CN103380181A - 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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CN103380181A
CN103380181A CN2011800609419A CN201180060941A CN103380181A CN 103380181 A CN103380181 A CN 103380181A CN 2011800609419 A CN2011800609419 A CN 2011800609419A CN 201180060941 A CN201180060941 A CN 201180060941A CN 103380181 A CN103380181 A CN 103380181A
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coating composition
acrylate
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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

提供了可辐射固化的涂料组合物的各实施方案。在一个实施方案中，可辐射固化的涂料组合物包含(甲基)丙烯酸酯官能化合物和增粘(甲基)丙烯酸酯化合物。所述可辐射固化的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、多元醇和羟基官能的(甲基)丙烯酸酯在催化剂存在下的反应制备。

Description

用于金属的可辐射固化涂料组合物
发明背景
本发明涉及可辐射固化的涂料组合物，其可提供可用于包装材料如金属罐的涂层和经涂覆的表面。目前可得的可辐射固化的涂料，如通过紫外(UV)辐射或电子束(EB)辐射固化的那些存在非柔性固化涂层的倾向，其容易发生较高水平的收缩。因此，利用用于该固化的化学机理的涂料此前被本领域技术人员认为就与金属的直接粘合性、成形性和抗蒸馏性而言是不够的，且就粘合性和延展性而言在柔性包装工业中具有有限的应用。为解决这些关注所作的尝试可导致依赖于如下方面的缺点：(1)正如在聚氨酯分散体(PUD)中的那样，需要在引发辐射固化之前进行高温闪蒸的工艺；(2)阳离子化学机理，其具有固化、光引发剂的湿度抑制，以及由于供应问题所导致的目前的高成本；(3)使用高温烘烤、后辐射固化和/或施加底涂层以赋予粘合性；和/或(4)依赖于常规溶剂和水基热固化化学体系，这倒退至释放出挥发性有机化合物(VOC)的缺点，BADGE/NOGE结构部分。因此，解决辐射固化涂料化学中的一个或多个这些问题且同时还不具有一个或多个这些缺点的任何组合物均应提供一个或多个应用益处，同时对所关注的安全、健康和环境产生正面影响。
尽管增粘剂是本领域所已知的，但是令人惊讶的是，比供应商文献或其他公开信息中通常所用的更高水平的这些化合物提供了粘合性的该显著改善，且不导致固化的涂层发生严重的耐发白性问题。该更高水平尤其可用于未经预处理的“仅清洁”的金属基材和无铬基材。
发明简述
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的涂料组合物，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的涂料组合物。本发明还涵盖包装，其包括：金属基材以及置于所述基材上的可辐射固化的涂料组合物。
此外，本发明还涵盖涂覆包装的方法，包括：a)制备本文所述的可辐射固化的涂料组合物；和b)将所述涂料组合物施加至所述包装上。已发现本发明的可辐射固化的涂料组合物是硬质的、柔性的且显示出对金属基材的良好粘合性。本发明的涂膜可在发生最低发白和最低粘合性损失下经受蒸馏条件。
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的涂料组合物，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的涂料组合物。作为非限制性实例，所述(甲基)丙烯酸酯官能化合物可由单官能异氰酸酯、多元醇和羟基官能的(甲基)丙烯酸酯在催化剂存在下的反应制备。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，且措辞“单体”应理解为涵盖低聚物，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占所述涂料组合物的至多约50重量%的量存在。所述(甲基)丙烯酸酯官能化合物可由本领域所已知的不同物质制备，例如但不限于(甲基)丙酸酯官能的聚酯、(甲基)丙酸酯官能的聚丙烯酸酯、(甲基)丙酸酯官能的聚醚、(甲基)丙酸酯官能的聚碳酸酯、油多元醇醚、(甲基)丙烯酸酯官能的氨基甲酸酯、WO2008/151286(其内容通过引用并入本文)的(甲基)丙酸酯官能的化合物或其组合。一种可能的(甲基)丙酸酯官能化合物为氨基甲酸酯，其可由但并非仅由多官能异氰酸酯、多元醇和羟基官能的(甲基)丙烯酸酯在催化剂存在下的反应容易地制备。
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羟基官能酯的磷酸酯。所述羧酸酯(甲基)丙烯酸系官能单体/低聚物可包含而不限于羧酸官能的酯、羧酸官能的醚及其组合。在本发明的一些实施方案中，所述磷酸酯(甲基)丙烯酸系官能单体/低聚物可以以占所述涂料组合物的至多约12重量%的量存在。所述羧酸酯(甲基)丙烯酸系官能单体/低聚物可以以占所述涂料组合物的约0.5-约50重量%的量存在。
所述增粘(甲基)丙烯酸酯化合物可以以占总涂料组合物成膜组分的至多约65重量%的量存在。
在本发明的一些实施方案中，所述聚(甲基)丙烯酸酯以占所述涂料组合物的至多约25重量%或者约5-约15重量%的量存在。所述聚(甲基)丙烯酸酯可包含但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占所述涂料组合物的至多约95重量%或者约20-约60重量%的量存在。所述反应性稀释剂可包括但不限于单(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。在本发明的一些实施方案中，所述多元醇具有约100-约10,000或者约500-约5000的分子量。
合适的羟基官能的(甲基)丙烯酸酯包括但不限于羟基单体、(甲基)丙烯酸4-羟丁酯、丁二醇单(甲基)丙烯酸酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟乙酯、扩链的羟基(甲基)丙烯酸酯、聚己内酯(甲基)丙烯酸酯及其组合。所述羟基官能的(甲基)丙烯酸酯的量的范围可为约5-约95重量%，基于所述(甲基)丙烯酸酯官能化合物的重量，且在其他实例中为约25-约75重量%，基于所述(甲基)丙烯酸官能化合物的重量。
在本发明的一些实施方案中，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，所述比例可为约1-约75%多官能异氰酸酯对至多约90%多元醇对约1-约99%羟基官能的(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，这允许所述反应进行至至少99%的多官能异氰酸酯转化。
所述羟基官能的(甲基)丙烯酸酯中可包含额外的羟基官能物质。额外的羟基官能物质可包括但不限于醇、二醇、多元醇、聚酯、聚醚(作为非限制性的实例，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，例如但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。催化剂的用量可为约1-约10,000ppm，约10-约1,000ppm，或者约20-约200ppm。通常便利地使用呈处于有机溶剂中的溶液形式的催化剂。合适溶剂的实例包括但不限于芳族烃溶剂、脂环族极性溶剂(如脂环族酮，包括环己酮)、极性脂族溶剂(如烷氧基链烷醇，包括2-甲氧基乙醇)、二醇原料及其组合。
可使用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、丁基化的羟基甲苯、吩噻嗪或其组合以防止所述羟基官能(甲基)丙烯酸酯单体/低聚物的自由基聚合。所述抑制剂可以以约10-约10,000ppm的量存在。所述多官能异氰酸酯、多元醇与羟基官能(甲基)丙烯酸酯的反应可在大致环境温度至约70°C或者约110°C，在其他实例为约90-约100°C的温度下进行。通常，在约1小时和90°C下可获得至少90%，且在一些实施方案中至少99%的异氰酸酯基团转化率。此外，在反应期间可添加稀释剂以降低粘度，作为非限制性实例，其例如为自由基反应性物质如(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)丙烯酸酯或其组合。所述稀释剂可以以占总批料重量为至多约75%或更高的量存在。
本发明的各实施方案提供了辐射固化的涂料组合物，其基本上不含BADGE和NOGE，即使是在使用低能固化，如电子束固化而固化时。本文所述的各辐射固化的涂料组合物具有改善的柔性，且例如比使用其他(甲基)丙烯酸酯涂料的涂层更柔软。本发明的涂料组合物也可为硬质包装应用提供根据已知用于硬质包装应用的最常用蒸馏测试的耐蒸馏性。本发明的涂料组合物可在无需底涂层下使用，从而与金属表面直接接触。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加至基材上。
下文实施例出于阐述所述体系和方法的目的给出，且不应理解为对本发明范围和主旨的限制。
实施例
实施例1
制备氨基甲酸酯低聚物
在1升烧瓶中，将99g Bayer N-3900与200g聚丙二醇2000、153g丙烯酸异冰片酯、57.6g丙烯酸4-羟丁酯和0.15g吩噻嗪混合。在空气保护下，将所述混合物置于90°C的热水浴中并搅拌。向所得混合物中添加处于甲基乙基酮中的0.5ml10%二月桂酸二丁基锡溶液。将所得混合物保持2小时，然后冷却。
实施例2
在搅拌下添加下述成分，同时在中速搅拌下进行混合操作。将所述成品涂料拉至金属基材上并在电子束下以3兆拉德/90千伏的最低设置固化。
配制剂的重量百分比
*等级0-5，5=优异
**发白等级：5—不发白，4—非常轻微，3—轻微，2—发白，1和0—失败

Claims (16)

1.一种可辐射固化的涂料组合物，其包含(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。
2.根据权利要求1的涂料组合物，其中所述聚(甲基)丙烯酸酯以占所述涂料组合物的至多约20重量%的量存在。
3.根据权利要求1的涂料组合物，其中所述聚(甲基)丙烯酸酯包含三环癸基二甲醇二丙烯酸酯、二丙二醇二丙烯酸酯或其组合。
4.根据权利要求1的涂料组合物，其中所述反应性稀释剂以占所述涂料组合物的约20-约95重量%的量存在。
5.根据权利要求1的涂料组合物，其中所述反应性稀释剂包括单(甲基)丙烯酸酯。
6.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、多元醇和羟基官能的(甲基)丙烯酸酯在催化剂存在下的反应制备。
7.根据权利要求6的涂料组合物，其中多官能异氰酸酯/多元醇/羟基官能的(甲基)丙烯酸酯的摩尔比为约1/0.1-2/0.2-5。
8.根据权利要求6的涂料组合物，其中所述羟基官能的(甲基)丙烯酸酯包括羟基单体、(甲基)丙烯酸4-羟丁酯、丁二醇单(甲基)丙烯酸酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸羟乙酯、扩链的羟基(甲基)丙烯酸酯、聚己内酯(甲基)丙烯酸酯及其组合。
9.根据权利要求6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。
10.根据权利要求6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、聚氧化四亚甲基及其组合
11.根据权利要求6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。
12.根据权利要求1的涂料组合物，进一步包含至少一种多官能(甲基)丙烯酸酯。
13.一种包装，其包括金属基材和根据权利要求1的可辐射固化的涂料组合物。
14.根据权利要求13的包装，其中所述可辐射固化的涂料组合物不经底涂层而与直接金属基材接触。
15.一种涂覆包装的方法，其包括：
a)制备根据权利要求1的可辐射固化的涂料组合物；和
b)将所述可辐射固化的涂料组合物施加至所述包装上。
16.根据权利要求15的方法，其中所述包装为金属基材。
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