CN106543858A - 一种涂料助剂组合物及其在制备涂料中的用途 - Google Patents
一种涂料助剂组合物及其在制备涂料中的用途 Download PDFInfo
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Abstract
本发明公开了一种涂料助剂,它包括以下重量份数的组分:纳米颗粒0.1~40份、热塑性弹性体0.1~40份、相容剂0.01~5份。本发明涂料助剂用于制备的涂料,形成具有超疏水性能(接触角≥150°)的涂层,且经过58~75次的冻融循环,仍然具有超疏水性能,大大延长了超疏水涂层的使用寿命。
Description
技术领域
本发明涉及一种涂料助剂组合物及其在制备涂料中的用途。
背景技术
涂料助剂,又称油漆辅料,系配制涂料的辅助材料,能改进涂料性能,促进涂膜形成。种类很多,包括催干剂、增韧剂、乳化剂、增稠剂、颜料分散剂、消泡剂、流平剂、抗结皮剂、消光剂、光稳定剂、防霉剂、抗静电剂(见塑料助剂)等。涂料助剂是涂料不可缺少的组分,它可以改进生产工艺,保持贮存稳定,改善施工条件,提高产品质量,赋予特殊功能。合理正确选用助剂可降低成本,提高经济效益。
启示于自然界的“荷叶效应”,具有微纳米结构的超疏水表面具有很多独特的表面性能,如自清洁、疏水、低摩擦系数、防结冰性能等。超疏水涂层材料可广泛应用于飞机、汽车车窗、大型建筑、输电电线、风力发电机叶片、服装等,具有广阔的市场前景和空间。
通过对荷叶、羽毛等疏水物质表面结构的研究表明:超疏水涂层是由表面的微纳米材料提供粗糙结构和低表面能化学物质组成。近三十年来,学者对超疏水涂层的制备方法和应用进行了大量的研究,制备了各种性能优异的疏水材料。然而,由于机械摩擦、气候老化等原因,特别是在融冰、结冰的动融循环过程中膨胀、收缩导致乳突结构的破损和运动,表面粗糙度下降,导致疏水性能降低,难以实现长期有效的疏水性能。
针对超疏水耐久性的研究,专利CN 201010294025报道了一种采用具有光催化活性的纳米粒子、低表面能聚合物和交联剂等物质经过干燥固化,制备耐久性的超疏水自清洁涂层材料。该技术能有效解决因杂质在表面聚集而引起的疏水性能降低,但仍未解决微纳的乳突结构在使用过程中的破坏问题。专利CN201380062223公布了一种通过共价键结合颗粒与树脂,实现对颗粒的疏水性修饰,使得疏水颗粒的三位表面形貌的保留,到达耐久性的目标。但该技术方法工艺复杂,处理难度大。
发明内容
本发明的目的在于提供一种涂料助剂,能够用于制备涂料,形成具有超疏水性能(接触角≥150°)的涂层,且经过50多次冻融循环,仍然具有超疏水性能。本发明的另一目的是提供了该涂料助剂的用途,以及采用该涂料助剂制备的涂料。
本发明提供的一种涂料助剂,它包括以下重量份数的组分:纳米颗粒0.1~40份、热塑性弹性体0.1~40份、相容剂0.01~5份。
进一步的,它是由以下重量份数的组分组成:纳米颗粒0.1~40份、热塑性弹性体0.1~40份、相容剂0.01~5份;
优选的,它是由以下重量份数的组分组成:纳米颗粒5~25份、热塑性弹性体1~30份、相容剂0.05~3份;
更优选的,它是由以下重量份数的组分组成:纳米颗粒15~25份、热塑性弹性体10~15份、相容剂0.2~1.5份。
进一步的,所述纳米颗粒的粒径为5~500nm;优选的,所述纳米颗粒的粒径为30~300nm。
进一步的,所述的纳米颗粒选自纳米二氧化硅中不同粒径的两种及以上,其中,颗粒的粒径比为4:1~1:4;所述“颗粒的粒径比”是指纳米颗粒中不同颗粒的粒径的比值。
所述的热塑性弹性体为苯乙烯系热塑性弹性体;所述的相容剂选自偶氮二异丁腈、过氧化苯甲酰、过氧化二异丙苯中的一种或两种以上。
进一步的,所述的苯乙烯系热塑性弹性体选自聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物、聚苯乙烯-氢化聚丁二烯-聚苯乙烯嵌段共聚物、聚苯乙烯-氢化聚异戊二烯-聚苯乙烯嵌段共聚物中的一种或两种以上。
本发明还提供了上述的助剂组合物在制备涂料中的用途。
本发明还提供了一种由上述的助剂组合物制备的涂料,它包括以下组分:纳米颗粒、热塑性弹性体、相容剂、有机溶剂、抗氧剂、光稳定剂;其中,有机溶剂100份,抗氧剂0.01~5份、光稳定剂0.01~5份、涂料助剂0.2~80份。
进一步的所述的组分的重量配比为:有机溶剂100份、抗氧剂0.1~3份、光稳定剂0.1~3份、涂料助剂6.05~58份。
进一步的,所述的有机溶剂选自环己烷、甲苯、无水乙醇、二甲苯中的一种或两种以上。
进一步的,所述的抗氧剂选自抗氧剂1330、抗氧剂1010、抗氧剂168、抗氧剂245中的一种或两种以上;所述的光稳定剂选自光稳定剂119、光稳定剂234、光稳定剂770、光稳定剂622中的一种或两种以上。
本发明涂料的制备方法,非常简便,取各组分,混匀,即可,便于操作和控制,安全、环保、清洁,生产效率高,成本低。
本发明由纳米颗粒、热塑性弹性体和相容剂组成的涂料助剂制备涂料,形成具有超疏水性能(接触角≥150°)的涂层,且经过58~75次的冻融循环,仍然具有超疏水性能,大大延长了超疏水涂层的使用寿命。
显然,根据本发明的上述内容,按照本领域的普通技术知识和惯用手段,在不脱离本发明上述基本技术思想前提下,还可以做出其它多种形式的修改、替换或变更。
以下通过实施例形式的具体实施方式,对本发明的上述内容再作进一步的详细说明。但不应将此理解为本发明上述主题的范围仅限于以下的实例。凡基于本发明上述内容所实现的技术均属于本发明的范围。
附图说明
图1为实施例2所得超疏水涂层进行冻融循环试验前的表面形貌图。
图2为实施例2所得超疏水涂层经50次冻融循环后的表面形貌图。
具体实施方式
本发明具体实施方式中使用的原料、设备均为已知产品,通过购买市售产品获得。
其中:
无水乙醇,AR:阿拉丁试剂;环己烷,AR:阿拉丁试剂;甲苯,AR:阿拉丁试剂;偶氮二异丁腈(AIBN),AR,阿拉丁试剂;过氧化苯甲酰(BPO),AR,阿拉丁试剂;过氧化二异丙苯(DCP),AR,阿拉丁试剂;
纳米二氧化硅,粒径15nm、30nm、50nm、100nm、200nm、300nm,德固赛;
热塑性弹性体,SBS(聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物)、SEBS(聚苯乙烯-氢化聚丁二烯-聚苯乙烯嵌段共聚物),中石化巴陵石化分公司(其中,硬段苯乙烯含量为32%(wt),软段丁二烯或氢化丁二烯含量为68%(wt));
抗氧剂1330、抗氧剂1010、抗氧剂168,瑞士Ciba特种化学品公司;
光稳定剂119、光稳定剂234、光稳定剂770,瑞士Ciba特种化学品公司。
实施例1 本发明涂料的制备
将100g环己烷,2.5g纳米二氧化硅(15nm),2.5g纳米二氧化硅(50nm),1g热塑性弹性体SBS,0.05g相容剂AIBN,0.1g抗氧剂1010,0.1g光稳定剂770,混合形成溶液,在50W的超声波中超声30min,得涂层溶液,即本发明涂料。
采用10μm的涂覆仪在铝合金表面涂覆,在20℃、湿度40%环境下处理3h,在80℃的真空烘箱中固化2h,即得超疏水材料。
实施例2 本发明涂料的制备
将2g无水乙醇,98g环己烷,5g纳米二氧化硅(15nm),20g纳米二氧化硅(50nm),30g热塑性弹性体SBS,3g相容剂DCP,0.6g抗氧剂1330,0.6g光稳定剂234,混合形成溶液,在200W的超声波中超声60min,得涂层溶液,即本发明涂料。
采用250μm的涂覆仪在铝合金表面涂覆,在35℃、湿度80%环境下处理8h,在140℃的真空烘箱中固化8h,即得超疏水材料。
实施例3 本发明涂料的制备
将50g环己烷,50g甲苯,10g纳米二氧化硅(100nm),15g纳米二氧化硅(300nm),15g热塑性弹性体SBS,1.5g相容剂BPO,0.3g抗氧剂168,0.3g光稳定剂770,混合形成溶液,在100W的超声波中超声45min,得涂层溶液,即本发明涂料。
采用100μm的涂覆仪在铝合金表面涂覆,在30℃、湿度60%环境下处理6h,在120℃的真空烘箱中固化6h,即得超疏水材料。
实施例4 本发明涂料的制备
将48g环己烷,48g甲苯,4g无水乙醇,10g纳米二氧化硅(100nm),12.5g纳米二氧化硅(200nm),10g热塑性弹性体SBS,5g热塑性弹性体SEBS,0.1g相容剂BPO,0.1g相容剂AIBN,0.1g抗氧剂168,0.1g抗氧剂1330,0.1g光稳定剂770,0.3g光稳定剂234,混合形成溶液,在100W的超声波中超声45min,得涂层溶液,即本发明涂料。
采用100μm的涂覆仪在铝合金表面涂覆,在30℃、湿度60%环境下处理6h,在120℃的真空烘箱中固化4h,即得超疏水材料。
实施例5 本发明涂料的制备
将2g无水乙醇,98g甲苯,5g纳米二氧化硅(50nm)、,20g纳米二氧化硅(100nm),10g热塑性弹性体SBS,0.1g相容剂AIBN,0.1g相容剂DCP,0.5g抗氧剂1330,0.5g抗氧剂1010,0.5g抗氧剂168,0.1g光稳定剂234,0.1g光稳定剂770,0.1g光稳定剂119,混合形成溶液,在150W的超声波中超声40min,得涂层溶液,即本发明涂料。
采用70μm的涂覆仪在铝合金表面涂覆,在25℃、湿度70%环境下处理5h,在110℃的真空烘箱中固化7h,即得超疏水材料。
实施例6 本发明涂料的制备
将10g无水乙醇,90g环己烷,10g纳米二氧化硅(100nm)、5g纳米二氧化硅(30nm),10g热塑性弹性体SEBS,0.2g相容剂DCP,0.5g抗氧剂168,0.3g光稳定剂119,混合形成溶液,在50W的超声波中超声50min,得涂层溶液,即本发明涂料。
采用10μm的涂覆仪在铝合金表面涂覆,在20℃、湿度80%环境下处理7h,在130℃的真空烘箱中固化5h,即得超疏水材料。
通过以下试验例来说明本发明的有益效果。
试验例1、性能测试
将实施例1-6制备的涂层与下述对比例比较:
对比例1
将2g无水乙醇,98g环己烷,5g纳米二氧化硅15nm,10g纳米二氧化硅50nm,0.3g相容剂AIBN,0.3g抗氧剂1330,0.3g光稳定剂234,混合形成溶液,在100W的超声波中超声40min,得涂层溶液,采用70μm的涂覆仪在铝合金表面涂覆,在25℃、湿度60%环境下处理6h,在120℃的真空烘箱中固化4h,即得对比涂层B-1。
对比例1中涂料助剂中不含有垫塑性弹性体。
对比例2
将2g无水乙醇,98g甲苯,10g热塑性弹性体SBS,0.3g相容剂BPO,0.3g抗氧剂1010,0.3g光稳定剂770,混合形成溶液,在100W的超声波中超声40min,得涂层溶液,采用70μm的涂覆仪在铝合金表面涂覆,在
25℃、湿度60%环境下处理7h,在110℃的真空烘箱中固化3h,即得对比涂层B-2。
对比例2中涂料助剂不含有纳米颗粒。
对比例3
将2g无水乙醇,98g甲苯,5g纳米二氧化硅15nm,10g纳米二氧化硅(50nm),10g热塑性弹性体SBS,0.3g抗氧剂168,0.3g光稳定剂119,混合形成溶液,在80W的超声波中超声50min,得涂层溶液,采用80μm的涂覆仪在铝合金表面涂覆,在20℃、湿度60%环境下处理4h,在130℃的真空烘箱中固化6h,即得对比涂层B-3。
对比例3中不含有相容剂。
通过冻融循环试验与对比例1-3对比如下:
冻融循环试验:将蒸馏水在-20℃冰箱中冷冻3h的形成过冷水;将过冷水从倾斜成30°的涂层顶端慢慢倾倒,使涂层表面完全结冰;将结冰的涂层在-20℃的冰箱中冷冻8h;将冷冻的涂层在室温解冻16h,并在60℃的真空烘箱中干燥8h,取出在室温放置16h。以上为1次冻融循环,如此反复进行试验。
采用接触角测试仪测试经冻融循环的涂层接触角,测试结果见表1。
冻融循环周期的数值越大,表示涂层保持超疏水性能的能力越强,表示超疏水涂层的使用寿命延长。
表1、超疏水涂层的耐久性比较
本发明涂料,利用微纳米结构的组合和热塑性弹性体的微相结构的协同作用形成乳突,既能使这种乳突结构均匀的分散,又能使这种微纳米结构在使用中得到自动修复,使得微纳米结构得到很好的保持,有效的克服了因乳突结构的破坏而导致的疏水性能下降。试验结果表明,由纳米颗粒、热塑性弹性体和相容剂组成的助剂组合物制备的涂料,形成具有超疏水性能(接触角≥150°)的涂层,且经过58~75次的冻融循环,仍然具有超疏水性能,大大延长了超疏水涂层的使用寿命。
Claims (11)
1.一种涂料助剂,其特征在于:它包括以下重量份数的组分:
纳米颗粒0.1~40份、热塑性弹性体0.1~40份、相容剂0.01~5份。
2.根据权利要求1所述的涂料助剂,其特征在于:它是由以下重量份数的组分组成:纳米颗粒0.1~40份、热塑性弹性体0.1~40份、相容剂0.01~5份。
3.根据权利要求2所述的涂料助剂,其特征在于:它是由以下重量份数的组分组成:纳米颗粒5~25份、热塑性弹性体1~30份、相容剂0.05~3份。
4.根据权利要求1-3任意一项所述的涂料助剂,其特征在于:所述纳米颗粒的粒径为5~500nm。
5.根据权利要求1-3任意一项所述的涂料助剂,其特征在于:所述的纳米颗粒选自纳米二氧化硅中不同粒径的两种及以上混合,颗粒的粒径比为4:1~1:4;所述的热塑性弹性体为苯乙烯系热塑性弹性体;所述的相容剂选自偶氮二异丁腈、过氧化苯甲酰、过氧化二异丙苯中的一种或两种以上。
6.根据权利要求5所述的涂料助剂,其特征在于:所述的苯乙烯系热塑性弹性体选自聚苯乙烯-聚丁二烯-聚苯乙烯嵌段共聚物、聚苯乙烯-氢化聚丁二烯-聚苯乙烯嵌段共聚物、聚苯乙烯-氢化聚异戊二烯-聚苯乙烯嵌段共聚物中的一种或两种以上。
7.权利要求1~6任意一项所述的涂料助剂在制备涂料中的用途。
8.一种涂料,它是由权利要求1~6任意一项所述的涂料助剂、有机溶剂、抗氧剂、光稳定剂组成;组分的重量配比为:有机溶剂100份,抗氧剂0.01~5份、光稳定剂0.01~5份、涂料助剂0.2~80份。
9.根据权利要求8所述的涂料,其特征在于:所述的组分的重量配比为:有机溶剂100份、抗氧剂0.1~3份、光稳定剂0.1~3份、涂料助剂6.05~58份。
10.根据权利要求8或9所述的涂料,其特征在于:所述的有机溶剂选自环己烷、甲苯、无水乙醇、二甲苯中的一种或两种以上;所述的抗氧剂选自抗氧剂1330、抗氧剂1010、抗氧剂168、抗氧剂245中的一种或两种以上;所述的光稳定剂选自光稳定剂119、光稳定剂234、光稳定剂770、光稳定剂622中的一种或两种以上。
11.权利要求8所述的涂料在制备超疏水材料中的应用。
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