CN107987643B - Application of waterproof corrosion-resistant traffic sign luminous material - Google Patents

Application of waterproof corrosion-resistant traffic sign luminous material Download PDF

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CN107987643B
CN107987643B CN201711405098.9A CN201711405098A CN107987643B CN 107987643 B CN107987643 B CN 107987643B CN 201711405098 A CN201711405098 A CN 201711405098A CN 107987643 B CN107987643 B CN 107987643B
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traffic sign
luminous paint
organic solvent
resistant traffic
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CN107987643A (en
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李蕊
王延泽
宋维伟
王中恺
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Shandong Haisen Weiye New Material Co.,Ltd.
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Lianjiang Wei Jia Industrial Design Co Ltd
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Abstract

the invention discloses an application of a waterproof corrosion-resistant traffic sign luminous paint, which is prepared from the following raw materials in percentage by weight: 30-45 wt% of hydrophobic film-forming agent, 10-20 wt% of rare earth doped alkaline earth metal aluminate long afterglow luminescent material, 10-15 wt% of organic solvent, 5-15 wt% of gas phase nano silicon dioxide and the balance of organic bentonite anti-settling agent. The waterproof corrosion-resistant traffic sign luminous paint disclosed by the invention is non-toxic, non-radioactive and stable in chemical performance, can automatically and continuously emit light after absorbing various visible lights such as sunlight, lamplight and ambient stray light, can prevent most of rare earth doped alkaline earth metal aluminate long-afterglow luminous materials from hydrolyzing after being corroded by water, can continuously emit light, and has good waterproofness and corrosion resistance.

Description

Application of waterproof corrosion-resistant traffic sign luminous material
The invention relates to a divisional application of a parent application of a waterproof and corrosion-resistant traffic sign noctilucent material, a preparation method and application thereof, wherein the parent application has an application number of 2015110336865, and the application date of 2015 is 12 months and 30 days.
Technical Field
The invention belongs to the field of luminescent materials, and particularly relates to an application of a waterproof and corrosion-resistant traffic sign noctilucent material.
Background
The road traffic sign is a graphic symbol for displaying traffic laws and regulations and road information, and can express the traffic laws and regulations visually, specifically and concisely, and can also express the contents which are difficult to describe by characters, so as to manage traffic and indicate the driving direction, thereby ensuring the facilities of smooth road and driving safety. Most of the road traffic signs used at present are coated with reflective coatings, and generally do not have the function of night luminescence. However, if there is no street light on the road, such passive reflective traffic signs can only function at night with vehicles having illumination means, but substantially not with pedestrians and cyclists having no illumination means. Therefore, the active luminous type luminous traffic sign coating is very important. As a traffic sign luminous paint, the paint needs to be exposed to rainwater and humid environment for a long time, and has high requirements on the waterproofness and the corrosion resistance of the paint. At present, the luminous traffic sign is generally formed by directly coating luminous paint on a road, and rare earth doped alkaline earth metal aluminate long-afterglow luminescent materials are added into the luminous paint, so that the luminous traffic sign is easy to hydrolyze with rainwater and water vapor in the air, and the guiding and dredging effects of the luminous traffic sign are lost. Rare earth doped alkaline earth metal aluminate long afterglow luminescent material SrAl2O4：Eu2+，Dy3+For example, in SrAl2O4：Eu2+，Dy3+When contacting with water, the hydrolysis reaction of SrAl occurs slowly2O4+4H2O→Sr2++2OH-+2Al(OH)3×) and the reaction can generate aluminum hydroxide, and the pH value of the system is increased, thereby destroying the original crystal structure of the luminescent powder and influencing the acid-base balance of the system. Under the influence of rain and moisture, the luminous intensity of the rare earth doped alkaline earth metal aluminate long afterglow luminescent material is reduced by at least 50 percent, even no luminescence at all.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a waterproof corrosion-resistant traffic sign luminous material containing a rare earth doped alkaline earth metal aluminate long-afterglow luminescent material, a preparation method and application thereof.
the purpose of the invention is realized by the following technical scheme.
A waterproof corrosion-resistant traffic sign luminous paint is prepared from the following raw materials in percentage by weight: 30-45 wt% of hydrophobic film-forming agent, 10-20 wt% of rare earth doped alkaline earth metal aluminate long afterglow luminescent material, 10-15 wt% of organic solvent, 5-15 wt% of gas phase nano silicon dioxide and the balance of organic bentonite anti-settling agent; wherein the organic solvent is a mixture of xylene, ethyl acetate and butanol, the hydrophobic film-forming agent is organic silicon resin, a mixture of organic fluororesin and acrylic resin or organic fluorine-silicon modified acrylic resin, and the rare earth doped alkaline earth metal aluminate long-afterglow luminescent material is SrAl2O4：Eu2+，Dy3+、CaAl2O4：Eu2+，Nd3+or Sr4Al14O25：Eu2+，Dy3+The ratio of xylene, butanol and ethyl acetate in the organic solvent is (4-35) by mass: (4-35): 1, the ratio of the organic silicon resin, the organic fluororesin and the acrylic resin in the hydrophobic film forming agent is (0.2-0.5): (0.2-0.5): 1.
In the technical scheme, 35-40 wt% of hydrophobic film-forming agent, 13-17 wt% of rare earth doped alkaline earth metal aluminate long afterglow luminescent material, 12-14 wt% of organic solvent, 7-13 wt% of gas phase nano silicon dioxide and the balance of organic bentonite anti-settling agent.
in the technical scheme, the particle size of the gas-phase nano silicon dioxide is 5-50 nanometers.
In the above technical scheme, the ratio of xylene, butanol and ethyl acetate in the organic solvent is (20-30) by mass: (20-30): 1.
a preparation method of the waterproof corrosion-resistant traffic sign luminous paint comprises the step of uniformly mixing a hydrophobic film-forming agent, a rare earth-doped alkaline earth metal aluminate long-afterglow luminescent material, an organic solvent, gas-phase nano silicon dioxide and an organic bentonite anti-settling agent in proportion at the room temperature of 20-25 ℃ to obtain the waterproof corrosion-resistant traffic sign luminous paint.
In the technical scheme, 35-40 wt% of hydrophobic film-forming agent, 13-17 wt% of rare earth doped alkaline earth metal aluminate long afterglow luminescent material, 12-14 wt% of organic solvent, 7-13 wt% of gas phase nano silicon dioxide and the balance of organic bentonite anti-settling agent.
In the technical scheme, the particle size of the gas-phase nano silicon dioxide is 5-50 nanometers.
In the above technical scheme, the ratio of xylene, butanol and ethyl acetate in the organic solvent is (20-30) by mass: (20-30): 1.
the application of the waterproof corrosion-resistant traffic sign luminous paint as an indicating luminous body is characterized in that a plurality of layers of the waterproof corrosion-resistant traffic sign luminous paint are uniformly sprayed or brushed on the surface of a road, wherein after one layer of the waterproof corrosion-resistant traffic sign luminous paint is sprayed or brushed, the layer of the waterproof corrosion-resistant traffic sign luminous paint is dried at the temperature of 20-80 ℃ for 0.5-6 hours until the waterproof corrosion-resistant traffic sign luminous paint layer is solidified.
The waterproof corrosion-resistant traffic sign luminous paint disclosed by the invention is non-toxic, non-radioactive and stable in chemical performance, can automatically and continuously emit light without a power supply after absorbing various visible lights such as sunlight, lamplight and environmental stray light, can prevent most of rare earth doped alkaline earth metal aluminate long-afterglow luminous materials from hydrolyzing after being corroded by water, can continuously emit light after being contacted with the rare earth doped alkaline earth metal aluminate long-afterglow luminous materials, and has good waterproofness and corrosion resistance.
Detailed Description
Xylene, ethyl acetate, fumed nano-silica, and butanol in this example were all purchased from alatin reagent (shanghai) ltd, where the molecular weight of xylene was 106.17, product number was X112050; the molecular weight of the ethyl acetate is 88.11, and the product number is E116131; the butanol is n-butanol, has molecular weight of 74.12, and product number of B111573; the product number of the gas phase nano silicon dioxide is S104599, and the particle size is 7-40 nanometers. The organic bentonite anti-settling agent is purchased from Shanghai Dabang chemical Co., Ltd and has the model of DP-122. The organic fluororesin is purchased from Xuzhou Mitsu science and technology Co., Ltd, and has a model of zy-1 and a number average molecular weight of 20000-30000. The organic silicon resin is purchased from Shanghai micro-spectrum chemical technology service Limited company, and the number average molecular weight is 500-10000. The acrylic resin is purchased from Guangzhou Ling Tree commercial Co., Ltd, has a weight average molecular weight of 55000, and comprises 30-45 parts of methyl isobutyl ketone, 15-25 parts of acrylic acid, 7-12 parts of methacrylic acid, 1-7 parts of n-butyl acrylate and 4-15 parts of methyl isobutyl ketone.
Noctilucent paint is purchased from the yellow chemical industry. The test instrument is a CY-1000 long afterglow fluorescent powder (light storage fluorescent material) light color performance test system (Hangzhou remote photoelectric information corporation).
The preparation method of the organic fluorine-silicon modified acrylic resin refers to the following documents:
[1] Synthesis and performance research of organic fluorine-silicon modified acrylic resin [ D ] Shandong university, 2009.
[2] Synthesis and research of Chenmeiling, Xilimin, Dingfan, Yanli and Gaomo. organic fluorine modified acrylic resin [ J ] chemical novel material, 2010,10:113-115.
[3] Study on synthesis of organic fluorine modified acrylic resin and coating thereof [ D ] university of continental traffic, 2010.
[4] Yellow gecko, Liu Xiao Guo, fluorosilicone modified acrylic resin synthesis technology and current application [ J ]. Guangzhou chemical industry, 2012,22:19-20+36.
[5] The development and application of Wangchen blue, Zhang Xiaohong, Husheng, Fluorosilicone modified acrylic resin and coating [ J ]. Shandong Industrial technology, 2015,24:43.
SrAl2O4:Eu2+,Dy3+the preparation method is as follows: adding analytically pure Eu into strontium carbonate (99.2%) and aluminum oxide (99.99%)2O3，Dy2O3Then evenly mixing, sintering in a reducing atmosphere at 1300 ℃ for 2 hours, and crushing to obtain a luminescent material sample. Wherein, the mass percentage of strontium carbonate (99.2 percent), aluminum oxide (99.99 percent),Eu2O3And Dy2O3The ratio of (1) to (2) is 9:10:0.1: 0.4.
CaAl2O4：Eu2+，Nd3+The preparation method of the fluorescent powder refers to the following steps:
Respectively measuring appropriate amount of Ca (NO) according to stoichiometric ratio3)2，Al(NO3)3，Eu(NO3)3，Nd(NO3)3Adding a certain amount of urea into a crucible until the urea is uniformly mixed, directly putting the mixture into a muffle furnace at 450-850 ℃, starting to react when water is quickly evaporated to dryness, releasing a large amount of gas, foaming and expanding reactants, forming loose white foam along with combustion, and carrying out the whole reaction process for 5 min. And (3) after the sintering is finished, preserving the heat for 3min in a furnace, then taking out the sample, naturally cooling the sample to room temperature in the air, and grinding the sample to obtain the fluorescent powder. Wherein, in terms of the amount of substance, Ca (NO)3)2，Al(NO3)3，Eu(NO3)3And Nd (NO)3)3In a ratio of 984:200:15: 1.
Sr4Al14O25：Eu2+，Dy3+The preparation method of the fluorescent powder refers to the following steps:
accurately weighing SrCO according to stoichiometric ratio3,Al2O3,Eu2O3,Dy2O3Adding a certain amount of H3BO3. Fully grinding the raw materials to uniformly mix the raw materials, then putting the raw materials into an alumina porcelain boat, putting the alumina porcelain boat into a tube furnace, heating the raw materials to a preset temperature under the protection of hydrogen-argon mixed gas, preserving the temperature for a period of time, and naturally cooling the raw materials. The product is crushed, ground and sieved to obtain the powdery blue-green long afterglow luminescent material Sr4Al14O25∶Eu2+,Dy3+. Wherein, in terms of the amount of substance, H3BO3，SrCO3,Al2O3,Eu2O3,Dy2O3the ratio of (1: 36:7:1: 1).
The test method comprises the following steps: the waterproof corrosion-resistant traffic sign luminous paint is coated on a substrate with the diameter of 5 cm by brushing once, dried at 50 ℃ for 0.5 to 6 hours until the waterproof corrosion-resistant traffic sign luminous paint is cured, and then put into a CY-1000 long afterglow fluorescent powder (light storage fluorescent material) light color performance test system for testing. After the test, the substrate with the waterproof and corrosion-resistant traffic sign luminous paint is placed into tap water to be soaked for 6 hours at the room temperature of 20-25 ℃, is naturally dried at the room temperature of 20-25 ℃ after being soaked, and is placed into a CY-1000 long afterglow fluorescent powder (light storage fluorescent material) light color performance test system to be tested again.
And (3) comparison test: the purchased luminous paint (yellow chemical industry) is coated on a substrate with the diameter of 5 cm, dried for 0.5 to 6 hours at the temperature of 50 ℃ until the luminous paint is cured, and then put into a CY-1000 long afterglow fluorescent powder (light storage fluorescent material) light color performance testing system for testing. After the test, the substrate with the luminous paint is put into tap water to be soaked for 6 hours at the room temperature of 20-25 ℃, is naturally dried at the room temperature of 20-25 ℃ after being soaked, and is put into a CY-1000 long afterglow fluorescent powder (light storage fluorescent material) light color performance test system to be tested again.
The following describes the waterproof and corrosion-resistant traffic sign luminous material and the application thereof in detail with reference to the examples.
in the examples of the present invention, 1 part by mass was 1 g.
Example 1
Hydrophobic film-forming agent and SrAl2O4：Eu2+The organic solvent, the gas phase nano silicon dioxide and the organic bentonite anti-settling agent are mixed evenly at the room temperature of 20-25 ℃ to obtain the waterproof and anti-corrosion traffic sign luminous paint, wherein the hydrophobic film forming agent accounts for 30 parts by mass, and SrAl2O4：Eu2+12 parts by mass of an organic solvent, 11 parts by mass of a gas-phase nano silicon dioxide, and 41 parts by mass of an organic bentonite anti-settling agent; wherein the organic solvent is a mixture of xylene, ethyl acetate and butanol, and the ratio of the xylene, the butanol and the ethyl acetate in the organic solvent is as follows by mass: 20: 30: 1; the hydrophobic film-forming agent is a mixture of organic silicon resin, organic fluororesin and acrylic resin, wherein the organic silicon resin, the organic fluororesin and the acrylic resin are contained in the hydrophobic film-forming agent by massthe ratio of acrylic resin is 0.2: 0.2: 1.
Example 2
hydrophobic film-forming agent and SrAl2O4：Eu2+The organic solvent, the gas phase nano silicon dioxide and the organic bentonite anti-settling agent are mixed evenly at the room temperature of 20-25 ℃ to obtain the waterproof and anti-corrosion traffic sign luminous paint, wherein the hydrophobic film forming agent accounts for 35 parts by mass, and SrAl2O4：Eu2+15 parts by mass of an organic solvent, 12 parts by mass of a gas-phase nano silicon dioxide, 9 parts by mass of an organic bentonite anti-settling agent and 29 parts by mass of an organic bentonite anti-settling agent; wherein the organic solvent is a mixture of xylene, ethyl acetate and butanol, and the ratio of the xylene, the butanol and the ethyl acetate in the organic solvent is as follows by mass: 30: 20: 1; the hydrophobic film former is a mixture of organic silicon resin, organic fluororesin and acrylic resin, wherein the ratio of the organic silicon resin, the organic fluororesin and the acrylic resin in the hydrophobic film former is 0.3: 0.3: 1.
Example 3
Hydrophobic film-forming agent and SrAl2O4：Eu2+The organic solvent, the gas phase nano silicon dioxide and the organic bentonite anti-settling agent are mixed evenly at the room temperature of 20-25 ℃ to obtain the waterproof and anti-corrosion traffic sign luminous paint, wherein the hydrophobic film forming agent accounts for 40 parts by mass, and SrAl2O4：Eu2+17 parts by mass of an organic solvent, 13 parts by mass of a gas-phase nano silicon dioxide, and 18 parts by mass of an organic bentonite anti-settling agent; wherein the organic solvent is a mixture of xylene, ethyl acetate and butanol, and the ratio of xylene, butanol and ethyl acetate in the organic solvent is 20: 20: 1; the hydrophobic film former is a mixture of organic silicon resin, organic fluororesin and acrylic resin, wherein the ratio of the organic silicon resin, the organic fluororesin and the acrylic resin in the hydrophobic film former is 0.4: 0.3: 1.
Example 4
Hydrophobic film-forming agent and CaAl2O4：Eu2+，Nd3+An organic solvent,Uniformly mixing the gas-phase nano-silica and the organic bentonite anti-settling agent at the room temperature of 20-25 ℃ to obtain the waterproof and anti-corrosion traffic sign luminous paint, wherein the hydrophobic film-forming agent accounts for 45 parts by mass, and the CaAl is2O4：Eu2+，Nd3+19 parts by mass of an organic solvent, 14 parts by mass of gas-phase nano silicon dioxide and 7 parts by mass of an organic bentonite anti-settling agent; wherein the organic solvent is a mixture of xylene, ethyl acetate and butanol, and the ratio of the xylene, the butanol and the ethyl acetate in the organic solvent is as follows by mass: 10: 15: 1; the hydrophobic film former is a mixture of organic silicon resin, organic fluororesin and acrylic resin, wherein the ratio of the organic silicon resin, the organic fluororesin and the acrylic resin in the hydrophobic film former is 0.2: 0.5: 1.
Example 5
hydrophobic film-forming agent, Sr4Al14O25：Eu2+，Dy3+The organic solvent, the gas phase nano silicon dioxide and the organic bentonite anti-settling agent are mixed evenly at the room temperature of 20-25 ℃ to obtain the waterproof and anti-corrosion traffic sign luminous paint, wherein the hydrophobic film forming agent is 30 parts by mass, and Sr is used as the material4Al14O25：Eu2+，Dy3+12 parts by mass of an organic solvent, 11 parts by mass of a gas-phase nano silicon dioxide, and 41 parts by mass of an organic bentonite anti-settling agent; wherein the organic solvent is a mixture of xylene, ethyl acetate and butanol, and the ratio of the xylene, the butanol and the ethyl acetate in the organic solvent is as follows by mass: (4-35): (4-35): 1; the hydrophobic film forming agent is organic fluorine/silicon modified acrylic resin.
The waterproof and corrosion-resistant traffic sign luminous paint of the embodiment 1-5 is sequentially brushed on the substrate according to the test method, the luminous intensity of the substrate before soaking (i.e. the substrate which is not soaked) is set as 100%, and the luminous intensity of the substrate after soaking in tap water for 6 hours is the relative value of the luminous intensity of the substrate before soaking. The luminescence intensity and the luminescence time of the un-soaked substrate and the soaked substrate are as follows:
as can be seen from the above table, the substrate prepared from the waterproof and corrosion-resistant traffic sign luminescent coating of examples 1-5 has a maximum decrease of 27% in luminous intensity after being soaked in tap water for 6 hours. The luminescence time of the substrate prepared by the waterproof and corrosion-resistant traffic sign noctilucent coating of the embodiments 1-5 is reduced by 25%.
The luminous paint brush is coated on the substrate according to the method of the comparison test, the luminous intensity of the substrate before soaking is set as 100%, and the luminous intensity of the substrate after soaking in tap water for 6 hours is the relative value of the luminous intensity of the substrate before soaking. The luminescence intensity and time of the substrates after soaking for 6 hours without soaking and in tap water are given in the following table:
As can be seen from the above table, the luminous intensity of the substrate coated with the noctilucent paint is reduced by 70% and the luminous time is shortened by 78% after the substrate is soaked in tap water for 6 hours.
From the test results, the luminous intensity of the waterproof and corrosion-resistant traffic sign luminous paint is reduced by 27% at most after the waterproof and corrosion-resistant traffic sign luminous paint is soaked in tap water for 6 hours, and the luminous intensity of the luminous paint is reduced by 70% after the luminous paint is soaked in the tap water for 6 hours.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (4)

1. The application of the waterproof corrosion-resistant traffic sign luminous paint is characterized in that a plurality of layers of the waterproof corrosion-resistant traffic sign luminous paint are uniformly sprayed or brushed on the road surface, wherein after each layer of the waterproof corrosion-resistant traffic sign luminous paint is sprayed or brushed, the layer of the waterproof corrosion-resistant traffic sign luminous paint is dried at the temperature of 20-80 ℃ for 0.5-6 hours until the waterproof corrosion-resistant traffic sign luminous paint layer is cured;
The waterproof corrosion-resistant traffic sign luminous paint is prepared from the following raw materials in percentage by weight: 30-45 wt% of hydrophobic film-forming agent, 10-20 wt% of rare earth doped alkaline earth metal aluminate long afterglow luminescent material, 10-15 wt% of organic solvent, 5-15 wt% of gas phase nano silicon dioxide and the balance of organic bentonite anti-settling agent; wherein the organic solvent is a mixture of xylene, ethyl acetate and butanol, the hydrophobic film-forming agent is organic silicon resin, a mixture of organic fluororesin and acrylic resin or organic fluorine-silicon modified acrylic resin, and the rare earth doped alkaline earth metal aluminate long-afterglow luminescent material is SrAl2O4：Eu2+，Dy3+、CaAl2O4：Eu2+，Nd3+Or Sr4Al14O25：Eu2+，Dy3+The ratio of xylene, butanol and ethyl acetate in the organic solvent is (4-35) by mass: (4-35): 1, the ratio of the organic silicon resin, the organic fluororesin and the acrylic resin in the hydrophobic film forming agent is (0.2-0.5): (0.2-0.5): 1.
2. The use according to claim 1, wherein the hydrophobic film-forming agent is 35-40 wt%, the rare earth doped alkaline earth metal aluminate long-afterglow luminescent material is 13-17 wt%, the organic solvent is 12-14 wt%, the fumed nano silica is 7-13 wt%, and the balance is the organic bentonite anti-settling agent.
3. Use according to claim 1, wherein the fumed nanosilica has a particle size of 5-50 nm.
4. Use according to claim 1, characterized in that the ratio of xylene, butanol and ethyl acetate in the organic solvent is (20-30): (20-30): 1.
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