CN103443209A - 用于金属的可辐射固化涂料组合物 - Google Patents

用于金属的可辐射固化涂料组合物 Download PDF

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CN103443209A
CN103443209A CN2011800623098A CN201180062309A CN103443209A CN 103443209 A CN103443209 A CN 103443209A CN 2011800623098 A CN2011800623098 A CN 2011800623098A CN 201180062309 A CN201180062309 A CN 201180062309A CN 103443209 A CN103443209 A CN 103443209A
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CN103443209B (zh
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G·P·克劳恩
K·J·加德纳
P·米勒
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Akzo Nobel Coatings International BV
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Abstract

本发明提供可辐射固化涂料组合物的各个实施方案。在一个实施方案中，可辐射固化涂料组合物包含(甲基)丙烯酸酯官能化合物和增粘(甲基)丙烯酸酯化合物。所述可辐射固化涂料组合物还可包含(甲基)丙烯酸酯官能化合物、聚(甲基)丙烯酸酯和反应性稀释剂。所述(甲基)丙烯酸酯官能化合物可由多官能异氰酸酯、多元醇和羟基官能(甲基)丙烯酸酯在催化剂的存在下反应而制备。

Description

用于金属的可辐射固化涂料组合物
发明背景
本公开内容涉及可提供有用的涂层和包装材料如金属罐的涂覆表面的可辐射固化涂料组合物。目前可得的可辐射固化涂料如通过紫外线(“UV”)辐射或电子束辐射(“EB”)固化的那些倾向于为不可挠曲的固化涂层，其倾向于更高的收缩水平。因此，迄今本领域技术人员认识到使用这种固化化学的涂料在直接金属粘合性、可成形性和耐干馏性方面是不合适的，以及在挠性包装工业内的粘合性和延展性方面的应用中受限。解决这些顾虑的尝试可导致依赖于如下方面的缺点：(1)在引发辐射固化以前需要高温闪蒸的方法，如在聚氨酯分散体(“PUD”)中，(2)阳离子化学，其遭遇固化的湿度抑制、光引发剂和目前由于供应问题导致的高成本的缺点，(3)高温烘烤、后辐射固化的应用，和/或底涂层的应用以赋予粘合性，和/或(4)依赖于常规溶剂和水基热固性化学，其回归至释放挥发性有机化合物(“VOC”)、BADGE/NOGE结构部分的缺点。因此，解决这些问题中的一个或多个，同时还省去辐射固化涂料化学中的这些缺点中的一个或多个的任何组合物会提供一个或多个使用优点，同时积极影响安全性、健康和环境考虑。
尽管增粘剂是本领域中已知的，令人惊讶的是，比供应商文献或其它公开信息中常用的更高的这些化合物含量提供粘合性的显著改进并且不导致固化涂层抗发白性的严重问题。较高含量尤其用于不经预处理的“仅清洁的”金属基材和无铬基材上。
发明概述
本发明涵盖包含(甲基)丙烯酸酯官能化合物和增粘(甲基)丙烯酸酯化合物的可辐射固化涂料组合物以及包含(甲基)丙烯酸酯官能化合物、聚(甲基)丙烯酸酯和反应性稀释剂的可辐射固化涂料组合物。本发明还涵盖包含金属基材和置于基材上的可辐射固化涂料组合物的包装。
另外，本发明涵盖涂覆包装的方法，所述方法包括：a)制备如本文所述的可辐射固化涂料组合物；和b)将涂料组合物施涂于包装上。发现本发明可辐射固化涂层是硬的、挠性的，并显示出在金属基材上的良好粘合性。本发明涂膜可以最小的白化和最小的粘合性损失经得住干馏条件。
发明详述
本发明涵盖包含(甲基)丙烯酸酯官能化合物和增粘(甲基)丙烯酸酯化合物的可辐射固化涂料组合物以及包含(甲基)丙烯酸酯官能化合物、聚(甲基)丙烯酸酯和反应性稀释剂的可辐射固化涂料组合物。作为非限制性实例，(甲基)丙烯酸酯官能化合物可由多官能异氰酸酯、多元醇和羟基官能(甲基)丙烯酸酯在催化剂的存在下反应而制备。所述(甲基)丙烯酸酯官能化合物和增粘(甲基)丙烯酸酯化合物各自可为单体、低聚物或其组合，提及单体，应当理解包括低聚物，反之亦然。
在一些实施方案中，所述(甲基)丙烯酸酯官能化合物以至多约50重量%涂料组合物的量存在。所述(甲基)丙烯酸酯官能化合物可由本领域中已知的各种材料制备，例如而不限于(甲基)丙烯酸酯官能聚酯、(甲基)丙烯酸酯官能聚丙烯酸酯、(甲基)丙烯酸酯官能聚醚、(甲基)丙烯酸酯官能聚碳酸酯、油多元醇醚、(甲基)丙烯酸酯官能氨基甲酸酯、WO2008/151286(通过引用将其内容并入本文中)的(甲基)丙烯酸酯官能化合物或其组合。一种可能的(甲基)丙烯酸酯官能化合物为氨基甲酸酯，其容易地但不仅仅由多官能异氰酸酯、多元醇和羟基官能(甲基)丙烯酸酯在催化剂的存在下反应而制备。
作为非限制性实例，所述增粘(甲基)丙烯酸酯化合物可为磷酸酯(甲基)丙烯酸系官能单体、羧酸酯(甲基)丙烯酸系官能单体、磷酸酯(甲基)丙烯酸系官能低聚物、羧酸酯(甲基)丙烯酸系官能低聚物或其组合。在一些实施方案中，所述磷酸酯(甲基)丙烯酸系官能单体可包括甲基丙烯酸的磷酸酯或羟基官能酯。羧酸酯(甲基)丙烯酸系官能单体/低聚物可包括而不限于羧酸官能酯、羧酸官能醚及其组合。在本发明的某些实施方案中，所述磷酸酯(甲基)丙烯酸系官能单体/低聚物可以以至多约12重量%涂料组合物的量存在。所述羧酸酯(甲基)丙烯酸系官能单体/低聚物可以以约0.5-约50重量%涂料组合物的量存在。
所述增粘(甲基)丙烯酸酯化合物可以以至多约65重量%总涂料组合物成膜组分的量存在。
在本发明一些实施方案中，聚(甲基)丙烯酸酯以至多约25重量%涂料组合物或约5-约15重量%的量存在。聚(甲基)丙烯酸酯可包括而不限于三环癸基二甲醇二丙烯酸酯、二丙二醇二丙烯酸酯等，及其组合。
所述反应性稀释剂可以以至多约95重量%涂料组合物或约20-约60重量%的量存在。反应性稀释剂可包括而不限于单(甲基)丙烯酸酯。
用于本发明中的多官能异氰酸酯包括但不限于异氰酸酯、二异氰酸酯、多异氰酸酯、脂族异氰酸酯、芳族异氰酸酯、二-六亚甲基、聚六亚甲基、己烷二异氰酸酯、异佛尔酮(isophorane)、MDI及其组合。
用于本发明中的多元醇包括但不限于聚酯、二醇、醇、聚碳酸酯、聚丙二醇、聚乙二醇、聚氧化四亚甲基及其组合。在本发明一些实施方案中，所述多元醇具有约100-约10,000或约500-约5000的分子量。
合适的羟基官能(甲基)丙烯酸酯包括但不限于羟基单体、(甲基)丙烯酸4-羟基丁酯、丁二醇单(甲基)丙烯酸酯、(甲基)丙烯酸羟基丙酯、(甲基)丙烯酸羟基乙酯、增链(甲基)丙烯酸羟基酯、聚己酸内酯(甲基)丙烯酸酯及其组合。所述羟基官能(甲基)丙烯酸酯的量可基于(甲基)丙烯酸酯官能化合物的重量为约5-约95重量%，在其它实例中，基于(甲基)丙烯酸酯官能化合物的重量为约25-约75重量%。
在本发明一些实施方案中，多官能异氰酸酯/多元醇/羟基官能(甲基)丙烯酸酯的摩尔比为约1/0.1-2/0.2-5、约1/0.25-0.75/0.5-2.5或约1/0.5/2。基于重量，该比可为约1-约75%的多官能异氰酸酯:至多约90%的多元醇:约1-约99%的羟基官能(甲基)丙烯酸酯。在一些实施方案中，羟基官能度相对于异氰酸酯官能度稍微过量，其允许反应进行至至少99%的多官能异氰酸酯转化率。
其它羟基官能材料可与羟基官能(甲基)丙烯酸酯一起包含在内。其它羟基官能材料可包括但不限于醇、二醇、多元醇、聚酯、聚醚(作为非限制性实例，例如苄醇、三羟甲基丙烷、聚丙二醇、己二醇)及其组合。
所述催化剂可为适于聚合的催化剂，例如而不限于锡催化剂如二月桂酸二丁基锡或氧化二丁基锡、锆催化剂如丙酸锆、铋催化剂如新癸酸铋、叔胺催化剂如三亚乙基二胺或其组合。催化剂的量可为约1-约10,000ppm、约10-约1,000ppm或约20-约200ppm。通常方便的是使用在有机溶剂中的溶液形式的催化剂。合适溶剂的实例包括而不限于芳族烃溶剂、脂环族极性溶剂(例如脂环族酮，包括环己酮)、极性脂族溶剂(例如烷氧基链烷醇，包括2-甲氧基乙烷)、所述二醇原料及其组合。
空气气氛和有效的抑制剂如甲氧基氢醌、氢醌、二叔丁基氢醌、丁基化羟基甲苯、吩噻嗪或其组合可用于防止所述羟基官能(甲基)丙烯酸酯单体/低聚物的自由基聚合。抑制剂可以以约10-约10,000ppm的量存在。所述多官能异氰酸酯、多元醇和羟基官能(甲基)丙烯酸酯的反应可在约环境温度至约70℃或约110℃，在其它实例中，约90-约100℃的温度下进行。通常，至少90%转化率，在一些实施方案中至少99%的异氰酸酯基团转化率可在90℃下在约1小时内得到。另外，可在反应期间加入稀释剂以降低粘度，作为非限制性实例，例如自由基反应性物种，例如(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸叔丁基环己基酯、三环癸基二甲醇二(甲基)丙烯酸或其组合。稀释剂可以以至多约75%或更多的总批料重量的量存在。
本发明的各个实施方案提供当用低能固化如电子束固化固化时，基本不含BADGE和NOGE的辐射固化涂料组合物。本文所述各种辐射固化涂料组合物具有改进的挠性，且例如比具有其它(甲基)丙烯酸酯涂料的涂层更具挠性。本发明涂料组合物还可提供根据已知用于刚性包装应用的最常用干馏试验的刚性包装应用的耐干馏性。本发明的可固化涂料组合物可不需要底涂层而使用以直接接触金属基材。所述涂料组合物可以以本领域技术人员已知的任何方式施涂于基材上。
给出以下实施例以阐述所述体系和方法，且不应当理解为对其范围或精神的限制。
实施例
实施例1
氨基甲酸酯低聚物的制备
在1升烧瓶中将99g的Bayer N-3900与200g聚丙二醇2000、153g丙烯酸异冰片酯、57.6g丙烯酸4-羟基丁酯和0.15g吩噻嗪混合。将混合物置于在空气保护下的90℃热水浴中并搅拌。向所得混合物中加入0.5ml的二月桂酸二丁基锡的10%甲乙酮溶液。将所得混合物保持2小时，然后冷却。
实施例2
在搅拌下加入以下成分，同时在中速搅拌下进行混合操作。将最终涂料划涂在金属基材上并在3兆拉德/90千伏最小设置的电子束下固化。
Figure BDA00003393035000051
*评定0-5，5=优异
**白化评定：5-无白化，4-非常轻微，3-轻微，2-白化，1和0-失效。

Claims (20)

1.一种可辐射固化涂料组合物，其包含(甲基)丙烯酸酯官能化合物和增粘(甲基)丙烯酸酯化合物。
2.根据权利要求1的涂料组合物，其中所述增粘(甲基)丙烯酸酯化合物包括磷酸酯(甲基)丙烯酸系官能单体、羧酸酯(甲基)丙烯酸系官能单体、磷酸酯(甲基)丙烯酸系官能低聚物、羧酸酯(甲基)丙烯酸系官能低聚物或其组合。
3.根据权利要求1的涂料组合物，其中所述增粘(甲基)丙烯酸酯化合物以约2-约40重量%的量存在。
4.根据权利要求1的涂料组合物，其中所述(甲基)丙烯酸酯官能化合物以约0.5-约45重量%所述涂料组合物的量存在。
5.根据权利要求1的涂料组合物，其中所述(甲基)丙烯酸酯官能化合物包括(甲基)丙烯酸酯官能聚酯、(甲基)丙烯酸酯官能聚丙烯酸酯、(甲基)丙烯酸酯官能聚醚、(甲基)丙烯酸酯官能聚碳酸酯、油多元醇醚、(甲基)丙烯酸酯官能氨基甲酸酯或其组合。
6.根据权利要求5的涂料组合物，其中所述磷酸酯(甲基)丙烯酸系官能化合物为(甲基)丙烯酸的磷酸酯。
7.根据权利要求5的涂料组合物，其中所述羧酸酯(甲基)丙烯酸系官能化合物为羧酸官能(甲基)丙烯酸酯、羧酸官能(甲基)丙烯酸酯醚或其组合。
8.根据权利要求5的涂料组合物，其中所述磷酸酯(甲基)丙烯酸系官能化合物以至多约12重量%的涂料组合物的量存在。
9.根据权利要求5的涂料组合物，其中所述羧酸酯(甲基)丙烯酸系官能化合物以约0.5-约50重量%的涂料组合物的量存在。
10.根据权利要求1的涂料组合物，其中所述(甲基)丙烯酸酯官能化合物由多官能异氰酸酯、多元醇和羟基官能(甲基)丙烯酸酯在催化剂的存在下反应而制备。
11.根据权利要求8的涂料组合物，其中多官能异氰酸酯/多元醇/羟基官能(甲基)丙烯酸酯的摩尔比为约1/0.1-2/0.2-5。
12.根据权利要求10的涂料组合物，其中所述羟基官能(甲基)丙烯酸酯包括羟基单体、(甲基)丙烯酸4-羟基丁基酯、丁二醇单(甲基)丙烯酸酯、(甲基)丙烯酸羟基丙基酯、(甲基)丙烯酸羟基乙基酯、增链(甲基)丙烯酸羟基酯、聚己酸内酯(甲基)丙烯酸酯或其组合。
13.根据权利要求10的涂料组合物，其中所述多官能异氰酸酯包括异氰酸酯、二异氰酸酯、多异氰酸酯、脂族异氰酸酯、芳族异氰酸酯、二-六亚甲基、聚六亚甲基、己烷二异氰酸酯、异佛尔酮、MDI或其组合。
14.根据权利要求10的涂料组合物，其中所述多元醇包括聚酯、二醇、醇、聚碳酸酯、聚丙二醇、聚乙二醇、聚氧化四亚甲基或其组合。
15.根据权利要求10的涂料组合物，其中所述催化剂包括锡催化剂、二月桂酸二丁基锡、氧化二丁基锡、锆催化剂、丙酸锆、铋催化剂、新癸酸铋、叔胺、三亚乙基二胺或其组合。
16.根据权利要求1的涂料组合物，其进一步包含至少一种多官能(甲基)丙烯酸酯。
17.一种包装，其包含：金属基材；和根据权利要求1的可辐射固化涂料组合物。
18.根据权利要求17的包装，其中所述可辐射固化涂料组合物直接接触金属基材而不具有底涂层。
19.一种涂覆包装的方法，其包括：
a)制备根据权利要求1的可辐射固化涂料组合物；和
b)将所述可辐射固化涂料组合物施涂于包装上。
20.根据权利要求19的方法，其中所述包装为金属基材。
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