Anti-icing Coating Composition and Anti-icing Pavement Material Using the Same

Abstract

The present invention provides a composition for anti-freezing road paving comprising 50 to 200 parts by weight of an anti-freezing filler coated with hydrophobic wax per 100 parts by weight of an acrylate mixed resin. Since the anti-freezing coating composition according to the present invention is based on an acrylate-based mixed resin and uses a filler coated with hydrophobic wax, the period during which the paving film maintains anti-freezing performance after the coating composition is applied can be extended.

Description

Technology Field

[0001] The present invention relates to a freezing-inhibiting coating composition and a freezing-inhibiting packaging material using the same, and more specifically, to a freezing-inhibiting coating composition and a freezing-inhibiting packaging material using the same in which the duration of freezing inhibition is improved by using a freezing-inhibiting filler coated with hydrophobic wax. Background Technology

[0002] To ensure the safety of vehicles and pedestrians on road surfaces such as roads, sidewalks, and parking lots, the formation of a pavement layer with excellent skid resistance is required. Particularly during the winter season, as the risk of traffic accidents and pedestrian safety incidents increases due to road freezing, there is a continuously growing demand for functional paving materials that provide skid resistance along with freezing inhibition or de-icing capabilities.

[0003] For example, Patent Document 1 discloses a road composition having an anti-freezing function comprising methyl methacrylate (MMA) resin as the base resin and calcium chloride and / or sodium chloride, wherein a high-performance admixture such as butyl acrylate and poly(perfluoroalkyl methacrylate) is added to achieve excellent adhesion strength to paved roads or structures, thereby stably maintaining the anti-freezing function for a long period of time.

[0004] Patent Document 2 discloses a freezing-inhibiting surface treatment agent composition in which an antifreeze agent solution is supported on a porous carrier in a composition mixed with an acrylic copolymer and a filler such as calcium carbonate, and a method for preventing freezing on roads using the same. This technology has the advantage of being free of chloride-based components, which can prevent corrosion of paved roads and vehicle tires.

[0005] In addition, Patent Document 3 discloses a cross-linked fast-drying anti-freezing packaging material manufactured by curing a composition including ethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, sodium chloride, calcium carbonate, silica sand, etc., using an MMA mixed resin as a base resin.

[0006] While the aforementioned technologies aim to impart antifreeze functions, there is room for improvement regarding corrosion and environmental burden issues arising from the use of chloride-based components, limitations in durability due to the leaching of de-icing agents, and the stability of dispersion between fillers and the resin matrix, as well as the securing of film density. Furthermore, compositional designs that simultaneously satisfy initial curing performance, long-term durability, and slip resistance in room-temperature fast-drying systems have not been sufficiently established, and some technologies rely on specific inorganic fillers, which imposes restrictions on raw material management and application scope. Therefore, there is a need to develop functional antifreeze coating and paving compositions that can simultaneously achieve long-term stable antifreeze performance along with excellent adhesion, wear resistance, and weather resistance, and possess continuous release characteristics without excessive leaching of de-icing agents. Prior art literature

[0007] Republic of Korea Registered Patent No. 10-2496186 Republic of Korea Registered Patent No. 10-2697531 Republic of Korea Registered Patent No. 10-2844896 The problem to be solved

[0008] The objective of the present invention is to provide a novel anti-freezing coating composition that cures rapidly at room temperature while maintaining excellent anti-freezing performance on road surfaces for a long period.

[0009] Another objective of the present invention is to provide a freezing-inhibiting packaging material manufactured using the above composition. means of solving the problem

[0010] To achieve the above objective, the present invention provides a composition for anti-freezing road paving comprising 50 to 200 parts by weight of an anti-freezing filler coated with hydrophobic wax per 100 parts by weight of an acrylate mixed resin.

[0011] In one embodiment of the present invention, the acrylate mixed resin comprises 50 to 200 parts by weight of an acrylate monomer per 100 parts by weight of PMMA (poly(methyl methacrylate)).

[0012] In one embodiment of the present invention, the acrylate monomer is methyl methacrylate (MMA), methyl acrylate (MA), or a mixture thereof.

[0013] In one embodiment of the present invention, the acrylate mixed resin may further include one or more C4 to C12 acrylate monomers selected from the group consisting of butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, and lauryl acrylate.

[0014] In one embodiment of the present invention, the content of the C4 to C12 acrylate monomer is 1 to 50 parts by weight per 100 parts by weight of PMMA.

[0015] In one embodiment of the present invention, the hydrophobic wax is one or more selected from the group consisting of paraffin wax, polyethylene wax, C16-C22 aliphatic alkyl esters and C16-C22 aliphatic alkyl amide waxes.

[0016] In one embodiment of the present invention, the antifreezing filler to which the hydrophobic wax is applied is one or more selected from the group consisting of sodium chloride (NaCl), calcium chloride (CaCl2), and magnesium chloride (MgCl2).

[0017] In one embodiment of the present invention, the composition further comprises 1 to 100 parts by weight of calcium carbonate (CaCO3).

[0018] In addition, the present invention provides a paving material for inhibiting road surface freezing, which is manufactured by applying the above composition to a road surface and then curing it. Effects of the invention

[0019] The antifreeze coating composition according to the present invention uses a filler coated with hydrophobic wax while being based on an acrylate-based mixed resin, thereby extending the period during which the paving film maintains antifreeze performance after the coating composition is applied. Specific details for implementing the invention

[0020] The freezing-inhibiting coating composition according to the present invention will be described in detail below.

[0021] The antifreezing coating composition according to the present invention comprises an acrylate mixed resin and an antifreezing filler coated with hydrophobic wax.

[0023] In the present invention, the acrylate mixed resin is based on PMMA (poly(methyl methacrylate)) and acrylate monomer.

[0024] In one embodiment of the present invention, the acrylate monomer may be methyl methacrylate (MMA), methyl acrylate (MA), or a mixture thereof.

[0025] The MMA or MA monomers included in the acrylate mixed resin of the present invention are low-viscosity liquids. When used alone, excessive film flow may occur, leading to film sagging and difficulty in controlling the coating thickness; therefore, high-molecular-weight PMMA is mixed in advance to form a mixed resin. When PMMA is dissolved in MMA or MA in advance, the viscosity of the mixed resin increases, making it possible to secure sufficient film thickness and improve coating stability.

[0026] In one embodiment of the present invention, the acrylate monomer may be used in a mixture with MA (methyl acrylate) monomer in a weight ratio of 50% or less.

[0027] In one embodiment of the present invention, the PMMA may have a weight-average molecular weight of 15,000 to 200,000 g / mol, but is not necessarily limited thereto. It is preferable to use polymethyl methacrylate having a weight-average molecular weight within the above range so that it can be uniformly mixed within the composition while sufficiently performing the role of an adhesive.

[0028] In one embodiment of the present invention, the acrylate mixed resin comprises 50 to 200 parts by weight of acrylate monomer per 100 parts by weight of PMMA. If the content of acrylate monomer in the mixed resin is less than 50 parts by weight, curing defects such as delayed gelation and increased curing time may occur during polymerization. Such curing defects lead to a decrease in film strength and can become a fatal disadvantage for road surface paving, where fast drying is essential. On the other hand, if the content of acrylate monomer exceeds 200 parts by weight, excessive volume shrinkage occurs during polymerization, which increases shrinkage due to internal stress after curing and may cause defects in the road surface film.

[0030] In one embodiment of the present invention, the acrylate mixed resin may additionally include a C4 to C12 alkyl acrylate monomer. The C4 to C12 alkyl acrylate monomer imparts flexibility to the coating film produced using the composition and improves impact resistance.

[0031] The above alkyl acrylate monomer may be one or more selected from the group consisting of, for example, butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, and lauryl acrylate.

[0032] In a preferred embodiment of the present invention, the alkyl acrylate may be 2-EHAM (2-ethylhexyl acrylate monomer), BAM (butyl acrylate monomer), lauryl acrylate, or a mixture thereof.

[0033] In one embodiment of the present invention, C4 to C12 alkyl acrylate monomers are included in an amount of 1 to 50 parts by weight per 100 parts by weight of PMMA. The amount of C4 to C12 alkyl acrylate monomers can be determined by taking into account the glass transition temperature (Tg) after the composition is cured and polymerized.

[0034] For example, for the purpose of preventing normal road surface freezing, the content of C4 to C12 alkyl acrylates can be controlled so that the glass transition temperature of the polymer is 15 to 20°C.

[0035] As another example, for the purpose of inhibiting freezing of the road surface and increasing skid resistance, the content of C4 to C12 alkyl acrylates can be controlled so that the glass transition temperature of the polymer is 10°C or lower, preferably 0°C or lower.

[0037] The anti-freezing road paving composition of the present invention further comprises an anti-freezing filler in which a hydrophobic wax is coated on the aforementioned acrylate mixed resin.

[0038] In one embodiment of the present invention, the freezing inhibitor filler is used as, for example, sodium chloride (NaCl), calcium chloride (CaCl2), magnesium chloride (MgCl2), or a combination of two or more of these.

[0039] Sodium chloride is a representative melting salt, and when it comes into contact with water, Na + and Cl - It dissociates into ions and serves to lower the freezing point of the solution. Additionally, the sodium chloride is added to prevent slipping of pedestrians or vehicles passing over the road surface by forming micro-protrusions (anti-skid texture) on the surface of the coating film after the curing of the MMA mixed resin. The sodium chloride is a relatively large, angular crystal, making particle size control easy; consequently, it offers the advantage of allowing for the design of roughness levels and tuning of the friction coefficient. An additional advantage of the sodium chloride is its solubility in water. This characteristic means that even if it dissolves or detaches in rain or other humid environments, micro-pores or new protrusions form on the surface of the coating film, allowing the friction coefficient to be maintained.

[0040] Calcium chloride and magnesium chloride generate heat upon contact with water and dissociate into a large amount of ions (Ca 2+ , Mg 2+ , Cl - By effectively lowering the freezing point of the solution, it provides rapid de-icing and long-term freezing inhibition performance even in low-temperature environments. In addition, due to its excellent hygroscopic and deliquescent properties, it forms a continuous brine film on the surface of the packaging material, thereby preventing re-freezing.

[0041] Sodium chloride, calcium chloride, and magnesium chloride applicable to the present invention may be used in both anhydrous salt and hydrate forms as long as they are commercially available, and may be applied to the present invention without limitation in form, such as flakes, pellets, or granules.

[0043] The freezing-inhibiting filler used in the present invention is the aforementioned sodium chloride, calcium chloride, and magnesium chloride, the surface of which is coated with a hydrophobic wax.

[0044] Hydrophobic waxes used for the above purposes include, for example, paraffin wax, polyethylene wax, C16-C22 aliphatic alkyl esters and C16-C22 aliphatic alkyl amide waxes, but the present invention is not limited to these.

[0045] In one embodiment of the present invention, the amount of hydrophobic wax applied is, for example, 1 to 30 parts by weight of hydrophobic wax per 100 parts by weight of filler for freezing inhibition.

[0046] If the above coating amount is less than 1 part by weight, the surface of the filler cannot be sufficiently covered, making it difficult to effectively suppress the hygroscopic and deliquescent properties of sodium chloride, calcium chloride, magnesium chloride, etc., and the de-icing component may rapidly leach out upon contact with moisture, which may reduce the sustainability of the anti-icing effect. On the other hand, if it exceeds 30 parts by weight, an excessively thick wax coating layer is formed on the surface of the filler, making it difficult for anti-icing components such as sodium chloride, calcium chloride, or magnesium chloride to come into contact with external moisture. Consequently, the leaching rate of the de-icing component is excessively delayed, which may cause the initial de-icing reaction to be slowed down.

[0048] The antifreezing filler coated with hydrophobic wax used in the present invention can be prepared, for example, by the following method.

[0049] 1) Melt the wax at a temperature above its melting point, then apply it to the surface of an antifreeze filler such as sodium chloride, calcium chloride, or magnesium chloride (e.g., spray application), and then cool and solidify.

[0050] 2) The wax is diluted in a volatile solvent such as pentane, hexane, or petroleum ether, then applied to the surface of a conventional antifreeze filler, and after application is complete, the temperature is raised to volatilize the volatile solvent.

[0051] In addition to the above method, methods disclosed in, for example, CN104585480B, etc. may be applied, and there are no special limitations on the method of applying hydrophobic wax to the surface of the antifreeze filler.

[0053] In one embodiment of the present invention, a freeze-inhibiting filler coated with hydrophobic wax comprises 50 to 200 parts by weight per 100 parts by weight of an acrylate mixed resin. If the content of the filler is less than 50 parts by weight, the amount of brine formed upon contact with moisture is insufficient, so the freeze-inhibiting performance may not be sufficient. On the other hand, if it exceeds 200 parts by weight, the bonding strength between the filler and the resin matrix decreases, and consequently, the mechanical strength and adhesive strength of the coating film decrease excessively.

[0055] In one embodiment of the present invention, a freeze-inhibiting filler coated with hydrophobic wax may be used together with a freeze-inhibiting filler not coated with hydrophobic wax. When a freeze-inhibiting filler not coated with hydrophobic wax is used together, the amount of the freeze-inhibiting filler coated with hydrophobic wax and the freeze-inhibiting filler not coated with hydrophobic wax may be adjusted within the range of 50 to 200 parts by weight per 100 parts by weight of the acrylate mixed resin. For example, the freeze-inhibiting filler coated with hydrophobic wax may be used in a ratio of 100, 80, 60, 50, 40, or 30% by weight of the total freeze-inhibiting filler.

[0057] In the present invention, the antifreezing coating composition may further include 1 to 100 parts by weight of calcium carbonate (CaCO3).

[0058] The above calcium carbonate is dispersed in the acrylate mixed resin in a fine particulate state and functions to improve the strength and abrasion resistance of the mixed resin polymer and inhibit polymer shrinkage. The strength of the polymer contributes not only to controlling the coating thickness and maintaining the strength of the road surface paving material but also to inhibiting the detachment of calcium chloride.

[0059] In one embodiment of the present invention, the calcium carbonate may be, for example, mineral-derived calcium carbonate (GCC) or CO2 mineralized calcium carbonate (CCU CaCO3).

[0060] In one embodiment of the present invention, the calcium carbonate is included in an amount of 1 to 100 parts by weight per 100 parts by weight of the acrylate mixed resin. If the content of the calcium carbonate does not reach 1 part by weight, the strength-reinforcing effect of the cured product is negligible. On the other hand, if the content of the calcium carbonate exceeds 100 parts by weight, a decrease in workability when applying the composition to the road surface and a decrease in the anti-freezing function after curing may occur.

[0062] In addition to the acrylate mixed resin, calcium chloride, and calcium carbonate described above, the antifreeze coating composition of the present invention includes additives common to the art, such as polymerization inhibitors, paraffin wax, pigments, and antifreeze silica sand.

[0063] As the polymerization inhibitor, one or more selected from the group consisting of hydroquinone, methoxyhydroquinone, t-butylcatechol, phenothiazine, benzoquinone, TEMPO-based compounds, and mixtures thereof may be used. It is preferable to use the polymerization inhibitor in an amount of 0.0005 to 0.1 parts by weight per 100 parts by weight of the acrylate mixed resin, within a range that inhibits the self-polymerization of MMA monomers during storage without inhibiting the curing reaction by the initiator.

[0064] The paraffin wax moves to the surface of the composition during the curing process to form an oxygen barrier layer, thereby preventing surface inhibition of radical polymerization and improving the non-stick properties and water resistance of the cured film. The paraffin wax can be used in an amount of 0.05 to 5 parts by weight per 100 parts by weight of the acrylate mixed resin at a level where it can move to the surface during the curing process to form an oxygen barrier layer.

[0065] The above pigment is intended to improve the distinctiveness and visibility of the road by adding color, and may be used without special limitation as long as it is commonly used in the industry. As a specific example, it may be one or more selected from the group consisting of iron oxide, iron hydroxide, chromium oxide, barium sulfate, barium carbonate, titanium oxide, titanium dioxide, manganese dioxide, titanium dioxide, zirconium silicate, carbon black, calcium aluminosilicate, and pearl pigments. The above pigment is typically used in an amount of 2 parts by weight or less per 100 parts by weight of acrylate mixed resin.

[0067] The anti-freezing composition of the present invention can form an anti-freezing pavement layer by applying it after cleaning and drying the road surface and curing it at room temperature. It is preferable to mix the initiator immediately before use and apply the composition within the pot life, and it is preferable to apply it to a substrate surface in a dry state from which moisture and contaminants have been removed.

[0068] As the polymerization initiator, conventional initiators in the art, such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide, may be used alone or in a mixture of two or more. In particular, benzoyl peroxide has excellent rapid drying properties and curing stability at room temperature, so it can be preferably used in the road surface coating composition of the present invention.

[0070] The present invention will be explained in more detail below through examples. The following examples are presented to aid understanding and are merely illustrative of the invention; the scope of the invention is not limited to these examples.

[0072] Preparation of antifreeze filler coated with hydrophobic wax

[0073] Granular calcium chloride was introduced into a rotary drum mixer preheated to 50°C, and then thoroughly mixed while spraying a solution of paraffin wax (melting point 45~65°C) dissolved in hexane.

[0074] Subsequently, calcium chloride coated with a paraffin wax solution was thoroughly dried to prepare a freezing inhibitory filler coated with hydrophobic wax (weight increase of the filler after drying: 8%).

[0076] Example 1

[0077] An acrylate mixed resin was prepared with the following composition: 100 parts by weight of PMMA / 100 parts by weight of MMA / 20 parts by weight of 2-EHAM / 30 parts by weight of BAM / 0.5 parts by weight of hydroquinone (polymerization inhibitor) / 1 part by weight of pigment.

[0078] Based on 100 parts by weight of the above mixed resin, 80 parts by weight of a freezing-inhibiting filler coated with hydrophobic wax and 80 parts by weight of calcium carbonate were added and well mixed to prepare a freezing-inhibiting coating composition.

[0080] Comparative example

[0081] A freezing-inhibiting coating composition was prepared in the same manner as in the example, except that calcium chloride without hydrophobic wax was used instead of a freezing-inhibiting filler coated with hydrophobic wax.

[0083] Test Example 1

[0084] The Korea Institute of Construction & Living Environment Testing was commissioned to evaluate the above composition as a road paving material, and the results are summarized below.

[0085] Test items Standard value unit Example 1 Compressive strength 20 or more MPa 35 Adhesion strength (concrete) 1.5 or higher MPa 1.9 Adhesion strength (asphalt) 1.0 or higher MPa 1.2 Wear resistance test (500,000 cycles) wear rate 1.0 or less % 0.1 Slip resistance 55 or more BPN 69

[0087] Test Example 2

[0088] First, the surface of an asphalt substrate (100 x 100 x 10 mm) was cleaned and dried, and then the anti-freezing coating composition of the present invention was applied to form a film with a thickness of 3.5 ± 0.5 mm.

[0089] To simulate rainfall and moisture contact conditions in an actual road environment, the following repeated washing treatments were performed:

[0090] 1) Uniformly spray approximately 50 mL of distilled water onto the surface of the test specimen.

[0091] 2) Dry the specimen at room temperature for 1 hour.

[0092] 3) Repeat the above process a total of 10 times, with one rinse treatment.

[0094] After the above washing test, the freezing start time was measured at -10℃ based on a drop of 0.5 mL of water and summarized in the table below.

[0095] Number of washes Example 1 Comparative example 5th time 8.0 3.0 10th time 6.0 2.2

[0096] From Table 2 above, it can be seen that in the case of a packaging material coated with the composition according to the present invention, the reduction in freezing delay time is small even when washing is repeated. This is because, in the case of a packaging material coated with the composition according to the present invention, the loss of salt is relatively small even when washing is repeated, so the performance maintenance decreases gradually. Industrial applicability

[0098] The anti-icing composition of the present invention can be applied to paving materials such as roads, bridges, tunnels, sidewalks, and parking lots to effectively inhibit slipping and winter freezing, and thus can be utilized in the fields of construction and road maintenance. In particular, due to the freezing point depression and exothermic properties of calcium chloride, rapid de-icing performance can be achieved even in low-temperature environments. Furthermore, work efficiency and safety can be improved compared to conventional de-icing agent spraying methods.

Claims

Claim 1 A composition for antifreezing road paving, characterized by comprising 50 to 200 parts by weight of an antifreezing filler coated with hydrophobic wax per 100 parts by weight of an acrylate mixed resin, wherein the antifreezing filler is one or more selected from the group consisting of sodium chloride, calcium chloride, and magnesium chloride, and 1 to 30 parts by weight of paraffin wax having a melting point of 45 to 65°C is coated per 100 parts by weight of the filler. Claim 2 A composition for anti-freezing road paving according to claim 1, characterized in that the acrylate mixed resin comprises 50 to 200 parts by weight of an acrylate monomer per 100 parts by weight of PMMA (poly(methyl methacrylate)). Claim 3 A composition for anti-freezing road paving according to claim 2, characterized in that the acrylate monomer is methyl methacrylate (MMA), methyl acrylate (MA), or a mixture thereof. Claim 4 A freezing-inhibiting coating composition according to claim 2, characterized in that the acrylate mixed resin further comprises one or more C4 to C12 acrylate monomers selected from the group consisting of butyl acrylate, isobutyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, and lauryl acrylate. Claim 5 A composition for anti-freezing road paving according to claim 4, characterized in that the content of C4 to C12 acrylate monomer is 1 to 50 parts by weight per 100 parts by weight of PMMA. Claim 6 delete Claim 7 delete Claim 8 A composition for anti-freezing road paving according to claim 1, further comprising 1 to 100 parts by weight of calcium carbonate (CaCO3). Claim 9 A paving material for inhibiting road surface freezing, manufactured by applying the composition of claim 1 to a road surface and then curing it.