CN107987643A - The application of waterproof is anti-corrosion traffic mark Noctilucent material - Google Patents
The application of waterproof is anti-corrosion traffic mark Noctilucent material Download PDFInfo
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Abstract
The invention discloses a kind of application of the anti-corrosion traffic mark luminescent coating of waterproof, waterproof is anti-corrosion, and traffic mark luminescent coating is made of the raw material of following weight percents：Hydrophobic film-forming agent is 30 45wt%, and rear-earth-doped alkali earth metal aluminate long after glow luminous material is 10 20wt%, and organic solvent is 10 15wt%, and gas phase nano silica is 5 15wt%, and surplus is organobentonite anti-settling agent.The anti-corrosion traffic mark luminescent coating of waterproof of the invention is nontoxic, "dead", stable chemical performance, after the various visible rays such as daylight, light, environment veiling glare are absorbed, automatic continuous it can shine, and after the erosion of contact water, the waterproof is anti-corrosion, and traffic mark luminescent coating can prevent most rear-earth-doped alkali earth metal aluminate long after glow luminous material hydrolysis, rear-earth-doped alkali earth metal aluminate long after glow luminous material is sustainable to shine, and has good water proofing property and corrosion resistance.
Description
The present patent application is point of parent application " waterproof is anti-corrosion traffic mark Noctilucent material and preparation method and applications "
Case application, the Application No. 2015110336865 of parent application, the applying date are on December 30th, 2015.
Technical field
The invention belongs to field of light emitting materials, relates in particular to a kind of answering for the anti-corrosion traffic mark Noctilucent material of waterproof
With.
Background technology
Road traffic mark is the graphical symbol for showing traffic law and road information, it can be vivid, specific and concise
Traffic law is expressed, while can also express the content being difficult to word description, to manage traffic and instruction direction of traffic, to protect
Demonstrate,prove the coast is clear and the facility of traffic safety.The road traffic mark majority used at present is coated with reflection-type coating, generally not
There is noctilucence.But if without street lamp on road, can only be to there be photograph at this kind of passive reflection-type traffic mark night
The vehicle of bright instrument plays a role, and the pedestrian and cyclist for no illuminations cannot then play its effect substantially.Therefore,
The noctilucence traffic mark coating of active illuminant is particularly significant.As traffic mark luminescent coating, rainwater need to be exposed to for a long time, tide
Under wet environment, water proofing property and corrosion resistance to coating require very high.Noctilucence traffic mark is generally direct by luminous paint at present
Coated in being formed on road, and with the addition of in luminous paint rear-earth-doped alkali earth metal aluminate long after glow luminous material easily with rain
Steam in water and air hydrolyzes so that noctilucence traffic mark loses guide elicitation effect.With rear-earth-doped alkaline-earth metal
Aluminate long after glow luminous material SrAl2O4：Eu2+, Dy3+Exemplified by, in SrAl2O4：Eu2+, Dy3+When being contacted with water, can slowly it send out
Raw following hydrolysis:SrAl2O4+4H2O→Sr2++2OH-+2Al(OH)3↑, which can generate aluminium hydroxide, and make system
PH value rise, not only destroyed the original crystal structure of luminescent powder, but also have impact on the acid-base balance of system.In rainwater and moisture
Under the influence of, the luminous intensity of rear-earth-doped alkali earth metal aluminate long after glow luminous material declines at least 50%, or even completely not
Shine.
The content of the invention
In view of the deficiencies of the prior art, grown the object of the present invention is to provide one kind containing rear-earth-doped alkali earth metal aluminate
The anti-corrosion traffic mark Noctilucent material of waterproof and preparation method and applications of afterglow materials.
The purpose of the present invention is what is be achieved by following technical proposals.
A kind of anti-corrosion traffic mark luminescent coating of waterproof, is made of the raw material of following weight percents：Hydrophobic film-forming agent
For 30-45wt%, rear-earth-doped alkali earth metal aluminate long after glow luminous material is 10-20wt%, organic solvent 10-
15wt%, gas phase nano silica are 5-15wt%, and surplus is organobentonite anti-settling agent；Wherein, the organic solvent is
The mixture of dimethylbenzene, ethyl acetate and butanol, the hydrophobic film-forming agent are organic siliconresin, organic fluorine and acrylic acid
The mixture of resin or organic fluorinated silicone modified acrylic resin, the rear-earth-doped alkali earth metal aluminate long after glow luminous material
For SrAl2O4：Eu2+, Dy3+、CaAl2O4：Eu2+, Nd3+Or Sr4Al14O25：Eu2+, Dy3+, by mass, in the organic solvent
The ratio of middle dimethylbenzene, butanol and ethyl acetate is (4-35)：(4-35)：1, in the hydrophobic film-forming agent organic siliconresin,
The ratio of organic fluorine and acrylic resin is (0.2-0.5)：(0.2-0.5)：1.
In the above-mentioned technical solutions, hydrophobic film-forming agent is 35-40wt%, rear-earth-doped alkali earth metal aluminate long afterglow
Luminescent material is 13-17wt%, and organic solvent 12-14wt%, gas phase nano silica is 7-13wt%, and surplus is organic
Bentonite anti-settling agent.
In the above-mentioned technical solutions, the particle diameter of the gas phase nano silica is 5-50 nanometers.
In the above-mentioned technical solutions, by mass, the ratio of dimethylbenzene, butanol and ethyl acetate is in the organic solvent
(20-30)：(20-30)：1.
A kind of preparation method of the anti-corrosion traffic mark luminescent coating of above-mentioned waterproof, in 20-25 DEG C of room temperature by hydrophobic film-forming
Agent, rear-earth-doped alkali earth metal aluminate long after glow luminous material, organic solvent, gas phase nano silica and organobentonite
Anti-settling agent is mixed to uniform in proportion, that is, obtains the anti-corrosion traffic mark luminescent coating of waterproof.
In the above-mentioned technical solutions, hydrophobic film-forming agent is 35-40wt%, rear-earth-doped alkali earth metal aluminate long afterglow
Luminescent material is 13-17wt%, and organic solvent 12-14wt%, gas phase nano silica is 7-13wt%, and surplus is organic
Bentonite anti-settling agent.
In the above-mentioned technical solutions, the particle diameter of the gas phase nano silica is 5-50 nanometers.
In the above-mentioned technical solutions, by mass, the ratio of dimethylbenzene, butanol and ethyl acetate is in the organic solvent
(20-30)：(20-30)：1.
A kind of application of anti-corrosion traffic mark luminescent coating of above-mentioned waterproof as indication light body, uniformly sprays in road surface
The anti-corrosion traffic mark luminescent coating of waterproof described in multilayer is applied or brushes, wherein, often spray or one layer of waterproof of brushing is resistance to
After losing traffic mark luminescent coating, when by the anti-corrosion traffic mark luminescent coating layer of this layer of waterproof, drying 0.5-6 is small at 20-80 DEG C
Cure to the anti-corrosion traffic mark luminescent coating layer of waterproof.
The anti-corrosion traffic mark luminescent coating of waterproof of the invention is nontoxic, "dead", stable chemical performance, is absorbing day
After the various visible rays such as light, light, environment veiling glare, without power supply, you can it is automatic continuous to shine, and in the erosion of contact water
Afterwards, the anti-corrosion traffic mark luminescent coating of the waterproof can prevent the most long-persistence luminous material of rear-earth-doped alkali earth metal aluminate
Material hydrolysis, rear-earth-doped alkali earth metal aluminate long after glow luminous material is sustainable to shine, and has good water proofing property and anti-corrosion
Property.
Embodiment
Dimethylbenzene, ethyl acetate, gas phase nano silica and butanol in the present embodiment are bought from Aladdin reagent
The molecular weight of (Shanghai) Co., Ltd., wherein dimethylbenzene is 106.17, product identification X112050；The molecular weight of ethyl acetate
For 88.11, product identification E116131；Butanol is n-butanol, its molecular weight is 74.12, product identification B111573；Gas phase
The product identification of nano silicon dioxide is S104599, and particle diameter is 7-40 nanometers.Organobentonite anti-settling agent is bought from the big huge rock in Shanghai
Chemical Co., Ltd., model DP-122.From Xuzhou Zhong Yan Science and Technology Ltd.s, model zy-1, counts for organic fluorine purchase
Average molecular weight is 20000-30000.The organic siliconresin purchase is divided equally from Shanghai Wei Pu Chemical Engineering Technologies Services Co., Ltd, number
Son amount is 500-10000.Acrylic resin is bought from Guangzhou Lian Shu commerce and trade Co., Ltd, weight average molecular weight 55000, acrylic acid
Resin includes following component, and 30-45 parts of methyl iso-butyl ketone (MIBK), 15-25 parts of acrylic acid, 7-12 parts of methacrylic acid, acrylic acid is just
1-7 parts of butyl ester, 4-15 parts of methyl iso-butyl ketone (MIBK).
Luminous paint is bought from Huang Shi chemical industry.Test equipment is CY-1000 long lad phosphors (light accumulation type fluorescent material) light
Color Performance Test System (Hangzhou Everfine Inc.).
The preparation method of organic fluorinated silicone modified acrylic resin refers to following documents：
The synthesis of the super organic fluorinated silicone modified acrylic resins of of rice and performance study [D] Shandong University when [1], 2009.
[2] Chen Meiling, Xu Limin, Ding Fan, Yang Li, the synthesis of the high grand organic fluorin modified crylic acid resins of and research [J]
New Chemical Materials, 2010,10:113-115.
[3] research [D] the Dalian University Of Communications of the synthesis of the organic fluorin modified crylic acid resins of the quick of Xu Li and its coating,
2010.
[4] Huang is maintained the achievements of one's predecessors, the fluorinated silicone modified acrylic resin synthetic technologys of Liu Xiao states and application present situation [J] Chemical Industry in Guangzhou,
2012,22:19-20+36.
[5] exploitation of the fluorinated silicone modified acrylic resins of Wang Senlan, Zhang Xiaohong, Hu Shengchu and coating and application [J] Shandong
Industrial technology, 2015,24:43.
SrAl2O4:Eu2+,Dy3+Preparation method with reference to as follows：By strontium carbonate (99.2%), alundum (Al2O3)
(99.99%) analytically pure Eu is added in2O3, Dy2O3After be uniformly mixed, burnt till when 2 is small in reducing atmosphere at 1300 DEG C,
Through crushing, luminescent material sample is obtained.Wherein, by the gauge of material, strontium carbonate (99.2%), alundum (Al2O3) (99.99%),
Eu2O3And Dy2O3Ratio be 9:10:0.1:0.4.
CaAl2O4：Eu2+, Nd3+The preparation method of fluorescent powder is with reference to as follows：
Suitable Ca (NO are stoichiometrically measured respectively3)2, Al (NO3)3, Eu (NO3)3, Nd (NO3)3In crucible, add
Enter a certain amount of urea to being uniformly mixed, be directly placed into 450 DEG C~850 DEG C of Muffle furnace, start when moisture is quickly evaporated anti-
Should, a large amount of gases are discharged, reactant blisters and expands, and loose white foam, whole reaction process are formed with burning
5min.3min is kept the temperature after burning in stove, then takes out sample, in atmosphere cooled to room temperature, ground
To fluorescent powder.Wherein, by the gauge of material, Ca (NO3)2, Al (NO3)3, Eu (NO3)3With Nd (NO3)3Ratio be 984:200:15:
1。
Sr4Al14O25：Eu2+, Dy3+The preparation method of fluorescent powder is with reference to as follows：
According to stoichiometric ratio precise SrCO3,Al2O3,Eu2O3,Dy2O3, add a certain amount of H3BO3.By raw material
Fully milling is uniformly mixed it, is then charged into aluminium oxide porcelain boat, and is put into tube furnace, under hydrogen-argon-mixed protection, rises
Temperature is to predetermined temperature, after keeping the temperature a period of time, natural cooling.By product crushing grinding and sieve, that is, be made powdered bluish-green
Color long after glow luminous material Sr4Al14O25∶Eu2+,Dy3+.Wherein, by the gauge of material, H3BO3, SrCO3,Al2O3,Eu2O3,
Dy2O3Ratio be 1:36:7:1:1.
Test method：The anti-corrosion traffic mark luminescent coating of waterproof of the present invention is brushed on a diameter of 5 centimetres of substrate
Once, cure at 50 DEG C to the anti-corrosion traffic mark luminescent coating of waterproof within dry 0.5-6 hours, be put into after dry more than CY-1000 long
Brightness fluorescent powder (light accumulation type fluorescent material) Photochromic Properties test system is tested.After test, it will be somebody's turn to do with the anti-corrosion friendship of waterproof
The substrate of logical mark luminescent coating is put into tap water when 20-25 DEG C of immersion 6 of room temperature is small, after immersion at 20-25 DEG C of room temperature certainly
So dry, and be put into CY-1000 long lad phosphors (light accumulation type fluorescent material) Photochromic Properties test system and surveyed again
Examination.
Contrast test：The luminous paint (Huang Shi chemical industry) of purchase is brushed on a diameter of 5 centimetres of substrate, in 50 DEG C of dryings
Cure to luminous paint within 0.5-6 hours, the survey of CY-1000 long lad phosphors (light accumulation type fluorescent material) Photochromic Properties is put into after dry
Test system is tested.After test, which is put into tap water when 20-25 DEG C of immersion 6 of room temperature is small,
After immersion at 20-25 DEG C of room temperature naturally dry, and be put into CY-1000 long lad phosphors (light accumulation type fluorescent material) photochromism
System can be tested to be tested again.
The anti-corrosion traffic mark Noctilucent material of waterproof of the present invention and its application are described in detail with reference to embodiment.
In an embodiment of the present invention, 1 mass parts are 1g.
Embodiment 1
By hydrophobic film-forming agent, SrAl2O4：Eu2+, organic solvent, gas phase nano silica and organobentonite it is anti-settling
Agent is mixed to uniform in 20-25 DEG C of room temperature, that is, obtains the anti-corrosion traffic mark luminescent coating of waterproof, wherein, hydrophobic film-forming agent is
30 mass parts, SrAl2O4：Eu2+For 12 mass parts, organic solvent is 11 mass parts, and gas phase nano silica is 6 mass parts,
Organobentonite anti-settling agent is 41 mass parts；Wherein, the organic solvent is the mixture of dimethylbenzene, ethyl acetate and butanol,
By mass, the ratio of dimethylbenzene, butanol and ethyl acetate is in the organic solvent：20：30：1；The hydrophobic film-forming agent
For the mixture of organic siliconresin, organic fluorine and acrylic resin, wherein, by mass, in the hydrophobic film-forming agent
The ratio of organic siliconresin, organic fluorine and acrylic resin is 0.2：0.2：1.
Embodiment 2
By hydrophobic film-forming agent, SrAl2O4：Eu2+, organic solvent, gas phase nano silica and organobentonite it is anti-settling
Agent is mixed to uniform in 20-25 DEG C of room temperature, that is, obtains the anti-corrosion traffic mark luminescent coating of waterproof, wherein, hydrophobic film-forming agent is
35 mass parts, SrAl2O4：Eu2+For 15 mass parts, organic solvent is 12 mass parts, and gas phase nano silica is 9 mass parts,
Organobentonite anti-settling agent is 29 mass parts；Wherein, the organic solvent is the mixture of dimethylbenzene, ethyl acetate and butanol,
By mass, the ratio of dimethylbenzene, butanol and ethyl acetate is in the organic solvent：30：20：1；The hydrophobic film-forming agent
For the mixture of organic siliconresin, organic fluorine and acrylic resin, wherein, by mass, in the hydrophobic film-forming agent
The ratio of organic siliconresin, organic fluorine and acrylic resin is 0.3：0.3：1.
Embodiment 3
By hydrophobic film-forming agent, SrAl2O4：Eu2+, organic solvent, gas phase nano silica and organobentonite it is anti-settling
Agent is mixed to uniform in 20-25 DEG C of room temperature, that is, obtains the anti-corrosion traffic mark luminescent coating of waterproof, wherein, hydrophobic film-forming agent is
40 mass parts, SrAl2O4：Eu2+For 17 mass parts, organic solvent is 13 mass parts, and gas phase nano silica is 12 mass parts,
Organobentonite anti-settling agent is 18 mass parts；Wherein, the organic solvent is the mixture of dimethylbenzene, ethyl acetate and butanol,
By mass, the ratio of dimethylbenzene, butanol and ethyl acetate is 20 in the organic solvent：20：1；The hydrophobic film-forming agent
For the mixture of organic siliconresin, organic fluorine and acrylic resin, wherein, organosilicon tree in the hydrophobic film-forming agent
The ratio of fat, organic fluorine and acrylic resin is 0.4：0.3：1.
Embodiment 4
By hydrophobic film-forming agent, CaAl2O4：Eu2+, Nd3+, organic solvent, gas phase nano silica and organobentonite
Anti-settling agent is mixed to uniform in 20-25 DEG C of room temperature, that is, obtains the anti-corrosion traffic mark luminescent coating of waterproof, wherein, hydrophobic film-forming
Agent is 45 mass parts, CaAl2O4：Eu2+, Nd3+For 19 mass parts, organic solvent is 15 mass parts, and gas phase nano silica is
14 mass parts, organobentonite anti-settling agent are 7 mass parts；Wherein, the organic solvent is dimethylbenzene, ethyl acetate and butanol
Mixture, by mass, the ratio of dimethylbenzene, butanol and ethyl acetate is in the organic solvent：10：15：1；It is described hydrophobic
Property film forming agent be organic siliconresin, organic fluorine and acrylic resin mixture, wherein, by mass, the hydrophobicity
The ratio of organic siliconresin, organic fluorine and acrylic resin is 0.2 in film forming agent：0.5：1.
Embodiment 5
By hydrophobic film-forming agent, Sr4Al14O25：Eu2+, Dy3+, organic solvent, gas phase nano silica and organic swelling
Native anti-settling agent is mixed to uniform in 20-25 DEG C of room temperature, that is, obtains the anti-corrosion traffic mark luminescent coating of waterproof, wherein, hydrophobicity into
Film is 30 mass parts, Sr4Al14O25：Eu2+, Dy3+For 12 mass parts, organic solvent is 11 mass parts, gas phase nano titanium dioxide
Silicon is 6 mass parts, and organobentonite anti-settling agent is 41 mass parts；Wherein, the organic solvent is dimethylbenzene, ethyl acetate and fourth
The mixture of alcohol, by mass, the ratio of dimethylbenzene, butanol and ethyl acetate is in the organic solvent：(4-35)：(4-
35)：1；The hydrophobic film-forming agent is Organic fluoride/fluorine-silicon modified acrylic resin.
The anti-corrosion traffic mark luminescent coating of the waterproof of embodiment 1-5 is carried out on substrate successively according to above-mentioned test method
Brush, the luminous intensity of the substrate (i.e. unsoaked substrate) before immersion is set to 100%, in tap water immersion 6 it is small when after
Substrate luminous intensity for immersion before substrate luminous intensity relative value.Unsoaked substrate shines with immersion meron
Intensity and fluorescent lifetime are as follows：
As seen from the above table, the substrate prepared by the anti-corrosion traffic mark luminescent coating of the waterproof of embodiment 1-5 is immersed in originally
In water 6 it is small when after, its luminous intensity at most have dropped 27%.The anti-corrosion traffic mark luminescent coating of waterproof of embodiment 1-5 is made
The fluorescent lifetime of standby substrate is done reduces 25% more.
Luminous paint is brushed on substrate according to the method for above-mentioned contrast test, the luminous intensity before which is not soaked
Be set to 100%, in tap water soak 6 it is small when after substrate luminous intensity for immersion before substrate luminous intensity it is opposite
Value.Do not soak and in tap water immersion 6 it is small when after substrate luminous intensity and time such as following table：
As seen from the above table, its luminous intensity have dropped after the substrate after luminous paint brushing is when immersion 6 is small in tap water
70%, fluorescent lifetime shortens 78%.
Can be obtained by above-mentioned test result, in tap water soak 6 it is small when after the anti-corrosion traffic mark luminescent coating of waterproof hair
Luminous intensity at most have dropped 27%, and luminous paint soaked in tap water 6 it is small when after its luminous intensity have dropped 70%, thus may be used
Know, waterproof of the invention is anti-corrosion traffic mark luminescent coating is after the erosion of contact water, and the waterproof is anti-corrosion, and traffic mark noctilucence applies
Rear-earth-doped alkali earth metal aluminate long after glow luminous material in material is sustainable to shine, and has good water proofing property and anti-corrosion
Property.
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal
Fall into protection scope of the present invention.
Claims (4)
1. a kind of application of the anti-corrosion traffic mark luminescent coating of waterproof, it is characterised in that in road surface even application or brush
The anti-corrosion traffic mark luminescent coating of multilayer flashing is applied, wherein, often spray or brush one layer of waterproof anti-corrosion traffic mark night
After optical coating, the anti-corrosion traffic mark luminescent coating layer of this layer of waterproof is dried 0.5-6 hours to the anti-corrosion friendship of waterproof at 20-80 DEG C
Logical mark luminescent coating layer cures；
Waterproof is anti-corrosion, and traffic mark luminescent coating is prepared by the raw material of following weight percents：Hydrophobic film-forming agent is 30-
45wt%, rear-earth-doped alkali earth metal aluminate long after glow luminous material are 10-20wt%, organic solvent 10-15wt%, gas
Phase nano silicon dioxide is 5-15wt%, and surplus is organobentonite anti-settling agent；Wherein, the organic solvent is dimethylbenzene, second
The mixture of acetoacetic ester and butanol, the hydrophobic film-forming agent are the mixed of organic siliconresin, organic fluorine and acrylic resin
Compound or organic fluorinated silicone modified acrylic resin, the rear-earth-doped alkali earth metal aluminate long after glow luminous material are
SrAl2O4：Eu2+, Dy3+、CaAl2O4：Eu2+, Nd3+Or Sr4Al14O25：Eu2+, Dy3+, by mass, in the organic solvent
The ratio of dimethylbenzene, butanol and ethyl acetate is (4-35)：(4-35)：1, in the hydrophobic film-forming agent organic siliconresin, have
The ratio of machine fluororesin and acrylic resin is (0.2-0.5)：(0.2-0.5)：1.
2. application according to claim 1, it is characterised in that the hydrophobic film-forming agent is 35-40wt%, rear-earth-doped
Alkali earth metal aluminate long after glow luminous material is 13-17wt%, organic solvent 12-14wt%, gas phase nano silica
For 7-13wt%, surplus is organobentonite anti-settling agent.
3. application according to claim 1, it is characterised in that the particle diameter of the gas phase nano silica is received for 5-50
Rice.
4. application according to claim 1, it is characterised in that by mass, dimethylbenzene, butanol in the organic solvent
Ratio with ethyl acetate is (20-30)：(20-30)：1.
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| CN108949165A (en) * | 2017-12-29 | 2018-12-07 | 张世远 | The method of inexpensive high-grade large-scale production succession ancient architecture structure |
| CN109370410A (en) * | 2018-09-28 | 2019-02-22 | 合众（佛山）化工有限公司 | A kind of high performance nanometer energy storage aqueous luminous paint |
| CN109627890B (en) * | 2018-11-27 | 2020-08-25 | 浙江欧路德交通科技有限公司 | Fluorine-silicon modified water-based marking paint |
| CN113845804A (en) * | 2021-11-18 | 2021-12-28 | 广东电网有限责任公司 | Energy storage type luminous paint and preparation method thereof |
| CN114671707B (en) * | 2022-04-22 | 2023-01-03 | 江苏路强智慧交通科技有限公司 | Weather-resistant luminous protective paint for concrete traffic guardrail and preparation method thereof |
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| CN107987643B (en) | 2019-12-13 |
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