CN118339238A - 具有碳酸铈(iii)和光引发剂的涂料组合物 - Google Patents

具有碳酸铈(iii)和光引发剂的涂料组合物 Download PDF

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CN118339238A
CN118339238A CN202280079458.3A CN202280079458A CN118339238A CN 118339238 A CN118339238 A CN 118339238A CN 202280079458 A CN202280079458 A CN 202280079458A CN 118339238 A CN118339238 A CN 118339238A
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K·A·奥尔德弗
T·P·莫尼彭尼
J·C·勃林
J·F·卡列哈斯
S·M·博托克
D·J·布乐德尔
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Abstract

本发明涉及包含碳酸铈(III)和光引发剂的组合物。该组合物可用于受益于耐积垢性和颜色随时间的保持性的漆配方。

Description

具有碳酸铈(III)和光引发剂的涂料组合物
背景技术
本发明涉及涂料组合物，更具体地涉及包含碳酸铈(III)和光引发剂的漆组合物。本发明的组合物提供改进的耐积垢性和着色保持性。
设计用于外部应用的涂料的耐积垢性(DPUR)可以通过添加光引发剂诸如二苯甲酮及其衍生物来改进。光引发剂通过形成UV引发的自由基引发受控交联，该自由基在膜表面处与聚合物膜反应。不幸的是，由于光引发剂添加剂的存在而产生的DPUR的改进随着时间推移被涂层的增加的粉化和褪色所抵消。因此，寻找一种改进DPUR而没有明显褪色或粉化的方法将是外用漆领域的一个进步。
发明内容
本发明通过提供一种包含水、光引发剂和碳酸铈(III)的混合物的组合物来解决本领域中的需求。本发明的组合物可用于漆配方，特别是外用漆配方，其中需要耐积垢性和颜色保持性。
具体实施方式
本发明是包含水、光引发剂和碳酸铈(III)颗粒的混合物的组合物。另一方面，本发明是水、胶乳粘结剂颗粒、遮光颜料颗粒、流变改性剂、光引发剂和碳酸铈(III)颗粒的混合物。
胶乳粘结剂颗粒在室温下单独或在聚结剂的存在下是成膜的。胶乳粘结剂颗粒的示例包括例如基于丙烯酸、苯乙烯-丙烯酸、苯乙烯-丁二烯、聚氨酯、酯、烯烃、氯乙烯、乙烯乙酸乙烯酯、环氧化物、和聚乙酸乙烯酯的胶乳粘结剂颗粒，其中丙烯酸和苯乙烯-丙烯酸胶乳粘结剂颗粒是优选的。胶乳粘结剂颗粒优选地具有如通过动态光散射测量的在80nm、或100nm至500nm、或至350nm范围内的z平均粒度。
遮光颜料颗粒具有至少1.8或至少2.0的折射率以及优选地在150nm或200nm至500nm或至350nm范围内的平均粒径。颜料颗粒的平均粒径通常由颜料颗粒供应商提供。合适的遮光颜料的示例包括TiO2和ZnO，优选TiO2。
本文所用的光引发剂是当暴露于UV光时产生自由基的芳族有机化合物。一类特别的光引发剂含有在芳环α位的羰基：
其中Ar是取代或未取代的单环芳族基团，诸如苯基或被C1-C6-烷基、C1-C6-烷氧基、C1-C6-烷硫基、羰-C1-C10-烷氧基、卤素或苯基基团或其组合取代的苯基；或多环芳族基团诸如萘基、噻吨酮基、芴基、蒽基、或菲基。
光引发剂的示例包括二苯基酮诸如二苯甲酮和甲基-2-苯甲酰基苯甲酸酯；1-苯甲酰基环烷醇，诸如1-苯甲酰基环己醇；单酰基膦和二酰基膦，诸如(2,4,6-三甲基苯甲酰基)二苯基氧化膦和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦；α-羟基苯酮，诸如2-羟基-2-甲基-1-苯基-1-丙酮；C1-C6-烷基噻吨酮，诸如异丙基噻吨酮；C1-C10-烷基二甲基氨基苯甲酸酯，包括2-乙基己基-(4-N,N-二甲基氨基)苯甲酸酯；苯甲酰甲酸C1-C6-烷基酯，包括苯甲酰甲酸甲酯和苯甲酰甲酸乙酯；以及2,2-二-C1-C6-烷基-和二-C1-C6-烷氧基乙-1-酮，包括2,2-二甲氧基-1,2-二苯基乙-1-酮。
光引发剂也可以化学结合到胶乳颗粒中。例如，具有烯属不饱和度的光引发剂可以与单体共聚以形成光引发剂官能化的胶乳粘结剂颗粒。因此，在另一个方面中，组合物包含水、光引发剂、遮光颜料颗粒、流变改性剂和碳酸铈(III)颗粒的混合物，其中光引发剂为用光引发剂基团官能化的胶乳粘结剂颗粒的形式。如本文所用，“光引发剂基团”是当暴露于UV光时产生自由基的基团。可通过烯属不饱和光引发剂和其它单体诸如丙烯酸酯和甲基丙烯酸酯的乳液共聚将光引发剂化学结合到胶乳粘结剂颗粒中。光引发剂单体的示例是2-苯甲酰基苯甲酸2-羟基-3-(甲基丙烯酰氧基)丙酯：
基于组合物的重量，组合物中的光引发剂的浓度通常在0.05重量％或0.1重量％或0.2重量％至5重量％或至3重量％或至1重量％的范围内。如果光引发剂为用光引发剂基团官能化的胶乳粘结剂颗粒的形式，则浓度是指基于组合物的重量的光引发剂侧基的重量浓度。
基于遮光颜料的重量，优选TiO2的重量，碳酸铈在组合物中的浓度通常在0.2重量％或0.5重量％或1重量％至20重量％或至10重量％的范围内。碳酸铈(III)可以通过本领域已知的方法制备，例如US2020/0339435A1，从第[0100]段开始。
该组合物优选是适用于外部涂料应用的漆组合物。因此，组合物优选地还包含一种或多种选自由以下项组成的组的附加材料：表面活性剂、分散剂、聚结剂、消泡剂、杀生物剂、增量剂、着色剂和中和剂。尽管存在碳酸铈，但由本发明的组合物制备的涂料显示出非常好的DPUR，碳酸铈以前被认为可能降解DPUR。
实施例
中间体实施例1-碳酸铈糊剂的制备
在搅拌下将四水合硝酸铯(III)铵水溶液(200g的(NH4)2Ce(NO3)5·4H2O在2000g去离子水中)快速加入到碳酸铵水溶液((100g的(NH4)2CO3)在500g去离子水中)中。将反应混合物在室温下搅拌10分钟，然后通过过滤收集并用DI H2O洗涤三次，得到固体含量为18.7％的白色浆液。
表1示出了用于测试耐积垢性的漆配方。所有数字都是相对重量，并以重量份(pbw)报告。防腐剂1是指Kathon LX 1.5％防腐剂；防腐剂2是指Bioban 200防腐剂；分散剂是指TAMOLTM165A分散剂；表面活性剂是指TRITONTMHW-1000表面活性剂；有机硅添加剂是指DOWSILTM8590添加剂；TiO2是指Ti-Pure R-706TiO2；增量剂是指Minex NephelineSyenite；碳酸铈是指18.7重量％的水性碳酸铈(III)糊剂；表面活性剂2是指TERGITOLTM15-S-12表面活性剂；氨是指28重量％水性氨；胶乳是指基于丙烯酸丁酯、甲基丙烯酸甲酯、甲基丙烯酸、脲基甲基丙烯酸酯的胶乳的按重量计50％固体的水性分散体，其具有如通过Fox方程计算的2℃的Tg，通过动态光散射测量的135nm的z平均粒度；胶乳pH为8；聚结剂是指Optifilm Enhancer 400聚结剂；RM1是指ACRYSOLTMRM-3030流变改性剂；RM2是指ACRYSOLRM-995流变改性剂；并且光引发剂是指甲基-2-苯甲酰基苯甲酸酯(M2BB)在丙酮中的50重量％。(TAMOL、TRITON、DOWSIL、TERGITOL、以及ACRYSOL都是陶氏化学公司或其附属公司的商标)。
表1-漆配方
比较实施例1 比较实施例2 比较实施例3 实施例
研磨(pbw)
水 60.8 60.8 60.8 60.8
防腐剂1 1.8 1.8 1.8 1.8
防腐剂2 6.0 6.0 6.0 6.0
分散剂 8.4 8.4 8.4 8.4
表面活性剂1 2.0 2.0 2.0 2.0
有机硅添加剂 1.0 1.0 1.0 1.0
250.0 250.0 250.0 250.0
增量剂 50.0 50.0 50.0 50.0
研磨总量 380 380 380 380
添加后研磨
碳酸铈a 0.0 0.0 53.5 53.5
调稀(pbw)
水 104.2 104.2 104.2 104.2
表面活性剂2 2.0 2.0 2.0 2.0
乳胶 463.5 463.5 463.5 463.5
氨 1.0 1.0 1.0 1.0
有机硅添加剂 0.5 0.5 0.5 0.5
丙二醇 2.2 2.2 2.2 2.2
聚结剂
RM1 10.4 10.4 10.3 10.3
RM2 5.7 5.8 5.7 5.5
水 97.4 96.9 52.0 50.2
光引发剂 0.0 3.8 0.0 3.8
a将碳酸铈加入到研磨物中并使用FlackTek混合器共混。
加速实验室DPUR方法：
用于测试耐积垢性(DPUR)的加速实验室方法如下进行：将测试涂层刮涂在7.5cm×15cm铝板(约5密耳)上，随后1天的固化时间、3天的QUV调理、施用褐色氧化铁水浆以及清洁染污的板。用微热自来水温和搅拌来清洁染污的板；反射率测量用于确定涂层保持污垢的趋势。L*反射率(45/0)测量在被染污之前和在清洁污垢浆料施用之后在板上进行。从反射率读数计算ΔL*(最终L*-初始L*)值。ΔL*值越负表示污垢收集越高，即耐积垢性越差。光引发剂为M2BB。碳酸铈百分比是基于TiO2的w/w固体％。表2示出了QUV调理后的ΔL*值。
表2-QUV调理后的ΔL*值
比较实施例1 比较实施例2 比较实施例3 实施例1
光引发剂％ 0 0.8 0.8 0
碳酸铈％ 0 0 4.0 4.0
ΔL* -10.5 -0.2 -7.2 -0.4
令人惊讶地，数据显示，与仅具有光引发剂的样品相比，在含有光引发剂的漆中包含碳酸铈(III)没有不利地影响耐积垢性。由于碳酸铈(III)在单独的实验中显示出保持着色强度，因此光引发剂和碳酸铈(III)的组合给出了改进的耐积垢性和着色强度保持的难以捉摸的组合。

Claims (12)

1.一种组合物，所述组合物包含水、光引发剂和碳酸铈(III)颗粒的混合物。
2.根据权利要求1所述的组合物，所述组合物还包含胶乳粘结剂颗粒、遮光颜料颗粒、和流变改性剂。
3.根据权利要求2所述的组合物，其中所述胶乳粘结剂颗粒是基于丙烯酸、苯乙烯-丙烯酸、苯乙烯-丁二烯、聚氨酯、酯、烯烃、氯乙烯、乙烯乙酸乙烯酯、环氧化物、或聚乙酸乙烯酯的胶乳粘结剂颗粒。
4.根据权利要求2所述的组合物，其中所述遮光颜料为TiO2。
5.根据权利要求1所述的组合物，其中所述光引发剂选自由以下项组成的组：二苯基酮、1-苯甲酰基环烷醇；单酰基膦、二酰基膦；α-羟基苯酮；C1-C6-烷基噻吨酮；C1-C10-烷基二甲基氨基苯甲酸酯；2,2-二-C1-C6-烷基乙-1-酮和二-C1-C6-烷氧基乙-1-酮。
6.根据权利要求4所述的组合物，其中所述光引发剂选自由以下项组成的组：二苯甲酮；甲基-2-苯甲酰基苯甲酸酯；(2,4,6-三甲基苯甲酰基)二苯基氧化膦；双(2,4,6-三甲基苯甲酰基)苯基氧化膦；2-羟基-2-甲基-l-苯基-1-丙酮；异丙基噻吨酮；2-乙基己基-(4-N,N-二甲基氨基)苯甲酸酯；苯甲酰甲酸甲酯；苯甲酰甲酸乙酯；和2,2-二甲氧基-1,2-二苯基乙-1-酮，并且所述胶乳粘结剂颗粒是丙烯酸或苯乙烯-丙烯酸类粘结剂颗粒。
7.根据权利要求4所述的组合物，其中基于所述组合物的重量，所述光引发剂的浓度在0.1重量％至5重量％的范围内。
8.根据权利要求7所述的组合物，其中基于所述TiO2颗粒的重量，所述碳酸铈(III)的浓度在0.2重量％至20重量％的范围内。
9.根据权利要求6所述的组合物，其中基于所述TiO2颗粒的重量，所述碳酸铈(III)的浓度在0.5重量％至10重量％的范围内，并且基于所述组合物的重量，所述光引发剂的浓度在0.1重量％至1重量％的范围内；并且其中所述胶乳粘结剂颗粒是丙烯酸或苯乙烯-丙烯酸类粘结剂颗粒。
10.根据权利要求9所述的组合物，其中所述光引发剂为二苯甲酮或甲基-2-苯甲酰基苯甲酸酯。
11.根据权利要求2所述的组合物，所述组合物还包含一种或多种选自由以下项组成的组的材料：表面活性剂、分散剂、聚结剂、消泡剂、杀生物剂、增量剂、着色剂和中和剂，其中所述组合物是外用漆。
12.根据权利要求1所述的组合物，所述组合物还包含遮光颜料和流变改性剂，其中所述光引发剂为用光引发剂基团官能化的胶乳粘结剂颗粒的形式。
CN202280079458.3A 2021-12-17 2022-12-06 具有碳酸铈(iii)和光引发剂的涂料组合物 Pending CN118339238A (zh)

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