KR20220163682A - High functional paint composition having anti-freezing function and construction method for road pavement using the same - Google Patents

Abstract

The present invention relates to a high-functional paint composition having an excellent anti-freezing function and a road pavement construction method using the same. The composition comprises: 45 to 75 wt% of methyl methacrylate (MMA) resin; 0.1 to 5 wt% of a high functional admixture; 10 to 30 wt% of a high functional filler; 1 to 10 wt% of an anti-freezing agent; and 1 to 10 wt% of a curing agent. The high-functional admixture contains: 100 parts by weight of butyl acrylate; 1 to 20 parts by weight of poly(perfluoroalkyl methacrylate); 1 to 20 parts by weight of a siliconate-based compound; 0.1 to 10 parts by weight of hexamethyl disilazane; 0.1 to 10 parts by weight of guanidine thiocyanate; and 0.1 to 10 parts by weight of an infrared reflective pigment. The high-functional filler contains: 100 parts by weight of titanium dioxide; 10 to 30 parts by weight of titanium carbonitride; 10 to 30 parts by weight of pegmatite; 1 to 20 parts by weight of hollow magnesium oxide; and 1 to 20 parts by weight of tin oxide. The anti-freezing agent contains: 100 parts by weight of sodium chloride; 30 to 70 parts by weight of one or more polyhydric alcohols selected from a group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol and mixtures thereof; and 10 to 30 parts by weight of oxalic acid chloride. By using the composition, damage caused by skidding accidents and slipping on icy roads in winter is minimized, and the corrosion and deterioration of paved roads and vehicle tires are effectively prevented.

Description

High functional paint composition having anti-freezing function and construction method for road pavement using the same}

The present invention relates to a highly functional paint composition having an excellent anti-icing function capable of minimizing damage due to snow skidding accidents and slipping in winter and effectively preventing corrosion and deterioration of paved roads and vehicle tires, and a road pavement construction method using the same it's about

On the road, a slip phenomenon occurs due to various causes, and as a result, a driving vehicle is not controlled, which may lead to a serious accident. In general, highways, national roads, and local roads have many curved roads or downhill roads compared to the driving speed of a running vehicle, and the slip phenomenon in these places can be more dangerous. In particular, it is easy to freeze when it snows in winter, and in this case, vehicle accidents and pedestrian safety accidents may occur. Record-breaking heavy snowfall frequently occurs due to abnormal weather phenomena, so much attention is paid to preventing icing of roads in winter.

Conventionally, to prevent freezing of roads, a method of sprinkling sand or calcium chloride has been used. However, in the case of sudden heavy snowfall, since sand or calcium chloride must be directly sprayed on the road, rapid snow melting is difficult, and a large number of personnel and equipment are required. In addition, calcium chloride has a problem in that the anti-icing performance is expressed only once after spraying, so the calcium chloride must be re-sprayed every time, and if it snows continuously, the concentration of calcium chloride is lowered and eventually freezing may occur again. In addition, excessive calcium chloride has a problem of causing corrosion of paved roads and vehicle tires.

Accordingly, it is necessary to develop an anti-icing coating composition that can exhibit an anti-icing function for a long period of time with one pavement while having an excellent anti-icing function, and can minimize corrosion of pavements and vehicle tires due to low salt emission. .

Republic of Korea Patent No. 10-1310271 Republic of Korea Patent No. 10-1885813 Republic of Korea Patent No. 10-2155570

The present invention has been made to solve the above-described problems, and one embodiment of the present invention has an excellent anti-icing function, and stably maintains the excellent anti-icing function for a long period of time, thereby causing damage due to snow sliding accidents and slip phenomena in winter. It is an object of the present invention to provide a highly functional paint composition having an excellent anti-icing function capable of effectively preventing corrosion and deterioration of paved roads and vehicle tires and a road pavement construction method using the same.

Various problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

One embodiment of the present invention is 45 to 75% by weight of methyl methacrylate (MMA) resin, 0.1 to 5% by weight of a high functional admixture, 10 to 30% by weight of a high functional filler, 1 to 10% by weight of an anti-icing agent and 1 to 10% by weight of a curing agent 10% by weight;

The high-functional admixture is 100 parts by weight of butyl acrylate, 1 to 20 parts by weight of poly (perfluoroalkyl methacrylate), 1 to 20 parts by weight of a siliconate compound, 0.1 to 10 parts by weight of hexamethyl disilazane, guanidine 0.1 to 10 parts by weight of thiocyanate and 0.1 to 10 parts by weight of an infrared reflective pigment;

The high-functional filler includes 100 parts by weight of titanium dioxide, 10 to 30 parts by weight of titanium carbonitride, 10 to 30 parts by weight of pegmatite, 1 to 20 parts by weight of hollow magnesium oxide, and 1 to 20 parts by weight of tin oxide;

The anti-icing agent comprises 100 parts by weight of sodium chloride, 30 to 70 parts by weight of one or more polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol and mixtures thereof, and 10 to 30 parts by weight of oxalic acid chloride It provides a high-functional coating composition having an excellent anti-icing function.

The titanium carbonitride is prepared by preparing a mixture of titanium oxide (TiO ₂ ) powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture at a temperature of 1300 to 1500 ° C. in a nitrogen gas atmosphere. It may be prepared by a method comprising the step of heat treatment for 2 to 5 hours.

The expanded graphite is a mixture of 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15 ° C. to deposit graphite for 24 to 36 hours, washing and drying the deposited graphite obtaining graphite before expansion, and expanding the graphite before expansion at a temperature of 500 to 800 ° C. for 10 to 30 minutes so that the expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion)) is 450 It may be high expansion graphite prepared by a method including the step of preparing high expansion graphite that is 600 to 600 times higher.

The tin oxide is tin oxide sulfated with halosulfonic acid represented by Formula 1 below;

The tin oxide sulfated with halosulfonic acid is SnCl ₂ , SnCl ₂ ㆍ2H ₂ O, CH ₃ (CH ₂ ) ₃ SnCl ₃ , SnCl ₄ ㆍ5H ₂ O, SnCl ₄ and mixtures thereof. Dissolving the above tin precursor in distilled water, adding ammonia to induce hydrolysis of the tin precursor until the pH reaches 7.5 to 9.5; After filtering the precipitate by the hydrolysis reaction, drying at a temperature of 60 to 110 ° C. to produce tin hydroxide (Sn(OH) ₄ ); The resulting tin hydroxide (Sn(OH) ₄ ) is impregnated and stirred in an aqueous solution containing halosulfonic acid represented by Formula 1 at a concentration of 0.5 to 8 M, filtered, and dried at a temperature of 60 to 110 ° C. obtaining a solid product; and heat-treating the solid product at a temperature of 250 to 450 °C to produce sulfated tin oxide.

[Formula 1]

In the above formula, X represents a halogen atom.

In addition, another embodiment of the present invention is a road pavement construction method using the high-functional paint composition having the excellent anti-icing function,

A pre-processing step of removing and cleaning lattice, impurities and deterioration parts of the road surface; An undercoating step of forming a undercoating by pouring and drying a primer composition for undercoating containing a white or transparent infrared reflective pigment on the road surface that has passed through the pretreatment step; and a top coat forming step of forming a top coat by pouring and drying the highly functional paint composition having an excellent anti-icing function on the road surface that has undergone the under coat forming step.

According to the high-functional coating composition having excellent anti-icing function and the road pavement construction method using the same according to an embodiment of the present invention, it has an excellent anti-icing function and stably maintains the excellent anti-icing function for a long period of time, resulting in slipping on snowy roads in winter It has the effect of minimizing damage caused by accidents and slip phenomena.

In addition, corrosion and deterioration of paved roads and vehicle tires can be effectively prevented due to low salt emission, and adhesion to spheres made of asphalt or concrete, abrasion resistance, water resistance, and weather resistance are excellent, so that the pavement surface can be damaged by load and impact. It has excellent durability, such as not being easily cracked, worn, or discolored, and has excellent heat shielding performance.

At the same time, there is almost no elution of harmful substances such as various VOC-related organic solvents, formaldehyde, ammonia, and heavy metals such as lead, so there is an eco-friendly effect.

As a result, an effect that can be applied very usefully to paved roads such as driveways, sidewalks, sidewalks or bicycle roads made of asphalt or concrete, as well as to floors such as rooftops, roofs, and outdoor parking lot surfaces of structures made of asphalt or concrete. have.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, and the present invention is not limited thereby, and the present invention is only defined by the scope of the claims to be described later.

One embodiment of the present invention is 45 to 75% by weight of methyl methacrylate (MMA) resin, 0.1 to 5% by weight of a high functional admixture, 10 to 30% by weight of a high functional filler, 1 to 10% by weight of an anti-icing agent and 1 to 10% by weight of a curing agent 10% by weight;

The high-functional admixture is 100 parts by weight of butyl acrylate, 1 to 20 parts by weight of poly (perfluoroalkyl methacrylate), 1 to 20 parts by weight of a siliconate compound, 0.1 to 10 parts by weight of hexamethyl disilazane, guanidine 0.1 to 10 parts by weight of thiocyanate and 0.1 to 10 parts by weight of an infrared reflective pigment;

The high-functional filler includes 100 parts by weight of titanium dioxide, 10 to 30 parts by weight of titanium carbonitride, 10 to 30 parts by weight of pegmatite, 1 to 20 parts by weight of hollow magnesium oxide, and 1 to 20 parts by weight of tin oxide;

The anti-icing agent comprises 100 parts by weight of sodium chloride, 30 to 70 parts by weight of one or more polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol and mixtures thereof, and 10 to 30 parts by weight of oxalic acid chloride It provides a high-functional coating composition having an excellent anti-icing function.

According to the high-functional coating composition having excellent anti-icing function and the road pavement construction method using the same according to an embodiment of the present invention, it has an excellent anti-icing function and stably maintains the excellent anti-icing function for a long period of time, resulting in slipping on snowy roads in winter It has the effect of minimizing damage caused by accidents and slip phenomena.

In addition, corrosion and deterioration of paved roads and vehicle tires can be effectively prevented due to low salt emission, and adhesion to spheres made of asphalt or concrete, abrasion resistance, water resistance, and weather resistance are excellent, so that the pavement surface can be damaged by load and impact. It has excellent durability, such as not being easily cracked, worn, or discolored, and has excellent heat shielding performance.

At the same time, there is almost no elution of harmful substances such as various VOC-related organic solvents, formaldehyde, ammonia, and heavy metals such as lead, so there is an eco-friendly effect.

As a result, an effect that can be applied very usefully to paved roads such as driveways, sidewalks, sidewalks or bicycle roads made of asphalt or concrete, as well as to floors such as rooftops, roofs, and outdoor parking lot surfaces of structures made of asphalt or concrete. have.

More specifically, the high-functional coating composition having an excellent anti-icing function according to an embodiment of the present invention includes 45 to 75% by weight of methyl methacrylate (MMA) resin, 0.1 to 5% by weight of a high-functional admixture, and 10 high-functional fillers. to 30% by weight, 1 to 10% by weight of an anti-icing agent and 1 to 10% by weight of a curing agent.

First, the methyl methacrylate (MMA) resin has excellent durability, chemical resistance, UV safety, and excellent weather resistance, which is a property of resisting weather and climate such as sunlight, to prevent corrosion due to external environmental changes (weather and climate change) At the same time, it penetrates into the package and integrates it to improve adhesion strength and toughness, and to improve colorability by pigments. The methyl methacrylate (MMA) resin is preferably contained in the range of 45 to 75% by weight with respect to the high-functional coating composition having excellent anti-icing function of the present invention in consideration of the above-described improvement effect.

In addition, the high-functional admixture functions to stably maintain an excellent anti-icing function for a long period of time. In addition, it realizes improved adhesion strength to paved roads or structures, realizes improved durability with excellent resistance to corrosion and deterioration, has excellent material and construction stability against external temperature changes, and provides greatly improved workability. function to In addition, there is almost no elution of harmful substances such as various VOC-related organic solvents, formaldehyde, ammonia, and heavy metals such as lead, so there is an eco-friendly effect. The high-functional admixture is preferably contained in the range of 0.1 to 5% by weight with respect to the high-functional coating composition having an excellent anti-icing function of the present invention in consideration of the above-described improvement effect.

The highly functional admixture is 100 parts by weight of butyl acrylate, 1 to 20 parts by weight of poly(perfluoroalkyl methacrylate), 1 to 20 parts by weight of a siliconate compound, 0.1 to 10 parts by weight of hexamethyl disilazane, One containing 0.1 to 10 parts by weight of guanidine thiocyanate and 0.1 to 10 parts by weight of an infrared reflective pigment can be preferably used.

The butyl acrylate functions to realize excellent adhesion strength to paved roads or structures.

Hereinafter, the content of components constituting the high-functional admixture is based on 100 parts by weight of the butyl acrylate.

The poly (perfluoroalkyl methacrylate), together with the butyl acrylate, improves adhesion to realize excellent adhesion strength, provides excellent resistance to corrosion and deterioration, and at the same time provides excellent anti-icing effect. do.

The poly(perfluoroalkyl methacrylate) is preferably contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the butyl acrylate. If the content of the poly (perfluoroalkyl methacrylate) is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the poly (perfluoroalkyl methacrylate) is too large, the manufacturing cost is high. There is a problem that the price competitiveness may be lowered due to an increase in the price.

The siliconate-based compound functions to realize excellent adhesion strength and excellent resistance to corrosion and deterioration. In addition, it has an excellent anti-icing function and a function to stably maintain this excellent anti-icing function for a long period of time.

The siliconate-based compound is sodium methylsiliconate, sodium ethylsiliconate, sodium propylsiliconate, sodium phenylsiliconate, potassium methylsiliconate ), potassium ethylsiliconate (potassium ethylsiliconate), potassium propylsiliconate (potassium propylsiliconate), potassium phenylsiliconate (potassium phenylsiliconate) and the above improvement using at least one selected from the group consisting of The effect can be further improved.

The siliconate-based compound is preferably contained in the range of 1 to 20 parts by weight based on 100 parts by weight of the butyl acrylate. If the content of the siliconate-based compound is too small, there is a problem that the above-described improvement effect may be insufficient, and if the content of the siliconate-based compound is too large, manufacturing costs may increase and price competitiveness may decrease. .

The hexamethyl disilazane functions to stably maintain an excellent anti-icing function for a long period of time, and realizes improved durability through excellent resistance to corrosion and deterioration.

The hexamethyl disilazane is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the butyl acrylate. If the content of the hexamethyl disilazane is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the hexamethyl disilazane is too large, the manufacturing cost may increase and price competitiveness may decrease there is

The guanidine thiocyanate has an excellent anti-icing function and functions to stably maintain this excellent anti-icing function for a long period of time. In addition, it realizes improved durability with excellent resistance to corrosion and deterioration, has excellent material and construction stability against external temperature changes, and functions to provide greatly improved workability.

The guanidine thiocyanate is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the butyl acrylate. If the content of the guanidine thiocyanate is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the guanidine thiocyanate is too large, the manufacturing cost may increase and price competitiveness may decrease. .

The infrared reflective pigment highly reflects (eg, reflectance of 50% or more, preferably 60% or more) infrared rays, which account for most (about 52%) of the heat converted from sunlight, to prevent heat storage on the road function. More preferably, a black black heat-shielding pigment (eg, IR BLACK, etc.) may be used as the infrared reflective pigment.

The infrared reflective pigment is preferably contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the butyl acrylate. If the content of the infrared reflective pigment is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the infrared reflective pigment is too large, durability may be reduced.

In addition, the high-functional filler implements improved anti-icing performance, thermal insulation performance, and excellent anti-slip performance, and provides excellent dimensional stability, abrasion resistance, and thixotropic properties to prevent cracks and lifting. As a result, durability and weather resistance can be improved such that the pavement surface is not easily cracked, abraded, or discolored by a load or impact. In addition, it is possible to provide a fast curing time at room temperature, so that not only is the construction convenient, but also the rapid passage of vehicles after construction is possible, which has the effect of dramatically reducing the risk of traffic congestion and traffic accidents. The high-functional filler is preferably contained in the range of 10 to 30% by weight with respect to the high-functional coating composition having an excellent anti-icing function of the present invention in consideration of the above-described improvement effect.

The high-functional filler preferably includes 100 parts by weight of titanium dioxide, 10 to 30 parts by weight of titanium carbonitride, 10 to 30 parts by weight of pegmatite, 1 to 20 parts by weight of hollow spherical magnesium oxide, and 1 to 20 parts by weight of tin oxide. can be used

The titanium dioxide functions to provide improved heat shielding performance and anti-icing performance.

The titanium dioxide is used as porous hollow titanium dioxide nanoparticles to further improve the above improvement effect, as well as to provide excellent dimensional stability, wear resistance, and thixotropic properties to prevent cracks and lifting. As a result, durability and weather resistance can be improved such that the pavement surface is not easily cracked, abraded, or discolored by a load or impact.

More specifically, the porous hollow titanium dioxide nanoparticles are prepared by hydrothermal synthesis of a mixture of potassium titanium oxide oxalate dihydrate and polyethylene glycol at a temperature of 100 to 200 ° C. for 7 to 20 hours, and have an outer diameter of 50 to 800 nm And, porous hollow titanium dioxide nanoparticles having a surface pore size of 3 to 15 nm and a specific surface area of 25 to 35 m 2 /g may be preferably used.

Hereinafter, the content of components constituting the high-functional filler is based on 100 parts by weight of the titanium dioxide.

The titanium carbo-nitride functions to implement improved thermal insulation performance, excellent anti-slip performance, and provide excellent wear resistance to prevent cracks and lifting. As a result, durability and weather resistance can be improved such that the pavement surface is not easily cracked, abraded, or discolored by a load or impact.

The titanium carbonitride is prepared by preparing a mixture of titanium oxide (TiO ₂ ) powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture at a temperature of 1300 to 1500 ° C. in a nitrogen gas atmosphere. Prepared by a method comprising a heat treatment step for 2 to 5 hours, a composition having a composition in the range of TiC _0.3 N _0.7 to TiC _0.7 N _0.3 and an average particle diameter of 10 nm to 50 μm may be preferably used.

At this time, the expanded graphite is a mixture of 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15 ° C. to deposit graphite for 24 to 36 hours, washing the deposited graphite and drying to obtain graphite before expansion, and expanding the graphite before expansion at a temperature of 500 to 800 ° C. for 10 to 30 minutes to obtain an expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion)) High-expansion graphite prepared by a method including the step of preparing high-expansion graphite that is 450 to 600 times higher than this can be more preferably used. At this time, drying of the deposited graphite may be performed at a temperature of 85 to 105 ° C for 2 to 10 hours.

The titanium carbo-nitride is preferably contained in the range of 10 to 30 parts by weight based on 100 parts by weight of the titanium dioxide. When the content of the titanium carbonitride is too small, there is a problem that the above improvement effect may be insufficient, and when the content of the titanium carbonitride is too large, the manufacturing cost increases and price competitiveness may decrease.

The pegmatite, as a natural mineral, can exhibit improved heat shielding performance, implement excellent anti-slip performance, and function to enhance long-term strength, water resistance, and durability.

The pegmatite may preferably be pulverized with an average particle diameter of 0.05 to 0.3 μm.

The pegmatite is preferably contained in the range of 10 to 30 parts by weight based on 100 parts by weight of the titanium dioxide. If the content of the pegmatite is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the pegmatite is too large, it is difficult to expect any further performance improvement effect, and the manufacturing cost may increase, resulting in a decrease in price competitiveness. There is a problem with

The hollow spherical magnesium oxide improves corrosion resistance, chemical resistance, and chemical resistance, realizes improved anti-icing performance, thermal insulation performance, and excellent anti-slip performance, and provides excellent dimensional stability, abrasion resistance, and thixotropic properties, thereby causing cracks and lifting function to prevent it from happening. In addition, it has excellent resistance to drying shrinkage and functions to improve resistance to long-term cracks including initial shrinkage cracks. It also serves to provide a fast curing time at room temperature.

Preparing a precursor solution of the hollow spherical magnesium oxide by dissolving magnesium nitrate, magnesium sulfate, bead-shaped polystyrene, and carboxylic acid in a solvent; generating droplets by applying ultrasonic waves to the precursor solution, and spraying the droplets into a reactor using a carrier gas; preparing hollow spherical magnesium oxide by thermally decomposing the droplets at a temperature of 400 to 900 °C; and preparing hollow spherical magnesium oxide having increased crystallinity by heat-treating the prepared hollow spherical magnesium oxide at a temperature of 150 to 350 °C.

At this time, the bead-type polystyrene may preferably be used having an average particle size of 50 to 120 nm.

In addition, the carboxylic acid may preferably be at least one selected from the group consisting of oxalic acid, succinic acid, tartaric acid, glutamic acid, adipic acid, terephthalic acid, phthalic acid, malonic acid, maleic acid, fumaric acid, and mixtures thereof.

In addition, the solvent is dimethylacetamide, dimethylformamide, acetic acid, n-methyl-2-pyrrolidone (NMP), formic acid, nitromethane, methanol, ethanol, propanol, iso-propanol, tert-butanol, n-butanol , It may be at least one selected from the group consisting of methoxyethanol, ethoxyethanol, water, and mixtures thereof, preferably, it may be a mixed solvent of dimethylacetamide and acetic acid, more preferably, dimethylacetamide and acetic acid in a volume ratio of 1:1 to 10, respectively.

In addition, the carrier gas may be preferably used at least one selected from the group consisting of air, nitrogen, oxygen, helium, argon, and mixture gases thereof.

Preferably, the hollow spherical magnesium oxide is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the titanium dioxide. If the content of the hollow sphere-shaped magnesium oxide is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the hollow sphere-shaped magnesium oxide is too large, it is difficult to expect any further performance improvement effect, and the manufacturing cost is high. There is a problem that the price competitiveness may be lowered due to an increase in the price.

The tin oxide serves to improve corrosion resistance, chemical resistance, and chemical resistance, thereby realizing improved anti-icing performance and heat shielding performance. In addition, it has excellent resistance to drying shrinkage and functions to improve resistance to long-term cracks including initial shrinkage cracks.

The above effect can be further improved by using tin oxide sulfated with halosulfonic acid represented by Formula 1 below.

More specifically, the tin oxide sulfated with halosulfonic acid is from the group consisting of SnCl ₂ , SnCl ₂ 2H ₂ O, CH ₃ (CH ₂ ) ₃ SnCl ₃ , SnCl ₄ 5H ₂ O, SnCl ₄ and mixtures thereof. After dissolving at least one selected tin precursor in distilled water, adding ammonia to induce hydrolysis of the tin precursor until the pH reaches 7.5 to 9.5; After filtering the precipitate by the hydrolysis reaction, drying at a temperature of 60 to 110 ° C. to produce tin hydroxide (Sn(OH) ₄ ); The resulting tin hydroxide (Sn(OH) ₄ ) is impregnated and stirred in an aqueous solution containing halosulfonic acid represented by Formula 1 at a concentration of 0.5 to 8 M, filtered, and dried at a temperature of 60 to 110 ° C. obtaining a solid product; and heat-treating the solid product at a temperature of 250 to 450 °C to produce sulfated tin oxide.

[Formula 1]

In the above formula, X represents a halogen atom.

The tin oxide is preferably contained in the range of 1 to 20 parts by weight based on 100 parts by weight of the titanium dioxide. If the content of the tin oxide is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the tin oxide is too large, it is difficult to expect any further performance improvement effect, and the manufacturing cost increases, resulting in a decrease in price competitiveness. There are problems that could be.

In addition, the anti-icing agent serves to realize improved anti-icing performance and heat shielding performance. It also serves to provide a fast curing time at room temperature. The anti-icing agent is preferably contained in the range of 1 to 10% by weight with respect to the high-functional coating composition having an excellent anti-icing function of the present invention in consideration of the above-described improvement effect.

The anti-icing agent includes 100 parts by weight of sodium chloride, 30 to 70 parts by weight of one or more polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol, and mixtures thereof, and 10 to 30 parts by weight of oxalic acid chloride It can be used preferably.

More specifically, the sodium chloride is a water-soluble inorganic salt having excellent hygroscopicity and water retention, and functions to realize improved anti-icing performance by absorbing moisture and melting snow or ice.

Hereinafter, the content of components constituting the anti-icing agent is based on 100 parts by weight of the sodium chloride.

At least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol, and mixtures thereof functions to realize improved anti-icing performance and heat shielding performance.

It is preferable that at least one polyhydric alcohol selected from the group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol, and mixtures thereof is contained in an amount of 30 to 70 parts by weight based on 100 parts by weight of the sodium chloride. If the content of the polyhydric alcohol is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the polyhydric alcohol is too large, it is difficult to expect any further performance improvement effect, and the manufacturing cost increases, resulting in a decrease in price competitiveness. There are problems that could be.

The oxalic acid chloride functions to realize further improved anti-icing performance and heat shielding performance.

The oxalic acid chloride is preferably contained in the range of 10 to 30 parts by weight based on 100 parts by weight of the sodium chloride. If the content of the oxalic acid chloride is too small, there is a problem that the above improvement effect may be insufficient, and if the content of the oxalic acid chloride is too large, it is difficult to expect any further performance improvement effect, and the manufacturing cost increases, resulting in a decrease in price competitiveness. There are problems that could be.

In addition, the curing agent serves to form a coating layer having excellent strength and durability by curing and combining various components included in the composition. The curing agent is preferably contained in the range of 1 to 10% by weight with respect to the high-functional coating composition having excellent anti-icing function of the present invention in consideration of the above-described improvement effect.

More specifically, the curing agent may preferably use a peroxide-based curing agent, and the peroxide-based curing agent is benzoyl peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide (methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethylhexyl-2,5-diperoxybenzoate, acetone peroxide , at least one selected from the group consisting of pinane peroxide, diethyl ether peroxide, and mixtures thereof may be used. More preferably, benzoyl peroxide may be used as the curing agent.

In addition, the high-functional coating composition having excellent anti-icing function of the present invention may further include a curing accelerator in order to improve the reactivity and more quickly improve the curing rate. The curing accelerator is preferably contained in the range of 0.01 to 1% by weight with respect to the high-functional coating composition having excellent anti-icing function of the present invention in consideration of the above improvement effect.

More specifically, the curing accelerator includes n,n-dimethyl aniline (DMA), 2-ethylhexonate, cobalt carboxylate, n,n-diethyl One selected from the group consisting of aniline (nn-diethyl aniline; EMA), n-di-p-toluidine, d-methyl acylamide, and mixtures thereof Any of the above can be used preferably.

In addition, another embodiment of the present invention is a road pavement construction method using the high-functional paint composition having the excellent anti-icing function,

A pre-processing step of removing and cleaning lattice, impurities and deterioration parts of the road surface; An undercoating step of forming a undercoating by pouring and drying a primer composition for undercoating containing a white or transparent infrared reflective pigment on the road surface that has passed through the pretreatment step; and a top coat forming step of forming a top coat by pouring and drying the highly functional paint composition having an excellent anti-icing function on the road surface that has undergone the under coat forming step.

More specifically, the preprocessing step of removing and cleaning the laitance, impurities, and deterioration parts of the road surface physically removes the raytance, impurities, and deterioration parts present on the surface of the road to be constructed, and smooths the surface to adjust the background After that, it can be performed by cleaning.

In this case, shot blasting, planing machine, polishing machine, etc. may be used to remove raytans, impurities, and deteriorated parts of the road surface, but the present invention is not limited thereto.

In addition, if there is a crack or a damaged part on the road surface, it can be performed by cleaning and cleaning the road surface to be constructed by filling it with a putty or sealing agent after V-cutting or polishing.

At this time, when the road surface is a bottom surface of a bicycle road or a concrete structure as well as a general road, the road surface is cleaned and sufficiently dried to ensure a good water gradient, and foreign substances such as oil and rust are removed. and cleaning.

The primer composition for undercoating serves to facilitate adhesion of the high-functional coating composition having an excellent anti-icing function to the road surface.

The primer composition for primer is generally used in the art, and the type is not particularly limited. For example, 1 selected from the group consisting of styrene butadiene rubber latex, polyacrylic ester, ethylene vinyl acetate, and mixtures thereof Those containing more than one species may be used. However, the present invention is not limited thereto.

In addition, the white or transparent infrared reflective pigment highly reflects (eg, reflectance of 50% or more, preferably 60% or more) infrared rays, which account for most (about 52%) of heat converted from sunlight, It has a function to further prevent heat storage in the

The white or transparent infrared reflective pigment is preferably included in an amount of 5 to 50% by weight based on the primer composition for undercoating. If the content of the white or transparent infrared reflective pigment is too small, there is a problem that the improvement effect may be insufficient, and if the content of the white or transparent infrared ray reflective pigment is too large, the effect of improving adhesion is reduced or However, there is a problem in that the manufacturing cost increases and price competitiveness may decrease.

In addition, the thickness of the lower coating is preferably formed to 100 to 800 μm, more preferably 300 to 500 μm; The thickness of the top coat is preferably formed to 1 to 4 mm, more preferably 1.5 to 2.5 mm.

According to the high-functional coating composition having excellent anti-icing function and the road pavement construction method using the same according to an embodiment of the present invention, it has an excellent anti-icing function and stably maintains the excellent anti-icing function for a long period of time, resulting in slipping on snowy roads in winter It has the effect of minimizing damage caused by accidents and slip phenomena.

In addition, corrosion and deterioration of paved roads and vehicle tires can be effectively prevented due to low salt emission, and adhesion to spheres made of asphalt or concrete, abrasion resistance, water resistance, and weather resistance are excellent, so that the pavement surface can be damaged by load and impact. It has excellent durability, such as not being easily cracked, worn, or discolored, and has excellent heat shielding performance.

At the same time, there is almost no elution of harmful substances such as various VOC-related organic solvents, formaldehyde, ammonia, and heavy metals such as lead, so there is an eco-friendly effect.

As a result, an effect that can be applied very usefully to paved roads such as driveways, sidewalks, sidewalks or bicycle roads made of asphalt or concrete, as well as to floors such as rooftops, roofs, and outdoor parking lot surfaces of structures made of asphalt or concrete. have.

Although the preferred embodiment of the present invention has been described in detail above, the present invention is not limited to the above embodiment, and various modifications are made by those skilled in the art within the scope of the technical idea of the present invention. this is possible

<Production Example 1>

Preparation of porous hollow titanium dioxide nanoparticles

0.266 g of potassium titanium oxide oxalate dihydrate (hereinafter, also referred to as PTO) was put into 45 mL of ultrapure water (DI-water) and completely dissolved for 2 hours, and then 225 mL of polyethylene glycol (hereinafter, also referred to as PEG). ) is added and stirred to prepare a first mixed solution. After further stirring the first mixed solution for 30 minutes, it was reacted at 180° C. for 15 hours using an autoclave. After the reaction was completed, the precipitate was centrifuged to obtain porous hollow titanium dioxide nanoparticles (hereinafter, referred to as MTHS), washed several times with water and ethanol, and then dried. The drying process was performed overnight in an oven at 50 °C. Next, heat treatment was performed at 500° C. for 30 minutes to remove organic components remaining in the synthesized porous hollow titanium dioxide nanoparticles (MTHS). As a result, porous hollow titanium dioxide nanoparticles having an outer diameter of about 280 nm, an inner diameter of about 250 nm, a surface pore size of about 7 nm, and a specific surface area of 29.3 m 2 /g were obtained.

<Production Example 2>

Manufacture of titanium carbonitride

Preparing a mixed mixture by mixing titanium oxide (TiO ₂ ) powder and carbon black so that the molar ratio of Ti:C is 1:1, pulverizing the mixture, and pulverizing the pulverized mixture in a nitrogen gas atmosphere heat treatment at a temperature of 1400 ° C. for 5 hours; prepared by a method including, to prepare titanium carbonitride having an average particle diameter of 19 μm.

<Production Example 3>

Manufacture of titanium carbonitride

Preparing a mixture by mixing titanium oxide (TiO ₂ ) powder and expanded graphite so that the molar ratio of Ti:C is 1:0.7, pulverizing the mixture, and pulverizing the pulverized mixture at 1400 °C in a nitrogen gas atmosphere. Heat treatment at a temperature of °C for 3 hours; prepared by a method including, to prepare titanium carbo-nitride having an average particle diameter of 12 μm. At this time, the expanded graphite is prepared by mixing 100 parts by weight of sulfuric acid, 2.5 parts by weight of graphite and 7.5 parts by weight of hydrazine at a temperature of 5 ° C. to deposit graphite for 24 hours, washing the deposited graphite several times to remove sulfuric acid, and Drying at a temperature of ° C. for 7 hours to obtain graphite before expansion, and expanding the graphite before expansion at a temperature of 700 ° C. for 20 minutes to obtain an expansion ratio ((volume of high expansion graphite) / (volume of graphite before expansion) )) was used, which is high expansion graphite prepared by a method including the step of preparing high expansion graphite having a 507-fold increase.

<Production Example 4>

Preparation of magnesium oxide having a hollow sphere shape

After dissolving a mixture of magnesium nitrate and magnesium sulfate in a 1: 1 weight ratio in a mixed solvent of dimethylacetamide and acetic acid in a volume ratio of 1: 2.5 until the solution becomes transparent, polystyrene beads with an average particle size of 75 nm A precursor solution was prepared by further mixing 42 g and 3 g of oxalic acid. The precursor solution in an oil bath was injected into an ultrasonic nebulizer for use in spray pyrolysis. Ultrasound was applied to the precursor solution to generate droplets, and the droplets were transferred to an electric furnace using nitrogen gas and pyrolyzed at a temperature of 600° C. to prepare hollow spherical magnesium oxide. Thereafter, by heat-treating the prepared hollow spherical magnesium oxide in an argon gas atmosphere at a temperature of 300° C., hollow spherical magnesium oxide having increased crystallinity was prepared.

<Production Example 5>

Preparation of tin oxide sulphated with halosulfonic acid

After dissolving 25 g of SnCl ₄ 5H ₂ O (tin chloride pentahydrate) in 500 ml of distilled water, while stirring at room temperature, aqueous ammonia (concentration of 30% by weight) was added until the pH of the aqueous solution reached 8. A hydrolysis reaction of SnCl ₄ •5H ₂ O was induced.

At this time, the precipitate by the hydrolysis reaction is filtered to obtain a solid product, washed sufficiently with distilled water, put in a drying oven and dried at 110 ° C. for 15 hours to produce 5.5 g of tin hydroxide (Sn(OH) ₄ ). did

The resulting tin hydroxide (Sn(OH) ₄ ) was impregnated with an aqueous solution containing a halosulfonic acid represented by Formula 1-1 at a concentration of 3 M at a rate of 15 ml per g, stirred for 1 hour, and then filtered to obtain a solid product. After washing the obtained solid product with distilled water, it was placed in a drying oven and dried at 110 °C for 2 hours.

The dried solid product was put in an electric furnace and heat-treated at 400 °C for 5 hours under an air atmosphere to prepare 5.4 g of tin oxide sulfate as a final product.

The content of sulfate ions (SO ₄ ^2- ) in the final product, sulfated tin oxide, was measured by thermogravimetric analysis (TGA), and the measured content was 7.8% by weight.

[Formula 1-1]

In the above formula, X is Cl.

<Examples and Comparative Examples>

A high-functional coating composition having excellent anti-icing function and a comparative composition were prepared with the components and contents shown in Table 1 below.

Classification (% by weight) Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Methyl methacrylate (MMA) resin 63 62 62 65 62 High-functional admixture 3.5 5 5 - 3 (parts by weight) butyl acrylate 100 100 100 - 100 Poly(perfluoroalkyl methacrylate) 12 12 12 - - sodium methylsiliconate 14 - 7 - - Potassium Phenylsiliconate - 14 7 Hexamethyl Disilazane 4 4 4 - - Guanidine thiocyanate 5 5 5 - - infrared reflective pigment
(IR BLACK) 3 3 3 - - High-functional filler 23 23 23 22 22 (parts by weight) titanium dioxide 100
(normal
titanium dioxide powder) 100
(Production Example 1) 100
(Production Example 1) 100 100 titanium carbonitride 19
(Production Example 2) 19
(Production Example 2) 19
(Production Example 3) - - pegmatite
(Average particle diameter: 0.12 μm) 21 21 21 - - hollow spherical magnesium oxide
(Production Example 4) 8 8 8 - - tin oxide 7
(normal
tin oxide powder) 7
(Production Example 5) 7
(Production Example 5) - - anti-icing agent 7 7 7 10 10 (parts by weight) sodium chloride 100 100 100 100 100 Ethylene glycol 52 26 39 - 35 glycerin - 26 13 - - oxalic acid chloride 18 18 18 - - Curing agent (benzoyl peroxide) 3.5 2.7 2.7 3 3 Curing accelerator (di-methyl acrylamide) - 0.3 0.3 - -

The following test examples are experiments comparing the characteristics of Examples 1 and 2 according to the present invention and Comparative Examples 1 and 2 so that the characteristics of Examples 1 to 3 according to the present invention described above can be more easily grasped. that showed the results.

<Test Example>

The basic properties of the high-functional coating composition having excellent anti-icing function prepared in the above example and the comparative composition prepared in Comparative Example were evaluated and are shown in Table 2 below.

-. The pot life was evaluated by measuring the time at which fluidity of the paint disappeared after mixing the composition.

-. The curing time was evaluated by measuring the time at which fingerprints of the hand do not remain on the coating film after mixing the composition, coating the paint to a thickness of 500 μm on a cover sheet, and then twisting the coating film by applying force to the thumb.

-. The adhesion strength was evaluated by measuring according to the method specified in KS F 4936 (coating material for concrete protection).

-. Wear resistance was evaluated by measuring the wear rate after 500,000 cycles using a wheel load wear resistance test equipment.

-. Water resistance was evaluated by measuring according to the method specified in the KS M ISO 1514 method. After drying for 48 hours, immersed in water for 72 hours and dried at room temperature for 2 hours, the state of the coating film was measured on a 5-point scale. Similar to ~ 1 point: A lot of lifting, cracking, and splitting of the coating film occur)

-. Accelerated weather resistance was evaluated by measuring according to the method specified in KS F 2274 (accelerated exposure test method of synthetic resin materials for construction) and KS M ISO 7724-2.

-. The slip resistance was evaluated by measuring using the sliding friction coefficient (British Pendulum Tester, BPN) according to the non-slip packaging standard (KS F 2375).

-. The heat shielding performance was measured by painting the composition on a portion of the concrete surface, drying it, irradiating near-infrared rays set at 60 ° C and leaving it for 1 hour, measuring the temperature difference between the paint film and the concrete surface, and measuring the temperature of the paint film in the concrete surface temperature measurement value. The higher the temperature difference value minus the measured surface temperature value, the better the thermal insulation property of the coating film was evaluated. (Temperature difference from concrete substrate)

-. Heavy metal content was evaluated by measuring according to the method specified in KS M ISO 3856.

-. The VOC content was evaluated by measuring according to the method specified in US EFA methods 24.

-. Ice breaking tensile strength (MPa): A test body was prepared by coating and paving the composition on an asphalt specimen (width and length: each 300 mm, thickness 50 mm). Thereafter, the non-woven fabric attached to the bottom of the jig was immersed in 12 ° C. tap water for 1 hour, and then sufficiently absorbed, the jig was placed on the prepared test body, and the steel ball (420 ± 10 g) was 10 times at a height of 25 cm. It was allowed to fall freely and stick with a constant pressure. Next, the test specimen with the jig attached was left in a freezer at minus 5 ° C for 2 hours to freeze the specimen and the nonwoven fabric, and then the ice crushing tensile strength was measured using a hydraulic tensile tester in the freezer. This process was repeated three times to calculate the average value.

-. Long-term ice breaking tensile strength (MPa): Test specimens were prepared in the same manner as the test specimens prepared for measuring the ice breaking tensile strength (MPa), and then washed 20 times by rubbing in running water for 20 minutes each time. Afterwards, the ice-attachment tensile strength (MPa) was measured in the same manner as the ice-attachment tensile strength (MPa) measurement method.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Pot life (min, 25℃) 3 3 3 2 2 Curing time (min, 25℃) 16 14 11 28 31 Bond strength (N/mm ² ) After standard curing 1.9 2.3 2.5 0.6 1.1 After repeated hot and cold tests 1.8 2.0 2.1 0.5 0.8 Wear resistance (wear rate, %) 0.3 0.2 0.1 0.4 0.4 water resistance 5 5 5 3 3 accelerated weathering Appearance nothing strange nothing strange nothing strange offshoot nothing strange Color difference (ΔE ^* ab) 0.7 0.4 0.2 1.8 1.3 Slip Resistance (BPN) 95 103 109 79 83 Thermal insulation performance (℃) 21 22 25 13 16 Heavy metal content (%) Lead (Pb) not detected not detected not detected not detected not detected Cadmium (Cd) not detected not detected not detected not detected not detected Hexavalent chromium (Cr ⁶⁺ ) not detected not detected not detected not detected not detected Mercury (Hg) not detected not detected not detected not detected not detected VOC content (%) 0.3 0.4 0.3 0.4 0.4 Ice breaking tensile strength (MPa) -5℃ 0 0 0 0.19 0.07 -10℃ 0.02 0 0 0.23 0.13 -15℃ 0.09 0.04 0.02 0.28 0.24 Long-term ice immersion tensile strength (MPa) -5℃ 0 0 0 0.20 0.12 -10℃ 0.07 0.03 0 0.28 0.17 -15℃ 0.11 0.08 0.04 0.32 0.26

As shown in Table 2, the high-functional coating composition having excellent anti-icing function prepared in Examples 1 to 3 of the present invention has a similar level of pot life compared to the comparative composition prepared in Comparative Examples 1 and 2. while having a short curing time; It was confirmed that it had excellent adhesion strength, abrasion resistance, water resistance, accelerated weather resistance, slip resistance and heat shielding performance.

In addition, the high-functional coating composition having excellent anti-icing function prepared in Examples 1 to 3 of the present invention and the comparative composition prepared in Comparative Examples 1 and 2 did not detect heavy metals and had a VOC content of 5.0 or less. As it satisfies all the standards, it was confirmed that it is environmentally friendly.

In addition, the high-functional coating composition having an excellent anti-icing function prepared in Examples 1 to 3 of the present invention was compared to the comparative composition prepared in Comparative Examples 1 and 2, under severe temperature conditions of -5 to 15 ° C below zero. Also, it was confirmed that the ice-attaching tensile strength was very low and had excellent anti-icing function. In addition, it was confirmed that the excellent anti-icing performance was stably maintained even after washing 20 times, and the ice-wearing tensile strength was very low even under severe temperature conditions of -5 to 15 ° C. below.

As described above, those skilled in the art to which the present invention pertains will understand that the present invention can be embodied in other specific forms without changing its technical spirit or essential features. Therefore, all of the embodiments described above are illustrative and should be understood as not limiting. The scope of the present invention should be construed as including all changes or modifications derived from the meaning and scope of the claims to be described later and their equivalent concepts rather than the above detailed description included in the scope of the present invention.

Claims (5)

45 to 75% by weight of methyl methacrylate (MMA) resin, 0.1 to 5% by weight of a high-functional admixture, 10 to 30% by weight of a high-functional filler, 1 to 10% by weight of an anti-icing agent, and 1 to 10% by weight of a curing agent;
The high-functional admixture is 100 parts by weight of butyl acrylate, 1 to 20 parts by weight of poly (perfluoroalkyl methacrylate), 1 to 20 parts by weight of a siliconate compound, 0.1 to 10 parts by weight of hexamethyl disilazane, guanidine 0.1 to 10 parts by weight of thiocyanate and 0.1 to 10 parts by weight of an infrared reflective pigment;
The high-functional filler includes 100 parts by weight of titanium dioxide, 10 to 30 parts by weight of titanium carbonitride, 10 to 30 parts by weight of pegmatite, 1 to 20 parts by weight of hollow magnesium oxide, and 1 to 20 parts by weight of tin oxide;
The anti-icing agent comprises 100 parts by weight of sodium chloride, 30 to 70 parts by weight of one or more polyhydric alcohols selected from the group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol and mixtures thereof, and 10 to 30 parts by weight of oxalic acid chloride A high-functional coating composition having an excellent anti-icing function, characterized in that.
According to claim 1,
The titanium carbonitride is
Preparing a mixture of titanium oxide (TiO ₂ ) powder and expanded graphite, pulverizing the mixture, and pulverizing the pulverized mixture at a temperature of 1300 to 1500 ° C. for 2 to 5 hours in a nitrogen gas atmosphere A high-functional coating composition having excellent anti-icing function, characterized in that it is prepared by a method comprising the step of heat treatment.
According to claim 2,
The expanded graphite is
Depositing graphite by mixing 100 parts by weight of sulfuric acid, 0.5 to 10 parts by weight of graphite, and 1 to 30 parts by weight of hydrazine at a temperature of 5 to 15 ° C. for 24 to 36 hours, washing and drying the deposited graphite to obtain graphite before expansion Obtaining, and expanding the graphite before expansion at a temperature of 500 to 800 ° C. for 10 to 30 minutes to obtain a high expansion ratio ((volume of high expansion graphite)/(volume of graphite before expansion)) of 450 to 600 times. A high-functional coating composition having excellent anti-icing function, characterized in that it is high-expansion graphite prepared by a method comprising the step of preparing expanded graphite.
According to claim 1,
The tin oxide is tin oxide sulfated with halosulfonic acid represented by Formula 1 below;
Tin oxide sulfated with the halosulfonic acid is
After dissolving at least one tin precursor selected from the group consisting of SnCl ₂ , SnCl ₂ ㆍ2H ₂ O, CH ₃ (CH ₂ ) ₃ SnCl ₃ , SnCl ₄ ㆍ5H ₂ O, SnCl ₄ and mixtures thereof in distilled water. , adding ammonia to induce hydrolysis of the tin precursor until the pH reaches 7.5 to 9.5; After filtering the precipitate by the hydrolysis reaction, drying at a temperature of 60 to 110 ° C. to produce tin hydroxide (Sn(OH) ₄ ); The resulting tin hydroxide (Sn(OH) ₄ ) is impregnated and stirred in an aqueous solution containing halosulfonic acid represented by Formula 1 at a concentration of 0.5 to 8 M, filtered, and dried at a temperature of 60 to 110 ° C. obtaining a solid product; and generating sulfated tin oxide by heat-treating the solid product at a temperature of 250 to 450 °C.
[Formula 1]

In the above formula, X represents a halogen atom.
A road pavement construction method using the highly functional paint composition having excellent anti-icing function according to any one of claims 1 to 4,
A pre-processing step of removing and cleaning lattice, impurities and deterioration parts of the road surface; An undercoating step of forming a undercoating by pouring and drying a primer composition for undercoating containing a white or transparent infrared reflective pigment on the road surface that has passed through the pretreatment step; and a top coat forming step of forming a top coat by pouring and drying the highly functional paint composition having an excellent anti-icing function on the road surface that has passed through the under coat forming step.