CN107001856A - 辐射固化涂料组合物 - Google Patents

辐射固化涂料组合物 Download PDF

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CN107001856A
CN107001856A CN201580065570.1A CN201580065570A CN107001856A CN 107001856 A CN107001856 A CN 107001856A CN 201580065570 A CN201580065570 A CN 201580065570A CN 107001856 A CN107001856 A CN 107001856A
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V·茂林
P·凯利
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Perstorp AB
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Abstract

公开了一种UV固化涂料组合物，其包含：(a)40‑70重量％的至少一种氨基甲酸酯(甲基)丙烯酸酯，其是至少一种聚己内酯多元醇(a1)与至少一种加合物(a2)之间反应的产物，所述加合物(a2)是至少一种多异氰酸酯(a3)与至少一种(甲基)丙烯酸羟烷基酯(a4)之间反应的产物，所述聚己内酯多元醇(a1)是至少一种多烷氧基化多元醇(a5)与至少一种己内酯单体(a6)之间反应的产物，(b)20‑50重量％的至少一种反应性稀释剂，其具有至少一个烯属碳‑碳双键，和(c)0.5‑10重量％的至少一种光引发剂，和任选地(d)1‑15重量％的至少一种消光剂。

Description

辐射固化涂料组合物
本发明涉及UV固化涂料组合物，其包含：(a)至少一种氨基甲酸酯(甲基)丙烯酸酯，其是包含烷氧基单元的至少一种聚己内酯多元醇与至少一种多异氰酸酯和至少一种(甲基)丙烯酸羟烷基酯的至少一种加合物之间的反应产物，(b)至少一种反应性稀释剂，和(c)至少一种光引发剂，和任选地(d)至少一种消光剂。
本领域中已知获自聚己内酯和其他聚酯多元醇的包含氨基甲酸酯(甲基)丙烯酸酯的辐射固化涂料组合物。尽管是已知技术，但是本领域还没有公开具有良好的化学耐性、柔性和韧性的快速UV固化涂料组合物，其包含基于聚己内酯多元醇的氨基甲酸酯(甲基)丙烯酸酯，聚己内酯多元醇包含烷氧基例如乙氧基、丙氧基和/或丁氧基单元。本领域中已知的组合物的问题是，它们倾向于产生缺少挠曲性质的保护膜和/或装饰膜，尤其是当包含消光剂例如触觉消光剂，这预示着裂缝。所以，本发明的目标是提供涂料组合物，其产生保护膜和/或装饰膜，尤其是触觉膜，这些膜具有改进的挠曲性质，而不使硬度、耐性和其他必要性质劣化。
柔软感/触觉性质经常被描述为用于电子装置和汽车内部零件的高品质涂料的主要标准，不过在用于消费品和家具的许多其他应用也经常需要。塑料涂层是主要应用之一，但木材涂层和其他应用同样引起关注。触觉性质在多数情况中应当与高耐性尤其是对化学品(水、护手霜或驱虫剂)的高耐性相结合，并且表现出良好至优异的耐刮擦性。
作为创造性研究的成果，本发明人通过使用具有烷氧基单元的聚己内酯多元醇作为氨基甲酸酯(甲基)丙烯酸酯生产中的中间体，已经能够获得表现出良好至优异的硬度、柔性和耐性的软膜。
根据本发明的涂料组合物是UV固化涂料组合物，其包含：(a)40-70重量％，例如50-60重量％或40-50重量％的至少一种氨基甲酸酯(甲基)丙烯酸酯，(b)20-50％，例如30-40重量％或40-50重量％的具有至少一个烯属碳-碳双键的至少一种反应性稀释剂，和(c)0.5-10重量％，例如1-10重量％，2-8重量％或3-6重量％的至少一种光引发剂。在优选的实施方案中，所述氨基甲酸酯(甲基)丙烯酸酯(a)是在(a1)至少一种聚己内酯多元醇与(a3)至少一种多异氰酸酯和(a4)至少一种(甲基)丙烯酸羟烷基酯的(a2)至少一种加合物之间的反应中获得的产物。在同样优选的实施方案中，所述聚己内酯多元醇(a1)是在(a5)至少一种多烷氧基化多元醇与(a6)至少一种己内酯单体例如α-、β-、γ-、δ-或最优选地ε-己内酯之间的反应中获得的产物。
本发明的氨基甲酸酯(甲基)丙烯酸酯可以根据本领域中已知的获得氨基甲酸酯(甲基)丙烯酸酯的任何方法来生产，例如在50-70℃的温度，在抑制剂例如4-甲氧基醇、丁基化羟基甲苯、对苯二酚、2,6-二硝基-4-甲基酚或对羟基苯甲醚，催化剂例如辛酸亚锡、月桂酸二丁基锡或2-乙基己酸锡(II)，和溶剂例如甲苯、苯、二甲苯的存在下。
在一些优选的实施方案中，，本发明的涂料组合物另外包含：(d)基于所述组分(a)至(c)的小计计算的1-15重量％，例如1-10重量％或5-10重量％的至少一种消光剂，例如触觉消光剂。适合的消光剂可以例如但不限于聚酰胺例如聚酰胺6、聚酰胺11和/或聚酰胺12，微细的生物聚合物、合成的无定形和任选经表面处理的二氧化硅，微粒隐晶无定形二氧化硅、层状高岭土和/或无机改性的聚乙烯蜡分散体。
在优选的实施方案中，所述聚己内酯多元醇(a1)具有2-10例如3-7或5-6个己内酯单元/分子，低于-40℃例如低于-50℃或甚至低于-60℃的玻璃化转变温度(Tg)，和1000-6000例如1500-5000或2000-4000g/mol的分子量(Mw)。聚己内酯多元醇可以通过本领域中已知的任何方法来生产，其中在例如160-220℃如180-190℃的温度，在本领域中已知的催化剂例如羧酸锡如月桂酸锡(II)或支链或支链的辛酸锡(II)、月桂酸二丁基锡、乙酸二丁基锡、辛酸亚锡、异辛酸钾和/或异辛酸锌的存在下，己内酯单体和多元醇经过开环和缩合。所述多烷氧基化多元醇(a5)的优选实例包括但不限于具有1-30例如1-20或2-10个乙氧基、丙氧基和/或丁氧基单元/分子的多乙氧基化、多丙氧基化和/或多丁氧基化二醇、三醇和多元醇，并且可以适合地例示为多乙氧基化和/或多丙氧基化新戊二醇、甘油、二-甘油、三羟甲基乙烷、三羟甲基丙烷、三羟甲基丁烷、二-三羟甲基乙烷、二-三羟甲基丙烷、二-三羟甲基丁烷、季戊四醇和二-季戊四醇。
在优选的实施方案中，所述加合物(a2)以所述多异氰酸酯(a3)与所述(甲基)丙烯酸羟烷基酯(a4)1:0.8至1:1的摩尔比获得，并且在本领域中已知的获得异氰酸酯与不饱和化合物之间的加合物的任何方法中，例如在60-90℃的温度，在催化剂例如月桂酸锡(II)、直链或支链的辛酸锡(II)、月桂酸二丁基锡、乙酸二丁基锡、辛酸亚锡、异辛酸钾和/或异辛酸锌，和抑制剂例如4-甲氧基酚、丁基化羟基甲苯、对苯二酚、2,6-二硝基-4-甲基酚和/或对羟基苯甲醚的存在下的反应。在加合物(a2)的这些实例中，多异氰酸酯(a3)适合地是脂族或脂环族二异氰酸酯和/或三异氰酸酯例如但不限于六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、四氢呋喃二异氰酸酯、亚环己基二异氰酸酯和/或壬烷三异氰酸酯，和/或NCO-官能的二聚体、三聚体和它们的或与它们的聚合物例如缩二脲、异氰尿酸酯和脲基甲酸酯。当然也可以使用芳族的和不饱和的多异氰酸酯例如甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、二甲苯二异氰酸酯、萘二异氰酸酯、亚苯基二异氰酸酯、三苯基甲烷三异氰酸酯和/或呋喃二异氰酸酯，和/或NCO-官能的二聚体、三聚体和它们的或与它们的聚合物。在加合物(a2)的这些实例中，(甲基)丙烯酸羟烷基酯(a4)优选地和适合地是但不限于(甲基)丙烯酸羟乙基酯、(甲基)丙烯酸羟丙基酯、三羟甲基乙烷二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丁烷二(甲基)丙烯酸酯和/或季戊四醇三(甲基)丙烯酸酯。当然也可以使用巴豆酸酯(甲基丙烯酸酯)。
所述具有至少一个烯属双键的反应性稀释剂(b)的实例包括但不限于，例如单、二或多不饱和的物类如(甲基)丙烯酸酯类、(甲基)丙烯酸乙烯酯类、(甲基)丙烯酸(甲基)烯丙基酯类、聚酯(甲基)丙烯酸酯类、环氧(甲基)丙烯酸酯类、氨基甲酸酯(甲基)丙烯酸酯类和三聚氰胺(甲基)丙烯酸酯类或者相应的巴豆酸酯。所述反应性稀释剂适合地选自2-烷基-1,3-丙二醇、2,2-二烷基-1,3-丙二醇、2-烷基-2-羟烷基-1,3-丙二醇、2,2-二羟烷基-1,3-丙二醇、多烷氧基化2-烷基-1,3-丙二醇、多烷氧基化2,2-二烷基-1,3-丙二醇、多烷氧基化2-烷基-2-羟烷基-1,3-丙二醇和多烷氧基化2,2-二羟烷基-1,3-丙二醇的(甲基)丙烯酸酯类，其中烷基是C1-C8直链或支链的烷基，和多烷氧基化是多乙氧基化、多丙氧基化和/或多丁氧基化，具有1-30个烷氧基。所述反应性稀释剂(b)可以进一步例示但不限于(甲基)丙烯酸异冰片基酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯和三羟甲基丙烷三(甲基)丙烯酸酯。
在实施方案中，所述光引发剂(c)适合地选自苯偶姻及其衍生物例如苯偶姻醚，苯乙酮及其衍生物例如2,2-二乙酰氧基苯乙酮、1,1-二甲氧基-1-羟基苯乙酮、二苯甲酮及其衍生物、噻吨酮及其衍生物、蒽醌、芳酰基脂环族醇例如1-苯甲酰基环己醇、有机磷化合物例如酰基膦氧化物、酰基膦和氨基烷基苯基酮。
根据本发明的涂料组合物的进一步的实例还包括至少一种颜料、填料和/或染料和/或包含本领域中常规使用的添加剂的添加剂包，添加剂包括但不限于流动/流平剂，流变剂例如热解二氧化硅，包含脲基并且由胺和多异氰酸酯制备的反应产物(所谓的“流挂控制剂”)、抑制过早的自由基聚合的抑制剂，热自由基抑制剂，催化剂，UV-吸收剂，抗氧化剂，聚合物微粒例如二氧化硅微凝胶和/或纳米颗粒。
在另一方面中，本发明涉及本文公开的涂料组合物的用途，用于获得包含所述组分(a)至(c)的装饰性面漆和/或保护性面漆，或者包含组分(a)至(d)的触觉装饰性面漆和/或触觉保护性面漆。触觉性质仅能使用正确的消光剂来获得。但是，粘合剂性质对于确保消光剂良好的流动性和分布来说至关重要。所以，本发明的涂料组合物所获得的柔性、粘度和反应性是至关重要的。
不必进一步详细描述，据信本领域技术人员能够使用之前的描述来最大程度地利用本发明。所以，以下优选的具体实施方案被解释为仅为示例，无论如何不以任何方式为限制性。在下面，实施例1和2例示由化合物(a5)和(a6)的实例制备实例聚己内酯多元醇(a1)，来自化合物(a3)和(a4)的实例的实例加合物(a2)，实施例3例示由在实施例1和2中制备的实例化合物(a1)和(a2)制备实例聚氨酯丙烯酸酯(a)。实施例4涉及包含在实施例1-3中制备的实例组分(a)至(c)的根据本发明的实施方案的涂料组合物的制备和评价。实施例5提供了根据本发明的实施方案的涂料组合物与类似涂料组合物之间的比较，在类似涂料组合物中在实例聚氨酯丙烯酸酯(a)的制备中用作中间体的己内酯伸长的烷氧基化物结构(a1)被非烷氧基化结构代替。实施例6涉及包含在实施例1-3中制备的实例组分(a)至(c)并添加消光剂(d)的根据本发明的实施方案的涂料组合物的制备和评价。
实施例1
通过使ε-己内酯与烷氧基化三羟甲基丙烷Polyol 3165TM、Polyol 3380TM(瑞典Perstorp AB)之一或者丙氧基化新戊二醇Polyol R2490TM(瑞典Perstorp AB)反应(开环和缩合)来生产聚己内酯多元醇，具有以下性质：
Polyol 3165 3380 R2490
羟基官能度 3 3 2
羟值(mg KOH/g) 165±25 380±25 485±25
分子量(g/mol) 1010 440 220
乙氧基单元/分子 20 7 ---
丙氧基单元/分子 --- 2
以获得具有以下性质的聚己内酯多元醇的摩尔比：
己内酯多元醇 1 2 3 4 5
己内酯单元/分子 2.6 5.2 3.9 6.1 6.8
计算分子量(g/mol) 2010 3022 1957 2826 1993
酸值(mg KOH/g) 0.10 0.09 0.09 0.06 0.14
羟值(mg KOH/g) 84 56 86 60 56
着色(雾化) 287 157 117 45 162
60℃的粘度(mPas) 214 429 296 620 450
Tg-DSC(℃) -67 -64 -65 -63 -66
熔点(℃) 31 37 34 41 45
反应在180-190℃，在作为催化剂的羧酸锡存在下进行，并且由剩余ε-己内酯的GC测定来监控。当剩余ε-己内酯的量接近零时，结束反应。
实施例2
在65-70℃，使用4-甲氧基酚作为抑制剂和月桂酸二丁基锡作为催化剂，以异佛尔酮二异氰酸酯与2-羟乙基丙烯酸酯1.0:0.95的摩尔比，生产所述二异氰酸酯与所述丙烯酸酯之间的加合物。
实施例3
通过使在实施例1中获得的聚己内酯多元醇与在实施例2中获得的加合物以羟基与异氰酸酯基1.0:0.9的摩尔比来反应，生产聚氨酯丙烯酸酯。反应在60℃，使用丁基化羟基甲苯作为抑制剂，月桂酸二丁基锡作为催化剂，和甲苯作为溶剂来进行。通过分析NCO-含量来监控反应，当NCO-值接近零时停止反应。获得具有以下性质的产物：
聚氨酯丙烯酸酯 A B C D E
使用的聚己内酯多元醇 1 2 3 4 5
计算分子量(g/mol) 10600 16500 10800 15200 10600
C＝C浓度(meq/g) 1.07 0.81 1.07 0.82 0.66
25℃的粘度(Pas) 260 320 470 450 固体
70℃的粘度(Pas) 7 11 9 11 7
由DSC测得的Tg(℃) -39 -48 -35 -46 -50
-C＝C浓度：使用FTIR光谱测定。
-由DSC测得的Tg(玻璃化转变温度)：在Mettler DSC上测定。在40μL铝盘中分析10mg样品。温度为-100至+120℃。升温速率10℃/分钟。
实施例4
通过混合44.8重量份在实施例3中获得的聚氨酯丙烯酸酯A、B、C或D，49.7重量份作为反应性稀释剂的三丙二醇二丙烯酸酯和5.5重量份作为光引发剂的1173(BASF AG)，来制备UV固化涂料。使用K棒将获得的涂料涂覆在玻璃和铝面板上，获得具有30-40μm厚度的湿膜。H蒸气灯(Fusion F600，最大240 W/cm)下，以5-6J/cm2的UV剂量进行固化。固化膜表现出以下性质：
-MEK(甲乙酮)双摩擦：根据ASTM D4752评价。
-丙酮点滴试验：根据SS 839118评价。
-由DMA测得的Tg(℃最大E")：使用张力模式的Mettler DMA，在-100至150℃(升温速率3℃/分钟)的温度范围下测定。振幅和频率分别等于15μm和1Hz。测试每个样品的三个试样，记录平均值。
实施例5
通过混合44.8重量份在实施例3中获得的聚氨酯丙烯酸酯C或44.8重量份的聚氨酯丙烯酸酯(其中聚己内酯多元醇中使用的多烷氧基化三羟甲基丙烷(Polyol 3380TM)被非烷氧基化三羟甲基丙烷代替)，49.7重量份作为反应性稀释剂的二丙二醇二丙烯酸酯，和5.5重量份作为光引发剂的1173(BASF AG)，来制备UV固化涂料。将获得的涂料涂覆在玻璃和铝面板上，并如实施例4中一样固化。固化膜表现出以下性质：
-MEK(甲乙酮)双摩擦：根据ASTM D4752评价。
-丙酮点滴试验：根据SS 839118评价。
-由DMA测得的Tg(℃最大E")和E'：使用张力模式的Mettler DMA，在-100至150℃(升温速率3℃/分钟)的温度范围下测定。振幅和频率分别等于15μm和1Hz。测试每个样品的三个试样，记录平均值。
-Mc∝(3ρRT)/E'，其中E'橡胶态高弹区上的储能模量(J·m-3)，ρ是T时的材料密度(kg·m3)，R是气体常数(8,314J·mol-1·K-1)，和T是橡胶态高弹区的温度(K)。
实施例6
通过混合在实施例3中获得的44.8重量份的聚氨酯丙烯酸酯A或C或者44.8重量份的聚氨酯丙烯酸酯C和E的60/40(重量)混合物，49.7重量份作为反应性稀释剂的二丙二醇二丙烯酸酯，和5.5重量份作为光引发剂的1173(BASF AG)，来制备UV固化涂料。将 UV RS20(无机改性的聚乙烯蜡分散体，Deuteron GmbH)或2001UD NAT1(聚酰胺12，法国Arkema)作为消光剂，以按获得的组合物计10重量％的量添加到所述组合物中。将获得的涂料如实施例4中涂覆到玻璃和铝面板上。固化膜表现出以下性质：
-MEK(甲乙酮)双摩擦：根据ASTM D4752评价。
-丙酮点滴试验：根据SS 839118评价。

Claims (21)

1.涂料组合物，其特征在于所述涂料组合物是UV固化涂料组合物，包含：(a)40-70重量％的至少一种氨基甲酸酯(甲基)丙烯酸酯，其是至少一种聚己内酯多元醇(a1)与至少一种加合物(a2)之间反应的产物，所述加合物(a2)是至少一种多异氰酸酯(a3)与至少一种(甲基)丙烯酸羟烷基酯(a4)之间反应的产物，其中所述聚己内酯多元醇(a1)是至少一种多烷氧基化多元醇(a5)与至少一种己内酯单体(a6)之间反应的产物，(b)20-50重量％的至少一种反应性稀释剂，其具有至少一个烯属碳-碳双键，和(c)0.5-10重量％的至少一种光引发剂。
2.根据权利要求1所述的涂料组合物，其特征在于其还包含：(d)基于所述组分(a)至(c)的小计计算1-15重量％的至少一种消光剂。
3.根据权利要求2所述的涂料组合物，其特征在于所述消光剂(d)是触觉消光剂。
4.根据权利要求2或3所述的涂料组合物，其特征在于所述消光剂(d)是聚酰胺、微细的生物聚合物、合成的无定形和任选经表面处理的二氧化硅、微粒隐晶无定形二氧化硅、层状高岭土和/或无机改性的聚乙烯蜡分散体。
5.根据权利要求1-4中任一项所述的涂料组合物，其特征在于所述聚己内酯多元醇(a1)具有2-10个己内酯单元/分子。
6.根据权利要求1-5中任一项所述的涂料组合物，其特征在于所述聚己内酯多元醇(a1)具有低于-40℃的玻璃化转变温度(Tg)。
7.根据权利要求1-6中任一项所述的涂料组合物，其特征在于所述聚己内酯多元醇(a1)具有1000-6000g/mol的分子量(Mw)。
8.根据权利要求1-7中任一项所述的涂料组合物，其特征在于所述加合物(a2)以多异氰酸酯(a3)与(甲基)丙烯酸羟烷基酯(a4)1:0.8至1:1的摩尔比获得。
9.根据权利要求1-8中任一项所述的涂料组合物，其特征在于所述多异氰酸酯(a3)是脂族或脂环族的二或三异氰酸酯和/或NCO-官能的二聚体、三聚体或者它们的或与它们的聚合物。
10.根据权利要求1-9中任一项所述的涂料组合物，其特征在于所述多异氰酸酯(a3)是六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、四氢呋喃二异氰酸酯、亚环己基二异氰酸酯和/或壬烷三异氰酸酯，和/或NCO-官能的二聚体、三聚体或者它们的或与它们的聚合物。
11.根据权利要求1-10中任一项所述的涂料组合物，其特征在于所述(甲基)丙烯酸羟烷基酯(a4)是(甲基)丙烯酸羟乙基酯、(甲基)丙烯酸羟丙基酯、三羟甲基乙烷二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丁烷二(甲基)丙烯酸酯和/或季戊四醇三(甲基)丙烯酸酯。
12.根据权利要求1-11中任一项所述的涂料组合物，其特征在于所述多烷氧基化多元醇(a5)是多乙氧基化、多丙氧基化和/或多丁氧基化二醇或三醇，其具有1-30个乙氧基、丙氧基和/或丁氧基单元/分子。
13.根据权利要求1-12中任一项所述的涂料组合物，其特征在于所述多烷氧基化多元醇(a5)是多乙氧基化和/或多丙氧基化新戊二醇、甘油、三羟甲基乙烷、三羟甲基丙烷或三羟甲基丁烷。
14.根据权利要求1-13中任一项所述的涂料组合物，其特征在于所述己内酯单体(a6)是ε-己内酯。
15.根据权利要求1-14中任一项所述的涂料组合物，其特征在于所述反应性稀释剂(b)是至少一种(甲基)丙烯酸烷基酯、(甲基)丙烯酸乙烯酯、(甲基)丙烯酸(甲基)烯丙基酯、聚酯(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯和/或三聚氰胺(甲基)丙烯酸酯。
16.根据权利要求1-15中任一项所述的涂料组合物，其特征在于所述反应性稀释剂(b)是(甲基)丙烯酸异冰片基酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯和/或三羟甲基丙烷三(甲基)丙烯酸酯。
17.根据权利要求1-16中任一项所述的涂料组合物，其特征在于所述光引发剂(c)是苯偶姻醚、酰基膦、苯乙酮、氨基烷基苯基酮、二苯甲酮和/或蒽醌。
18.根据权利要求1-17中任一项所述的涂料组合物，其特征在于其还包含至少一种颜料、填料和/或染料。
19.根据权利要求1-18中任一项所述的涂料组合物，其特征在于其还包含至少一种UV稳定剂、流动/流平剂、流变剂、抑制剂和/或UV吸收剂。
20.根据权利要求1-19中任一项所述的涂料组合物的用途，用于获得装饰性面漆和/或保护性面漆。
21.根据权利要求3-19中任一项所述的涂料组合物的用途，用于获得触觉装饰性面漆和/或触觉保护性面漆。
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