室温下将具有60×10×1mm尺寸的基底试样浸没在20ml的溶剂中24小时，来测试TOU对替代底漆组合物中的有害物质诸如NMP或NEP的适用性。替代底漆组合物中的NMP或NEP的溶剂应当示出对各种基底材料的显著攻击，至少相当于由当前使用中的有害物质NMP或NEP获得的结果。观察到的结果如下文所指出的那样评分：
0-无攻击
1-表面略攻击
2-材料溶胀
3-强攻击与材料变形
4-完全溶解
获得的测试结果示于下表中：
如上可见，为非有害溶剂的TOU示出对不同基底材料的至少相当于待替代的有害物质的作用的特征。因此，TOU适于替代底漆组合物中的NMP或NEP。
实施例1
通过将TOU、1,3-二氧杂环戊烷和具有低于0℃的玻璃化转变温度的半结晶聚酯组合来获得非有害底漆组合物。将Vitel 7400用作PES。此外，还添加荧光增白剂(OptiplancPL)。下表中所示的以重量百分比计的量基于所述底漆组合物的总重量。
量[重量％]
TOU 92.95
1,3-二氧杂环戊烷 5
PES 2
荧光增白剂 0.05
将上述组合物施加于PVC基底并干燥。随后，使用HMMC粘合剂(购自HB Fuller的lock 4077)将PVC箔在线粘结到经处理的基底。出于比较的目的，进行相同的规程，不同的是使用基于NMP/NEP的标准底漆(购自HB Fuller的底漆4912)，而不是根据实施例1的组合物。为测定底漆组合物的效率，利用获得的层压体进行根据RAL GZ 716的剥离测试。结果如下：
如由上文可见，由根据本发明的底漆组合物获得强粘附性，其相当于由基于NEP/NMP的底漆获得的粘附性。因此，即使在避免使用通常用于常规底漆中的有害物质诸如NMP和NEP时，根据本发明的组合物也适合用作底漆组合物。

Claims (14)

1.一种底漆组合物，其包含：
(a)2,5,7,10-四氧杂十一烷(TOU)，和
(b)聚合物，其中所述聚合物选自聚酯(PES)、热塑性聚氨酯(TPU)和氯化聚氯乙烯(CPVC)。
2.根据权利要求1所述的底漆组合物，其中所述组合物不含N-甲基-吡咯烷酮(NMP)或N-乙基-吡咯烷酮(NEP)，并且优选地不含N-甲基-吡咯烷酮(NMP)和N-乙基-吡咯烷酮(NEP)。
3.根据权利要求1或2所述的底漆组合物，其还包含
(c)1,3-二氧杂环戊烷。
4.根据权利要求1至3中任一项所述的底漆组合物，其中所述聚合物为聚酯(PES)。
5.根据权利要求4所述的底漆组合物，其中所述PES具有
根据DIN ISO 4625所测量的约60℃至约160℃，优选地约80℃至约140℃的软化点；和/或
根据DIN 53765所测量的约10℃或更低，优选地约0℃或更低的玻璃化转变温度。
6.根据权利要求1至5中任一项所述的底漆组合物，其中所述组合物包含，基于所述总体组合物，
(a)含量为至少约40重量％，优选地约45重量％至约97重量％，更优选地约50重量％至约93重量％的2,5,7,10-四氧杂十一烷(TOU)；和/或
(b)含量为至多约10重量％，优选地约1重量％至约8重量％，更优选地约2重量％至约5重量％的聚合物；和/或
(c)含量为至多约25重量％，优选地约2重量％至约15重量％，更优选地约5重量％至约10重量％的1,3-二氧杂环戊烷。
7.根据权利要求1至5中任一项所述的底漆组合物，其中所述组合物包含，基于所述总体组合物，
(a)总量小于约50重量％，优选地约40重量％至约49重量％的TOU和1,3-二氧杂环戊烷，其中TOU与1,3-二氧杂环戊烷的重量比优选地为约30:1至约5:1，更优选地约20:1至约10:1；
(b)含量为至多约10重量％，优选地约1重量％至约8重量％，更优选地约2重量％至约5重量％的聚合物；以及
(c)选自下列的其它有机溶剂：戊二酸二甲酯、琥珀酸二甲酯、己二酸二甲酯、2-甲基戊二酸二甲酯、2-乙基己醛以及它们的组合，
其中TOU、1,3-二氧杂环戊烷和其它有机溶剂的总量为约89重量％至约99重量％，优选地约90重量％至约98重量％。
8.一种对基底进行表面处理以改善对其的粘合剂粘结的方法，所述方法包括：
将如权利要求1至7中任一项所定义的底漆组合物的层施加于待处理的基底的表面上，以及
将所述组合物干燥以形成底漆涂层。
9.根据权利要求8所述的方法，其中所述基底包含聚氯乙烯(PVC)、丙烯腈-丁二烯-苯乙烯(ABS)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚酯浸渍纸或三聚氰胺浸渍纸，并且优选地包含PVC或ABS，更优选地PVC。
10.根据权利要求8或9所述的方法，其中施加所述底漆组合物以获得约0.01g/m2至约25g/m2，优选地约0.05g/m2至约15g/m2，更优选地约0.1g/m2至约10g/m2的涂层干重。
11.一种制品，其包括：
具有至少一个表面的基底，以及
如根据权利要求1至6中任一项所定义的底漆组合物的层，所述底漆组合物的层涂覆在所述基底的至少一个表面上。
12.根据权利要求11所述的制品，其中所述基底包含聚氯乙烯(PVC)、丙烯腈-丁二烯-苯乙烯(ABS)、聚丙烯(PP)、聚对苯二甲酸乙二醇酯(PET)、聚酯浸渍纸或三聚氰胺浸渍纸，并且优选地包含PVC或ABS，更优选地PVC。
13.根据权利要求11或12所述的制品，其中所述制品包括镶边、窗型材或PVC型材，优选地窗型材。
14.根据权利要求11至13中任一项所述的制品，其中所述制品还包含粘合剂，优选地热熔融粘合剂，更优选地选自下列的热熔融粘合剂：热熔融湿固化聚氨酯粘合剂(HMMC)、热熔融乙烯-乙酸乙烯酯粘合剂(HM EVA)、和基于无定形聚-α-烯烃的热熔融粘合剂(HM APAO)，其中还更优选地所述粘合剂为HMMC粘合剂。
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