KR102435526B1 - Composition for surface coating with excellent anti-icing properties - Google Patents

Abstract

The present invention relates to a composition for surface coating with excellent anti-icing properties. By providing the composition for surface coating with excellent anti-icing properties and improved durability, even if ice freezes and melts several times under conditions of repeatedly changing climatic conditions, the coating does not come off, thereby maintaining excellent anti-icing properties.

Description

Composition for surface coating with excellent anti-icing properties

The present invention relates to a composition for surface coating having excellent anti-icing properties.

When a slip phenomenon occurs on the road due to various causes, the driving vehicle is not controlled and it leads to a major accident. In addition, icing has a serious impact on industrial sites such as transmission lines, aircraft, solar panels, and wind power generators.

Conventionally, to prevent freezing of the road, a method of sprinkling sand or sprinkling calcium chloride, etc. has been used. However, since calcium chloride or sand must be directly sprayed on the road, rapid snow melting work is impossible and requires a lot of time and personnel equipment. If snow continues to fall after spraying, the concentration of calcium chloride decreases and eventually freezes again. Similarly, attempts to spray hot water before takeoff of an aircraft to prevent icing or to melt ice on metal surfaces with electric heating systems have serious disadvantages, including road damage, metal corrosion, excessive energy consumption, and environmental destruction.

To solve this problem, a superhydrophobic surface has been proposed to have anti-icing properties. However, the anti-icing technology using the superhydrophobic surface is difficult to apply to the surface exposed to strong force or continuous physical friction, and the anti-icing property is rapidly reduced under the conditions of repeated freezing and melting of ice, so it is difficult to apply. Therefore, there is an urgent need to develop a technology for forming an anti-freeze coating film having improved durability.

Accordingly, the present inventors studied a surface coating composition comprising a silicone silane having a very weak affinity with water and a fluoroalkylsilane having a very low surface energy in order to express a surface having excellent anti-freezing properties and improved durability, invention was completed.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a composition for surface coating having excellent anti-freezing properties and durability, including silicone silane and fluoroalkylsilane.

In order to achieve the above object,

The present invention provides a composition for surface coating comprising a silicone silane, a fluoroalkyl silane and a solvent.

In addition, the present invention is a forming method for forming an anti-freeze coating film with improved durability,

(a) chemically etching the metal plate using an acid solution;

(b) immersing the metal plate etched in step (a) in boiling water to form a hierarchical structure surface; and

(c) immersing the metal plate immersed in step (b) in the composition for surface coating to form an anti-freeze coating film; provides a method for forming an anti-freeze coating film comprising.

In addition, the present invention provides an anti-freeze coating film formed by the method of forming the anti-freeze coating film.

The present invention provides a composition for surface coating having excellent anti-icing properties and improved durability, so that the coating does not peel off even when ice is frozen and melted several times under conditions of repeatedly changing climatic environments, thereby maintaining excellent anti-freezing properties there is

1 is a diagram schematically showing a process for manufacturing a superhydrophobic aluminum surface having a micro-nano structure using the composition for surface coating of the present invention.
2a and 2b are diagrams confirming the surface of the chemically etched aluminum plate using a scanning electron microscope (SEM).
2C and 2D are views illustrating the surface of the etched aluminum plate after treatment with boiling water using a scanning electron microscope (SEM).
3 is a graph showing the results of ¹ H-NMR analysis of FD-PDMS _6.5 under CDCl ₃ (Chloroform-d) solvent conditions.
4 shows the contact angles of the aluminum plate samples (FD-PDMS _1.4 , FD-PDMS _2.9 , FD-PDMS _4.0 , FD-PDMS _6.5 , FD ₁₀₀ and PDMS ₁₀₀ ) prepared in Examples 1 to 4, Comparative Examples 1 and 2 is the diagram shown.
5 shows the ice adhesion of the aluminum plate samples prepared in Examples 1 to 4, Comparative Examples 1 and 2 (FD-PDMS _1.4 , FD-PDMS _2.9 , FD-PDMS _4.0 , FD-PDMS _6.5 , FD ₁₀₀ and PDMS ₁₀₀ ). is a graph showing
6 is an aluminum plate sample prepared in Examples 1 to 4, Comparative Examples 1 and 2 (FD-PDMS _1.4 , FD-PDMS _2.9 , FD-PDMS _4.0 , FD-PDMS _6.5 , FD ₁₀₀ and PDMS ₁₀₀ ) Freezing delay of It is a graph showing time.
7 is an aluminum plate sample prepared in Examples 1 to 4, Comparative Examples 1 and 2 (FD-PDMS _1.4 , FD-PDMS _2.9 , FD-PDMS _4.0 , FD-PDMS _6.5 , FD ₁₀₀ and PDMS ₁₀₀ ) 40 times Alternatively, it is a graph showing the ice adhesion of each sample after repeated freezing/melting 100 times.
8a and 8b are diagrams confirming the surface of the sample using a scanning electron microscope (SEM) after repeating the freezing / melting of the aluminum plate sample (PDMS ₁₀₀ ) prepared in Comparative Example 2 40 times.
8c and 8d are diagrams confirming the surface of the sample using a scanning electron microscope (SEM) after repeating the freezing / melting of the aluminum plate sample (FD ₁₀₀ ) prepared in Comparative Example 1 100 times.
8e and 8f are diagrams confirming the surface of the sample using a scanning electron microscope (SEM) after repeating freezing/melting 100 times of the aluminum plate sample (FD-PDMS _2.9 ) prepared in Example 2;

Hereinafter, the composition for surface coating having excellent anti-freeze properties according to the present invention will be described in detail.

The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a composition for surface coating comprising a silicone silane and a fluoroalkylsilane.

The silicon silane may be a compound in which one substituent bonded to Si is a polysiloxyl group, and at least one substituent of the remaining three bonded to Si is an alkoxy group. Silicone resin represented by dimethylsiloxane has a higher surface energy than fluoroalkyl, but has a very low interaction force with water or ice, so its anti-freezing performance is high. In the present invention, silicon silane in which alkoxysilane is functionalized in silicon is used for the purpose of increasing durability by inducing covalent bonding on the surface of the base metal. For example, the silicon silane may have a structure of Formula 1 below:

[Formula 1]

In this case, the molecular weight of Formula 1 is 500 to 1000 g / mol, wherein R ¹ to R ⁵ are independently hydrogen or a C ₁ to C ₄ alkyl group, and the OR is independently a C ₁ to C ₄ alkoxy group, wherein a is an integer from 1 to 10.

Preferably, the silicone silane may be monotriethoxysilylethyl-terminated polydimethylsiloxane (PDMS-TES).

In addition, monoaminopropyl-terminated polydimethylsiloxane, monoacrylamidopropyl-terminated polydimethylsiloxane, monocarbinol-terminated polydimethylsiloxane, monodica It may contain any one or more silicone silanes selected from the group consisting of monodicarbinol-terminated polydimethylsiloxane and monovinyl-terminated polydimethylsiloxane, but they freeze compared to PDMS-TES It may be unsuitable for surface coatings due to poor protection properties, poor coating durability, or poor adhesion.

In the composition for surface coating, the silicone silane may be included in an amount of 10 to 50% by weight, more preferably 15 to 40% by weight, and most preferably 20 to 30% by weight. When the content of silicon silane is less than 20% by weight, the interaction energy of the coated metal surface with water or ice may be increased, and thus the anti-freezing properties may be deteriorated. On the other hand, when the content of the silicon silane is more than 50 weight, the access of the additional silicon silane to the metal surface is prevented due to the steric hindrance of the silicon-based chain, which may not properly coat the metal surface.

The fluoroalkylsilane is a compound in which one substituent bonded to Si is a C ₁ to C ₂₁ alkyl group in which one or more hydrogens are substituted with fluorine (F), and at least one of the other three substituents bonded to Si is an alkoxy group. can For example, the fluoroalkylsilane may have the structure of Formula 2:

[Formula 2]

In this case, the OR is independently a C ₁ to C ₄ alkoxy group, and a and b are integers of 1 to 10.

Preferably, the fluoroalkylsilane may be 1H,1H,2H,2H-heptadecafluorodecyl-trimethoxysilane (1H,1H,2H,2H-heptadecafluorodecyl-triethoxysilane, FD-TMS).

In the composition for surface coating, the fluoroalkylsilane may be included in an amount of 50 to 90% by weight, more preferably 60 to 85% by weight, and most preferably 70 to 80% by weight. When the content of the fluoroalkylsilane is less than 50% by weight, the coating may be unsuitable because it is difficult to apply to the hierarchical structure of the etched metal surface. On the other hand, the surface energy of the coated metal surface having a fluoroalkylsilane content of 90% by weight or more may be increased, so that the anti-freezing properties may be deteriorated.

In addition, the composition for surface coating may further include a solvent.

The solvent is dibutyl ether (DBE, dibutylether), toluene, tetrahydrofuran (THF, tetrahydrofuran), n-methylpyrrolidone (NMP, n-methyl pyrolidone), xylene (xylene), propylene glycol methyl ether acetate (PGMEA, propylene glycol methyl ether acetate), propylene glycol monomethyl ether acetate (PMA, propylene glycol monomethyl ether acetate), and may include any one or more selected from the group consisting of cyclohexane (cyclohexane), preferably The solvent may be toluene.

In addition, the present invention is a forming method for forming an anti-freeze coating film with improved durability,

(a) chemically etching the metal plate using an acid solution;

(b) immersing the metal plate etched in step (a) in boiling water to form a hierarchical structure surface; and

(c) forming an anti-icing coating film by immersing the metal plate immersed in the step (b) in the composition for surface coating of any one of claims 1 to 7; do.

Hereinafter, the method of forming the anti-freeze coating film of the present invention will be described in detail step by step.

In the method for forming an anti-freeze coating film of the present invention, step (a) is a step of chemically etching the metal plate using an acid solution.

The acid solution is not limited to any solution having acidity for chemically etching the metal plate, but preferably, the acid solution may be an HCl solution.

In the etching process of step (a), the metal plate may be chemically etched at 20 to 30° C. for 5 to 20 minutes using an HCl solution.

In addition, the method may include washing with deionized water to remove the acid component remaining on the etched metal plate after step (a).

In the method for forming an anti-freeze coating film of the present invention, step (b) is a step of immersing the metal plate etched in step (a) in boiling water to form a hierarchical structure surface.

In the boiling water immersion process of step (b), the etched metal plate may be immersed in boiling water for 20 to 40 minutes.

In addition, after the step (b), the step of drying the metal plate on which the hierarchical structure surface is formed at 110 to 150° C. for 1 to 4 hours may be included.

In the method for forming an anti-freeze coating film of the present invention, step (c) is a step of immersing the metal plate immersed in the step (b) in the composition for surface coating to form an anti-freeze coating film.

In the surface coating composition immersion process of step (c), the metal plate may be immersed at 20 to 30° C. for 1 to 4 hours, and then washed with toluene.

In addition, it may include drying the metal plate immersed in the composition for surface coating after step (c) at 120 to 180° C. for 12 to 20 hours.

In addition, the present invention provides an anti-freeze coating film formed by the method of forming the anti-freeze coating film.

The coating layer may include a polysiloxane silyl group and a fluoroalkylsilyl group.

The polysiloxane silyl group may be fixed by a covalent bond between the silicon silane compound included in the composition for surface coating and the etched surface of the metal plate, and the composition for surface coating containing silicon silane in an amount of 10 to 50 wt% In the case of coating using a polysiloxane silyl group in an amount of 1 to 10% by weight, it is possible to form an anti-freeze coating film.

The polysiloxanesilyl group may be a polydimethylsiloxanesilyl (PDMS-Si) group.

The fluoroalkylsilyl group may be fixed by a covalent bond between the fluoroalkylsilane included in the composition for surface coating and the etched metal plate surface, and the fluoroalkylsilane is included in an amount of 50 to 90% by weight. In the case of coating using a composition for surface coating, an anti-freezing coating film including a fluoroalkylsilyl group in an amount of 90 to 99% by weight may be formed.

The fluoroalkylsilyl group may be a 1H, 1H, 2H, 2H-perfluorodecylsilyl (FD-Si) group.

Hereinafter, the composition for surface coating having excellent anti-freeze properties according to the present invention through Preparation Examples, Examples and Experimental Examples will be described in more detail. However, the following Preparation Examples, Examples and Experimental Examples are merely references for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of effectively describing specific preparations, examples, and experimental examples only, and is not intended to limit the present invention. In addition, the unit of additives not specifically described in the specification may be weight %.

<Production Example 1>

To prepare an aluminum plate having a superhydrophobic surface, the method disclosed in FIG. 1 was used. Specifically, first, an aluminum plate cut into a square piece having a size of 50 mm × 50 mm × 0.8 mm was ultrasonically cleaned with acetone and ethanol sequentially to remove grease and other contaminants. Then, the aluminum plate was chemically etched in HCl (2.5M) solution at 25° C. for 10 minutes, followed by rinsing with deionized water to remove residual acid ( FIGS. 2A and 2B ).

Next, the etched aluminum plate was immersed in boiling water for 30 minutes and dried at 120° C. for 2 hours to prepare an aluminum plate having a hierarchical micro/nanostructure surface ( FIGS. 2C and 2D ).

<Example 1>

First, 1H,1H,2H,2H-heptadecafluorodecyl-trimethoxysilane (1H,1H,2H,2H-heptadecafluorodecyl-triethoxysilane, FD-TMS) and monotriethoxysilyl in 1 wt% toluene solution A coating solution was prepared by mixing ethyl group-terminated polydimethylsiloxane (monotriethoxysilylethyl-terminated polydimethylsiloxane, PDMS-TES) in a weight ratio of 90:10. Thereafter, the aluminum plate prepared by the method described in Preparation Example 1 was immersed in the coating solution at 25° C. for 2 hours, and then washed with toluene.

Then, the coated substrate was dried in an oven at 150° C. for 15 hours to finally prepare an aluminum plate having a superhydrophobic surface.

Results of confirming the weight ratio of 1H,1H,2H,2H-perfluorodecylsilyl group (FD-Si) and polydimethylsiloxanesilyl group (PDMS-Si) fixed to the surface of the prepared aluminum plate through 1H NMR analysis , FD-Si: It was confirmed that PDMS-Si was coated at a weight ratio of 98.6: 1.4. Therefore, the aluminum plate sample prepared in Example 1 was named FD-PDMS _1.4 .

<Example 2>

All processes were carried out in the same manner as in Example 1 except that the FD-TMS and PDMS contents were mixed in a toluene solution in a weight ratio of 80:20.

As a result of confirming the weight ratio of FD-Si and PDMS-Si fixed to the surface of the prepared aluminum plate through 1H NMR analysis, it was confirmed that FD-Si:PDMS-Si was coated at a weight ratio of 97.1:2.9. Therefore, the aluminum plate sample prepared in Example 2 was named FD-PDMS _2.9 .

<Example 3>

All processes were performed in the same manner as in Example 1, except that the FD-TMS and PDMS contents were mixed in a toluene solution at a weight ratio of 70:30.

As a result of confirming the weight ratio of FD-Si and PDMS-Si fixed to the surface of the prepared aluminum plate through 1H NMR analysis, it was confirmed that FD-Si:PDMS-Si was coated at a weight ratio of 96.0:4.0. Therefore, the aluminum plate sample prepared in Example 3 was named FD-PDMS _4.0 .

<Example 4>

All processes were performed in the same manner as in Example 1, except that the FD-TMS and PDMS contents were mixed in a toluene solution at a weight ratio of 50:50.

As a result of confirming the weight ratio of FD-Si and PDMS-Si fixed to the surface of the prepared aluminum plate through 1H NMR analysis, it was confirmed that FD-Si:PDMS-Si was coated at a weight ratio of 93.5:6.5 ( FIG. 3 ). . Therefore, the aluminum plate sample prepared in Example 4 was named FD-PDMS _6.5 .

<Comparative Example 1>

All processes were carried out in the same manner as in Example 1 except for mixing the FD-TMS content in the toluene solution at 100% by weight, and the aluminum plate sample prepared by the process was named FD ₁₀₀ .

<Comparative Example 2>

The aluminum plate prepared by the method described in Preparation Example 1 was immersed in a toluene solution in which PDMS-TES was mixed at 100% by weight at 60° C. for 2 hours, and then washed with toluene. Then, the coated substrate was dried in an oven at 150° C. for 15 hours to finally prepare an aluminum plate having a superhydrophobic surface. The aluminum plate sample prepared by the above process was named PDMS ₁₀₀ .

sample name PDMS content (wt%) PDMS in coating solution Surface-fixed PDMS Example 1 FD-PDMS _1.4 10 1.4 Example 2 FD-PDMS _2.9 20 2.9 Example 3 FD-PDMS _4.0 30 4.0 Example 4 FD-PDMS _6.5 50 6.5 Comparative Example 1 FD ₁₀₀ 0 0 Comparative Example 2 PDMS ₁₀₀ 100 100

<Experimental Example 1> Coating amount comparison

Since the amount of coating of the anti-freeze agent may affect the wettability of the metal surface, the surface coating amounts of the aluminum plate samples prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were compared. Specifically, the difference in weight before and after coating the aluminum plate sample was measured using a microbalance, and the total weight of the coated material per unit area was confirmed.

sample name Total coating amount (mg/m ² ) Example 1 FD-PDMS _1.4 871 Example 2 FD-PDMS _2.9 830 Example 3 FD-PDMS _4.0 669 Example 4 FD-PDMS _6.5 474 Comparative Example 1 FD ₁₀₀ 940 Comparative Example 2 PDMS ₁₀₀ 373

As a result of the experiment, it was confirmed that as the content of PDMS fixed on the surface of the aluminum plate sample increased, the amount of the coating solution coated on the sample surface decreased (Table 2). That is, it was confirmed that the higher the content of PDMS-TES in the coating solution, the higher the steric hindrance due to the low reactivity of the TES group and the length of the PDMS chain, and the lower the reactivity between the coating solution and the sample surface, the coating density decreased.

<Experimental Example 2> Comparison of contact angle (CA) and sliding angle (SA)

In order to confirm the superhydrophobicity and wettability of the surface treated with the coating composition of the present invention, the contact angle (CA) and sliding of the surface of the aluminum plate samples prepared in Examples 1 to 4 and Comparative Examples 1 and 2 The sliding angle (SA) was measured. Specifically, the contact angle was measured according to ASTM D 5946-2009 standard test method. For the measurement of the contact angle, 8 μl of deionized water was dropped on the coated surface at 25° C. through the sessile drop method, and the measurement was performed within 5 minutes. The sliding angle was measured when the droplet rolls off the surface by tilting the coated aluminum plate. The values of the contact angle and the sliding angle were calculated by averaging the values of 5 measurements performed at 5 points on each surface.

sample name contact angle (deg) angle of sliding (deg) Example 1 FD-PDMS _1.4 175±2.0 1.4±0.3 Example 2 FD-PDMS _2.9 176±2.0 1.4±0.2 Example 3 FD-PDMS _4.0 176±2.5 1.8±0.2 Example 4 FD-PDMS _6.5 174±1.5 1.8±0.3 Comparative Example 1 FD ₁₀₀ 176±1.5 1.4±0.2 Comparative Example 2 PDMS ₁₀₀ 165±0.5 5.2±1.2

As a result of the experiment, the surfaces of the aluminum plate samples prepared in Examples 1 to 4 had contact angles of 175±2.0°, 176±2.0°, 176±2.5° and 174±1.5°, respectively, and the aluminum plate sample prepared in Comparative Example 2 (165±0.5°) was confirmed to have excellent superhydrophobicity (Table 3 and FIG. 4). In addition, the sliding angles of the aluminum plate samples prepared in Examples 1 to 4 were 1.4±0.3°, 1.4±0.2°, 1.8±0.2° and 1.8±0.3°, respectively, and the aluminum plate samples prepared in Comparative Example 2 (5.2 By confirming that the droplet rolls down at a low angle compared to ±1.2°), it was confirmed that it has excellent superhydrophobicity.

<Experimental Example 3> Ice adhesion comparison

In order to confirm the anti-freezing properties of the surface treated with the coating composition of the present invention, the ice adhesion strength of each surface of the aluminum plate samples prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was measured. First, a refrigerator with a polystyrene foam door was prepared, and the internal temperature of the device was set at -20.5°C, and the relative humidity (RH) was set to 47.5%, 65%, or 75%. Relative humidity was maintained by controlling the amount of water vapor supplied using a humidifier. A bottomless cell (10 mm × 10 mm × 30 mm) in a refrigerator was placed on the surface of the aluminum plate sample, filled with 1 mL of deionized water, and then completely frozen for 3 hours. Then, to measure the adhesion strength between the surface and the ice column, a force was applied perpendicularly to the attached ice column using a force transducer (Imada, model ZP, 11). When the ice column detached from the surface was calculated using the equation τ = F/A to convert the maximum force of

As a result of the experiment, it was confirmed that, when the metal was coated using the composition for surface coating of the present invention, it had relatively weak ice adhesion. At a relative humidity of 75%, the aluminum plate samples prepared in Examples 1 to 4 showed ice adhesion values of 75.7, 25.3, 70.4, and 103.5 kPa, respectively, while the aluminum plates prepared in Comparative Examples 1 and 2 under the same conditions. The samples exhibited ice adhesion values of 141.3 and 255.6 kPa, respectively (Fig. 5). This means that when the metal is coated using the composition for surface coating of the present invention, the anti-freeze property is very excellent.

<Experimental Example 4> Comparison of freezing delay time

In order to confirm the anti-freezing properties of the surface treated with the coating composition of the present invention, the freezing delay time on the surface of the aluminum plate samples prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was measured. Specifically, the surface of the sample was cut and inserted into a differential scanning calorimeter (DSC). Thereafter, 5 μl of deionized water was dropped on the surface and maintained at 0° C. for 3 minutes so that the surface temperature was the same as the temperature set in the DSC cooling step. Then, the temperature was continuously lowered from 0 to -18°C at a cooling rate of 10°C/min and maintained at -18°C until the ice was completely frozen. The freezing delay time was measured by defining the time from when the water droplet came into contact with the surface (at 0° C.) until the start of freezing.

As a result of the experiment, it was confirmed that when the metal was coated using the composition for surface coating of the present invention, the ice formation time on the surface was significantly delayed. For the aluminum plate samples prepared in Comparative Examples 1 and 2, it took 71.5 and 18.8 minutes for ice to form on the surface, respectively, whereas for the aluminum plate samples prepared in Examples 2 to 4, 152.8, 204.5 and It was measured to take 170 minutes (FIG. 6). This means that the composition for surface coating of the present invention suppresses the formation of ice on the surface of the substrate and has very good anti-freeze properties.

<Experimental Example 5> Comparison of ice adhesion after freezing/melting cycle

In order to confirm the durability of the surface treated with the coating composition of the present invention, the aluminum plate samples prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were repeatedly frozen and melted, and then ice adhesion on the surface was measured. did. Specifically, a high-temperature/low-temperature cycle environment was created by attaching a 120W light bulb to the refrigerator used in Experimental Example 3. A bottomless cell (10 mm × 10 mm × 30 mm) in a refrigerator was placed on the surface of the aluminum plate sample, filled with 1 mL of deionized water, and the column of water was frozen (RH = 35%) at -25 ° C for 90 minutes (RH = 35%) and then a 120 W bulb was heated for 15 minutes to melt the ice (T = 35 °C, RH = 5%). Relative humidity (RH) was adjusted to 35% upon freezing and then decreased to 5% after the temperature reached 35°C. The freezing and melting process was defined as 1 cycle. After the alloy plate sample was frozen/melted 40 times and 100 times, the ice adhesion strength was measured using the force transducer used in Experimental Example 3 to measure the durability of the sample.

As a result of the experiment, when the metal was coated using the composition for surface coating of the present invention, it was confirmed that the durability of the coated surface was very excellent. It was confirmed that the aluminum plate sample prepared in Comparative Example 1 under a relative humidity condition of 47.5% had ice adhesion of 45.8 and 118.1 kPa after repeating freezing/melting 40 times and 100 times, and in the case of Comparative Example 2, freezing/melting It was confirmed that it was seriously damaged due to condensation/expansion of water during the cycle ( FIGS. 8A to 8D ). On the other hand, the sample of Example 1 under 47.5% relative humidity conditions showed ice adhesion of 32.5 and 86.9 kPa, respectively, after repeated freezing/melting 40 and 100 times, and the sample of Example 2 was 40 and 100 times. It was confirmed that ice adhesion of 26.3 and 47.2 kPa, respectively, after repeated freezing/melting was observed ( FIGS. 8e , 8f and 9 ). In addition, in the case of the sample of Example 3, after repeated freezing/melting 40 times and 100 times, values of 47.7 and 93.6 kPa were shown, respectively. This means that when a metal is coated using the composition for surface coating of the present invention, excellent anti-freezing properties can be maintained even under repeatedly changing environmental conditions.

Although the present invention has been described through the specific matters and limited preparation examples, examples and experimental examples as described above, these are only provided to help the overall understanding of the present invention, and the present invention is not limited to the above examples. , various modifications and variations are possible from these descriptions by those of ordinary skill in the art to which the present invention pertains.

Therefore, the spirit of the present invention should not be limited to the described manufacturing examples, examples and experimental examples, and all of the claims described below, as well as equivalent or equivalent modifications to the claims, are of the spirit of the present invention. would be said to belong to the category.

Claims (12)

A composition for surface coating comprising a silicone silane and a fluoroalkyl silane represented by the following formula (1):
[Formula 1]

(In this case, the molecular weight of Formula 1 is 500 to 1000 g/mol, R ¹ to R ⁵ are independently hydrogen or a C ₁ to C ₄ alkyl group, and OR is independently a C ₁ to C ₄ alkoxy group, , wherein a is an integer from 1 to 10.)
delete According to claim 1,
The silicone silane is monotriethoxysilylethyl-terminated polydimethylsiloxane (PDMS-TES), a composition for surface coating.
According to claim 1,
The fluoroalkylsilane is a composition for surface coating, characterized in that represented by the following formula 2:
[Formula 2]

(In this case, the OR is independently a C ₁ to C ₄ alkoxy group, and a and b are integers of 1 to 10.)
5. The method of claim 4,
The fluoroalkylsilane is 1H,1H,2H,2H-heptadecafluorodecyl-trimethoxysilane (1H,1H,2H,2H-heptadecafluorodecyl-triethoxysilane, FD-TMS) for surface coating, characterized in that it is composition.
According to claim 1,
The composition for the surface coating, silicone silane 10 to 50% by weight; And fluoroalkylsilane 50 to 90% by weight; characterized in that it comprises a, surface coating composition.
A method of forming an anti-freeze coating film with improved durability, the method comprising:
(a) chemically etching the metal plate using an acid solution;
(b) immersing the metal plate etched in step (a) in boiling water to form a hierarchical structure surface; and
(c) forming an anti-icing coating film by immersing the metal plate immersed in the step (b) in the composition for surface coating of any one of claims 1 and 3 to 6; Formation method.
An anti-freeze coating film formed by the method of forming an anti-freeze coating film of claim 7.
9. The method of claim 8,
The coating film is characterized in that it comprises a polysiloxane silyl group and a fluoroalkylsilyl group, anti-freeze coating film.
10. The method of claim 9,
The polysiloxane silyl group is a polydimethylsiloxane silyl (PDMS-Si) group, characterized in that the anti-freeze coating film.
10. The method of claim 9,
The fluoroalkylsilyl group is a 1H, 1H, 2H, 2H-perfluorodecylsilyl (FD-Si) group, characterized in that the anti-freeze coating film.
10. The method of claim 9,
The anti-freeze coating film, characterized in that it comprises 1 to 10% by weight of the polysiloxanesilyl group and 90 to 99% by weight of the fluoroalkylsilyl group.

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