Concrete-damage-suppressing additive composition for eco-friendly solid snow removal agent, and eco-friendly solid snow removal agent comprising same

Abstract

The present invention relates to an additive composition for an eco-friendly solid snow removal agent, and an eco-friendly solid snow removal agent comprising same, the composition comprising a waterproof agent and a corrosion inhibitor, thereby enabling concrete damage caused by a snow removal agent to be effectively prevented. According to the present invention, the provided additive for a snow removal agent uses a waterproofing agent and a corrosion inhibitor in combination and has optimized components and a content ratio thereof, and thus can effectively suppress concrete damage while having excellent deicing performance and corrosion prevention performance. In addition, the snow removal agent prepared using the additive of the present invention has a water-insoluble matter of 1% or less, which satisfies environmental designation certification standards, and thus can be effectively used as an eco-friendly solid snow removal agent.

Description

An environmentally friendly solid de-icing agent additive composition that suppresses concrete damage and an environmentally friendly solid de-icing agent comprising the same

[0001] The present invention relates to an environmentally friendly solid de-icing agent additive composition that suppresses concrete damage and an environmentally friendly solid de-icing agent comprising the same, and more particularly, to an environmentally friendly solid de-icing agent additive composition that includes a waterproofing agent and a corrosion inhibitor and has excellent de-icing performance while effectively preventing concrete damage and an environmentally friendly solid de-icing agent comprising the same.

[0002] Due to recent climate change, heavy snowfall has become more frequent in winter, not only in Korea but also around the world. This has led to an increase in the use of deicing agents. While the types of deicing agents used vary slightly across countries, Korea primarily uses general chloride-based deicing agents.

[0003] Chloride-based deicers contain calcium chloride (CaCl2) and sodium chloride (NaCl) as their main ingredients. Chloride-based deicers melt ice through rapid dissolution and exothermic reactions due to their deliquescent nature. This melting effect is maintained by freezing point depression caused by ions. Chloride-based deicers command approximately 90% of the deicer market, boasting excellent deicing performance and low prices.

[0004] However, chloride-based deicers commonly contain chloride ions (Cl - ) contain large amounts of sulfur dioxide, which has the property of corroding the steel of vehicle undercarriages and bridges, yellowing plants, and deteriorating concrete. In particular, the deicing agent solution that melts with snow penetrates the pores of concrete, causing repeated freezing and thawing, accelerating concrete damage. Concrete damage is directly related to numerous public goods and causes great social damage, so the market demand for deicing agents that do not cause concrete damage is increasing.

[0005] The most popular eco-friendly deicers are solid-state deicers, which combine a solid chloride-based deicer with a corrosion inhibitor. While solid-state deicers containing corrosion inhibitors are effective in preventing corrosion of steel, they have the disadvantage of hardening during long-term storage, reducing their usability. Furthermore, in areas requiring immediate deicing, such as ramps and bridges, they must be applied in advance to ensure proper deicing performance. Furthermore, the solution generated after deicing can penetrate concrete pores, causing concrete deterioration, a problem difficult to resolve.

[0006] For example, Korean Patent Publication No. 10-2141869 describes a solid deicing agent composition that entraps sodium chloride and calcium chloride in a carrier to provide strong durability, and Korean Patent Publication No. 10-2217389 describes a chloride-based deicing agent containing chloride, citric acid, and triphosphate. However, existing technologies only consider deicing performance or corrosion prevention performance, and the development of technologies that can simultaneously satisfy water permeation and freeze-thaw resistance for concrete is minimal.

[0007] Accordingly, there is a need for the development of an eco-friendly deicing agent that can prevent corrosion of steel while also exhibiting excellent ice melting performance and suppressing damage to concrete.

[0008] The purpose of the present invention is to provide an environmentally friendly solid-state deicing agent additive composition that suppresses concrete damage.

[0009] Another object of the present invention is to provide an environmentally friendly solid deicer capable of suppressing concrete damage by including the additive composition.

[0010] To achieve the above object, the present invention provides an environmentally friendly solid-state deicing agent additive composition containing a silicone-based sealer and a corrosion inhibitor that suppresses concrete damage.

[0011] In the present invention, the content of the waterproofing agent may be 2 to 40 wt% based on the total weight of the additive composition.

[0012] In the present invention, the content of the corrosion inhibitor may be 60 to 98 wt% based on the total weight of the additive composition.

[0013] In the present invention, the waterproofing agent may include a silane waterproofing agent, a siloxane waterproofing agent, or a combination thereof.

[0014] In the present invention, the waterproofing agent may include at least one selected from the group consisting of octyltriethoxysilane, triethoxy-(2,4,4-trimethylpentyl silane), methyltrimethoxysilane, polydimethylsiloxane, polymethylhydrosiloxane, and octamethylcyclotetrasiloxane.

[0015] In the present invention, the corrosion inhibitor may include a porous structure derived from starfish and sodium hexametaphosphate.

[0016] In the present invention, the weight ratio of the porous structure derived from starfish and sodium hexametaphosphate may be 1:0.5 to 1:30.

[0017] In the present invention, the corrosion inhibitor may include gluconate and nitrite compounds.

[0018] In the present invention, the weight ratio of the gluconate and nitrite may be 0.5:1 to 5:1.

[0019] In the present invention, the gluconate may include at least one selected from the group consisting of sodium gluconate, calcium gluconate, and potassium gluconate, and the nitrite may include at least one selected from the group consisting of sodium nitrite, calcium nitrite, and potassium nitrite.

[0020]

[0021] The present invention also provides an environmentally friendly solid deicing agent that suppresses concrete damage, comprising an additive composition including chloride and a silicone-based waterproofing agent and corrosion inhibitor.

[0022] In the present invention, the chloride may be at least one selected from the group consisting of calcium chloride (CaCl2), sodium chloride (NaCl), potassium chloride (KCl), and magnesium chloride (MgCl2).

[0023] In the present invention, the content of the waterproofing agent may be 0.05 to 1.5 wt% based on the total weight of the deicing agent.

[0024] In the present invention, the content of the corrosion inhibitor may be 0.5 to 4 wt% based on the total weight of the deicer.

[0025] According to the present invention, by combining a waterproofing agent and a corrosion inhibitor and optimizing the components and content ratios thereof, it is possible to manufacture an additive for a deicing agent having excellent melting performance, excellent resistance to freezing and thawing of concrete, and low water permeability. A deicing agent that applies the deicing agent additive of the present invention to a chloride deicing agent has excellent corrosion prevention performance for steel and has a water-insoluble content of 1% or less, satisfying the standards for eco-labeling certification, and can be usefully used as an environmentally friendly solid deicing agent that effectively suppresses concrete damage while having excellent corrosion prevention performance.

[0026] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In general, the nomenclature used herein is well known and commonly used in the art.

[0027]

[0028] The present invention relates to an additive composition for an environmentally friendly solid de-icing agent that suppresses concrete damage and an environmentally friendly solid de-icing agent comprising the same.

[0029] Solid deicers sometimes include a deicing dispersant, such as glycerin, to enhance the deicing effect. However, these deicing dispersants have limitations in improving the water permeability and freeze-thaw resistance of solid deicers applied to concrete.

[0030] The present invention is intended to overcome the limitations of the prior art, and is characterized by producing a deicing agent having excellent ice melting performance and corrosion prevention performance, as well as excellent water permeability and freeze-thaw resistance of concrete, by applying a waterproofing agent to a solid deicing agent and optimizing the type and / or content ratio of the waterproofing agent and the type of corrosion inhibitor.

[0031] To achieve the above purpose, the solid-state deicing agent additive composition of the present invention includes a sealer and a corrosion inhibitor.

[0032] In the present invention, the solid-state deicing agent additive is characterized by including a sealer. When applying a deicing agent to concrete, chlorides dissolve and penetrate the concrete pores, causing repeated freezing and thawing due to the heat of dissolution and freezing point depression generated by the deliquescent nature of the chlorides. In the present invention, by applying an additive including a sealer to the solid-state deicing agent, moisture penetration into the concrete is prevented, and the concrete damage prevention effect is maximized depending on the ratio and type of the sealant.

[0033] The waterproofing agent used in the present invention may be a silicone-based waterproofing agent, and it is preferable to use a silane waterproofing agent, a siloxane waterproofing agent, or a combination thereof.

[0034] In general, silicone-based waterproofing agents are highly reactive, which can lead to problems such as reduced corrosion resistance. Therefore, when mixed with general corrosion inhibitors, it is difficult to secure the standard corrosion inhibition efficiency. Furthermore, when applied to solid-state deicing agents such as those of the present invention, silicates and siliconeates among silicone-based waterproofing agents may react with calcium ions to form calcium salts, which can inactivate the waterproofing agent's function. In addition, the deicing agent may have a high water-insoluble content.

[0035] However, when a silane or siloxane waterproofing agent is applied to the solid deicing additive of the present invention, a deicing additive having excellent deicing performance and concrete damage prevention performance can be produced through optimization of the ratio, and despite corrosion acceleration due to the waterproofing agent, a standard corrosion prevention function can be secured by the corrosion inhibitor used in the present invention. Accordingly, by using the additive composition according to the present invention, a deicing agent having excellent deicing performance, excellent water permeability and freeze-thaw resistance, and low water-insoluble content can be produced.

[0036] In relation to this, in an embodiment of the present invention, it was confirmed that when a deicer was manufactured using silane or siloxane as a silicone-based waterproofing agent in an additive for a solid deicer to which a corrosion inhibitor according to the present invention was applied, the deicer had excellent melting performance according to temperature and time compared to sodium chloride, while having high water permeability and freeze-thaw resistance and a low water insoluble content of 0.57 to 0.89%, whereas when silicate or siliconate was used, the water permeability and freeze-thaw resistance were low, the water insoluble content exceeded 1%, and when siliconate was applied, the deicing performance was also low.

[0037] In the present invention, as the silane waterproofing agent, one or more of octyltriethoxysilane, triethoxy-(2,4,4-trimethylpentyl silane), methyltrimethoxysilane, etc. can be used, and as the siloxane waterproofing agent, one or more of polydimethylsiloxane, polymethylhydrosiloxane, octamethylcyclotetrasiloxane, etc. can be used.

[0038] In the present invention, the content of the waterproofing agent may be 2 to 40 wt% based on the total weight of the additive composition. If the content of the waterproofing agent is high, the initial melting performance may be reduced, and if the content is low, the improvement in the water permeability and freeze-thaw resistance of the concrete may be minimal. In this respect, the content of the waterproofing agent is preferably 4 to 35 wt% based on the total weight of the additive composition.

[0039] In relation to this, in the embodiment of the present invention, when the content of the waterproofing agent is about 2.4 or 3.6 wt% based on the total weight of the additive composition, it was confirmed that the water permeability and the resistance to freezing and thawing are low, and when it is about 37.5 wt%, the ice melting performance is low, whereas when the content of the waterproofing agent is about 4.8 to 33.3 wt%, the ice melting performance is excellent, and the water permeability and the resistance to freezing and thawing are also excellent.

[0040] As a corrosion inhibitor used in the environmentally friendly solid-state deicing agent additive of the present invention, a mixture of a porous structure derived from starfish and sodium hexametaphosphate, or a mixture of gluconate and nitrite can be used.

[0041] In the present invention, by using the above combination as a corrosion inhibitor, excellent corrosion inhibition efficiency can be secured despite accelerated corrosion of the waterproofing agent.

[0042] In the present invention, the corrosion inhibitor may be included in an amount of 60 to 98 wt%, preferably 65 to 96 wt%, based on the total weight of the additive composition. Within this range, the additive composition can effectively improve the melting performance of the deicer while enhancing the water permeability and freeze-thaw resistance of concrete.

[0043] In one embodiment of the present invention, the corrosion inhibitor may include a porous structure derived from starfish and sodium hexametaphosphate (SHMP).

[0044] The porous structure derived from starfish used in the present invention can be obtained by removing protein from starfish. Starfish is a living organism composed of protein and calcium carbonate. When starfish is treated with a protein-decomposing enzyme such as pepsin, trypsin, or effective microorganisms (EM) to decompose the protein, a calcium carbonate porous structure precipitates, which can be extracted to obtain a three-dimensional porous structure composed of calcium carbonate. The temperature at which the starfish is treated with the protein-decomposing enzyme may be 45 to 50°C, and the treatment time may be 24 to 72 hours.

[0045] In the present invention, the porous structure derived from starfish adsorbs chloride ions based on the principle of physical adsorption of water molecule clusters through the three-dimensional porous structure and chemical adsorption due to electrical attraction within the structure.

[0046] Sodium hexametaphosphate, which is used together with the porous structure derived from the starfish, has the property of being soluble and slowly changing into a viscous liquid state in moist air, and has the characteristics of high solubility, slow dissolution, and strong hygroscopicity. The pH of a 1% aqueous solution of sodium hexametaphosphate is 5.0 to 6.8, and it has a cyclic structure and very strong ion-sequestering power among phosphates.

[0047] Sodium hexametaphosphate possesses the strongest calcium complexing ability among phosphates. Aqueous solutions of sodium hexametaphosphate form complex ions with calcium, magnesium, barium, copper, and iron ions, inhibiting their activity and thereby preventing metal corrosion.

[0048] In the present invention, the sodium hexametaphosphate interacts with the porous structure derived from starfish, thereby exhibiting significantly superior corrosion inhibition performance compared to sodium hexametaphosphate alone or other corrosion inhibitors. Specifically, sodium hexametaphosphate can form a structured corrosion inhibitor by coordinating with the calcium carbonate porous structure in an ionic form, thereby providing superior corrosion inhibition performance.

[0049] In the present invention, the weight ratio of the porous structure derived from starfish and sodium hexametaphosphate may be 1:0.5 to 1:30, for example, 1:1 to 1:25, and in terms of metal corrosion prevention performance, may be 1:1 to 1:10, preferably 1:2 to 1:4. If the ratio of the porous structure derived from starfish is too low, it is difficult to prevent metal corrosion, and as the ratio of sodium hexametaphosphate increases, the water-insoluble content of the deicing agent may increase due to excessive complex formation. In addition, if the ratio of the porous structure derived from starfish is too high, the water-insoluble content may increase due to the calcium carbonate component.

[0050] In relation to this, in an embodiment of the present invention, it was confirmed that when the weight ratio of the porous structure derived from starfish and sodium hexametaphosphate was 1:3, the corrosion rate of steel was 1 / 3 lower than when the weight ratio was 1:1.

[0051] Additionally, in another embodiment of the present invention, the corrosion inhibitor may include gluconate and nitrite compounds.

[0052] For example, as the gluconate, one or more of sodium gluconate, calcium gluconate, potassium gluconate, etc. can be used, and as the nitrite, one or more of sodium nitrite, calcium nitrite, potassium nitrite, etc. can be used, and preferably, the corrosion inhibitor may include sodium gluconate and sodium nitrite.

[0053] In this way, when gluconate and nitrite are used in combination as corrosion inhibitors, they can exhibit excellent corrosion inhibitory performance even when used in combination with a silane or siloxane waterproofing agent, unlike when conventional corrosion inhibitors (e.g., dibasic sodium phosphate, sodium citrate, etc.) are used or when gluconate or nitrite is used alone.

[0054] In addition, the weight ratio of gluconate and nitrite may be 0.5:1 to 5:1, and preferably 2:1 to 4:1 in terms of metal corrosion prevention performance. In this regard, in an embodiment of the present invention, it was confirmed that when the weight ratio of gluconate and nitrite was 3:1, the corrosion rate of steel was lower than when the weight ratio was 1:1.

[0055] In this way, by using an additive that combines a silane or siloxane waterproofing agent and a specific corrosion inhibitor in the present invention, it is possible to manufacture a deicing agent having excellent ice melting performance and excellent corrosion prevention performance by mutually compensating for the defects caused by the use of the waterproofing agent and the corrosion inhibitor.

[0056]

[0057] In the present invention, the additive composition can be applied to a solid-state deicing agent to exhibit the effect of inhibiting concrete damage. Therefore, the present invention can also provide an environmentally friendly solid-state deicing agent comprising a chloride, a silicone-based waterproofing agent, and a corrosion inhibitor.

[0058] The chloride used in the present invention is a substance containing chloride ions, which has deliquescent properties and acts as a melting agent. For example, the chloride may be at least one selected from the group consisting of calcium chloride (CaCl2), sodium chloride (NaCl), potassium chloride (KCl), and magnesium chloride (MgCl2). In particular, calcium chloride is preferred as a melting agent because it exhibits excellent deliquescent properties and exhibits the greatest freezing point depression.

[0059] The chloride content may be 95 to 99% by weight of the total weight of the deicing agent. If the chloride content is too low, it may be difficult to achieve ice-melting performance, while if the content is too high, metal corrosion may occur. In this regard, it is preferable that the chloride content be 96 to 98% by weight of the total weight of the deicing agent.

[0060] In the present invention, the additive composition including the waterproofing agent and corrosion inhibitor may be included in an amount of 1 to 5 wt%, preferably 2 to 4 wt%, based on the total weight of the deicing agent.

[0061] Specifically, the content of the waterproofing agent may be 0.05 to 1.5 wt% based on the total weight of the deicing agent. Excessive use of the waterproofing agent may result in a decrease in initial ice melting performance, while use of a small amount may result in insufficient improvement in the concrete's water permeability and freeze-thaw resistance. In this regard, the content of the waterproofing agent is preferably 0.1 to 1.0 wt% based on the total weight of the deicing agent.

[0062] In relation to this, in the embodiment of the present invention, when the content of the waterproofing agent is 0.05 or 0.075 wt% with respect to the total weight of the deicing agent, it was confirmed that the water permeability and the resistance to freezing and thawing were low, and when it was 1.2 wt%, the ice melting performance was low, whereas when the waterproofing agent was used at 0.1 to 1.0 wt%, the ice melting performance was excellent, and the water permeability and the resistance to freezing and thawing were also excellent.

[0063] Additionally, the corrosion inhibitor may be included in an amount of 0.5 to 4 wt% based on the total weight of the deicer, for example, 1 to 3 wt%.

[0064] According to one embodiment of the present invention, when the corrosion inhibitor includes a porous structure derived from starfish and sodium hexametaphosphate, the porous structure may be included in an amount of 0.1 to 1 wt%, and preferably 0.3 to 0.8 wt%, based on the total weight of the solid deicing agent. If the proportion of the porous structure derived from starfish is too low, it is difficult to prevent corrosion of the metal, and if the proportion is too high, the water-insoluble content of the deicing agent may increase due to the calcium carbonate component of the structure, which may exceed 1 wt%, which is the standard for eco-labeling certification.

[0065] In addition, the sodium hexametaphosphate may be included in an amount of 0.5 to 3 wt%, and preferably 1 to 2 wt%, based on the total weight of the solid deicer. If the content of sodium hexametaphosphate is too low, it is difficult to prevent metal corrosion due to chloride, and if the content is too high, a problem may occur in which the water-insoluble content of the deicer exceeds 1% due to excessive complex formation.

[0066] According to another embodiment of the present invention, when the corrosion inhibitor includes a gluconate and a nitrite compound, the gluconate compound may be included in an amount of 0.5 to 3 wt%, preferably 0.8 to 2 wt%, based on the total weight of the solid deicer. In addition, the nitrite compound used in combination therewith may be used in an amount of 0.1 to 2 wt%, preferably 0.2 to 1.5 wt%, based on the total weight of the solid deicer. Within the above content range, corrosion of the metal can be effectively prevented.

[0067]

[0068] The solid deicer of the present invention may further include additives such as an additional corrosion inhibitor and an ice-melting performance dispersant.

[0069] As the above-mentioned additional corrosion inhibitor, any component that can act as a corrosion inhibitor by reacting with chloride ions on metals or the like by coating them may be used without any particular restrictions. For example, orthophosphate, polyphosphate, silicate, citrate, etc. can be used as corrosion inhibitors.

[0070] The above-mentioned de-icing performance dispersant is added to increase the penetration speed of the de-icing agent and to increase the depth and diffusion property, and a viscous substance such as glycerin, propylene glycol, sorbitol, molasses, etc. can be used.

[0071] The above additional additive may be included in an amount of 0.1 to 10 wt%, for example 0.2 to 5 wt%, based on the total weight of the entire deicing agent.

[0072] The eco-friendly solid snow removal agent of the present invention can be manufactured by mixing the components of the above snow removal agent, and can be used by granulating it into an average particle size of 0.1 to 13 mm in terms of sprayability and workability.

[0073] The eco-friendly solid deicer according to the present invention combines a deicing agent, chloride, with a waterproofing agent and a corrosion inhibitor, and optimizes the components and content ratio thereof to provide excellent deicing performance while satisfying the standards for eco-labeling certification with a water-insoluble content of less than 1%. In addition, the solid deicer has excellent resistance to freezing and thawing of concrete, such that freezing and thawing occurs very little, less than 10% compared to sodium chloride, and the water permeability is less than 70% compared to an untreated sample, effectively preventing water penetration. In addition, the solid deicer of the present invention has excellent corrosion prevention performance of steel, such that depending on the combination and ratio of the components, a low corrosion rate of up to 2.7% can be achieved.

[0074]

[0075] Example

[0076]

[0077] The present invention is described in more detail through the following examples. However, these examples are provided to illustrate some experimental methods and compositions for the purpose of illustratively explaining the present invention, and the scope of the present invention is not limited to these examples.

[0078]

[0079] Manufacturing example: Manufacturing of an eco-friendly solid deicer that suppresses concrete damage.

[0080]

[0081] An environmentally friendly solid deicer was prepared by mixing 33 wt% of calcium chloride and 64.6 wt% of sodium chloride as chloride, 0.5 wt% of a starfish porous structure and 1.5 wt% of sodium hexametaphosphate (SHMP) as corrosion inhibitors, and 0.4 wt% of octyltriethoxysilane as a waterproofing agent.

[0082]

[0083] Experimental Example 1: Comparative Analysis of Deicing Agent Performance According to Waterproofing Agent Dosage

[0084]

[0085] Using the manufacturing method, a deicing agent was manufactured by adjusting the amount of waterproofing agent added according to the ratio (unit: weight %) described in Table 1 below, and the performance of the manufactured deicing agent was compared.

[0086]

[0087] Number CaCl2NaClSHMP Starfish Porous Structure Octyltriethoxysilane Example 1-1 3364.9 1.50.50.1 Example 1-2 3364.8 1.50.50.2 Example 1-33364.6 1.50.50.4 Example 1-4 3364.4 1.50.50.6 Example 1-5 3364.2 1.50.50.8 Example 1-6 3364 1.50.51 Comparative Example 1-13364.95 1.50.50.05 Comparative Example 1-23364.92 51.50.50.075 Comparative Example 1-33363.8 1.50.51.2

[0088]

[0089] For the above Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3, the melting performance was measured at -3 or -7°C for 15, 30 and 60 minutes, and the melting ratio (%) relative to sodium chloride (NaCl) was calculated to confirm the melting performance. The results are shown in Table 2 below.

[0090]

[0091] Number - 3℃ - 7℃ 15 minutes 30 minutes 60 minutes 15 minutes 30 minutes 60 minutes Example 1-1 1 2 6 1 2 8 1 3 1 1 2 8 1 2 8 1 2 9 Example 1-2 1 2 2 7 1 3 4 1 1 9 1 2 4 1 3 3 Example 1-3 1 2 0 1 2 7 1 2 9 1 2 1 3 0 1 2 8 Example 1-4 1 1 1 2 7 1 2 5 1 1 9 1 2 5 1 2 ...

[0092]

[0093] In addition, for the above Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3, water permeability and freeze-thaw rate were measured to confirm resistance.

[0094] For the water permeability test, the method described in KS F 4930:2012 was used, and the water permeability (%) was calculated compared to the untreated sample to confirm the water permeation resistance. The concrete freeze-thaw resistance measurement test was used in accordance with the method described in EM502-2:2014, and the freeze-thaw resistance (%) was calculated compared to sodium chloride (NaCl) to confirm the effect of the deicer on the concrete freeze-thaw resistance. For the concrete test specimens, they were cured according to the test specimen standards described in EM502-2, and test specimens with a compressive strength of 15 MPa after 7 days of curing were manufactured and used.

[0095] The water permeability and freezing-thawing rate calculated according to the above method are shown in Table 3 below.

[0096]

[0097] Water permeability (%) compared to the number-treated sample Concrete freezing-thawing rate (%) compared to NaCl Example 1-1688.9 Example 1-2653.4 Example 1-3562.5 Example 1-455-1.7 Example 1-559-0.3 Example 1-648-2.4 Comparative Example 1-18124.3 Comparative Example 1-27811.8 Comparative Example 1-351-3.5

[0098]

[0099] According to the above experimental results, when the amount of waterproofing agent added was less than 0.1 wt% based on the total weight of the deicer and less than 4 wt% based on the total weight of the additive, the water permeability of the concrete exceeded the target standard of 70%, and the freeze-thaw performance exceeded the standard of 10%. In addition, when the amount of waterproofing agent added exceeded 1 wt% based on the total weight of the deicer and 35 wt% based on the total weight of the additive, the waterproofing agent solution interfered with the contact between chloride and ice, inhibiting the exothermic reaction, resulting in the initial ice-melting performance falling short of the 100% standard for the environmental label certification (EL610).

[0100] Accordingly, it was confirmed that the amount of waterproofing agent to be added was 0.1 to 1.0 wt% based on the total weight of the deicing agent and 4 to 35 wt% based on the total weight of the additive, and in particular, it was confirmed that the amount of waterproofing agent to be added was 0.4 to 0.6 wt% based on the total weight of the deicing agent and 15 to 25 wt% based on the total weight of the additive were more preferable in terms of melting performance, water permeability, and freeze-thaw resistance.

[0101]

[0102] Experimental Example 2: Comparative Analysis of Deicing Agent Performance by Type of Waterproofing Agent

[0103]

[0104] An eco-friendly solid deicing agent was prepared by mixing 33 wt% of calcium chloride and 64.6 wt% of sodium chloride as chloride, 0.5 wt% of a starfish porous structure and 1.5 wt% of sodium hexametaphosphate (SHMP) as corrosion inhibitors, and 0.4 wt% of a waterproofing agent, and the solid deicing agent was prepared by varying the types of waterproofing agents as shown in Table 4 below.

[0105]

[0106] Number of waterproofing agent types Example 2-1 Octyltriethoxysilane Example 2-2 Triethoxy-(2,4,4-trimethylpentylsilane) Example 2-3 Methyltrimethoxysilane Example 2-4 Polydimethylsiloxane Example 2-5 Polymethylhydrosiloxane Example 2-6 Octamethylcyclotetrasiloxane Comparative Example 2-1 Sodium silicate Comparative Example 2-2 Sodium methylsiliconate

[0107]

[0108] For the above Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2, the melting performance (%) was measured by temperature and time according to the method described in Experimental Example 1, and the results are shown in Table 5 below.

[0109]

[0110] Number - 3℃ - 7℃ 15 minutes 30 minutes 60 minutes 15 minutes 30 minutes 60 minutes Example 2-11 20 12 7 12 9 12 2 13 0 12 8 Example 2-21 13 12 4 13 11 0 9 11 3 13 0 Example 2-3 12 7 12 4 12 8 12 0 13 11 2 4 Example 2-4 10 5 11 1 1 2 7 10 3 10 7 11 2 Example 2-5 12 4 13 7 14 4 11 9 12 9 13 6 Example 2-6 11 5 11 1 1 7 10 8 11 4 10 6 Comparative Example 2-11 2 2 12 1 1 3 0 1 1 6 11 9 10 8 Comparative Example 2-21 0 2 10 5 10 9 10 5 10 8 11 1

[0111]

[0112] In addition, for the above Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2, water permeability and freeze-thaw resistance were measured according to the method described in Experimental Example 1, and the results are shown in Table 6 below.

[0113] In addition, by dissolving 100 g of sample in 250 g of distilled water with reference to the method described in KS M ISO 2479:2012, the water-insoluble content was measured by deriving the weight % ratio of the remaining amount compared to the sample after filtering, and the results are shown in Table 7 below.

[0114]

[0115] Water permeability (%) compared to the number-treated sample Concrete freezing and thawing (%) compared to NaCl Example 2-1562.5 Example 2-2591.7 Example 2-351-3.1 Example 2-4679.5 Example 2-553-4.2 Example 2-653-0.3 Comparative Example 2-19327.7 Comparative Example 2-29121.5

[0116]

[0117] Number of insoluble matter (%) Example 2-10.76 Example 2-20.83 Example 2-30.57 Example 2-40.89 Example 2-50.71 Example 2-60.79 Comparative Example 2-11.34 Comparative Example 2-21.21

[0118]

[0119] According to the above experimental results, there is no significant difference in ice melting performance depending on the type of waterproofing agent, but in the case of waterproofing agents of the silicate or silicone series, rather than silane or siloxane series, calcium salts are immediately formed when the deicing agent is made into an aqueous solution, resulting in the generation of a large amount of sediment and the inactivation of the function as a waterproofing agent.

[0120] These sediments are the main cause of the water-insoluble content exceeding the 1% standard for environmental label certification (EL610), and are also the main cause of the lack of improvement in concrete water permeability and freeze-thaw resistance.

[0121] Accordingly, it was confirmed that silane or siloxane series compounds are preferable as waterproofing agents in terms of concrete damage prevention and ice melting performance.

[0122]

[0123] Experimental Example 3: Comparative Analysis of Deicing Agent Performance According to Type of Corrosion Inhibitor

[0124]

[0125] A solid deicer was manufactured using 33 wt% of calcium chloride and 64.6 wt% of sodium chloride (65 wt% in Comparative Example 3-5) as chlorides and 0.4 wt% of octyltriethoxysilane (0 wt% in Comparative Example 3-5) as a waterproofing agent, and using different corrosion inhibitors as shown in Table 8 below (unit: wt%).

[0126]

[0127] Number SHMP Starfish Porous Structure Sodium Gluconate Sodium Nitrite Sodium Dibasic Phosphate Sodium Citrate Example 3-11.50.5----Example 3-211----Example 3-3--1.50.5--Example 3-4--11--Comparative Example 3-1--2---Comparative Example 3-2---2--Comparative Example 3-3----2-Comparative Example 3-4-----2 Comparative Example 3-5--2---

[0128]

[0129] For the above Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-5, in order to test the effect of the deicing agent on steel corrosion, the corrosion rate (%) of the steel compared to sodium chloride was measured with reference to the method described in EM502-1:2014, and the results are shown in Table 9 below.

[0130]

[0131] Steel No. Corrosion Degree (%) Example 3-12.7 Example 3-27.8 Example 3-313.5 Example 3-417.2 Comparative Example 3-135.8 Comparative Example 3-231.3 Comparative Example 3-371.5 Comparative Example 3-449.8 Comparative Example 3-521.4

[0132]

[0133] Referring to the above experimental results, it can be seen that the waterproofing agent has a high reactivity and causes the problem of promoting corrosion of steel when used in combination with general corrosion inhibitors, whereas when a combination of a porous structure derived from starfish and sodium hexametaphosphate, or a combination of gluconate and nitrite is used as a corrosion inhibitor, it can be confirmed that it exhibits an excellent corrosion prevention function of less than 30%, which is the standard for environmental label certification (EL610), even when used in combination with a highly reactive silane waterproofing agent.

[0134] Accordingly, it was confirmed that a solid deicing agent that effectively prevents concrete damage can be manufactured by using a combination of a porous structure derived from starfish and sodium hexametaphosphate as a corrosion inhibitor, or a combination of gluconate and nitrite.

[0135]

[0136] From the above description, those skilled in the art will understand that the present invention can be implemented in other specific forms without altering its technical concept or essential characteristics. In this regard, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. The scope of the present invention should be interpreted as encompassing all changes or modifications derived from the meaning and scope of the following claims and their equivalent concepts, rather than the detailed description above.

Claims

1. An environmentally friendly solid-state deicing agent additive composition containing a silicone-based waterproofing agent and a corrosion inhibitor, which suppresses concrete damage. An environmentally friendly solid-state deicing agent additive composition that suppresses concrete damage, wherein the content of the waterproofing agent is 2 to 40 wt% based on the total weight of the additive composition.

2. In paragraph 1, An environmentally friendly solid-state deicing agent additive composition that suppresses concrete damage, wherein the content of the corrosion inhibitor is 60 to 98 wt% based on the total weight of the additive composition.

3. In paragraph 1, An environmentally friendly solid-state deicing agent additive composition for suppressing concrete damage, wherein the waterproofing agent comprises a silane waterproofing agent, a siloxane waterproofing agent, or a combination thereof.

4. In paragraph 1, An environmentally friendly solid-state deicing agent additive composition for suppressing concrete damage, wherein the waterproofing agent comprises at least one selected from the group consisting of octyltriethoxysilane, triethoxy-(2,4,4-trimethylpentyl silane), methyltrimethoxysilane, polydimethylsiloxane, polymethylhydrosiloxane, and octamethylcyclotetrasiloxane.

5. In paragraph 1, An environmentally friendly solid-state deicing agent additive composition for suppressing concrete damage, wherein the corrosion inhibitor comprises a porous structure derived from starfish and sodium hexametaphosphate.

6. In paragraph 5, An environmentally friendly solid-state deicing agent additive composition that suppresses concrete damage, wherein the weight ratio of the porous structure derived from the starfish and sodium hexametaphosphate is 1:0.5 to 1:

30.

7. In paragraph 1, An environmentally friendly solid-state deicing agent additive composition for suppressing concrete damage, wherein the corrosion inhibitor comprises gluconate and nitrite compounds.

8. In paragraph 7, An environmentally friendly solid-state deicing agent additive composition for suppressing concrete damage, wherein the weight ratio of the above gluconate and nitrite is 0.5:1 to 5:

1.

9. In paragraph 7, An environmentally friendly solid-state deicing agent additive composition for suppressing concrete damage, wherein the gluconate comprises at least one selected from the group consisting of sodium gluconate, calcium gluconate, and potassium gluconate, and the nitrite comprises at least one selected from the group consisting of sodium nitrite, calcium nitrite, and potassium nitrite.

10. An environmentally friendly solid deicing agent that suppresses concrete damage, comprising an additive composition including chloride and a silicone-based waterproofing agent and corrosion inhibitor. An environmentally friendly solid deicing agent that suppresses concrete damage, wherein the content of the waterproofing agent is 2 to 40 wt% based on the total weight of the additive composition.

11. In paragraph 10, An environmentally friendly solid deicing agent with suppressed concrete damage, wherein the chloride is at least one selected from the group consisting of calcium chloride (CaCl2), sodium chloride (NaCl), potassium chloride (KCl), and magnesium chloride (MgCl2).

12. In paragraph 10, An environmentally friendly solid deicing agent that suppresses concrete damage, wherein the content of the waterproofing agent is 0.05 to 1.5 wt% based on the total weight of the deicing agent.

13. In paragraph 10, An environmentally friendly solid deicing agent that suppresses concrete damage, wherein the content of the corrosion inhibitor is 0.5 to 4 wt% based on the total weight of the deicing agent.