CN107699095A - 涂料组合物 - Google Patents

涂料组合物 Download PDF

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CN107699095A
CN107699095A CN201710571734.9A CN201710571734A CN107699095A CN 107699095 A CN107699095 A CN 107699095A CN 201710571734 A CN201710571734 A CN 201710571734A CN 107699095 A CN107699095 A CN 107699095A
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G·W·东布罗夫斯基
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P·S·马宗达
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Abstract

本发明涉及一种深基(deep base)或强化(accent)涂料组合物，其包含丙烯酸类粘合剂和Zn++添加剂。本发明组合物与不含所述添加剂的类似调配物相比会更好地抗水渍。

Description

涂料组合物
背景技术
本发明涉及一种在抗水渍方面展示出改进的涂料组合物。
强化(accent)和深基(deep base)高光泽和半光泽涂料含有相当大含量的着色剂。当高度带色涂料涂覆于衬底并且使其干燥时，暴露于水滴随时间推移可产生水渍，其由水可溶材料从涂料膜浸出所致。在涂料涂覆于衬底不久后甚至更可能存在水渍：归因于不完整链扭结，膜可能形成不良，由此使得水穿透并且伴随水可溶材料的浸出。随时间推移，乳胶粒子变形的完成和聚合物链扩散改进膜整合性，其可改进对水渍的抗性。因此，研发抗水渍的高度带色涂料调配物持续成为挑战。
发明内容
本发明通过提供一种涂料组合物来解决本领域中的需求，所述涂料组合物包含丙烯酸类聚合物粒子的稳定水性分散液，以所述聚合物粒子的重量计，所述聚合物粒子通过0.2到12重量百分比的具有酮官能团的单体的结构单元官能化；着色剂，以所述涂料组合物的重量计，其浓度在5到25重量百分比范围内；以所述涂料组合物的重量计，0.5到5重量百分比的Zn++化合物；以及以所述涂料组合物的重量计，0.5到10重量百分比的二酰肼或多元胺；以及大体上不存在的填充剂；
其中所述聚合物粒子是两相聚合物粒子，其中软相的Tg不大于0℃，并且硬相的Tg不小于30℃；其中软相与硬相的比率在90:10到60:40范围内；其条件是所述聚合物粒子的总Tg小于15℃。
本发明的组合物通过提供一种抗水渍的深基或强化涂料调配物来解决本领域中的需求。
具体实施方式
本发明通过提供一种涂料组合物解决本领域中的需求，所述涂料组合物包含丙烯酸类聚合物粒子的稳定水性分散液，以所述聚合物粒子的重量计，所述聚合物粒子通过0.2到12重量百分比的具有酮官能团的单体的结构单元官能化；着色剂，以所述涂料组合物的重量计，其浓度在5到25重量百分比范围内；以所述涂料组合物的重量计，0.5到5重量百分比的Zn++化合物；以及以所述涂料组合物的重量计，0.5到10重量百分比的二酰肼或多元胺；以及大体上不存在的填充剂；
其中所述聚合物粒子是两相聚合物粒子，其中软相的Tg不大于0℃，并且硬相的Tg不小于30℃；其中软相与硬相的比率在90:10到60:40范围内；其条件是所述聚合物粒子的总Tg小于15℃。
如本文所用，术语“丙烯酸类聚合物粒子”指的是包含至少30重量％的丙烯酸单体的结构单元的聚合物粒子。术语“丙烯酸单体”指的是一种或多种丙烯酸酯和/或甲基丙烯酸酯单体，其实例包括甲基丙烯酸甲酯(Tg＝105℃)、甲基丙烯酸乙酯(Tg＝65℃)、甲基丙烯酸丁酯(Tg＝20℃)、甲基丙烯酸脲基酯(Tg＝100℃)、丙烯酸乙酯(Tg＝-22℃)、丙烯酸丁酯(Tg＝-54℃)、丙烯酸2-乙基己酯(Tg＝-85℃)以及丙烯酸2-丙基庚酯(Tg＝-68℃)。丙烯酸单体的优选组合包括甲基丙烯酸甲酯和一种或多种选自由以下组成的群组的单体：丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸脲基酯、丙烯酸2-丙基庚酯以及丙烯酸2-乙基己酯。丙烯酸单体的更优选组合包括甲基丙烯酸甲酯和丙烯酸丁酯；甲基丙烯酸甲酯和丙烯酸2-乙基己酯；以及甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸乙酯，其中甲基丙烯酸甲酯和丙烯酸2-乙基己酯的组合最优选。
指定单体的术语“结构单元”指的是在聚合之后所述单体的残余物。举例来说，甲基丙烯酸甲酯的结构单元如下说明：
其中虚线表示结构单元连接到聚合物主链的点。
以聚合物粒子的重量计，丙烯酸类聚合物粒子进一步包含优选地0.5、更优选地1、并且最优选地2重量百分比到优选地10重量百分比的具有酮官能团的单体(即，含有酮基或醛基的单体)的结构单元。具有酮官能团的优选单体是甲基丙烯酸乙酰乙酰氧基乙酯(AAEM，Tg＝3℃)，优选地，以聚合物粒子的重量计，其浓度在4到10重量百分比范围内；或二丙酮丙烯酰胺(DAAM，(Tg＝85℃))，优选地，以聚合物粒子的重量计，其浓度在1到5重量百分比范围内。
丙烯酸类聚合物粒子还可包括至多70重量百分比的其它非丙烯酸单体(如苯乙烯(Tg＝100℃))的结构单元。另外，聚合物粒子优选地包含0.2、更优选地0.5、并且最优选地1重量百分比到优选地5、并且更优选地到3重量百分比的羧酸单体的结构单元，羧酸单体如丙烯酸(Tg＝103℃)、甲基丙烯酸(Tg＝185℃)或衣康酸(Tg＝154℃)。
Tg指的是如通过福克斯方程式(Fox equation)计算的玻璃态转变温度。(参见T.G.Fox,美国物理学会会刊(Bull.Am.Phys.Soc).1,123(1956).)聚合物粒子是2相聚合物粒子，优选地具有小于5℃的总Tg。聚合物粒子具有优选地小于10℃、更优选地小于0℃并且最优选地小于-10℃的第一相Tg；和优选地大于40℃、更优选地大于60℃并且最优选地大于80℃的第二相Tg。
在一个优选实施例中，以聚合物粒子的第一相的重量计，第一相包含45、更优选地48、最优选地50到优选地70、更优选地到65并且最优选地到60重量百分比的丙烯酸2-乙基己酯的结构单元；和以聚合物粒子的第一相的重量计，优选地20、更优选地30并且最优选地35到优选地50、更优选地到45重量百分比的甲基丙烯酸甲酯或苯乙烯(优选甲基丙烯酸甲酯)的结构单元。
在另一优选实施例中，第一相包含以聚合物粒子的第一相的重量计，1、更优选地7并且最优选地10到80、更优选地到60并且最优选地到40重量百分比的丙烯酸丁酯；和以聚合物粒子的第一相的重量计，0、更优选地15、更优选地25并且最优选地40到70、更优选地到65并且最优选地到60重量百分比的丙烯酸2-乙基己酯；以及以聚合物粒子的第一相的重量计，10、更优选地20、更优选地30并且最优选地35到优选地50、更优选地到45重量百分比的甲基丙烯酸甲酯或苯乙烯(优选甲基丙烯酸甲酯)的结构单元。
第一相进一步包含以聚合物粒子的第一阶的重量计，优选地4到10重量百分比的AAEM的结构单元或1到5重量百分比的DAAM的结构单元，和优选地0.5到5重量百分比的丙烯酸或甲基丙烯酸的结构单元。
聚合物粒子的第二相优选地包含80、更优选地85并且最优选地90重量百分比到98.5、更优选地到98并且最优选地到97重量百分比的甲基丙烯酸甲酯或苯乙烯的结构单元，优选甲基丙烯酸甲酯。第二相进一步包含以聚合物粒子的第二相的重量计，优选地4到10重量百分比的AAEM的结构单元或1到5百分比的DAAM的结构单元，和优选地0.5到5重量百分比的丙烯酸或甲基丙烯酸的结构单元。
第一相与第二相的比率优选地在85:15、更优选地80:20并且最优选地75:25到优选地65:35的范围内。
本发明的组合物以组合物的重量计包含5、优选地8、更优选地10到25、更优选地到20范围内的浓度的着色剂。着色剂是非白色着色剂并且可为有机或无机。有机着色剂的实例包括酞菁蓝、酞菁绿、单芳基化物黄、二芳基化物黄、苯并咪唑酮黄、杂环式黄、DAN橙、喹吖啶酮洋红、喹吖啶酮紫、有机红(包括金属化偶氮红和非金属化偶氮红)。无机着色剂包括碳黑、灯黑、黑色氧化铁、黄色氧化铁、棕色氧化铁、红色氧化铁。
以组合物的重量计，组合物进一步包含0.2、优选地0.5到5、优选地到4并且最优选地到3重量百分比的Zn++化合物。适合的Zn++化合物的实例包括ZnO、Zn(NH3)2(CO3)2、ZnCl2以及Zn(OAc)2。
以组合物的重量计，组合物进一步包含0.1、并且优选地0.2到10、更优选地到5重量百分比的二酰肼或多元胺。多元胺的实例包括二胺，如3,3'-(乙烷-1,2-二基双(伸氧基))双(丙-1-胺)；4,9-二氧十二烷-1,12-二胺；4,9-二氧十二烷-1,12-二胺；4,7-二氧十二烷-1,10-二胺；和4,7,10-三氧十三烷-1,13-二胺。多元胺的市售实例是聚醚胺，如JEFFAMINE D-230、JEFFAMINE D-400、JEFFAMINE D-2000、JEFFAMINE M-600、JEFFAMINE M-1000、JEFFAMINE ED-600、JEFFAMINE ED-900、T-403以及JEFFAMINE T-3000聚醚胺。
二酰肼的实例包括己二酸二酰肼(ADH)、碳二酰肼(carbodihydrazide；CDH)、癸二酸二酰肼(SDH)、缬氨酸二酰肼(VDH)、间苯二甲酸二酰肼(ISODH)以及二十烷二酰肼ICODH)。优选地，二酰肼是ADH。
组合物进一步包含大体上不存在的填充剂。如本文所用，组合物中大体上不存在的填充剂指的是小于10、优选地小于5、更优选地小于1并且最优选地0PVC的任何白色、透明或半透明的无机粒子填充剂，除了含锌化合物之外，其不赋予明显(非白色)色彩或色调。因此，组合物包含大体上不存在的TiO2；BaSO4；硅酸盐和铝硅酸盐，如滑石、粘土、云母以及绢云母；CaCO3；霞石；长石；硅灰石；高岭土；磷酸二钙；以及硅藻土。
本发明的组合物宜包括多种其它添加剂，如流变改性剂、消泡剂、中和剂、表面活性剂以及分散剂。已出人意料地发现本发明的组合物与不含Zn++添加剂的深基调配物相比展示优良的抗水污染性。
实例
实例1-制备具有ZnO的深基粘合剂
单体乳液1(ME1)通过混合DI水(409.69g)、Disponil FES-32表面活性剂(55.95g)、随后二丙酮丙烯酰胺(36.29g)、丙烯酸2-乙基己酯(666.59g)、甲基丙烯酸甲酯(482.7g)以及甲基丙烯酸(24.2g)来制备。单体乳液2(ME2)通过混合DI水(142.83g)、Disponil FES-32表面活性剂(24.71g)、二丙酮丙烯酰胺(14.82g)、甲基丙烯酸甲酯(469.43g)以及甲基丙烯酸(9.88g)来制备。
向配备有机械搅拌器、温度计、冷凝器、加热套以及温度控制器的1-g反应器馈入去离子水(944.5g)并且加热到85℃，同时用N2吹扫。向这一反应器添加于水(20g)中的Disponil FES-32表面活性剂(14.2g)、碳酸钠(3.42g)于水(60g)中的溶液、于水(22.5g)中的ME1(59.6g)以及过硫酸铵(4.55g)于水(40g)中的溶液。
五分钟之后，将过硫酸铵(1.6g)于水(119.28g)中的共进料催化剂溶液以0.91g/min的速率进料到反应器中，随后在85℃的受控反应温度下以10.4g/min的速率添加ME1。二十分钟之后，将ME1进料速率增加到20.8g/min。在完成添加ME1之后，单体乳液容器用DI水(50g)冲洗，中止共进料催化剂溶液，并且将反应温度控制在85℃。
三十分钟之后，以0.91g/min的速率重新开始共进料催化剂溶液进料，随后在85℃的受控反应温度下以22.5g/min的速率添加ME2。在完成添加ME2之后，单体乳液容器用DI水(32g)冲洗，并且将反应器冷却到60℃。随后将七水合硫酸亚铁的溶液(20g，0.15％水溶液)添加到反应器中，随后添加叔丁基过氧化氢(2.24g)于水(34.62g)中的溶液，以及Bruggolite FF6M还原剂(1.07g)于水(35.78g)中的溶液，两者均以1.2g/min的速率添加。在完成所有进料之后，将反应器冷却到室温。当反应器达到50℃时，添加氢氧化铵(10g，28％水溶液)，随后添加己二酸二酰肼(26.07g)于水(70g)中的浆液。在40℃下，添加KATHONTM LX杀菌剂(陶氏化学公司(The Dow Chemical Company)或其附属公司的商标，2.56g，1.5％)于水(20g)中的溶液。当反应器温度完全冷却时，过滤其内含物以去除凝胶。发现经过滤的分散液的固体含量是45.9％并且pH是8。水性ZnO浆液(2.5％ZnO，以聚合物固体的重量计)使用顶置式搅拌器与分散液掺合。
衍生自ME1单体的共聚物的Tg计算为-30℃，并且衍生自ME2单体的共聚物的Tg计算为106℃。聚合物粒子的总Tg是1.1℃。
实例2-制备具有Zinplex 15Zn错合物的深基粘合剂
组合物如实例1中所描述制备，但将Zinplex 15Zn错合物(1.5重量百分比Zn(NH3)2(CO3)2)，以聚合物固体的重量计)用作Zn++添加剂。
比较实例1-制备不含Zn++的深基粘合剂
组合物如实例1中所描述制备，但无Zn++化合物添加到调配物。
涂料制备
不含Zn++化合物的涂料组合物描述于表1中。
表1-涂料组合物
(TAMOL、TERGITOL以及ACRYSOL均是陶氏化学公司或其附属公司的商标)
涂料如下制备：在0.25L塑料容器中添加消泡剂、表面活性剂、分散剂、氨以及水并且在顶置式搅拌器下混合。随后，添加粘合剂和聚结剂并且混合2-3min。增大搅拌速度并且缓慢添加RM-3000。在这一添加期间观测到粘度升高。随后，在高速搅拌下添加RM-995和剩余调稀剂水以调整粘度。混合持续5-10min。最终混合物在室温下平衡一天，随后添加着色剂。Colortrend 808黄色氧化物着色剂以12流体oz/gal(94mL/L)的基底涂料的含量后添加。
水渍测试方法：
遵循ASTM D7190以评估对由水可溶材料的浸出导致的污染的抗性。使用7密耳(mil)下引棒，涂料跨越Black Leneta Vinyl记录纸下引。每一个下引分成三个部分以在干燥1天和4天时进行测试。使涂层在77℉(25℃)及50％相对湿度下干燥，随后测试。将水滴(0.1g/cm3)置放在涂层的第一指定区域顶部上并且使其静置10min，接着将记录纸抬升到垂直位置以允许水向下流动。
在相同温度及相对湿度下对干燥1天和4天之后的水渍进行测试。污染评定为几乎不可见到不充分可见-HV指的是高度可见，V指的是可见，并且BV指的是几乎不可见污染。
对由水可溶材料的浸出导致的污染的抗性结果展示于表2中。Comp 1指的是不含任何Zn++添加剂的涂料调配物；Ex 1和Ex 2分别指的是具有ZnO和Zn(NH3)2(CO3)2的涂料调配物。著色剂量以g/100mL的基底涂料为单位。
表2-使用Colortrend 808黄色氧化物着色剂的水渍结果
结果展示含锌的深基涂料与不含锌的涂料相比具有明显较好的对水渍的抗性。

Claims (10)

1.一种涂料组合物，其包含丙烯酸类聚合物粒子的稳定水性分散液，以所述聚合物粒子的重量计，所述聚合物粒子通过0.2到12重量百分比的具有酮官能团的单体的结构单元官能化；着色剂，以所述涂料组合物的重量计，其浓度在5到25重量百分比范围内；以所述涂料组合物的重量计，0.5到5重量百分比的Zn++化合物；以及以所述涂料组合物的重量计，0.5到10重量百分比的二酰肼或多元胺；以及大体上不存在的填充剂；
其中所述聚合物粒子是两相聚合物粒子，其中软相的Tg不大于0℃，并且硬相的Tg不小于30℃；其中所述软相与所述硬相的比率在90:10到60:40范围内；其条件是所述聚合物粒子的总Tg小于15℃。
2.根据权利要求1所述的涂料组合物，其中具有酮官能团的所述单体是甲基丙烯酸乙酰乙酰氧基乙酯或二丙酮丙烯酰胺，以所述丙烯酸类聚合物粒子的重量计，所述单体的浓度在1到5重量百分比范围内。
3.根据权利要求1或2所述的涂料组合物，其包含二酰肼、二胺或聚醚胺。
4.根据权利要求1到3中任一权利要求所述的涂料组合物，其中以所述组合物的重量计，所述着色剂的浓度在8到20范围内，其中所述组合物包含小于5PVC的TiO2、BaSO4、硅酸盐、铝硅酸盐、CaCO3、霞石、长石、硅灰石、高岭土、磷酸二钙以及硅藻土，并且其中所述涂料组合物包含二酰肼。
5.根据权利要求4所述的涂料组合物，其中所述着色剂是酞菁蓝、酞菁绿、单芳基化物黄、二芳基化物黄、苯并咪唑酮黄、杂环式黄、DAN橙、喹吖啶酮洋红、喹吖啶酮紫或有机红，其中所述组合物包含小于1PVC的TiO2、BaSO4、硅酸盐、铝硅酸盐、CaCO3、霞石、长石、硅灰石、高岭土、磷酸二钙以及硅藻土。
6.根据权利要求1到5中任一权利要求所述的涂料组合物，其中所述Zn++化合物是ZnO或Zn(NH3)2(CO3)2，以所述组合物的重量计，所述Zn++化合物以0.2到4重量百分比范围内的浓度存在。
7.根据权利要求3到6中任一权利要求所述的涂料组合物，其中所述二酰肼是己二酸二酰肼。
8.根据权利要求1所述的组合物，其中所述聚合物粒子具有a)第一相，以所述聚合物粒子的所述第一相的重量计，所述第一相包含45到70重量百分比的丙烯酸2-乙基己酯的结构单元，和20到50重量百分比的甲基丙烯酸甲酯或苯乙烯的结构单元；和b)第二相，以所述聚合物粒子的所述第二相的重量计，所述第二相包含85到98.5重量百分比的甲基丙烯酸甲酯或苯乙烯；
其中以所述聚合物粒子的重量计，所述聚合物粒子进一步包含4到10重量百分比的甲基丙烯酸乙酰乙酰氧基乙酯的结构单元或1到5重量百分比的二丙酮丙烯酰胺的结构单元，和0.5到5重量百分比的丙烯酸或甲基丙烯酸的结构单元。
9.根据权利要求1所述的组合物，其中所述聚合物粒子具有a)第一相，以所述聚合物粒子的所述第一相的重量计，所述第一相包含10到60重量百分比的丙烯酸丁酯的结构单元、15到65重量百分比的丙烯酸2-乙基己酯的结构单元以及10到50重量百分比的甲基丙烯酸甲酯或苯乙烯的结构单元；和b)第二相，其包含85到98.5重量百分比的甲基丙烯酸甲酯或苯乙烯；
其中以所述聚合物粒子的重量计，所述聚合物粒子进一步包含4到10重量百分比的甲基丙烯酸乙酰乙酰氧基乙酯的结构单元或1到5重量百分比的二丙酮丙烯酰胺的结构单元，和0.5到5重量百分比的丙烯酸或甲基丙烯酸的结构单元。
10.根据权利要求1到9中任一权利要求所述的涂料组合物，其进一步包括流变改性剂、消泡剂、中和剂、表面活性剂以及分散剂。
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