CN115975468A - Durable hot-melt marking paint and preparation method thereof - Google Patents
Durable hot-melt marking paint and preparation method thereof Download PDFInfo
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- CN115975468A CN115975468A CN202211580267.3A CN202211580267A CN115975468A CN 115975468 A CN115975468 A CN 115975468A CN 202211580267 A CN202211580267 A CN 202211580267A CN 115975468 A CN115975468 A CN 115975468A
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- 239000003973 paint Substances 0.000 title claims abstract description 42
- 239000012943 hotmelt Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000011324 bead Substances 0.000 claims abstract description 113
- 239000011521 glass Substances 0.000 claims abstract description 113
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003208 petroleum Substances 0.000 claims abstract description 30
- 239000004611 light stabiliser Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006004 Quartz sand Substances 0.000 claims abstract description 12
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 12
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000008096 xylene Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 62
- 238000005406 washing Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 16
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XJKVPKYVPCWHFO-UHFFFAOYSA-N silicon;hydrate Chemical compound O.[Si] XJKVPKYVPCWHFO-UHFFFAOYSA-N 0.000 claims description 4
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
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- 239000000377 silicon dioxide Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000012669 compression test Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a durable hot-melt marking paint which comprises the following raw materials in parts by weight: 50-150 parts of C5 petroleum resin, 10-50 parts of ground calcium carbonate, 50-80 parts of glass beads, 5-30 parts of EVA resin, 10-30 parts of quartz sand, 10-20 parts of talcum powder, 1-10 parts of titanium dioxide, 10-30 parts of nano silicon dioxide, 1-3 parts of dioctyl phthalate, 1-5 parts of KH550 coupling agent, 1-2 parts of sodium carbonate, 1-3 parts of PE wax, 0.1-1 part of catalyst, 1-2 parts of light stabilizer, 100-200 parts of sodium hydroxide solution, 50-100 parts of ethanol solution, 20-60 parts of xylene and 5-15 parts of water. The invention can effectively improve the compressive strength of the glass beads in the marking, effectively prevent the glass beads from sinking in the marking after the marking is rolled by an automobile on a road at high frequency, and improve the continuous high-inverse reaction of the glass beads.
Description
Technical Field
The invention relates to the technical field of marking coatings, in particular to a durable hot-melt marking coating and a preparation method thereof.
Background
The road marking coating has already formed a very large industry, and at present, in order to meet the use requirements of different regions, different climates and different construction environments, the road marking coating is gradually developed from low grade to high grade and from single function to multi-function direction.
Road markings are classified according to the type of coating used: normal temperature solvent type marking, heating solvent type marking and hot melting type marking. The hot-melt type road marking paint is developed successfully in Europe in the middle of the 50 th century, and is used in China after the 90 th century, and the hot-melt type road marking paint has the biggest characteristic that the coating thickness is about 1.5-2.5mm, which is 10 times of that of a normal-temperature solvent type marking, so that the hot-melt type road marking paint is more suitable for urban main roads with large vehicle flow, high-grade roads and the like, and the hot-melt type paint is basically adopted in the construction of newly-built highway pavement markings in China at present.
The hot-melt type coating material is generally composed of a thermoplastic resin, a pigment, a filler, an auxiliary agent and the like. The thermoplastic resin can be selected from rosin resin, petroleum resin, polyamide resin, polyester resin and the like, and the existing road marking coating contains glass beads and is used for reflecting light rays emitted by a vehicle lamp back to eyes of a driver, so that the road marking is brighter and the vehicle is safer to drive.
However, in practical use, along with the high frequency of the automobile on the marking, the curing modes of the hot-melt marking paint are physical drying film-forming, the resin in the paint is simply changed from a molten state to a solid state after cooling, the compatibility between the glass beads in the marking and the thermoplastic resin is poor, and after rolling of the wheels, the glass beads sink and fall off, thus seriously affecting the service life of the glass beads.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides a durable hot-melt marking paint and a preparation method thereof.
A durable hot-melt marking paint comprises the following raw materials in parts by weight: 50-150 parts of C5 petroleum resin, 10-50 parts of heavy calcium carbonate, 50-80 parts of glass beads, 5-30 parts of EVA resin, 10-30 parts of quartz sand, 10-20 parts of talcum powder, 1-10 parts of titanium dioxide, 10-30 parts of nano silicon dioxide, 1-3 parts of dioctyl phthalate, 1-5 parts of KH550 coupling agent, 1-2 parts of sodium carbonate, 1-3 parts of PE wax, 0.1-1 part of catalyst, 1-2 parts of light stabilizer, 100-200 parts of sodium hydroxide solution, 50-100 parts of ethanol solution, 20-60 parts of xylene and 5-15 parts of water.
Preferably, the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:1-5:1-5.
Preferably, the catalyst is boron trifluoride etherate.
Preferably, the concentration of the sodium hydroxide solution is 1-2mol/L.
Preferably, the concentration of the ethanol solution is 40-60wt%.
Preferably, the light stabilizer comprises at least one of light stabilizer UV-P, light stabilizer UV-326, light stabilizer UV-327, light stabilizer UV-5411, light stabilizer LS-744, light stabilizer LS-770, light stabilizer GW-540 and light stabilizer PDS.
The preparation method of the durable hot melt marking paint comprises the following steps:
s1, mixing heavy calcium carbonate, quartz sand, talcum powder and titanium dioxide according to a ratio, and stirring at a speed of 500-1500r/min for 1-2 hours to obtain a premix;
s2, adding the glass beads into a sodium hydroxide solution, stirring for 1-2 hours, filtering, washing, drying at the temperature of 70-80 ℃, adding an ethanol solution and a KH550 coupling agent, stirring for 5-10 hours at the temperature of 50-80 ℃, filtering, washing, and drying to obtain aminated glass beads;
s3, adding dimethylbenzene into C5 petroleum resin, carrying out reflux stirring at the temperature of 100-150 ℃ for 5-15min, cooling to 80-90 ℃, adding nano silicon dioxide and water for ultrasonic dispersion, carrying out ultraviolet irradiation treatment, adding a catalyst, continuing ultrasonic treatment for 1-2h, adding sodium carbonate, stirring at the speed of 1000-3000r/min for 10-20min, adding aminated glass beads, stirring at the temperature of 100-120 ℃ for 5-15min, sequentially carrying out alkali washing and water washing until the pH value of a system is neutral, and carrying out rotary evaporation and vacuum drying to obtain C5 petroleum resin compound glass beads;
and S4, mixing the light stabilizer, the EVA resin, the dioctyl phthalate, the PE wax and the C5 petroleum resin compounded glass beads, stirring at the speed of 1000-2000r/min for 10-30min, adding the premix, and continuously stirring for 1-2h to obtain the durable hot-melt marking paint.
Preferably, in S3, the ultraviolet light wavelength is 200-400nm and the irradiation time is 5-15S during the ultraviolet irradiation treatment.
Preferably, nano silicon dioxide and water are added into S3 for ultrasonic dispersion, wherein the ultrasonic dispersion time is 10-30min, the ultrasonic frequency is 10-20kHz, and the ultrasonic power is 300-500W.
The technical effects of the invention are as follows:
according to the invention, the C5 petroleum resin and the nano-silica are compounded, and are subjected to ultraviolet irradiation treatment, C-H bonds and C-C bonds in a C5 petroleum resin molecular chain are broken to generate free radicals, the free radicals react with oxygen in the air to generate ROO-, H is continuously taken from the molecular chain to generate carboxyl, and the carboxyl is further combined with hydroxyl on the surface of the nano-silica, so that the compatibility of the C5 petroleum resin and a premix is improved, the system has excellent fluidity, the system can enter pores of a pavement, the bonding strength of a marking coating film and the pavement is enhanced, the falling-off of a road marking coating is further prevented, the perfect combination of the strength and the toughness can be well realized, the compressive strength of a surface marking is improved, and in addition, due to the combination with the aminated glass beads, the bonding fastness of the glass beads among systems can be further improved, and the falling-off condition between the glass beads and the marking is obviously reduced.
The invention can effectively improve the compressive strength of the glass beads in the marking, effectively prevent the glass beads from sinking in the marking after the marking is rolled by an automobile on a road at high frequency, and improve the continuous high-inverse reaction of the glass beads.
Drawings
FIG. 1 is a graph comparing the results of the compression test for the road marking coatings of example 5 and comparative examples 1-2.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples.
Example 1
A preparation method of a durable hot-melt marking paint comprises the following steps:
s1, weighing 10kg of heavy calcium carbonate, 10kg of quartz sand, 10kg of talcum powder and 1kg of titanium dioxide, mixing, and stirring at the speed of 500r/min for 1h to obtain a premix;
s2, adding 50kg of glass beads into 100kg of sodium hydroxide solution with the concentration of 1mol/L, stirring for 1 hour, filtering, washing, drying at the temperature of 70 ℃, adding 50kg of 40wt% ethanol solution and 1kg of KH550 coupling agent, stirring for 5 hours at the temperature of 50 ℃, filtering, washing and drying to obtain the aminated glass beads;
the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:1:1;
s3, adding 20kg of dimethylbenzene into 50kg of C5 petroleum resin, carrying out reflux stirring at the temperature of 100 ℃ for 5min, cooling to 80 ℃, adding 10kg of nano-silica and 5kg of water, carrying out ultrasonic dispersion for 10min, wherein the ultrasonic frequency is 10kHz, the ultrasonic power is 300W, carrying out irradiation treatment by adopting ultraviolet rays with the wavelength of 200nm for 5S, adding 0.1kg of boron trifluoride diethyl etherate, continuing to carry out ultrasonic treatment for 1h, adding 1kg of sodium carbonate, stirring at the speed of 1000r/min for 10min, adding aminated glass beads, stirring at the temperature of 100 ℃ for 5min, carrying out alkali washing and water washing in sequence until the pH value of a system is neutral, carrying out rotary evaporation and vacuum drying to obtain the C5 petroleum resin compounded glass beads;
and S4, mixing 1kg of stabilizer UV-P, 5kg of EVA resin, 1kg of dioctyl phthalate, 1-3kg of PE wax and C5 petroleum resin compounded glass beads, stirring at the speed of 1000r/min for 10min, adding the premix, and continuously stirring for 1h to obtain the durable hot-melt marking paint.
Example 2
A preparation method of a durable hot-melt marking paint comprises the following steps:
s1, weighing 50kg of heavy calcium carbonate, 30kg of quartz sand, 20kg of talcum powder and 10kg of titanium dioxide, mixing, and stirring at the speed of 1500r/min for 2 hours to obtain a premix;
s2, adding 80kg of glass beads into 200kg of 2mol/L sodium hydroxide solution, stirring for 2h, filtering, washing, drying at the temperature of 80 ℃, adding 100kg of 60wt% ethanol solution and 5kg of KH550 coupling agent, stirring for 10h at the temperature of 80 ℃, filtering, washing, and drying to obtain the aminated glass beads;
the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:5:5;
s3, adding 60kg of dimethylbenzene into 150kg of C5 petroleum resin, carrying out reflux stirring at the temperature of 150 ℃ for 15min, cooling to 90 ℃, adding 30kg of nano-silica and 15kg of water, carrying out ultrasonic dispersion for 30min, wherein the ultrasonic frequency is 20kHz, the ultrasonic power is 500W, carrying out irradiation treatment for 15S by adopting ultraviolet rays with the wavelength of 400nm, adding 1kg of boron trifluoride diethyl etherate, continuing ultrasonic treatment for 2h, adding 2kg of sodium carbonate, stirring at the speed of 3000r/min for 20min, adding aminated glass beads, stirring at the temperature of 120 ℃ for 15min, carrying out alkali washing and water washing in sequence until the pH value of a system is neutral, and carrying out rotary evaporation and vacuum drying to obtain C5 petroleum resin compound glass beads;
and S4, mixing 2kg of light stabilizer UV-326, 30kg of EVA resin, 3kg of dioctyl phthalate, 3kg of PE wax and C5 petroleum resin compounded glass beads, stirring at the speed of 2000r/min for 30min, adding the premix, and continuously stirring for 2h to obtain the durable hot-melt marking paint.
Example 3
A preparation method of a durable hot-melt marking paint comprises the following steps:
s1, weighing 20kg of heavy calcium carbonate, 15kg of quartz sand, 12kg of talcum powder and 3kg of titanium dioxide, mixing, and stirring at the speed of 700r/min for 1.2 hours to obtain a premix;
s2, adding 55kg of glass beads into 120kg of 1.2ol/L sodium hydroxide solution with the concentration of 1.5L, stirring for 1.5h, filtering, washing, drying at the temperature of 72 ℃, adding 60kg of 42wt% ethanol solution and 2kg of KH550 coupling agent, stirring for 5-10h at the temperature of 55 ℃, filtering, washing, and drying to obtain aminated glass beads;
the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:2:2;
s3, adding 30kg of dimethylbenzene into 80kg of C5 petroleum resin, carrying out reflux stirring at the temperature of 110 ℃ for 6min, cooling to 81 ℃, adding 13kg of nano-silica and 7kg of water, carrying out ultrasonic dispersion for 11min, wherein the ultrasonic frequency is 12kHz, the ultrasonic power is 320W, carrying out irradiation treatment for 6S by adopting ultraviolet rays with the wavelength of 250nm, adding 0.14kg of boron trifluoride diethyl etherate, continuing to carry out ultrasonic treatment for 1.2h, adding 1.04kg of sodium carbonate, stirring at the speed of 1500r/min for 13min, adding aminated glass beads, stirring at the temperature of 105 ℃ for 8min, carrying out alkali washing and water washing in sequence until the pH value of a system is neutral, and carrying out rotary evaporation and vacuum drying to obtain C5 petroleum resin compound glass beads;
s4, mixing 1.2kg of light stabilizer LS-744, 10kg of EVA resin, 1.2kg of dioctyl phthalate, 1.5kg of PE wax and C5 petroleum resin compound glass beads, stirring at the speed of 1200r/min for 12min, adding the premix, and continuously stirring for 1.2h to obtain the durable hot-melt marking paint.
Example 4
A preparation method of a durable hot-melt marking paint comprises the following steps:
s1, weighing 41kg of heavy calcium carbonate, 25kg of quartz sand, 14kg of talcum powder and 8kg of titanium dioxide, mixing, and stirring at 1350r/min for 1.8h to obtain a premix;
s2, adding 72kg of glass beads into 180kg of sodium hydroxide solution with the concentration of 1.6mol/L, stirring for 1.5h, filtering, washing, drying at 76 ℃, adding 85kg of ethanol solution with the concentration of 52wt% and 3kg of KH550 coupling agent, stirring for 8h at 72 ℃, filtering, washing and drying to obtain the aminated glass beads;
the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:2:3;
s3, adding 55kg of dimethylbenzene into 125kg of C5 petroleum resin, carrying out reflux stirring at the temperature of 135 ℃ for 12min, cooling to 88 ℃, adding 26kg of nano-silica and 12kg of water, carrying out ultrasonic dispersion for 24min, wherein the ultrasonic frequency is 15kHz, the ultrasonic power is 400W, carrying out irradiation treatment by ultraviolet rays with the wavelength of 350nm for 10S, adding 0.2kg of boron trifluoride diethyl etherate, continuing to carry out ultrasonic treatment for 1.5h, adding 1.6kg of sodium carbonate, stirring at the speed of 2600r/min for 15min, adding aminated glass beads, stirring at the temperature of 118 ℃ for 12min, carrying out alkali washing and water washing in sequence until the pH value of the system is neutral, carrying out rotary evaporation and vacuum drying to obtain the C5 petroleum resin compound glass beads;
s4, mixing 1.8kg of light stabilizer LS-744, 25kg of EVA resin, 2.1kg of dioctyl phthalate, 2.5kg of PE wax and C5 petroleum resin compound glass beads, stirring at the speed of 1800r/min for 24min, adding the premix, and continuously stirring for 1.8h to obtain the durable hot-melt marking paint.
Example 5
A preparation method of a durable hot-melt marking paint comprises the following steps:
s1, weighing 35kg of heavy calcium carbonate, 20kg of quartz sand, 15kg of talcum powder and 5kg of titanium dioxide, mixing, and stirring at the speed of 1000r/min for 1.5 hours to obtain a premix;
s2, adding 70kg of glass beads into 160kg of sodium hydroxide solution with the concentration of 1.5mol/L, stirring for 1.5h, filtering, washing, drying at the temperature of 76 ℃, adding 80kg of ethanol solution with the concentration of 55wt% and 2kg of KH550 coupling agent, stirring for 6h at the temperature of 75 ℃, filtering, washing and drying to obtain aminated glass beads;
the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:2.5:2.5;
s3, adding 30kg of dimethylbenzene into 100kg of C5 petroleum resin, carrying out reflux stirring at the temperature of 120 ℃ for 10min, cooling to 85 ℃, adding 20kg of nano-silica and 12kg of water, carrying out ultrasonic dispersion for 28min, wherein the ultrasonic frequency is 12kHz, the ultrasonic power is 450W, carrying out irradiation treatment for 10S by adopting ultraviolet rays with the wavelength of 250nm, adding 0.4kg of boron trifluoride diethyl etherate complex, continuing to carry out ultrasonic treatment for 1.5h, adding 1.5kg of sodium carbonate, stirring at the speed of 2000r/min for 15min, adding aminated glass beads, stirring at the temperature of 110 ℃ for 10min, carrying out alkali washing and water washing in sequence until the pH value of a system is neutral, and carrying out rotary evaporation and vacuum drying to obtain C5 petroleum resin compound glass beads;
and S4, mixing 1.2kg of light stabilizer UV-326, 20kg of EVA resin, 2kg of dioctyl phthalate, 2kg of PE wax and C5 petroleum resin compounded glass beads, stirring at the speed of 1500r/min for 20min, adding the premix, and continuously stirring for 1.5h to obtain the durable hot-melt marking paint.
Comparative example 1
A preparation method of a hot-melt marking paint comprises the following steps:
weighing 35kg of heavy calcium carbonate, 20kg of quartz sand, 15kg of talcum powder and 5kg of titanium dioxide, mixing, and stirring at the speed of 1000r/min for 1.5h to obtain a premix;
1.2kg of light stabilizer UV-326, 20kg of EVA resin, 2kg of dioctyl phthalate, 2kg of PE wax, 100kg of C5 petroleum resin, 70kg of glass bead and 20kg of nano silicon dioxide are mixed, stirred at the speed of 1500r/min for 20min, added with the premix and continuously stirred for 1.5h to obtain the hot melt marking paint.
Wherein the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:2.5:2.5;
comparative example 2
A preparation method of a hot-melt marking paint comprises the following steps:
s1, weighing 35kg of heavy calcium carbonate, 20kg of quartz sand, 15kg of talcum powder and 5kg of titanium dioxide, mixing, and stirring at the speed of 1000r/min for 1.5 hours to obtain a premix;
s2, adding 70kg of glass beads into 160kg of sodium hydroxide solution with the concentration of 1.5mol/L, stirring for 1.5h, filtering, washing, drying at the temperature of 76 ℃, adding 80kg of ethanol solution with the concentration of 55wt% and 2kg of KH550 coupling agent, stirring for 6h at the temperature of 75 ℃, filtering, washing and drying to obtain aminated glass beads;
the glass beads comprise glass beads with the particle size of 0.1-0.4mm, glass beads with the particle size of 0.5-0.65mm and glass beads with the particle size of 1-1.2mm, and the weight ratio of the glass beads to the glass beads is 10:2.5:2.5;
s3, mixing 1.2kg of light stabilizer UV-326, 20kg of EVA resin, 2kg of dioctyl phthalate, 2kg of PE wax, 100kg of C5 petroleum resin, aminated glass beads and 20kg of nano silicon dioxide, stirring at the speed of 1500r/min for 20min, adding the premix, and continuously stirring for 1.5h to obtain the hot-melt marking paint.
1. Appearance and fastness testing
The marking paint of the embodiment 5 and the comparative examples 1-2 is put into a hot melting kettle, stirred evenly at the temperature of 180-200 ℃, then put into a small kettle of an engineering truck, put into a hopper through the small kettle, evenly spread the paint on the road surface according to the laying line, and naturally cured to obtain the road marking sample to be detected.
(1) The apparent condition is as follows: testing the color and the brightness factor of a marking sample to be tested according to JT/T280-2004 industrial standard, and simultaneously observing the surface quality of the marking to be tested by naked eyes;
(2) Fastness of glass beads and road markings: and (3) sequentially pressing each road marking sample in the idle load of an automobile with the weight of about 1.5t, circulating for 100 times, and observing the falling condition of the glass beads on the surface of the sample and the sinking condition of the glass beads.
The test results are shown in the following table:
test items | Apparent condition | Firmness of glass beads |
Example 5 | White, 0.77 | No detachment or sinking |
Comparative example 1 | White, 0.86 | A small amount of micro-beads fall off and sink |
Comparative example 2 | White, 0.75 | Does not fall off and sinks |
As can be seen from the above table, the road marking of the invention has the advantages of good surface quality, high whiteness, brightness factor of more than 0.75, high bonding fastness of the glass beads in the marking, no falling and sinking of the glass beads after continuous rolling of automobiles, and contribution to improving the continuous high adverse reaction of the road marking.
2. Mechanical Property test
According to the detection standard of JT/T280-2004, the hot-melt coating is heated to 190 ℃, the coating forms a uniform fluid and is placed in a sample device of each index and is placed for 24 hours under the standard environment, wherein:
the abrasion resistance test condition is 200rad/1000 load and then weight is reduced;
the low-temperature crack resistance test is a cycle under the conditions of 20-4h, 25-4 h, and the existence of cracks is observed by a 200-time microscope (the national standard requires 10-4h, 10-4 h is a cycle, and the existence of cracks is observed by a 5-time microscope and is the cycle times), and when the microcracks are observed under the 200-time microscope, the low-temperature test is finished;
when the drawing strength is tested, the thickness of a paint film is 2mm, and the base material is a cement asbestos board.
The test results are shown in the following table:
the invention can effectively improve the abrasion performance and the low-temperature crack resistance, effectively enhance the drawing strength and has excellent mechanical property.
3. Test for compressive Strength
The marking paint to be detected is cast into a compression test block with the size of 20mm multiplied by 20mm, the compression test is carried out after the marking paint is placed for 24h at the standard test temperature, wherein the preload of an electronic universal tester is 10N, the loading speed is 30mm/min, and the test result is shown in figure 1.
As can be seen from fig. 1, comparative example 1 is very susceptible to brittle fracture and does not undergo plastic deformation. Compared with the comparative example 2, the example 5 has the plastic deformation platform, namely, the first high point is firstly generated and a certain deformation amount is maintained and then is increased, and meanwhile, the deformation amount is large, the initial compression resistance value is high, and the compression resistance is excellent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The durable hot-melt marking paint is characterized by comprising the following raw materials in parts by weight: 50-150 parts of C5 petroleum resin, 10-50 parts of heavy calcium carbonate, 50-80 parts of glass beads, 5-30 parts of EVA resin, 10-30 parts of quartz sand, 10-20 parts of talcum powder, 1-10 parts of titanium dioxide, 10-30 parts of nano silicon dioxide, 1-3 parts of dioctyl phthalate, 1-5 parts of KH550 coupling agent, 1-2 parts of sodium carbonate, 1-3 parts of PE wax, 0.1-1 part of catalyst, 1-2 parts of light stabilizer, 100-200 parts of sodium hydroxide solution, 50-100 parts of ethanol solution, 20-60 parts of xylene and 5-15 parts of water.
2. The durable hot melt marking paint of claim 1, wherein the glass beads comprise 0.1-0.4mm glass beads, 0.5-0.65mm glass beads and 1-1.2mm glass beads in a weight ratio of 10:1-5:1-5.
3. The durable hot melt marking paint of claim 1, wherein the catalyst is boron trifluoride etherate.
4. The durable hot melt marking paint of claim 1, wherein the sodium hydroxide solution has a concentration of 1-2mol/L.
5. The durable hot melt marking paint of claim 1, wherein the ethanol solution concentration is 40-60wt%.
6. The durable hot melt marking paint of claim 1, wherein the light stabilizer comprises at least one of light stabilizer UV-P, light stabilizer UV-326, light stabilizer UV-327, light stabilizer UV-5411, light stabilizer LS-744, light stabilizer LS-770, light stabilizer GW-540, light stabilizer PDS.
7. A method of making a durable hot melt marking paint according to any of claims 1 to 6 comprising the steps of:
s1, mixing heavy calcium carbonate, quartz sand, talcum powder and titanium dioxide according to a ratio, and stirring at a speed of 500-1500r/min for 1-2 hours to obtain a premix;
s2, adding the glass beads into a sodium hydroxide solution, stirring for 1-2 hours, filtering, washing, drying at the temperature of 70-80 ℃, adding an ethanol solution and a KH550 coupling agent, stirring at the temperature of 50-80 ℃ for 5-10 hours, filtering, washing, and drying to obtain aminated glass beads;
s3, adding dimethylbenzene into C5 petroleum resin, carrying out reflux stirring at the temperature of 100-150 ℃ for 5-15min, cooling to 80-90 ℃, adding nano silicon dioxide and water for ultrasonic dispersion, carrying out ultraviolet irradiation treatment, adding a catalyst, continuing ultrasonic treatment for 1-2h, adding sodium carbonate, stirring at the speed of 1000-3000r/min for 10-20min, adding aminated glass beads, stirring at the temperature of 100-120 ℃ for 5-15min, sequentially carrying out alkali washing and water washing until the pH value of a system is neutral, and carrying out rotary evaporation and vacuum drying to obtain C5 petroleum resin compound glass beads;
and S4, mixing the light stabilizer, the EVA resin, the dioctyl phthalate, the PE wax and the C5 petroleum resin compounded glass beads, stirring at the speed of 1000-2000r/min for 10-30min, adding the premix, and continuously stirring for 1-2h to obtain the durable hot-melt marking paint.
8. The method for preparing the durable hot melt marking paint according to claim 7, wherein in S3, the wavelength of ultraviolet light is 200-400nm and the irradiation time is 5-15S in the ultraviolet irradiation treatment process.
9. The preparation method of the durable hot melt marking paint according to claim 7, wherein nano silicon dioxide and water are added into S3 for ultrasonic dispersion, wherein the ultrasonic dispersion time is 10-30min, the ultrasonic frequency is 10-20kHz, and the ultrasonic power is 300-500W.
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