CN100348336C - 用于施加可光化辐射固化的涂层的喷枪和方法 - Google Patents
用于施加可光化辐射固化的涂层的喷枪和方法 Download PDFInfo
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Abstract
本发明涉及一种用于施加涂层的喷枪，其具有喷嘴和至少一个光化辐射出口，其特征在于，该至少一个光化辐射出口位于外部，并且该辐射出口和喷嘴可同时指向待涂敷的基片；本发明还涉及一种施加可以至少部分地通过光化辐射固化的涂层组合物的方法。即使在光化辐射进行的引发和固化反应的实际开始之间没有诱导期，根据本发明的喷枪也适合于各种类型的可光化辐射固化的涂层组合物。紧接着涂料施加之后的涂层材料的流动和干燥速度的平衡尤其有利。
Description
技术领域
本发明涉及一种用于施加涂层的喷枪，其具有喷嘴和至少一个光化辐射(光化学辐射)出口，本发明还涉及一种施加可以至少部分地通过光化辐射固化的涂层组合物的方法。
背景技术
欧洲专利申请EP-A 1002587公开了一种用于涂料涂敷的UV光辅助喷枪，其具有一个或多个正好位于喷嘴附近的UV点源。涂层组合物在正好离开喷枪之前或之后被照射。仅在正好邻近喷嘴处引发可UV固化的涂层组合物的交联。这需要在用UV光进行的引发和交联反应的实际开始之间有一个诱导期。此需求不希望地限制了可通过该喷枪施加的可辐射固化涂层组合物的选择。因为辐射只是正好在喷嘴附近发生，所以将对紧接着涂料施加之后的涂层材料的流动与干燥速度之间的平衡造成负面影响。这会损坏外涂层的外观和底涂层的粘附力。
另外，在喷枪内的辐射出口的表面上可能沉积一层其厚度在操作期间增大的交联涂层材料。所述沉积限制了仍可用于引发固化反应的辐射量。最终，喷枪内的交联涂层材料的沉积会导致阻塞。同样，如果在喷枪内形成和遗留交联材料，则会阻塞喷嘴。当喷涂过程中断时，已被照射的涂层材料保留在喷嘴中。
此外，因为照射只是正好在涂层材料离开喷枪之前或之后进行，所以对于需要较大量的光化辐射以便进行引发的涂层组合物，在从EP-A1002587中已知的喷枪中会发生固化反应的不充分或不完全引发。这可能会导致所施加的涂层的延迟或不完全固化。在这种情况下，需要额外的UV照射设备，以便进一步照射所施加的涂层以确保快速和完全的固化。
发明内容
本发明提供了一种上述类型的喷枪和方法，它们不受上述缺陷的限制。
本发明的喷枪是一种用于施加涂层的喷枪，其具有喷嘴和至少一个光化辐射出口，其特征在于，该至少一个光化辐射出口位于外部，并且该辐射出口和喷嘴可同时指向待涂敷的基片。该几何结构可确保，在喷枪的操作期间，光化辐射的至少一部分会到达被涂敷的基片。
即使在光化辐射进行的引发和固化反应的实际开始之间没有诱导期，根据本发明的喷枪也适合各种类型的可光化辐射固化的涂层组合物，因为固化反应的引发发生在薄层形成期间和之后，并且不会只是正好在喷嘴附近发生。紧接着涂料施加之后的涂层材料的流动和干燥速度的平衡尤其有利。
因为所述引发是在涂层材料已离开该喷嘴之后在喷枪的外部进行的，所以，即使在喷涂过程中断时，根据本发明的喷枪也不会发生喷嘴被照射和固化的涂层材料阻塞的情况。由于根据本发明的喷枪的光化辐射出口的表面不与可光化辐射固化的涂层组合物直接接触，所以不会遇到交联材料沉积在辐射出口上的情况以及与此相关的问题。此外，因为照射期间并不局限于涂层材料正好离开喷枪之前或之后的时刻，所以需要较大量的光化辐射以进行引发的涂层组合物也可完全且无延迟地固化。如果需要的话，可利用本发明的喷枪对涂层表面进行额外的照射，而无需喷涂涂层材料。
根据本发明的喷枪的另一实施例的特征在于，光化辐射的平均辐射方向和喷嘴中的涂层的平均流动方向之间的角度小于90度，优选地小于45度。在该几何结构中，在喷枪的操作期间，比例增加的光化辐射达到被涂敷的基片。
在喷枪的一优选实施例中，所述至少一个光化辐射出口和所述喷嘴可相互指向，以允许光化辐射和喷嘴喷涂区域之间重叠。喷嘴喷涂区域是指喷雾在喷枪的操作期间到达的空间。此优选实施例的几何结构确保在喷枪的操作期间，利用光化辐射照射喷雾和刚刚涂敷的基片。
光化辐射是指能够引发化学反应的电磁辐射。用于根据本发明的喷枪的光化辐射的波长可在一宽范围内变化。适合于特定情况的波长取决于将使用该喷枪喷涂和固化的涂层系统。通常，可见光和紫外线(UV)辐射具有合适的波长。尤其合适的光化辐射波长小于600nm，尤其小于500nm，并且尤其小于450nm。一种尤其优选的光化辐射是在大约320nm到大约400nm的波长范围内的已知为UV-A辐射的部分电磁波长光谱。就UV-A辐射而言，生物活性及相关的健康危险的平衡和引发化学反应的能力是尤其可以接受的。因此，该喷枪的一优选实施例的特征在于，所述至少一个光化辐射出口为UV-A辐射出口。
但是，具有较短波长，例如280nm、200nm甚或更短例如100nm或20nm的光化辐射也是合适的。可使用滤波器从光化辐射中滤除不希望的波长。例如，可使用所谓的黑色滤光器从光化辐射中除去可见光波长。
可用于根据本发明的喷枪的合适的光化辐射源可在市场上得到。例如，可考虑荧光管、氘卤素光源、激光光源、汞蒸气灯、汞氙灯和金属卤化物灯。除了连续地提供光化辐射的灯之外，还可使用不连续的光化辐射源，例如氙气闪光灯或脉冲激光器。优选地，光化辐射源为UV-A辐射源。同样优选的是，光化辐射源为点源，例如UV-P 280/2 ex Panacol-Elosol。
可选地，用至少一个UV发光二极管(UV-LED)提供光化辐射。在本发明的喷枪中使用UV-LED具有若干优点。UV-LED允许瞬时接通/断开UV辐射源的开关，这样会提高组合的喷涂和辐射过程的灵活性。此外，UV-LED的使用寿命通常远长于传统的UV源的使用寿命，例如，UV-LED的使用寿命长达50000小时，而传统的UV源为大约1000小时。此外，UV-LED通常具有窄波长分布，并且使得可定制峰值波长。UV-LED的特征在于，电能高效地转化成UV辐射。这会导致低发热，并允许省去冷却部件或仅使用小的冷却部件，这有益于安装到喷枪上。UV-LED的另一优点是工作电压较低，与通常的UV灯所需的较高电压相比，这在涂料喷涂室环境中是优选的。
例如上述的光化辐射源可安装在根据本发明的喷枪的外部，以便引导光化辐射朝向喷雾和被涂敷的基片。可选地，所述至少一个光化辐射出口通过光导件连接在光化辐射源上。在此情况下，光化辐射源可位于远离喷枪处。光导件由透明材料制成，以便利用全反射引导光流。优选地，光导件由柔性材料制成，以允许喷枪相对于光化辐射源移动。用于光导件的材料的示例为塑料、包括大量细光导纤维的纤维光导件和液体光导件。
如上所述，根据本发明的喷枪具有至少一个光化辐射出口。但是，喷枪还可具有多个光化辐射出口，例如2、3、4个甚至更多个光化辐射出口。如上所述的单个UV-LED的尺寸通常非常小，并且发射较低水平的光化辐射。因此，如果这种UV-LED用作光化辐射源，优选的是，多个UV-LED在所谓的UV-LED阵列中集合在一起。可根据所需的尺寸、形状和所需的光化辐射输出定制UV-LED阵列中的单个UV-LED的数目。UV-LED阵列可包括几百乃至成千上万个单个UV-LED。所述至少一个光化辐射出口的形状并不重要。它可以具有任何合适的形状。例如，可考虑围绕喷枪的喷嘴设置的圆形UV-LED阵列。
如果根据本发明的喷枪具有一个以上的光化辐射出口，这些出口可设置成实质上沿相同方向引导从该出口发出的光化辐射，因此优选地，在喷枪的操作期间用光化辐射照射喷雾和刚刚被涂敷的基片。
可选地，至少一个光化辐射出口可设置成引导光化辐射主要朝向喷雾，而至少另一个光化辐射出口设置成引导光化辐射实质上朝向被涂敷的基片而不穿过喷雾。因此，可以改变穿过喷雾的光化辐射与直接达到刚刚被涂敷的基片的光化辐射的分配比率。为特定情况选择的分配比率可取决于将由根据本发明的喷枪涂敷的涂层系统。从而可将喷枪设计成经由喷雾传送大部分光化辐射。如果是希望和/或合适的，还可颠倒该分配比率，从而仅有小部分光化辐射通过喷雾。特定的光化辐射分配比率的选择将取决于若干因素，例如涂层材料的固化速度以及待涂敷和固化的涂层的厚度。
适用于调节光化辐射分配比率的方法是选择所述至少一个光化辐射出口相对于喷枪的喷嘴的特定位置、改变出自该至少一个光化辐射出口的光化辐射的平均传播方向和喷嘴中的涂层的平均流动方向之间的角度以及改变光化辐射出口的数目。还可在光化辐射束中引入合适的透镜和/或反射镜，以便控制光化辐射的分配和传播方向。还可使用可任意调节的孔来控制光化辐射的量和分配比率。当然，这些实施例的组合和变型也是可以的。
对于本发明可用的喷枪的类型没有限制，只要喷枪适于喷涂涂层材料即可。优选的喷枪是用于液体涂层组合物的喷枪。这种喷枪通常为技术人员所知，并由Klaus Chor在Lehrbuch für Fahrzeuglackierer，AudinVerlag，Munich 1999，pp.124-132中进行了说明。合适的喷枪的示例包括具有重力供给、抽吸供给和压力供给的手持式喷枪；高压和低压空气喷枪，以及无气喷枪；多组分喷枪例如双组分喷枪；和用于静电喷涂的喷枪。空气喷枪是优选的。
在一特定实施例中，根据本发明的喷枪形成自动涂覆系统例如涂敷机器人的一部分。在一实施例中，喷枪具有例如通过在喷枪的扳机中包括一用于光化辐射源的开关来同步启动和停止喷涂和光化辐射的照射的装置。但是，如果可以单独启动光化辐射也是有利的，从而可在喷涂之后对被涂敷的基片进行额外的照射，以便提高固化速度和/或确保涂层完全固化。
本发明还涉及一种用于施加可以至少部分地通过光化辐射固化的涂层组合物的方法，其中使用具有喷嘴和至少一个辐射出口的喷枪，其特征在于，该至少一个光化辐射出口位于外部，并且该出口和喷嘴同时指向待涂敷的基片。
该方法的一特定实施例的特征在于，在施加涂层之后，还用光化辐射照射刚刚被涂敷的涂层。
可使用任何可以至少部分地通过光化辐射固化的涂层组合物来实现根据本发明的方法。用于这种涂层组合物的合适的单体、低聚物、聚合物和光引发剂为技术人员所知，并且在例如Kirk-Othmer，Encyclopedia ofChemical Technology，3rd Edition，Volume 19，pp.607-624和本文引用的参考文献中有所说明。
可光化辐射固化的涂层组合物的示例是基于可自由基聚合的单体、低聚物和聚合物的可自由基固化的组合物。该可自由基聚合的基团可以是(甲基)丙烯酸酯基、烯丙基和乙烯基。另一类型的可光化辐射固化的涂层组合物通过阳离子机理固化，例如通过阳离子开环聚合或阳离子和/或酸催化交联机理固化。在那种情况下，可光化辐射固化的涂层组合物包括光潜酸。合适的对阳离子开环聚合敏感的基团包括环醚基，例如环氧基或氧杂环丁烷基。合适的对阳离子和/或酸催化交联机理敏感的基团的示例是乙烯基醚基团或含羟基的聚合物与三聚氰胺低聚物的组合。涂层组合物还可以仅部分地通过光化辐射固化，以及完全热固化。在此情况下，热固化反应可以与光化辐射诱导的固化反应相同或不同。因此，涂层组合物还可以包括对光化辐射诱导的固化不敏感的基团。
在上述方法的实施例中，可以尤其有利地使用根据本发明的喷枪，其中涂层组合物包括光潜碱和碱催化的可聚合或可固化的材料。固化反应将在光潜碱已通过光化辐射的作用转化成非潜碱之后以很少的延时或者没有延时地开始。从而可充分利用根据本发明的喷枪的优于已知的喷枪的优点。
欧洲专利申请EP-A 0882072、国际专利申请WO 94/28075和国际专利申请WO 01/92362中说明了合适的光潜碱的示例。
光潜碱优选地选自可选地用烷基醚和/或烷基酯基团替代的4-(邻硝基苯基)二氢吡啶、四元有机硼光引发剂和α-氨基苯乙酮。该优选的α-氨基苯乙酮是根据分子式(1)的化合物：
包括例如多官能乙酰乙酸酯或丙二酸酯的Michael给体和例如丙烯酰官能化化合物的多官能Michael受体的混合物适于作为碱催化的可固化材料。这种混合物在上述EP-A 0882072和WO 94/28075中得到了较详细的说明。
在一优选实施例中，该碱催化的可固化材料包括至少一种多异氰酸酯和至少一种包含至少一个巯基的化合物。WO 01/92362中说明了这种涂层组合物。
用于根据本发明的方法的涂层组合物可包括常用的添加剂和组分，例如溶剂、填料、匀涂剂、乳化剂、抗泡沫剂和流变控制剂、还原剂、抗氧化剂、HALS-稳定剂、UV-稳定剂、脱水器例如分子筛，和防沉剂。
该方法还适合着色的涂层组合物。在一优选实施例中，将用于此方法的涂层组合物为透明涂层或外涂层组合物。如果涂层组合物是透明涂层组合物，尤其优选的是透明涂层构成多层漆系统例如底涂层-透明涂层系统中的一层。
本发明的方法可用于涂敷任何基片。该基片可以是例如金属(例如铁、钢和铝)、塑料、木材、玻璃、合成材料、纸、皮革或另一涂层。该另一涂层可根据本发明方法或者不同的方法涂敷。
本方法适于涂敷物体例如桥梁、管道、工业设备或建筑物、油气设备或船。根据本发明的方法尤其适合于汽车和大型运输车辆例如火车、卡车、公共汽车和飞机的涂饰和再涂饰。
附图说明
下面将参照附图和以下示例进一步说明本发明。
图1示出根据本发明的喷枪1的示例。
具体实施方式
两个光导件5的两个光化辐射出口2邻近喷嘴6位于外部。光化辐射出口2和喷嘴6指向待涂敷基片4。引导光化辐射朝向喷雾3。箭头7和8分别示出光化辐射的平均传播方向和喷嘴中的涂层的平均流动方向。喷枪1为GTI ex Devilbiss型。光导件5连接在UV点源(图1中未示出)上。
示例1
用下列组分制备一种光敏化涂层组合物，pbw代表按重量计算的部分：
季戊四醇四(3-巯基丙酸酯) 10.0pbw
TolonateHDT-LV 17.9pbw
Byk306的10％乙酸丁酯溶液 0.6pbw
分子式(1)的α-氨基苯乙酮的10％乙酸丁酯溶液 1.1pbw
TolonateHDT-LV为Rhodia的六亚甲基二异氰酸酯的环状三聚体。Byk306为Byk Chemie的表面活性剂。
该组合物的贮存期为6小时。用根据图1的喷枪将该光敏化涂层组合物作为透明涂层喷涂。
在第一试验中，仅在喷涂期间进行照射。涂层的干燥时间为大约15分钟。
在第二试验中，在喷涂之后照射刚刚被喷涂的薄层，照射时间与在喷涂期间的时间相同。涂层的干燥时间为大约3分钟。
Claims (20)
1.一种用于施加涂层的喷枪，该喷枪具有喷嘴和至少一个光化辐射出口，其特征在于，该至少一个光化辐射出口位于外部，并且该光化辐射出口和喷嘴可同时指向待涂敷的基片。
2.一种根据权利要求1的喷枪，其特征在于，所述光化辐射的平均传播方向和所述喷嘴中的涂层的平均流动方向之间的角度小于90度。
3.一种根据权利要求1或2的喷枪，其特征在于，所述光化辐射的平均传播方向和所述喷嘴中的涂层的平均流动方向之间的角度小于45度。
4.一种根据权利要求1的喷枪，其特征在于，所述至少一个光化辐射出口和所述喷嘴可相互指向，以允许该光化辐射和喷嘴喷涂区域之间的重叠。
5.一种根据权利要求1的喷枪，其特征在于，所述喷枪为空气喷枪。
6.一种根据权利要求1的喷枪，其特征在于，所述喷枪形成自动涂覆系统的一部分。
7.一种根据权利要求1的喷枪，其特征在于，所述至少一个光化辐射出口为UV-A辐射出口。
8.一种根据权利要求1的喷枪，其特征在于，所述光化辐射由点源提供。
9.一种根据权利要求1的喷枪，其特征在于，所述至少一个光化辐射出口通过光导件连接在光化辐射源上。
10.一种根据权利要求1的喷枪，其特征在于，所述光化辐射由至少一个UV发光二极管(UV-LED)提供。
11.一种根据权利要求10的喷枪，其特征在于，在UV-LED阵列中，多个UV-LED集合在一起。
12.一种用于施加涂层组合物的方法，该涂层组合物可以至少部分地通过光化辐射固化，其特征在于，使用根据前述权利要求中任一项的喷枪。
13.一种根据权利要求12的方法，其特征在于，在利用所述喷枪同时进行喷涂和光化辐射之后，再利用所述喷枪对刚刚施加的涂层进行光化辐射。
14.一种根据权利要求12或13的方法，其特征在于，将包括光潜碱和碱催化的可聚合或可固化材料的组合物用作所述可以至少部分地通过光化辐射固化的涂层组合物。
15.一种根据权利要求14的方法，其特征在于，所述光潜碱选自可选地用烷基醚和/或烷基酯基团替代的4-(邻硝基苯基)二氢吡啶、四元有机硼光引发剂和α-氨基苯乙酮。
16.一种根据权利要求15的方法，其特征在于，所述α-氨基苯乙酮具有以下分子式(1)：
17.一种根据权利要求14的方法，其特征在于，使用包括至少一种多异氰酸酯和至少一种包含至少一个巯基的化合物的碱催化的可固化材料。
18.一种根据权利要求12的方法，其特征在于，所述可以至少部分地通过光化辐射固化的涂层组合物为透明涂层或外涂层组合物。
19.一种根据权利要求18的方法，其特征在于，所述透明涂层构成多层漆系统中的一层。
20.一种根据权利要求12的方法，其特征在于，该方法应用于汽车或大型运输车辆的涂饰或再涂饰。
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- 2004-02-04 JP JP2006501779A patent/JP2006520679A/ja active Pending
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- 2004-02-04 KR KR1020057014258A patent/KR101056491B1/ko not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| US20060108450A1 (en) | 2006-05-25 |
| EP1592522B1 (en) | 2006-06-21 |
| RU2332265C2 (ru) | 2008-08-27 |
| AU2004210096A1 (en) | 2004-08-19 |
| ATE330712T1 (de) | 2006-07-15 |
| DE602004001336D1 (de) | 2006-08-03 |
| WO2004069427A1 (en) | 2004-08-19 |
| BRPI0407273A (pt) | 2006-01-31 |
| CN1747796A (zh) | 2006-03-15 |
| EP1592522A1 (en) | 2005-11-09 |
| KR20050095885A (ko) | 2005-10-04 |
| DE602004001336T2 (de) | 2007-02-01 |
| RU2005127779A (ru) | 2006-01-27 |
| JP2006520679A (ja) | 2006-09-14 |
| KR101056491B1 (ko) | 2011-08-11 |
| ZA200507117B (en) | 2006-05-31 |
| AU2004210096B2 (en) | 2009-04-02 |
| ES2267042T3 (es) | 2007-03-01 |
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