CN115505311B - 一种包含mma树脂的环保型自发光涂料及其制备方法 - Google Patents
一种包含mma树脂的环保型自发光涂料及其制备方法 Download PDFInfo
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Abstract
本发明属于涂料制备技术领域,涉及一种包含MMA树脂的环保型自发光涂料及其制备方法。以质量份计,其原料包括:30‑50份MMA树脂、10‑20份纳米钛白粉、8‑12份纳米稀土发光材料、8‑12份钠质膨润土、30‑40份填料、3‑6份亚硫酸钠、3‑6份羧甲基纤维素、3‑10份助剂。本发明提供的自发光涂料余辉亮度高,在黑暗中持续时间较长,亮度衰减慢,其适合环保节能要求下的道路标识绘制。
Description
技术领域
本发明属于涂料制备技术领域,涉及一种包含MMA树脂的环保型自发光涂料及其制备方法。
背景技术
人类生产和使用涂料历史悠久,功能涂料是从传统涂料基础上发展起来的,能提供不同的特殊功能。自发光涂料不依靠外来能源而自身含有放射性物质而发光。自发光涂料使产品在黑暗处发出光亮,广泛应用于黑暗处作指示,特别适用于有危险或易爆场所,还能用在轻纺工业、工艺美术、印刷制品、塑料制品以及计算机键盘、显示器、钟表等方面。
MMA树脂是丙烯酸类树脂,其主要成份是甲基丙烯酸甲酯,是户外路面涂料的理想材料。MMA树脂具有良好的透光性、耐油性、耐氧化性和耐候性,对极性和非极性表面均具有很强的附着力,但其耐水性、耐沾污性差及低温变脆、高温变粘等缺点严重影响了其性能的发挥。在实际应用中,受限于道路的高温潮湿等外界环境的影响,MMA树脂用于自发光涂料的制备效果并不理想。MMA树脂所制得的自发光涂料受环境影响使用性能下降快,涂有其的道路标识线及标记亮度衰减快,使用寿命短。
发明内容
本发明的目的在于开发出路用性能好,使用寿命高,余辉亮度高,在黑暗中持续时间较长,亮度衰减慢,绿色环保的自发光涂料。
基于上述目的,本发明提供了一种包含MMA树脂的环保型自发光涂料及其制备方法来满足本领域的这种需要。
一方面,本发明提供了一种包含MMA树脂的环保型自发光涂料,以质量份计,其原料包括:30-50份MMA树脂、10-20份纳米钛白粉、8-12份纳米稀土发光材料、8-12份钠质膨润土、30-40份填料、3-6份亚硫酸钠、3-6份羧甲基纤维素、3-10份助剂;优选地,以质量份计,其原料包括:42份MMA树脂、15份纳米钛白粉、10份纳米稀土发光材料、10份钠质膨润土、35份填料、5份亚硫酸钠、5份羧甲基纤维素、5份助剂。
进一步地,本发明提供的环保型自发光涂料中,所述MMA树脂选用601树脂或765树脂中的一种。
进一步地,本发明提供的环保型自发光涂料中,所述填料选用为重钙、石英砂和沉淀硫酸钡中的一种或多种任意比例的混合物,所述填料细度为800目。
进一步地,本发明提供的环保型自发光涂料中,所述助剂为分散剂和防沉剂,所述分散剂和防沉剂选用丙烯酸改性的表面活性剂或有机硅改性的表面活性剂中的一种。
进一步地,本发明提供的环保型自发光涂料中,所述纳米钛白粉粒径为20nm。选用20nm的纳米钛白粉能有效减缓环保型自发光涂料的亮度衰减。
另一方面,本发明还提供了环保型自发光涂料的制备方法,具体包括:将MMA树脂、亚硫酸钠、羧甲基纤维素混合,将pH调至9-10,60-80℃下200-400转/分钟搅拌0.5-1h,将pH调至7-8,得到母液;将纳米钛白粉、纳米稀土发光材料、钠质膨润土、填料、助剂在常温下200-400转/分钟搅拌0.5-1h,得到预分散体;待所述母液冷却至室温,将所述预分散体研磨过300目筛,然后与所述母液500-800转/分钟搅拌0.5-1h,得到所述环保型自发光涂料。
本发明与现有技术相比具有以下有益效果或者优点:
本发明利用MMA树脂与纳米钛白粉的特点,采用亚硫酸钠和羧甲基纤维素实现对MMA树脂改性,并加入钠质膨润土进一步提高环保型自发光涂料的强度。所得环保型自发光涂料路用性能好,使用寿命高,余辉亮度高,在黑暗中持续时间较长,60min亮度衰减慢,绿色环保。
具体实施方式
为了使本领域技术人员更好地理解本发明的技术方案能予以实施,下面结合具体实施例对本发明作进一步说明,但所举实施例不作为对本发明的限定。
下述各实施例中所述实验方法和检测方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可在市场上购买得到。
实施例1
本实施例提供了一种包含MMA树脂的环保型自发光涂料的制备。
制备原料,以质量份计,30份聚甲基丙烯酸甲酯树脂601树脂、10份20nm纳米钛白粉、8份LaF3:Eu纳米片、8份钠质膨润土、30份细度为800目的重钙、3份亚硫酸钠、3份羧甲基纤维素、1份分剂散BYK163、2份防沉剂201。
将MMA树脂、亚硫酸钠、羧甲基纤维素混合,将pH调至9,60℃下200转/分钟搅拌0.5h,将pH调至7,得到母液;将纳米钛白粉、纳米稀土发光材料、钠质膨润土、填料、助剂在常温下200转/分钟搅拌0.5h,得到预分散体;待所述母液冷却至室温,将所述预分散体研磨过300目筛,然后与所述母液500转/分钟搅拌0.5h,得到所述环保型自发光涂料。
实施例2
本实施例提供了一种包含MMA树脂的环保型自发光涂料的制备。
制备原料,以质量份计,42份聚甲基丙烯酸甲酯树脂765树脂、15份20nm纳米钛白粉、10份LaF3:Eu纳米片、10份钠质膨润土、35份细度为800目的石英砂、5份亚硫酸钠、5份羧甲基纤维素、2份分剂散BYK163、3份防沉剂201。
将MMA树脂、亚硫酸钠、羧甲基纤维素混合,将pH调至9,60℃下400转/分钟搅拌1h,将pH调至7,得到母液;将纳米钛白粉、纳米稀土发光材料、钠质膨润土、填料、助剂在常温下400转/分钟搅拌1h,得到预分散体;待所述母液冷却至室温,将所述预分散体研磨过300目筛,然后与所述母液800转/分钟搅拌1h,得到所述环保型自发光涂料。
实施例3
本实施例提供了一种包含MMA树脂的环保型自发光涂料的制备。
制备原料,以质量份计,50份聚甲基丙烯酸甲酯树脂765树脂、20份20nm纳米钛白粉、12份LaF3:Eu纳米片、12份钠质膨润土、20份细度为800目的沉淀硫酸钡、20份细度为800目的石英砂、6份亚硫酸钠、6份羧甲基纤维素、4份分剂散BYK163、6份防沉剂201。
将MMA树脂、亚硫酸钠、羧甲基纤维素混合,将pH调至10,80℃下400转/分钟搅拌1h,将pH调至8,得到母液;将纳米钛白粉、纳米稀土发光材料、钠质膨润土、填料、助剂在常温下400转/分钟搅拌1h,得到预分散体;待所述母液冷却至室温,将所述预分散体研磨过300目筛,然后与所述母液800转/分钟搅拌1h,得到所述环保型自发光涂料。
实施例4
本实施例提供了一种包含MMA树脂的环保型自发光涂料的性能测试试验。
常规性能:依照GB/T 9755-2001《合成树脂乳液外墙涂料》规定进行。
耐酸雨性:按GB/T9274-1988中浸泡法进行,浸人模拟酸雨溶液48h。
紫外耐久性:按GB/T 23987-2009/ISO11507:2007《色添和清漆涂层的人工气候老化曝露曝露于荧光紫外线和水》规定进行。光源为UVA-340,辐照度为0.68W/m2。实验条件为黑板温度(60±3)℃紫外光照4h,黑板温度(50±3)℃凝露4h,连续循环交替进行。
余辉性能测试:参考DIN67510-2009第一部分《长余辉材料和制品生产厂的测量和标记》进行。将一定漆膜厚度的发光涂料测试样片制成直径50mm的圆片,测试前放入暗室24h以上,确保样片初始亮度小于0.32mcd/m2。测试时放入长余辉特性测定仪样品仓,打开激发光源照射一段时间后,测试不同时间的余辉亮度和隐没时间。
试验结果如表1所示。
表1,环保型自发光涂料性能测试
项目 | 实施例1 | 实施例2 | 实施例3 |
耐水性(168h) | 无异常 | 无异常 | 无异常 |
耐碱性(168h) | 无异常 | 无异常 | 无异常 |
耐酸雨性(168h) | 变色 | 轻微变色 | 变色 |
耐沾污性/% | 9 | 6 | 9 |
耐人工气候老化性/h | 1000 | 1200 | 1000 |
初始余辉亮度/(mcd/m2) | 875 | 901 | 871 |
60min余辉亮度/(mcd/m2) | 346 | 369 | 340 |
隐没时间/min | 744 | 828 | 749 |
如表1所示,本发明提供的耐水性、耐碱性、耐沾污性和耐人工气候老化性表现优秀,初始余辉亮度最高达到了901mcd/m2,60min余辉亮度最高为369mcd/m2,隐没时间最长达到了828。
为进一步说明20nm纳米钛白粉加入带来的性能改善效果,设置对照组1、对照组2和对照组3进行对比试验。对照组1制备原料与方法同实施例1,区别在于将20nm纳米钛白粉替换为普通钛白粉。对照组2原料与方法同实施例2,区别在于将20nm纳米钛白粉替换为普通钛白粉。对照组3材料原料与方法实施例3,区别在于将20nm纳米钛白粉替换为普通钛白粉。进行余辉性能测试,试验结果如表2所示。
表2,余辉性能对照测试
项目 | 对照组1 | 对照组2 | 对照组3 |
初始余辉亮度/(mcd/m2) | 884 | 908 | 868 |
60min余辉亮度/(mcd/m2) | 274 | 299 | 267 |
隐没时间/min | 541 | 609 | 547 |
综合表1和表2结果可知,本发明采用20nm纳米钛白粉所得自发光涂料对比各对照组,初始余辉亮度相近,但60min余辉亮度与隐没时间均高于采用普通钛白粉的对照组。本发明所得环保型自发光涂料路用性能好,使用寿命高,余辉亮度高,在黑暗中持续时间较长,60min亮度衰减慢,绿色环保。
本实施例对涂料的有害物质限量进行检测,检测结果如表3所示。
表3,有害物质检测
由表3可知,本发明提供的环保型自发光涂料无有害物质检出,产品环保性能优异。
如上所述,即可较好地实现本发明,上述的实施例仅仅是对本发明的优选实施方式进行描述,并非对本发明的范围进行限定,在不脱离本发明设计精神的前提下,本领域普通技术人员对本发明的技术方案做出的各种改变和改进,均应落入本发明确定的保护范围内。
Claims (4)
1.一种包含MMA树脂的环保型自发光涂料,其特征在于,以质量份计,其原料包括:30-50份MMA树脂、10-20份纳米钛白粉、8-12份纳米稀土发光材料、8-12份钠质膨润土、30-40份填料、3-6份亚硫酸钠、3-6份羧甲基纤维素、3-10份助剂;
所述MMA树脂选用601树脂或765树脂中的一种;
所述助剂为分散剂和防沉剂,所述分散剂和防沉剂选用丙烯酸改性的表面活性剂或有机硅改性的表面活性剂中的一种;
所述纳米钛白粉粒径为20nm;
所述环保型自发光涂料的制备方法包括:
将MMA树脂、亚硫酸钠、羧甲基纤维素混合,将pH调至9-10,60-80℃下200-400转/分钟搅拌0.5-1h,将pH调至7-8,得到母液;
将纳米钛白粉、纳米稀土发光材料、钠质膨润土、填料、助剂在常温下200-400转/分钟搅拌0.5-1h,得到预分散体;
待所述母液冷却至室温,将所述预分散体研磨过300目筛,然后与所述母液500-800转/分钟搅拌0.5-1h,得到所述环保型自发光涂料;
所述纳米稀土发光材料为LaF3:Eu纳米片。
2.根据权利要求1所述的环保型自发光涂料,其特征在于,以质量份计,其原料包括:42份MMA树脂、15份纳米钛白粉、10份纳米稀土发光材料、10份钠质膨润土、35份填料、5份亚硫酸钠、5份羧甲基纤维素、5份助剂。
3.根据权利要求1所述的环保型自发光涂料,其特征在于,所述填料选用为重钙、石英砂和沉淀硫酸钡中的一种或多种任意比例的混合物,所述填料细度为800目。
4.一种道路标识,其特征在于,采用权利要求1-3任一项所述的环保型自发光涂料绘制。
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