CN104136474B - 非水性液体涂料组合物 - Google Patents

非水性液体涂料组合物 Download PDF

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Publication number
CN104136474B
CN104136474B CN201380010851.8A CN201380010851A CN104136474B CN 104136474 B CN104136474 B CN 104136474B CN 201380010851 A CN201380010851 A CN 201380010851A CN 104136474 B CN104136474 B CN 104136474B
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coating composition
thiol
groups
mole
alkali
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CN104136474A (zh
Inventor
T·舍雷尔
贝伦 N·J·范
N·J·范贝伦
德尔 皮腾 A·J·范
A·J·范德尔皮腾
阿德里谢姆 A·A·J·M·范
A·A·J·M·范阿德里谢姆
D·E·布鲁因
M·加格利亚尔多
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Akzo Nobel Coatings International BV
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Akzo Nobel Coatings International BV
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings

Abstract

本发明涉及一种非水性液体涂料组合物，其包含：a)多元醇，b)多异氰酸酯交联剂，c)一种或多种硫醇官能化合物，d)用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂，e)具有的pKa值至少为7且不以降低碱性的方式与异氰酸酯基团反应的碱，以及f)一种或多种含酸基团化合物，其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为1或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中酸基团与碱基团的摩尔比为1:1或更高。

Description

非水性液体涂料组合物
本发明涉及一种非水性液体涂料组合物，其包含多元醇、多异氰酸酯交联剂、硫醇官能化合物、用于催化异氰酸酯基团与羟基的加成反应的基于金属的催化剂以及碱。
由国际专利申请WO2010/112441已知上述类型的涂料组合物。该文献描述一种其中使用光潜碱(photolatentbase)的组合物。所述组合物显现出固化速率与储存期的优异的平衡。然而，为了达到快速固化速率，要求通过紫外线活化。对于具有可用性且使用特殊紫外线发射设备的需求可认为是汽车车身修理店的缺点。
WO2010/046333描述一种非水性涂料组合物，其包含多异氰酸酯、具有每分子多于3个羟基的平均官能度的多元醇、基于金属的固化催化剂以及巯基羧酸。在其中描述的实施例中，来自受阻胺光稳定剂的碱的摩尔量超过硫醇基团的摩尔量。
美国专利US4788083教导在胺处理室中利用胺蒸气处理施加的涂层的处理。这种处理在汽车车身修理店中或对于非常大的物体，如公共汽车、卡车或飞机并非可行的选择。
因此，存在对于提供具有各性能，如良好硬度、优异膜表观、耐久性和耐受环境条件如日光、湿度、酸雨及其他污染物的良好平衡的涂膜的涂料组合物的需要。涂料组合物应适合配制成具有低含量的挥发性有机物含量，以符合目前和未来关于排放这些化合物的规程。施加的涂层应可在环境或低烘培温度下固化，而不需要使用特殊的紫外线发射设备。尤其是，涂料组合物在混合所有组分后应显现出足够的储存期。
现在本发明提供一种非水性液体涂料组合物，其包含
a)多元醇，
b)多异氰酸酯交联剂，
c)用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂，以及
d)一种或多种硫醇官能化合物，
e)具有的pKa值至少为7且不以降低碱性的方式与异氰酸酯基团反应的碱，
f)一种或多种含酸基团的化合物，
其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为1或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中酸基团与碱基团的摩尔比为1:1或更高。
已发现涂料组合物提供具有各性能，如良好硬度、优异膜表观、耐久性和耐受环境条件如日光、湿度、酸雨及其他污染物的良好平衡的涂膜。该涂料组合物高度适合配制成具有低含量的挥发性有机物含量，以符合目前和未来关于排放这些化合物的规程。施加的涂层可在环境或低烘培温度下固化，而不需要使用特殊的紫外线发射设备。特别令人惊奇的是即使使用具有的pKa值为7或更高的非潜在的碱，也可配制具有可接受的储存期的涂料组合物，而国际专利申请WO2010/113441教导使用要求通过紫外线活化的潜在的碱。
合适的多元醇的实例包括包含至少两个羟基的化合物。这些可为单体、低聚物、聚合物及其混合物。羟基官能低聚物和单体的实例为蓖麻油、三羟甲基丙烷及二醇。可特别地提及如国际专利申请WO98/053013中描述的支化二醇，例如2-丁基乙基-1,3-丙二醇。
合适的聚合物的实例包括聚酯多元醇、聚丙烯酸酯多元醇、聚碳酸酯多元醇、聚氨酯多元醇、三聚氰胺多元醇及其混合物和混杂物。这些聚合物通常为技术人员已知且可市购。合适的聚酯多元醇、聚丙烯酸酯多元醇及其混合物例如在国际专利申请WO96/20968和欧洲专利申请EP0688840A中描述。合适的聚氨酯多元醇的实例在国际专利申请WO96/040813中描述。
其他实例包括如在国际专利申请WO93/17060中描述的羟基官能环氧树脂、醇酸树脂和树枝状多元醇。涂料组合物也可包含潜在的羟基官能化合物，如含有双环原酸酯、螺原酸酯、螺原硅酸盐基团的化合物，或双环酰胺缩醛化合物。这些化合物以及它们的用途分别在国际专利申请WO97/31073、WO2004/031256和WO2005/035613中描述。
用于涂料组合物中的合适的异氰酸酯官能交联剂为含有至少两个异氰酸酯基团的异氰酸酯官能化合物。优选异氰酸酯官能交联剂为多异氰酸酯，如脂族、环脂族或芳族的二异氰酸酯、三异氰酸酯或四异氰酸酯。二异氰酸酯的实例包括1,2-亚丙基二异氰酸酯、三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、2,3-亚丁基二异氰酸酯、六亚甲基二异氰酸酯、八亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、ω,ω’-二丙基醚二异氰酸酯、1,3-环戊烷二异氰酸酯、1,2-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、4-甲基-1,3-二异氰酸酯基环己烷、反式-亚乙烯基二异氰酸酯、二环己基甲烷-4,4’-二异氰酸酯(W)、甲苯二异氰酸酯、1,3-二(异氰酸酯基甲基)苯、苯二甲撑二异氰酸酯、α,α,α’,α’-四甲基苯二甲撑二异氰酸酯1,5-二甲基-2,4-二(2-异氰酸酯基乙基)苯、1,3,5-三乙基-2,4-二(异氰酸酯基甲基)苯、4,4’-二异氰酸酯基联苯、3,3’-二氯-4,4’-二异氰酸酯基联苯、3,3’-二苯基-4,4’-二异氰酸酯基联苯、3,3’-二甲氧基-4,4’-二异氰酸酯基联苯、4,4’-二异氰酸酯基二苯基甲烷、3,3’-二甲基-4,4’-二异氰酸酯基二苯基甲烷以及二异氰酸酯基萘。三异氰酸酯的实例包括1,3,5-三异氰酸酯基苯、2,4,6-三异氰酸酯基甲苯、1,8-二异氰酸酯基-4-(异氰酸酯基甲基)辛烷以及赖氨酸三异氰酸酯。也包括多异氰酸酯的加合物和低聚物，例如缩二脲、异氰脲酸酯、脲基甲酸酯、亚氨基氧杂二嗪二酮、脲二酮、氨基甲酸酯及其混合物。这些低聚物和加合物的实例为2分子的二异氰酸酯(例如六亚甲基二异氰酸酯或异佛尔酮二异氰酸酯)与二醇如乙二醇的加合物，3分子的六亚甲基二异氰酸酯与1分子水的加合物(可以商品名Bayer的DesmodurN获得)，1分子的三羟甲基丙烷与3分子的甲苯二异氰酸酯的加合物(可以商品名Bayer的DesmodurL获得)，1分子的三羟甲基丙烷与3分子的异佛尔酮二异氰酸酯的加合物，1分子季戊四醇与4分子甲苯二异氰酸酯的加合物，3摩尔的m-α,α,α’,α’-四甲基苯二甲撑二异氰酸酯与1摩尔三羟甲基丙烷的加合物，1,6-二异氰酸酯基己烷的异氰脲酸酯三聚体，异佛尔酮二异氰酸酯的异氰脲酸酯三聚体，1,6-二异氰酸酯基己烷的脲二酮的二聚体，1,6-二异氰酸酯基己烷的缩二脲，1,6-二异氰酸酯基己烷的脲基甲酸酯及其混合物。此外，异氰酸酯官能单体如α,α’-二甲基-间异丙基苄基异氰酸酯的聚合物(共聚物)也适合使用。如果希望，也可使用疏水或亲水改性的多异氰酸酯以赋予涂料特殊性能。
在本发明涂料组合物中，异氰酸酯官能基团与羟基的当量比适合在0.5-4.0之间，优选在0.7-3.0之间，更优选在0.8-2.5之间。通常在涂料组合物中羟基官能基料与异氰酸酯官能交联剂的重量比基于非挥发物含量在85:15-15:85之间，优选在70:30-30:70之间。
如上所述，本发明的涂料组合物还包含用于异氰酸酯基团与羟基的加成反应的基于金属的催化剂。这些催化剂为技术人员已知。催化剂通常基于涂料组合物的非挥发性物质计算以0.001-10重量％，优选0.002-5重量％，更优选0.01-1重量％的量使用。合适的所述基于金属的催化剂中的金属包括锌、钴、锰、锆、铋和锡。优选涂料组合物包含基于锡的催化剂。基于锡的催化剂的公知实例为二月桂酸二甲基锡、二叔碳酸二甲基锡、二油酸二甲基锡、二月桂酸二丁基锡、二月桂酸二辛基锡以及辛酸锡。也合适的为硫醇化二烷基锡、马来酸二烷基锡和乙酸二烷基锡。也可使用基于金属的催化剂的混合物和组合。
合适的硫醇官能化合物包括十二烷硫醇、巯基乙醇、1,3-丙烷二硫醇、1,6-己烷二硫醇、甲基硫代乙醇酸酯、2-巯基乙酸、巯基琥珀酸和半胱氨酸。也合适的是硫醇官能羧酸与多元醇的酯，如2-巯基乙酸、3-巯基丙酸、2-巯基丙酸、11-巯基十一烷酸和巯基琥珀酸的酯。这些酯的实例包括季戊四醇四(3-巯基丙酸酯)、季戊四醇四(2-巯基乙酸酯)、三羟甲基丙烷三(3-巯基丙酸酯)、三羟甲基丙烷三(2-巯基丙酸酯)和三羟甲基丙烷三(2-巯基乙酸酯)。这种化合物的另一实例包括基于起始剂多元醇，例如三羟甲基丙烷和二羟甲基丙酸的超支化多元醇核，使其随后利用3-巯基丙酸和异壬酸酯化。这些化合物在欧洲专利申请EP-A-0448224和国际专利申请WO93/17060中描述。
其他合适的硫醇官能化合物在国际专利申请WO2010/112441中描述。
如上所述，一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为1或更高的量存在。当使用巯基羧酸，如2-巯基丙酸时，得到硫醇基团与金属原子的摩尔比为1:1的满意结果。在很多其他情况下，硫醇基团与金属原子更高的比例是合适的，例如至少2:1，4:1或甚至10:1或更高。
本发明涂料组合物进一步包含具有的pKa值至少为7的碱，该碱不以降低碱性的方式与异氰酸酯基团反应。合适的是，所述碱具有在7-9，优选7-8.5的范围内的pKa值。pKa值为质子化碱的离解常数KA的负对数：
KA＝[HB+]]/[B][H+]
离解常数通常在水性环境中在20℃的温度下测定。
所述碱为不需要通过利用紫外线辐照或通过热的活化步骤的非潜在的碱。如上所述，该碱不以降低碱性的方式与异氰酸酯反应。通常其在环境温度如20℃下测定，不论是否进行这样的反应。与异氰酸酯基团快速反应而形成脲基团的伯胺或仲胺不适合作为本发明中的碱。
所述碱优选在涂料组合物的固化条件下为不挥发的。合适的碱通常具有高于80℃，优选高于120℃，或甚至高于150℃的沸点。合适的碱的实例为叔胺和胺氧化物。
合适的叔胺的实例为1,4-二氮杂双环[2.2.2]辛烷、双(1,2,2,6,6-五甲基-4-哌啶基)-癸二酸酯、1-甲基-8-(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯及其混合物。其他合适的胺的实例为三苄基胺、三丁基胺、哌啶醇、三乙基胺、三亚乙基二胺、三乙醇胺、二甲基苯乙基胺、(1-苄基丙基)二甲基胺、N-(丁基缩水甘油醚)-N,N-二丁基胺、N-(苯基缩水甘油醚)-N,N-二丁基胺、2,4,6-三(二甲基胺甲基)苯酚、N-甲基哌啶、三异丙基胺、三异丙醇胺、N,N-二甲基乙醇胺、二甲基异丙基胺、N,N-二乙基乙醇胺、1-二甲基氨基-2-丙醇、3-二甲基氨基-1-丙醇、2-二甲基氨基-2-甲基-1-丙醇、N-甲基二乙醇胺、N-乙基二乙醇胺、N-丁基二乙醇胺、N,N-二甲基哌嗪及N-乙基吗啉。伯胺和仲胺与环氧化物官能化合物的反应产物也是合适的。这类胺的实例为二丁基胺与苯基缩水甘油醚或丁基缩水甘油醚的反应产物。如上所述，该碱以低于硫醇基团摩尔量的摩尔量存在于涂料组合物中。
在优选实施方案中，碱的摩尔量等于或高于基于金属的固化催化剂的金属原子的摩尔量，例如至少1:1或至少2:1。
涂料组合物也包含含酸基团化合物。这种酸基团可以聚合形式存在。通常所用的多元醇包含一定量的羧酸基团。典型的丙烯酸系多元醇具有1-15mgKOH/g的酸值。聚酯多元醇同样可包含羧酸基团。也可包括额外的羧酸或其他含酸基团化合物。在涂料组合物中的含酸基团化合物影响涂料组合物的储存期和固化速率的平衡。一般性地，已发现含酸基团化合物的加入提高储存期并略微降低固化速率。因此，通过包含含酸基团化合物可细微调整储存期和固化速率的平衡。
合适的含酸基团化合物的实例为羧酸，如苯甲酸、己酸、磺酸如十二烷基磺酸和甲苯磺酸以及磷酸酯如磷酸二丁酯。也可使用不同含酸基团化合物的混合物和组合。含酸基团化合物以等于或大于上述碱e)的摩尔量存在。酸基团与碱基团的摩尔比至少为1:1。通常该比例不超过15:1。
涂料组合物可不利用挥发性稀释剂而使用且施用，特别是在低分子量基料，任选地与一种或多种反应性稀释剂组合使用时。替换地，涂料组合物可任选地包含挥发性有机溶剂。优选涂料组合物包含基于总组合物小于500g/l的挥发性有机溶剂，更优选小于480g/l，最优选420g/l或更少。组合物中的非挥发物含量，通常称为固体含量，基于总组合物优选高于50重量％，更优选高于54重量％，最优选高于60重量％。
合适的挥发性有机稀释剂的实例为烃类，如甲苯、二甲苯、Solvesso100、酮类，萜烯类如二戊烯或松树油，卤代烃类如二氯甲烷，醚类如乙二醇二甲醚，酯类如乙酸乙酯、丙酸乙酯、乙酸正丁酯或醚酯类如乙酸甲氧基丙酯或丙酸乙氧基乙酯。也可使用这些化合物的混合物。
如果希望，可在涂料组合物中包含一种或多种所谓的“豁免溶剂(exemptsolvent)”。豁免溶剂是不参与大气光化学反应而形成烟雾的挥发性有机化合物。它可以是有机溶剂，但在阳光的存在下经过长时间才与氮氧化物反应，使得美国环境保护署认为它的反应性可忽略。批准用于漆和涂料的豁免溶剂的实例包括丙酮、乙酸甲酯、对氯三氟甲苯(可以名称Oxsol100市购)及挥发性甲基硅氧烷类。也可认为乙酸叔丁酯为豁免溶剂。
除了上述组分之外，其他化合物也可存在于本发明涂料组合物中。这些化合物可以是基料和/或反应性稀释剂，任选地包含可与上述羟基官能化合物和/或异氰酸酯官能交联剂交联的反应性基团。这些其他化合物的实例为酮树脂，潜在的氨基官能化合物如唑烷类、酮亚胺类、醛亚胺类和二亚胺类。这些和其他化合物为技术人员已知且在国际申请US5214086中提及。
涂料组合物可进一步包含其他在涂料组合物常用的成分、添加剂或助剂如颜料、染料、表面活性剂、颜料分散助剂、流平剂、润湿剂、防缩孔剂、消泡剂、抗流挂剂、热稳定剂、光稳定剂、UV吸收剂、抗氧剂和填料。
涂料组合物非常适合作为清漆使用。清漆基本不含颜料，且对于可见光透明。然而，清漆组合物可包含消光剂，例如基于二氧化硅的消光剂，以控制涂层的光泽水平。
涂料组合物适合通过包括以下步骤的方法制备：使多元醇、一种或多种硫醇官能化合物、用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂和具有的pKa值至少为7且不以降低碱性的方式与异氰酸酯基团反应的碱混合，形成基料组件(module)，以及使基料组件与多异氰酸酯混合，其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比例为1或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在。
如包含羟基官能基料和异氰酸酯官能交联剂的涂料组合物常见的一样，本发明组合物具有有限的储存期。因此，组合物适合以多组分组合物，例如以二组分组合物或以三组分组合物提供。因此本发明也涉及用于制备涂料组合物的成套部件，其包括：
i)基料组件，其包含多元醇、一种或多种硫醇官能化合物、用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂、具有的pKa值至少为7且不以降低碱性的方式与异氰酸酯基团反应的碱和一种或多种含酸基团化合物，以及
ii)交联剂组件，其包含多异氰酸酯交联剂，
其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为1或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中酸基团与碱基团的摩尔比为1:1或更高。
替换地，成套部件可包含三个组分，其包括：
i)基料组件，其包含多元醇，
ii)交联剂组件，其包含多异氰酸酯交联剂，以及
iii)稀释剂组件，其包含挥发性有机稀释剂，
其中使一种或多种硫醇官能化合物、用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂以及具有的pKa值至少为7且不以降低碱性的方式与异氰酸酯基团反应的碱分布于组件i)、ii)或iii)，且其中至少一种组件包含含酸基团化合物，且其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为1或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中酸基团与碱基团的摩尔比为1:1或更高。
也可使涂料组合物的组件以不同方式分布于如上所述的组件，只要组件显现出所需储存稳定性。彼此反应的涂料组合物的组件在储存时优选不组合成一个组件。
如果希望，可使涂料组合物的组分分布于甚至更多组件，例如4个或5个组件。
本发明涂料组合物可施用到任何基材上。基材可以例如为金属，例如铁、钢和铝，塑料，木材，玻璃，合成材料，纸，皮革，或其它涂层。其它涂层可包含本发明涂料组合物或可为不同的涂料组合物。本发明涂料组合物显示出作为清漆、底涂层、彩色面漆、底漆和填料的特别实用性。当本发明涂料组合物为清漆时，其优选施用到赋予颜色和/或效应的底涂层上。在那种情况下，清漆形成多道漆涂层的顶层，例如通常施用到汽车外部。底涂层可以是水性底涂层或溶剂型底涂层。
涂料组合物适合用于涂覆物体，例如桥、管线、工业设备或建筑、油气设施或船。这些组合物特别适合用于涂饰和重涂饰汽车和大型运输工具，如火车、卡车、公共汽车和飞机。
因此，本发明也涉及一种提供用于运输工具的至少一部分外表面的涂层的方法，其中该方法包括以下步骤：将本发明液体涂料组合物施用至运输工具的至少一部分外表面，以及使施用的涂料组合物在5-80℃的温度范围内固化。有利的是，固化步骤在中等温度如50或60℃下进行。
本发明涂料组合物同样可以作为粘合剂使用。因此，在此所用的表示“涂料组合物”也包含粘合剂组合物。
实施例
所用原料
聚丙烯酸酯多元醇溶液具有68.3重量％溶剂乙酸丁酯的非挥发物含量。由羟乙基甲基丙烯酸酯、甲基丙烯酸丁酯、甲基丙烯酸甲酯和苯乙烯制备聚合物。羟值为140mgKOH/g(基于非挥发物含量)，酸值为4.5mgKOH/g(基于非挥发物含量)，Mw为3,520，Mn为1,720(GPC，聚苯乙烯标样)。
聚酯多元醇如在WO2007/020269A的实施例E2中所描述。
Tinuvin292为两种活性叔胺成分：二(1,2,3,6,6-五甲基-4-哌啶基)癸二酸酯和甲基(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯的混合物，购自BASF。
Tinuvin1130为基于苯并***的UV吸收剂，购自BASF。
TolonateHDT90为基于六亚甲基二异氰酸酯的三聚体，购自Perstorp。
VestanatT1890为基于异佛尔酮二异氰酸酯的三聚体，购自Evonik。
实施例1
制备基料组件
通过混合以下组分制备基料组件：
组分 重量份
聚丙烯酸酯多元醇溶液 14.43
聚酯多元醇 17.06
乙酸丁酯 10.10
市购润湿剂的溶液 0.81
Tinuvin 292 0.14
Tinuvin 1130 0.34
制备交联剂组件
通过混合以下组分制备交联剂组件：
组分 重量份
Tolonate HDT90 20.04
甲基异戊基酮 8.23
Vestanat T1890E 16.10
制备稀释剂组件：
通过混合以下组分制备稀释剂组件
组分 重量份
乙酸丁酯 6.54
二甲苯 4.86
季戊四醇四巯基丙酸酯 1.11
二月桂酸二辛基锡 0.32
通过混合各组件制备透明涂料组合物。实施例1中的锡原子:SH基团:酸基团:碱基团的摩尔比为0.43:9.09:1.70:0.55。由Tinuvin292提供碱基团，且酸基团以来自聚丙烯酸酯多元醇的羧酸基团形式存在。使用DIN4杯测试初始粘度。形成凝胶的时间在室温下测定。挥发性有机溶剂的含量在420g/l以下。
通过喷涂将清漆施用到卷材涂覆的钢板并使其在环境温度(23℃)下干燥。干膜层厚度在40-80μm之间。
实施例2
按照与如以上对实施例1所述相同的程序。然而，二月桂酸二辛基锡的量为实施例1的摩尔量的三倍。
实施例3
按照与如以上对实施例1所述相同的程序。然而，碱的量增加。
对比实施例A
按照与如以上对实施例1所述相同的程序。然而，不使用硫醇官能化合物。
对比实施例B
按照与如以上对实施例1所述相同的程序。然而，不使用碱。
对比实施例C
按照与如以上对实施例1所述相同的程序。然而，通过三乙基胺补充碱的量(1.28重量份)。
表1总结了结果。前4行表明Sn固化催化剂的金属原子、硫醇官能化合物的硫醇基团、酸和碱的摩尔比。
施用的涂层的干燥阶段手动确定，其中识别10个干燥阶段：
1.仍湿润的涂层容易用拇指擦去。
2.通过用拇指接触涂层，可画出漆线。
3.涂层有粘合力，但用拇指温和摩擦容易被破坏至基材。
4.用拇指温和摩擦留下清晰标记。
5.用拇指温和摩擦很难留下标记。可吹掉落到漆上的一簇棉絮。涂层为不沾尘干的。
6.用拇指温和摩擦不留下标记。用手掌温和摩擦或推动时，感受到粘性作用。
7.用手掌温和摩擦或推动时，观察不到粘性。涂层为不粘的。
8.用拇指实推留下永久标记。
9.用拇指实推的标记在1-2分钟后消失。涂层为触干的。
10.涂料几乎几乎不能或根本不能通过用指甲擦拭而破坏。涂层为干透的。
清漆膜的图像清晰度(DOI)利用Byk-GardnerWavescanDOI设备在施用清漆至少一天后确定。较高的DOI值表明更好的膜外观。
表1
实施例 1 2 3 A B C
Sn 0.43 1.29 0.43 0.43 0.43 0.43
SH 9.09 9.09 9.09 0.00 9.09 9.09
酸 1.70 1.70 1.69 1.70 1.70 1.70
碱 0.55 0.55 1.10 0.55 0.00 13.20
起始粘度(Din 4杯，秒) 14.4 14.6 14.3 14.6 14.6 16.6
凝胶时间(min) >120 >60 >60 <20 >180 <20
15min后干燥阶段 1 1 3 2 1 3
30 5 6 5 5 1 9
45 6 7 8 7 1 9
60 7 9 9 9 2 9
DOI 92 92 95 93 92 94
一天后的珀苏兹硬度 162 241 98 131 229 104
由实施例和表1中的结果可以看出本发明涂料组合物提供了具有各性能，如良好硬度、优异膜表观的良好平衡的涂膜。该涂料组合物适合配制成具有低含量的挥发性有机物含量，以符合目前和未来关于排放这些化合物的规程。施加的涂层可在环境或低烘培温度下固化，而不需要使用特殊的紫外线发射设备。该涂料组合物在混合所有组分后显现出足够的储存期。本发明实施例1具有整体良好的性能。实施例2具有提高水平的锡催化剂但仍显现出足够的储存期。固化速率提高。实施例3表明提高碱的量的影响，其轻微提高固化速率。可总结出不含碱的对比实施例B具有非常长的储存期，但具有不足的固化速率。不含硫醇的对比实施例A在少于20分钟内形成凝胶且因此具有不足的储存期。同样，其中碱以高于硫醇基团摩尔量的摩尔量存在的对比实施例C在少于20分钟内形成凝胶且因此具有不足的储存期。

Claims (8)

1.一种非水性液体涂料组合物，包含
a)多元醇，
b)多异氰酸酯交联剂，
c)一种或多种硫醇官能化合物，
d)用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂，
e)具有的pKa值至少为7且不会以降低碱性的方式与异氰酸酯基团反应的碱，以及
f)一种或多种含酸基团化合物，
其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为10或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中酸基团与碱基团的摩尔比为1:1或更高。
2.根据权利要求1的涂料组合物，其中碱以等于或高于基于金属的固化催化剂的金属原子的摩尔量的摩尔量存在。
3.根据前述权利要求中任一项的涂料组合物，其中涂料组合物为清漆组合物。
4.一种用于制备根据前述权利要求中任一项的涂料组合物的方法，包括使多元醇、一种或多种硫醇官能化合物、用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂、具有的pKa值至少为7且不会以降低碱性的方式与异氰酸酯基团反应的碱以及一种或多种含酸基团化合物混合以形成基料组件，以及使基料组件与多异氰酸酯混合，其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为10或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中酸基团与碱基团的摩尔比为1:1或更高。
5.一种用于制备根据前述权利要求1-3中任一项的涂料组合物的成套部件，其包括：
i)基料组件，其包含多元醇、一种或多种硫醇官能化合物、用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂、具有的pKa值至少为7且不会以降低碱性的方式与异氰酸酯基团反应的碱和一种或多种含酸基团化合物，以及
ii)交联剂组件，其包含多异氰酸酯交联剂，
其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为10或更高的量存在，且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中酸基团与碱基团的摩尔比为1:1或更高。
6.一种用于制备根据前述权利要求1-3中任一项的涂料组合物的成套部件，其包括：
i)基料组件，其包含多元醇和具有的pKa值至少为7且不会以降低碱性的方式与异氰酸酯基团反应的碱，
ii)交联剂组件，其包含多异氰酸酯交联剂，以及
iii)稀释剂组件，其包含挥发性有机稀释剂、用于催化异氰酸酯基团与羟基的加成反应的基于金属的固化催化剂以及一种或多种硫醇官能化合物，其中一种或多种硫醇官能化合物以提供硫醇基团相对于基于金属的固化催化剂的金属原子的摩尔比为10或更高的量存在，
且其中碱以低于硫醇基团摩尔量的摩尔量存在，且其中至少一种组件包含含酸基团化合物，且其中酸基团与碱基团的摩尔比为1:1或更高。
7.一种为运输工具的外表面的至少一部分提供涂层的方法，其中所述方法包括以下步骤：将根据前述权利要求1-3中任一项的液体涂料组合物施用到运输工具的外表面的至少一部分，以及使施用的涂料组合物在5-80℃的温度范围内固化。
8.根据权利要求7的方法，其中将液体涂料组合物作为着色底涂层顶部的清漆施用。
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AU2013229673B2 (en) 2016-01-07
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