CN103013280B - Self-luminous road marking material doped with waste ceramic particles and preparation method - Google Patents
Self-luminous road marking material doped with waste ceramic particles and preparation method Download PDFInfo
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Abstract
本发明涉及公路路面标线材料，公开了一种掺废旧陶瓷颗粒的自发光道路标线涂料及其制备方法。该材料包括以下重量百分比组分：50%～60%的废旧陶瓷颗粒、10～15%的卤磷酸钙荧光粉、15～20%的环氧树脂、2～5%的593#固化剂、10～15%的二氧化钛或铬黄、0.2～0.8%的Triton X-405表面活性剂。其制备方法是：将废旧陶瓷颗粒、卤磷酸钙荧光粉、二氧化钛或铬黄、Triton X-405表面活性剂，依次放入拌合桶中搅拌均匀；然后，加入环氧树脂及593#固化剂，并将拌合桶置于加热炉上进行搅拌加热，温度控制在50℃～60℃，加热20min～30min，至混合均匀即可出料；最后冷却成型。The invention relates to a highway pavement marking material, and discloses a self-luminous road marking paint mixed with waste ceramic particles and a preparation method thereof. The material includes the following components in weight percent: 50% to 60% of waste ceramic particles, 10 to 15% of calcium halophosphate fluorescent powder, 15 to 20% of epoxy resin, 2 to 5% of 593 # curing agent, 10 ～15% titanium dioxide or chrome yellow, 0.2～0.8% Triton X-405 surfactant. The preparation method is as follows: put waste ceramic particles, calcium halophosphate fluorescent powder, titanium dioxide or chrome yellow, and Triton X-405 surfactant into a mixing tank and stir evenly; then, add epoxy resin and 593 #curing agent , and place the mixing barrel on a heating furnace for stirring and heating, the temperature is controlled at 50°C to 60°C, and it is heated for 20min to 30min until it is evenly mixed and the material can be discharged; finally, it is cooled and formed.
Description
技术领域technical field
本发明涉及公路路面标志线材料制备领域，特别涉及一种掺废旧陶瓷颗粒的自发光道路标线涂料及其制备方法。The invention relates to the field of preparation of highway pavement marking line materials, in particular to a self-luminous road marking paint mixed with waste ceramic particles and a preparation method thereof.
背景技术Background technique
随着社会经济及陶瓷工业的迅速发展，陶瓷工业产生的废料日益增多，它不仅对城市环境造成了巨大的影响，还限制了城市经济及陶瓷工业的可持续发展，合理地进行陶瓷工业废料的处理和回收利用废旧陶瓷显得尤为重要。With the rapid development of social economy and ceramic industry, the waste generated by the ceramic industry is increasing day by day. It not only has a huge impact on the urban environment, but also limits the sustainable development of the urban economy and the ceramic industry. It is particularly important to process and recycle waste ceramics.
事实上，废旧陶瓷是一种不容忽视的可再生资源。在国家发改委颁布的《“十二五”资源综合利用指导意见》中，明确提出“加强废陶瓷综合利用技术研发和推广应用，鼓励废陶瓷用于生产陶瓷建材产品以及建筑工程等”要求。由此可见，实现废旧陶瓷回收利用意义重大。在陶瓷产品的其他生产过程中，从原料处理、混料、球磨到坯体制备、成形、干燥等全过程都会产生废料，包括坯体废料、废釉料、半成品废料、烧成废料、废石膏、废匣钵及废棚板等。除此以外，废弃的建筑陶瓷产品、日用生活陶瓷、专用陶瓷的废料等陶瓷工业废料、废渣也日益增多。In fact, waste ceramics is a renewable resource that cannot be ignored. In the "Twelfth Five-Year Plan" Guidelines for the Comprehensive Utilization of Resources promulgated by the National Development and Reform Commission, it is clearly proposed to "strengthen the research and development, promotion and application of waste ceramic comprehensive utilization technologies, and encourage waste ceramics to be used in the production of ceramic building materials and construction projects." It can be seen that it is of great significance to realize the recycling of waste ceramics. In other production processes of ceramic products, waste materials will be generated in the whole process from raw material processing, mixing, ball milling to green body preparation, forming, drying, etc., including green body waste, waste glaze, semi-finished waste, firing waste, waste gypsum , waste saggers and waste shed boards, etc. In addition, ceramic industrial waste and slag such as discarded architectural ceramic products, daily-use ceramics, and special-purpose ceramics are also increasing.
在人们的日常生活中，人行横道线、安全线等道路交通标志线是疏导交通、指导车辆运行，保障行人安全的重要标志。目前，标线材料多为常温溶剂型、加热溶剂型和热熔型三种。但是，在使用中却存在耐久性差、易脱落、易耗损、低温开裂和变色等问题。In people's daily life, road traffic marking lines such as pedestrian crossing lines and safety lines are important signs to guide traffic, guide vehicle operation, and ensure pedestrian safety. At present, marking materials are mostly three types: normal temperature solvent type, heating solvent type and hot melt type. However, in use, there are problems such as poor durability, easy to fall off, easy to wear, low temperature cracking and discoloration.
发明内容Contents of the invention
本发明的目的在于在提供一种掺废旧陶瓷颗粒的自发光道路标线材料及制备方法，其成本低廉、工艺简单、性能优良、经济环保。The object of the present invention is to provide a self-luminous road marking material mixed with waste ceramic particles and a preparation method thereof, which has low cost, simple process, excellent performance, and is economical and environmentally friendly.
为了达到上述目的，本发明采用以下技术方案予以实现。In order to achieve the above object, the present invention adopts the following technical solutions to achieve.
（1）一种掺废旧陶瓷颗粒的自发光道路标线材料，其特征在于，包括以下重量百分比组分：50%～60%的废旧陶瓷颗粒、10～15%的卤磷酸钙荧光粉、15～20%的环氧树脂、2～5%的593#固化剂、10～15%的二氧化钛或铬黄、0.2～0.8%的Triton X-405表面活性剂。(1) A self-illuminating road marking material mixed with waste ceramic particles, which is characterized in that it includes the following components in weight percentage: 50% to 60% of waste ceramic particles, 10 to 15% of calcium halophosphate fluorescent powder, 15% ～20% epoxy resin, 2～5% 593 # curing agent, 10～15% titanium dioxide or chrome yellow, 0.2～0.8% Triton X-405 surfactant.
所述废旧陶瓷为粒径介于0.3mm～0.075mm的颗粒。The waste ceramics are particles with a particle size ranging from 0.3 mm to 0.075 mm.
所述环氧树脂为E-51环氧树脂，其化学成分是双酚A和环氧氯丙烷在碱性介质中缩聚合成的线型化合物，分子量约为300的环氧树脂，无臭无味，常温下为液体。The epoxy resin is E-51 epoxy resin, and its chemical composition is a linear compound formed by polycondensation of bisphenol A and epichlorohydrin in an alkaline medium. The epoxy resin with a molecular weight of about 300 is odorless and tasteless. It is liquid at room temperature.
所述593#固化剂，为二亚乙基三胺与丁基缩水甘油醚的加成物，毒性小，对湿气和空气中二氧化碳吸收量很小，不会产生涂层起雾、白化等问题。The 593# curing agent is an adduct of diethylenetriamine and butyl glycidyl ether, has low toxicity, has a small absorption of carbon dioxide in moisture and air, and will not cause coating fogging, whitening, etc. question.
所述卤磷酸钙荧光粉（CaHPO4），白色粉末，卤磷酸钙荧光粉是由激活剂锑（Sb）和锰（Mn）共同激活发光。The calcium halophosphate phosphor (CaHPO 4 ), a white powder, is activated by activators antimony (Sb) and manganese (Mn) to emit light.
所述二氧化钛和铬黄为着色颜料，分别为R930钛白粉和耐热铬黄，其中耐热铬黄分子式为PbCrO4，黄色单斜结晶或橙黄色粉末，密度为6.12g/cm3，不溶于水和油，着色力高。Described titanium dioxide and chrome yellow are colored pigments, are respectively R930 titanium dioxide and heat-resistant chrome yellow, wherein heat-resistant chrome yellow molecular formula is PbCrO4, yellow monoclinic crystal or orange-yellow powder, density is 6.12g/cm3, insoluble in water and Oil, high tinting strength.
所述Triton X-405表面活性剂（壬基酚聚氧乙烯醚），透明液体，25℃黏度为490mPa·s。The Triton X-405 surfactant (nonylphenol polyoxyethylene ether) is a transparent liquid with a viscosity of 490 mPa·s at 25°C.
（2）上述掺废旧陶瓷颗粒的自发光道路标线材料的制备方法，其特征在于，包括以下步骤：首先按照重量百分比称取各组分；再将废旧陶瓷颗粒、卤磷酸钙荧光粉、二氧化钛或铬黄、Triton X-405表面活性剂，依次放入拌合桶中搅拌均匀；然后，加入环氧树脂及593#固化剂，并将拌合桶置于加热炉上进行搅拌加热，温度控制在50℃～60℃，加热20min～30min，至混合均匀即可出料；最后，冷却成型。(2) The method for preparing the above-mentioned self-luminous road marking material mixed with waste ceramic particles is characterized in that it includes the following steps: firstly weigh each component according to weight percentage; then mix waste ceramic particles, calcium halophosphate fluorescent powder, titanium dioxide Or chrome yellow, Triton X-405 surfactant, put into the mixing barrel and stir evenly; Then, add epoxy resin and 593 # curing agent, and place the mixing barrel on the heating furnace for stirring and heating, temperature control Heat at 50°C-60°C for 20min-30min until the mixture is uniform and then discharge; finally, cool and form.
在本发明中，以废旧陶瓷颗粒为基体，废旧陶瓷的主要化学成分是SiO2和Al2O3。利用陶瓷本身耐高温、耐磨、耐腐蚀、抗氧化、电绝缘、强度大、硬度高等优良性能，使涂料具有强附着力、耐磨性、耐候性、抗污染、抗变色、抗滑性、自洁功能和经济环保性。In the present invention, the waste ceramic particles are used as the matrix, and the main chemical components of the waste ceramics are SiO 2 and Al 2 O 3 . Utilizing the excellent properties of ceramics such as high temperature resistance, wear resistance, corrosion resistance, oxidation resistance, electrical insulation, high strength and high hardness, the coating has strong adhesion, wear resistance, weather resistance, pollution resistance, discoloration resistance, skid resistance, Self-cleaning function and economic environmental protection.
环氧树脂与路面界面有着优良的粘结力，并且陶瓷颗粒与环氧树脂吸附、相容性较好，标线施工后，环氧树脂与固化剂产生化学交联作用，混溶体冷却固结形成一层致密的膜。The interface between epoxy resin and pavement has excellent bonding force, and the ceramic particles and epoxy resin have good adsorption and compatibility. After the marking construction, the epoxy resin and the curing agent produce chemical crosslinking, and the mixture is cooled and solidified form a dense film.
卤磷酸钙荧光粉加入该自发光道路标线材料中，使该材料具有自发光功能，增强标线夜间被识别能力，使夜间行车安全可靠性能得以提高。Calcium halophosphate fluorescent powder is added to the self-luminous road marking material, so that the material has a self-luminous function, enhances the ability of marking lines to be recognized at night, and improves the safety and reliability of driving at night.
本发明的掺废旧陶瓷颗粒的自发光道路标线材料及制备方法，其成本低廉、工艺简单、性能优良、经济环保。施工时，仅需将黏稠状态的掺废旧陶瓷颗粒的自发光道路标线材料，置于预先准备好的模子中，使其表面平滑，冷却大约1-2小时即可。The self-illuminating road marking material mixed with waste ceramic particles and the preparation method of the present invention have low cost, simple process, excellent performance, economical and environmental protection. During construction, it is only necessary to place the viscous self-illuminating road marking material mixed with waste ceramic particles into the pre-prepared mold to smooth the surface and cool it for about 1-2 hours.
具体实施方式Detailed ways
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于所述实施例。In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the examples.
实施例1（对照实施例）：Embodiment 1 (comparative embodiment):
通用的热塑性道路标线材料，组成为滑石粉、石油树脂、二氧化钛或耐热铬黄、矿物油；其重量百分比分别为：62%、18%、10%、10%。二氧化钛或耐热铬黄为颜料，本实施例择一选用二氧化钛。将上述组分混合、加热熔融，最后冷却成型。The common thermoplastic road marking material is composed of talcum powder, petroleum resin, titanium dioxide or heat-resistant chrome yellow, and mineral oil; its weight percentages are: 62%, 18%, 10%, and 10%, respectively. Titanium dioxide or heat-resistant chrome yellow is used as the pigment, and titanium dioxide is chosen in this embodiment. The above components are mixed, heated and melted, and finally cooled and shaped.
实施例2：Example 2:
称取废旧陶瓷颗粒（粒径介于0.3mm～0.075mm的颗粒）、卤磷酸钙荧光粉、E-51环氧树脂、593#固化剂、耐热铬黄、Triton X-405表面活性剂；其重量百分比分别为：53.5%、14%、15%、2%、15%、0.5%。Weigh waste ceramic particles (particles with a particle size between 0.3mm and 0.075mm), calcium halophosphate phosphor, E-51 epoxy resin, 593 # curing agent, heat-resistant chrome yellow, and Triton X-405 surfactant; The weight percentages are respectively: 53.5%, 14%, 15%, 2%, 15%, and 0.5%.
再将废旧陶瓷颗粒、卤磷酸钙荧光粉、铬黄、Triton X-405表面活性剂，依次放入拌合桶中搅拌均匀；然后，加入环氧树脂及593#固化剂，并将拌合桶置于加热炉上进行搅拌加热，温度控制在50℃，加热30min，至混合均匀即可出料；最后，冷却成型。Then put waste ceramic particles, calcium halophosphate fluorescent powder, chrome yellow, and Triton X-405 surfactant into the mixing bucket and stir evenly; then, add epoxy resin and 593 # curing agent, and put the mixing bucket Put it on a heating furnace for stirring and heating, the temperature is controlled at 50°C, and it is heated for 30 minutes until it is evenly mixed and then discharged; finally, it is cooled and formed.
实施例3：Example 3:
称取废旧陶瓷颗粒（粒径介于0.3mm～0.075mm的颗粒）、卤磷酸钙荧光粉、E-51环氧树脂、593#固化剂、二氧化钛（R930钛白粉）、Triton X-405表面活性剂；其重量百分比分别为：52%、13%、17%、2.6%、15%、0.4%。Weigh waste ceramic particles (particles with a particle size between 0.3mm and 0.075mm), calcium halophosphate phosphor, E-51 epoxy resin, 593 # curing agent, titanium dioxide (R930 titanium dioxide), Triton X-405 surface active agent; its weight percentages are: 52%, 13%, 17%, 2.6%, 15%, 0.4%.
再将废旧陶瓷颗粒、卤磷酸钙荧光粉、二氧化钛、Triton X-405表面活性剂，依次放入拌合桶中搅拌均匀；然后，加入环氧树脂及593#固化剂，并将拌合桶置于加热炉上进行搅拌加热，温度控制在60℃，加热20min，至混合均匀即可出料；最后，冷却成型。Then put waste ceramic particles, calcium halophosphate fluorescent powder, titanium dioxide, and Triton X-405 surfactant into the mixing bucket and stir evenly; then, add epoxy resin and 593 # curing agent, and put the mixing bucket Stir and heat on a heating furnace, control the temperature at 60°C, heat for 20 minutes, until the mixture is uniform and then discharge; finally, cool and shape.
实施例4：Example 4:
称取废旧陶瓷颗粒（粒径介于0.3mm～0.075mm的颗粒）、卤磷酸钙荧光粉、E-51环氧树脂、593#固化剂、二氧化钛（R930钛白粉）、Triton X-405表面活性剂；其重量百分比分别为：58%、12%、16%、2.5%、11%、0.5%。Weigh waste ceramic particles (particles with a particle size between 0.3mm and 0.075mm), calcium halophosphate phosphor, E-51 epoxy resin, 593 # curing agent, titanium dioxide (R930 titanium dioxide), Triton X-405 surface active agent; its weight percentages are: 58%, 12%, 16%, 2.5%, 11%, 0.5%.
再将废旧陶瓷颗粒、卤磷酸钙荧光粉、二氧化钛、Triton X-405表面活性剂，依次放入拌合桶中搅拌均匀；然后，加入环氧树脂及593#固化剂，并将拌合桶置于加热炉上进行搅拌加热，温度控制在55℃，加热25min，至混合均匀即可出料；最后，冷却成型。Put the waste ceramic particles, calcium halophosphate fluorescent powder, titanium dioxide, and Triton X-405 surfactant in turn into the mixing tank and stir evenly; then, add epoxy resin and 593 # curing agent, and put the mixing tank Stir and heat on the heating furnace, the temperature is controlled at 55°C, heat for 25 minutes, until the mixture is uniform and then discharge; finally, cool and shape.
实施例5：Example 5:
称取废旧陶瓷颗粒（粒径介于0.3mm～0.075mm的颗粒）、卤磷酸钙荧光粉、E-51环氧树脂、593#固化剂、二氧化钛（R930钛白粉）、Triton X-405表面活性剂；其重量百分比分别为：55%、12%、19.5%、3.2%、10%、0.3%。Weigh waste ceramic particles (particles with a particle size between 0.3mm and 0.075mm), calcium halophosphate phosphor, E-51 epoxy resin, 593 # curing agent, titanium dioxide (R930 titanium dioxide), Triton X-405 surface active agent; its weight percentages are: 55%, 12%, 19.5%, 3.2%, 10%, 0.3%.
再将废旧陶瓷颗粒、卤磷酸钙荧光粉、二氧化钛、Triton X-405表面活性剂，依次放入拌合桶中搅拌均匀；然后，加入环氧树脂及593#固化剂，并将拌合桶置于加热炉上进行搅拌加热，温度控制在55℃，加热25min，至混合均匀即可出料；最后，冷却成型。Then put waste ceramic particles, calcium halophosphate fluorescent powder, titanium dioxide, and Triton X-405 surfactant into the mixing bucket and stir evenly; then, add epoxy resin and 593 # curing agent, and put the mixing bucket Stir and heat on the heating furnace, the temperature is controlled at 55°C, heat for 25 minutes, until the mixture is uniform and then discharge; finally, cool and shape.
按照对照实施例1和实施例2、实施例3、实施例4、实施例5的配比关系制备5种道路标线材料样品。Prepare 5 kinds of road marking material samples according to the proportioning relation of comparative example 1 and embodiment 2, embodiment 3, embodiment 4, embodiment 5.
表1是本发明实施例样品与对照实施例样品的主要技术性能，包括：不粘胎干燥时间、常温抗压强度、高温动稳定度、耐磨性、夜间相对荧光强度的检测结果。Table 1 shows the main technical properties of the samples of the examples of the present invention and the samples of the comparative examples, including: the test results of non-stick tire drying time, normal temperature compressive strength, high temperature dynamic stability, wear resistance, and nighttime relative fluorescence intensity.
表1道路标线材料技术性能对比Table 1 Comparison of technical performance of road marking materials
*荧光强度测定一般以绿光（λ=546nm）为准。荧光强度随激发时间、激发光谱的不同而变化，测定值是在同一激发条件下与标准片相对比，换算而求得，以相对荧光强度值和绝对荧光强度值两种型式表示，相对荧光强度是以标准片的荧光强度为100而换算得到的荧光强度，绝对荧光强度值是与标准片的荧光强度精确值对比取得。*The measurement of fluorescence intensity is generally based on green light (λ=546nm). The fluorescence intensity varies with the excitation time and excitation spectrum. The measured value is obtained by comparing with the standard film under the same excitation conditions and converted. It is expressed in two types: relative fluorescence intensity value and absolute fluorescence intensity value. Relative fluorescence intensity The fluorescence intensity is obtained by converting the fluorescence intensity of the standard film into 100, and the absolute fluorescence intensity value is obtained by comparing with the accurate value of the fluorescence intensity of the standard film.
从表1中数据可以看出，掺加废旧陶瓷颗粒及荧光物质的道路标线材料，该材料的不粘胎干燥时间缩短，常温抗压强度、高温动稳定度、耐磨性均得到提高，荧光效果明显。It can be seen from the data in Table 1 that the road marking material mixed with waste ceramic particles and fluorescent substances can shorten the non-stick drying time of the material, and improve the compressive strength at room temperature, high-temperature dynamic stability and wear resistance. The fluorescent effect is obvious.
本发明本着绿色环保的理念，着眼于废旧陶瓷的回收利用技术，利用陶瓷耐高温、高强度等优良性能；同时添加荧光物质，使涂料夜间有荧光作用，避免玻璃珠质量和脱落引起的反光作用衰减的影响。制备的掺废旧陶瓷颗粒的自发光道路标线涂料，既能回收利用废旧陶瓷，又能解决一般道路标线所存在的耐久性差等一系列问题，其可实施性和应用前景符合低碳、绿色环保的可持续发展的要求。Based on the concept of green and environmental protection, the present invention focuses on the recycling technology of waste ceramics, and utilizes the excellent properties of ceramics such as high temperature resistance and high strength; at the same time, fluorescent substances are added to make the coating have fluorescent effect at night, and avoid the reflection caused by the quality and shedding of glass beads The effect of attenuation. The prepared self-luminous road marking paint mixed with waste ceramic particles can not only recycle waste ceramics, but also solve a series of problems such as poor durability of general road markings. Its implementability and application prospects are in line with low-carbon, green Environmentally friendly and sustainable development requirements.
本发明解决了传统的热熔型道路标线涂料所存在的耐久性差、易脱落、易耗损、低温易开裂和变色、成本高的问题，同时也提供了一种直接利用废旧陶瓷的新方法，为节约能源、解决“白色污染”问题开辟了新途径。该材料具备高耐磨性、防水耐腐、荧光效果好和绿色环保等优良性能。The invention solves the problems of poor durability, easy falling off, easy wear, easy cracking and discoloration at low temperature, and high cost existing in traditional hot-melt road marking paints, and also provides a new method for directly utilizing waste ceramics, It has opened up a new way to save energy and solve the problem of "white pollution". The material has excellent properties such as high wear resistance, waterproof and corrosion resistance, good fluorescent effect and green environmental protection.
尽管以上结合实施例对本发明的实施方案进行了描述，但本发明并不局限于上述的具体实施方案，上述的具体实施方案仅仅是示意性的、指导性的，而不是限制性的。本领域的普通技术人员在本说明书的启示下，在不脱离本发明权利要求所保护的范围的情况下，还可以做出很多种的形式，这些均属于本发明保护之列。Although the embodiments of the present invention have been described above in conjunction with the examples, the present invention is not limited to the above specific embodiments, and the above specific embodiments are only illustrative, instructive, and not restrictive. Under the enlightenment of this description, those skilled in the art can also make many forms without departing from the protection scope of the claims of the present invention, and these all belong to the protection of the present invention.
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| CN101177587A (en) * | 2006-11-07 | 2008-05-14 | 吕耀康 | Hot-melting road mark paint prepared by employing waste plastics |
| CN101817658A (en) * | 2010-03-11 | 2010-09-01 | 王健懿 | Reflective color vibration deceleration marked line composite and purpose thereof |
| CN102093764A (en) * | 2010-12-31 | 2011-06-15 | 长安大学 | Colorful selective solar heat reflective coating for asphalt pavement |
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| CN101177587A (en) * | 2006-11-07 | 2008-05-14 | 吕耀康 | Hot-melting road mark paint prepared by employing waste plastics |
| CN101817658A (en) * | 2010-03-11 | 2010-09-01 | 王健懿 | Reflective color vibration deceleration marked line composite and purpose thereof |
| CN102093764A (en) * | 2010-12-31 | 2011-06-15 | 长安大学 | Colorful selective solar heat reflective coating for asphalt pavement |
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