CN106349877B - 一种道路标线贴片及其制备方法 - Google Patents

一种道路标线贴片及其制备方法 Download PDF

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CN106349877B
CN106349877B CN201610774653.4A CN201610774653A CN106349877B CN 106349877 B CN106349877 B CN 106349877B CN 201610774653 A CN201610774653 A CN 201610774653A CN 106349877 B CN106349877 B CN 106349877B
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CN106349877A (zh
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刘春峰
吕会勇
李德刚
高萌
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Liaoning Shunfeng New Material Technology Co.,Ltd.
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Abstract

本发明属于涂料技术领域，尤其涉及一种道路标线贴片及其制备方法。该道路标线贴片的主要材料是采用聚氨酯包覆的人工染色玻璃微珠与水性环氧树脂复合而成的，并以氟化石墨烯作为填料、以网格布作为基底材料。此种制备方法克服了传统反光标线材料施工中加入玻璃微珠时时间不易控制的弊端，同时也增强了材料的耐水性能、耐碱性能、防滑性能和耐磨性能，大大提高了道路标线的经济价值。

Description

一种道路标线贴片及其制备方法
技术领域
本发明属于涂料技术领域，尤其涉及一种道路标线贴片及其制备方法。
背景技术
道路交通标线是由标划于路面上的各种线条、箭头、文字、立面标记、突起路标和轮廓标等所构成的交通安全设施。它的作用是管制和引导交通。道路交通标线主要划设于道路表面，经受日晒雨淋，风雪冰冻，遭受车辆的冲击磨耗，因此对其性能有严格的要求。首先要施工操作简单，以减少交通干扰；其次要求反射能力强，色彩鲜明，反光度强，使白天、夜晚都有良好的能见度；第三，应具有抗滑性和耐磨性，以保证行车安全和使用寿命。
目前，我国道路交通标线材料，主要以溶剂型标线材料与热熔型标线材料为主。但溶剂型材料，不但耐磨性差、寿命短，还对交通环境造成污染；而热熔型标线材料，具有对路面附着力好，耐候性好等特点，但施工时需加热且工艺复杂，使用其间存在易粘染灰尘和脏物等弊端。开发一种适宜我国国情，具有优良功能的道路标线材料显得尤为重要。
玻璃微珠是反光道路标线中常用的原材料，其具有良好的反光性和防滑性。但是目前反光标线材料施工过程中，在加入玻璃微珠时，存在弊端，即在施工过程中玻璃微珠的加入时间不易控制。若加入时间过早，珠体不能完全融入树脂基体，导致降低材料的反光效果；若加入时间太晚，珠体浮于树脂表面，易于脱落。因此，对于玻璃微珠进行包覆处理等更加深入的研究，将具有广阔的应用前景和巨大的经济价值。
发明内容
为了实现上述目的，本发明提供一种道路标线贴片及其制备方法。该制备方法能有效改善道路标线的反光性能、防滑性能和耐磨性能，提高道路标线的使用寿命和经济价值。
为了实现上述目的，本发明提供的道路标线贴片，其原料按质量份数配比组成如下：彩色的含有硅元素的聚氨酯预聚体40-70份、硅烷偶联剂改性的玻璃微珠10-30份、水性环氧树脂100-120份、氟化石墨烯10-20份、氯化1-烯丙基-3-甲基咪唑离子液体1-2份、聚酰胺651 5-10份；网格布尺寸为4 x 4mm,165g/m2,30cm x50cm。
道路标线贴片的制备方法，具体步骤如下。
步骤一、人工彩色玻璃微珠的包覆。
（1）彩色聚氨酯预聚体的制备：取5-10质量份的二丙二醇置于带有电动搅拌机、恒压滴液漏斗、温度计及干燥管的三口烧瓶中；在温度为110℃条件下，减压到0.02-0.04MPa，除水2h后自然冷却至65℃；加入10-30质量份浓度为30%的丙酮溶液进行稀释，同时打开电动搅拌机以1000-2000rpm搅拌。然后将1-5质量份二月桂酸二丁基锡加入到稀释液中；取10-30质量份的甲苯二异氰酸酯，用1-30质量份的浓度为30%的丙酮稀释后，全部加入到三口烧瓶中；然后加入5-10质量份色粉和1-10质量份羟基硅油，在65℃下以1000-2000rpm搅拌15-30分钟，冷却至室温，得到彩色的含有硅元素的聚氨酯预聚体。
（2）玻璃微珠的包覆：先取10-20质量份的硅烷偶联剂与10-50质量份粒径为400微米的玻璃微珠至于500ml的烧杯中，在50℃下用搅拌机以1000-2000rpm搅拌1-5分钟，制得由硅烷偶联剂改性的玻璃微珠。将10-30质量份硅烷偶联剂改性的玻璃微珠加入到40-70质量份的彩色聚氨酯预聚体中，并用高速搅拌机在1000-3000rpm下搅拌30-40分钟，即可得到被聚氨酯包覆的彩色玻璃微珠。
步骤二、道路标线贴片的制备：将100-120份水性环氧树脂加入到三口烧瓶中，在100℃的油浴中加热1-5分钟，然后真空脱水2h；再将已脱水的环氧树脂加热至50℃；将20-30份被聚氨酯包覆的人工染色玻璃微珠加入到已脱水的环氧树脂中，并加入10-20份氟化石墨烯、1-2质量份浓度为0.2%-0.3%的氯化1-烯丙基-3-甲基咪唑（[AMIM]cl）离子液体和5-10份的聚酰胺651，在1000-2000rpm在搅拌3-5分钟，得到聚氨酯与环氧树脂进行开环反应所制得的化合物；将其化合物用刮刀均匀的涂覆在尺寸为4 x 4mm,165g/m2,30cm x50cm的网格布上，涂覆厚度为1-3mm，静置4-6小时，制得道路标线贴片。
所述的水性环氧树脂为H228A环氧树脂、Ar555环氧树脂、E44环氧乳液、E20环氧乳液或E51环氧乳液中的一种。
所述的色粉为铅铬黄、铬黄或氧化铁黄中的一种。
所述的硅烷偶联剂为 Si-69、KH540、KH560、KH570、KH792或DL6021 中的一种或几种。
该标线贴片使用方法：该贴片在使用时要先将地面进行去污、除水、磨光处理，然后将贴片的另一面涂上胶黏剂，直接贴在地面上。
本发明的有益效果。
本发明中聚氨酯包覆的人工染色玻璃微珠与水性环氧树脂及氟化石墨稀三者相互作用，通过聚氨酯、氟化石墨稀和环氧树脂三者之间的反应，得到交联网状结构产物，从而提高了标线材料的耐水性能、耐碱性能、耐磨性能、抗滑性能以及使用寿命。
采用聚氨酯包覆玻璃微珠的方法，使聚氨酯与水性环氧树脂反应，进而增加了玻璃微珠与水性环氧树脂的粘结度，使玻璃微珠不易脱落。并且可以将大量的玻璃微珠堆砌在一起，而不是传统的技术中将玻璃微珠轻轻地播撒薄薄的一层，这样就避免了加入玻璃微珠的时间不易控制的弊端；玻璃微珠在贴片上端形成凹凸不平的界面，增加了标线贴片的防滑性能；加入氟化石墨烯作为填料，可以使标线贴片的耐磨性能提高；选用网格布作为基底材料，进一步的提高了标线贴片的抗拉强度和抗压强度。
与传统标线涂料繁琐的施工工艺相比，本发明的标线贴片在后期施工中简单易操作。
附图说明
图1为标线贴片结构示意图。
其中1为人工染色玻璃微珠，2为加入了氟化石墨烯的水性环氧树脂，3为网格布。
具体实施方式
下面通过具体实施例对本发明作进一步的说明。
实施例1。
道路标线贴片的制备方法，具体步骤如下。
步骤一、人工染色玻璃微珠的包覆。
（1）彩色聚氨酯预聚体的制备：取8质量份的二丙二醇置于带有电动搅拌机、恒压滴液漏斗、温度计、及干燥管的三口烧瓶中；在110℃下减压到0.04MPa除水2h后自然冷却至65℃，加入20质量份浓度为30%的丙酮溶液进行稀释，同时打开电动搅拌机并以1000rpm搅拌。然后将2质量份二月桂酸二丁基锡加入到稀释液中；取20质量份的甲苯二异氰酸酯，用20质量份浓度为30%的丙酮稀释后全部加入到三口烧瓶中，同时加入10质量份铅铬黄色粉和6质量份羟基硅油，在65℃下1000rpm搅拌30分钟，冷却至室温，得到彩色的含有硅元素的聚氨酯预聚体。
（2）玻璃微珠的包覆：先取15质量份的硅烷偶联剂与40质量份粒径为400微米的玻璃微珠至于500ml的烧杯中，在50℃下用搅拌机以1000rpm搅拌3分钟，制得由硅烷偶联剂改性的玻璃微珠（使包覆反应不能进行顺利进行）。将25质量份硅烷偶联剂改性的玻璃微珠加入到50质量份彩色聚氨酯预聚体中，并用高速搅拌机在1000rpm下搅拌30分钟，即可得到被聚氨酯包覆的彩色玻璃微珠。
步骤二、道路标线贴片的制备。
将100份E44环氧乳液加入到三口烧瓶中，在100℃的油浴中加热3分钟，然后真空脱水2h。再将已脱水的E44环氧树脂加热至50℃。将25份被聚氨酯包覆的人工染色玻璃微珠加入到E44环氧树脂中，并加入20份氟化石墨烯、2质量份的质量分数为0.2%的氯化1-烯丙基-3-甲基咪唑（[AMIM]cl）离子液体和10份的聚酰胺651，机械搅拌（1500r/min）5分钟后将其产物用刮刀均匀涂覆在网格布上，网格布尺寸为2x 4mm,165g/m2,20cm x50cm，涂覆厚度1.5mm,涂覆厚度可根据实际需要进行调整，静置4小时制得标线贴片。
实施例2。
（1）彩色聚氨酯预聚体的制备：取7质量份的二丙二醇置于带有电动搅拌机、恒压滴液漏斗、温度计、及干燥管的三口烧瓶中；在110℃下减压到0.03MPa除水2h后自然冷却至65℃，加入30质量份浓度为30%的丙酮溶液进行稀释，同时打开电动搅拌机并以1500rpm搅拌。然后将3质量份二月桂酸二丁基锡加入到稀释液中；取25质量份的甲苯二异氰酸酯，用30质量份浓度为30%的丙酮稀释后全部加入到三口烧瓶中，同时加入8质量份氧化铁黄色粉和7质量份羟基硅油，在65℃下2000rpm搅拌15分钟，冷却至室温，得到彩色的含有硅元素的聚氨酯预聚体。
（2）玻璃微珠的包覆：先取20质量份的硅烷偶联剂与50质量份粒径为400微米的玻璃微珠至于500ml的烧杯中，在50℃下用搅拌机以1500rpm搅拌2分钟，制得由硅烷偶联剂改性的玻璃微珠。将30质量份硅烷偶联剂改性的玻璃微珠加入到70质量份彩色聚氨酯预聚体中，并用高速搅拌机在1500rpm下搅拌35分钟，即可得到被聚氨酯包覆的彩色玻璃微珠。
步骤二、道路标线贴片的制备。
将110份H228A环氧树脂加入到三口烧瓶中，在100℃的油浴中加热4分钟，然后真空脱水2h。再将已脱水的H228A环氧树脂加热至50℃。将30份被聚氨酯包覆的人工染色玻璃微珠加入到H228A环氧树脂中，并加入15份氟化石墨烯、1质量份分数为0.2%的氯化1-烯丙基-3-甲基咪唑（[AMIM]cl）离子液体和5份的聚酰胺651，机械搅拌(1000rpm)4分钟后将其化合物用刮刀均匀涂覆在网格布上网格布尺寸为3 x 4mm,165g/m2,20cm x50cm，涂覆厚度2.5mm,涂覆厚度可根据实际需要进行调整，静置5小时制得标线贴片。
本发明制成的标线贴片的结构如图1所示，标号1为人工染色玻璃微珠，其在标线贴片的顶端形成了凹凸不平的界面，可以提高贴片的防滑性能。标号2为加入了氟化石墨烯的水性环氧树脂，利用其自身的特性及其与聚氨酯的反应使材料的强度以及耐磨性均有所提高，标线3为网格布，网格布的使用进一步的提高了标线贴片的抗拉强度和抗压强度，进而得到了极具使用性能的道路标线贴片。
将实施例1所制备的道路标线贴片所具备的性能与国标中的规定相比较，结果如表1所示。
表1 实施例1所制备的道路标线贴片所具备的性能。
由此可见，由此可见，本发明制备的道路标线中聚氨酯包覆的人工染色玻璃微珠与水性环氧树脂及氟化石墨稀三者相互作用得到交联网状结构，从而提高了标线材料的耐水性能、耐碱性能、耐磨性能。人工染色玻璃微珠的使用，不仅提高了表现材料的反光性，其在贴片上端形成凹凸不平的界面，还增加了标线贴片的防滑性能。

Claims (6)

1.一种道路标线贴片，其特征在于，其原料按质量份数配比组成如下：彩色的含有硅元素的聚氨酯预聚体40-70份、硅烷偶联剂改性的玻璃微珠10-30份、水性环氧树脂100-120份、氟化石墨烯10-20份、氯化1-烯丙基-3-甲基咪唑离子液体1-2份、聚酰胺651 5-10份；网格布，具体尺寸为4 x 4mm,165g/m2,30cm x50cm。
2.如权利要求1所述的道路标线贴片，其特征在于，所述的水性环氧树脂为H228A环氧树脂、Ar555环氧树脂、E44环氧乳液、E20环氧乳液或E51环氧乳液。
3.如权利要求1-2任一所述的道路标线贴片的制备方法，其特征在于，具体步骤如下：
步骤一、玻璃微珠的包覆：
（1）彩色聚氨酯预聚体的制备：取5-10质量份的二丙二醇置于带有电动搅拌机、恒压滴液漏斗、温度计及干燥管的三口烧瓶中；在温度为110℃条件下，减压到0.02-0.04MPa，除水2h后自然冷却至65℃；加入10-30质量份浓度为30%的丙酮溶液进行稀释，同时打开电动搅拌机以1000-2000rpm搅拌;然后将1-5质量份二月桂酸二丁基锡加入到稀释液中；取10-30质量份的甲苯二异氰酸酯，用1-30质量份的浓度为30%的丙酮稀释后，全部加入到三口烧瓶中；然后加入5-10质量份色粉和1-10质量份羟基硅油，在65℃下以1000-2000rpm搅拌15-30分钟，冷却至室温，得到彩色的含有硅元素的聚氨酯预聚体;
（2）玻璃微珠的包覆：先取10-20质量份的硅烷偶联剂与10-50质量份粒径为400微米的玻璃微珠至于500mL 的烧杯中，在50℃下用搅拌机以1000-2000rpm搅拌1-5分钟，制得由硅烷偶联剂改性的玻璃微珠；将10-30质量份硅烷偶联剂改性的玻璃微珠加入到40-70质量份的彩色聚氨酯预聚体中，并用高速搅拌机在1000-3000rpm下搅拌30-40分钟，即可得到被聚氨酯包覆的彩色玻璃微珠；
步骤二、道路标线贴片的制备：将100-120份水性环氧树脂加入到三口烧瓶中，在100℃的油浴中加热1-5分钟，然后真空脱水2h；再将已脱水的环氧树脂加热至50℃；将20-30份被聚氨酯包覆的彩色玻璃微珠加入到已脱水的环氧树脂中，并加入10-20份氟化石墨烯、1-2质量份浓度为0.2%-0.3%的氯化1-烯丙基-3-甲基咪唑（[AMIM]cl）离子液体和5-10份的聚酰胺651，1000-2000rpm搅拌3-5分钟，得到聚氨酯与环氧树脂进行开环反应所制得的化合物；将其化合物用刮刀均匀的涂覆在尺寸为4 x 4mm,165g/m2,30cm x50cm的网格布上，静置4-6小时，制得道路标线贴片。
4.如权利要求3所述的道路标线贴片的制备方法，其特征在于，所述的色粉为铅铬黄或氧化铁黄中的一种。
5.如权利要求3所述的道路标线贴片的制备方法，其特征在于，所述的硅烷偶联剂为Si-69、KH540、KH560、KH570、KH792或DL6021 中的一种或几种。
6.一种如权利要求1-5任一所述的道路标线贴片的使用方法，其特征在于，该贴片在使用时要先将地面进行去污、除水、磨光处理，然后将贴片的另一面涂上胶黏剂，直接贴在地面上。
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