KR102278825B1 - Super water-repellent structure with high strength and high durability and fabricating method of the same - Google Patents

Abstract

A super water-repellent structure is provided. The super water-repellent structure is a substrate, a super water-repellent pattern disposed on the substrate, and a super water-repellent pattern including concave and convex portions in which a plurality of super water-repellent particles are aggregated, and a polymer resin to improve adhesion between the substrate and the super water-repellent pattern. However, the polymer resin may include filling an empty space provided between the plurality of super water-repellent particles.

Description

Super water-repellent structure with high strength and high durability, and manufacturing method thereof {Super water-repellent structure with high strength and high durability and fabricating method of the same}

The present invention relates to a super water-repellent structure having high strength and high durability, and a manufacturing method thereof, and more particularly, to a super water-repellent structure having high strength and high durability with improved mechanical strength and durability, and a manufacturing method thereof.

The phenomenon that occurs when a liquid meets a solid surface is called wettability, and the property of forming water droplets without wetness is called hydrophobicity. Superhydrophobicity shows that water droplets from the surface do not form on the surface and when they come into contact with it, they immediately slide and leave the surface, and the contact angle is more than 150°. The superhydrophobic surface prevents corrosion of metal materials, prevents freezing of aircraft fuselage and wings, prevents weathering of expensive civil engineering and buildings, prevents adhesion of organisms such as fish and shellfish in the shipbuilding industry, automotive exterior coating, and prevents implantation of heat exchange machinery (Anti-frost) and precision release technology in the polymer processing field are applied in various ways, but there are problems in mechanical strength and friction durability.

Such a superhydrophobic surface can be controlled by imparting a micrometer or nanometer-sized surface roughness, and it is largely controlled by two methods: growing or etching a nanostructure on the surface of a solid. The method of providing surface roughness by growing a nanowire or rod structure requires a complicated process and sensitive reaction conditions, and has problems with high investment cost, mechanical strength, and low durability against friction. As a method of etching the surface, there is a method of etching the surface using acid or electrically etching using a photolithography method. It is a non-environmental method that is vulnerable to safety and also has weak mechanical strength and durability against friction. have. Accordingly, various studies have been made on a superhydrophobic coating method that can effectively impart superhydrophobicity to an object, as well as improve mechanical strength and durability against friction.

One technical problem to be solved by the present invention is to provide a super water-repellent structure having improved mechanical strength and high strength and high durability, and a method for manufacturing the same.

Another technical problem to be solved by the present invention is to provide a super water-repellent structure having high strength and high durability with improved durability and abrasion resistance, and a method for manufacturing the same.

Another technical problem to be solved by the present invention is to provide a super water-repellent structure having high strength and high durability that can provide super water-repellent properties in a simple way, and a method for manufacturing the same.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above technical problems, the present invention provides a super water-repellent coating method.

According to one embodiment, the super water-repellent coating method comprises the steps of preparing a source solution by mixing base nanoparticles, a self-assembled monolayer forming material, and a first solvent, drying the source solution, and from the source solution to the base nano Extracting super water-repellent particles comprising the particles, and a self-assembled monolayer (SAM) surrounding the base nanoparticles, mixing the super water-repellent particles with a second solvent to prepare a super water-repellent coating solution Step, and providing the super water-repellent coating solution on a substrate provided with a polymer resin, it may include the step of forming a super water-repellent pattern on the substrate.

According to an embodiment, the forming of the super water-repellent pattern includes providing the super water-repellent coating solution on the substrate provided with the polymer resin, and permeating the super water-repellent particles into the polymer resin, penetrating into the polymer resin It may include the step of stacking the super water-repellent particles, the formation of a preliminary super water-repellent pattern in which the shape of the polymer resin is deformed according to the shape of the stacked super water-repellent particles, and curing the preliminary super water-repellent pattern. .

According to an embodiment, the preliminary super water-repellent pattern includes an empty space formed between the plurality of super water-repellent particles, and in the step of forming the preliminary super water-repellent pattern, the polymer resin is It may include penetrating into the empty space to fill at least a part of the empty space.

According to one embodiment, the polymer resin filling the empty space, the bonding force between the plurality of super water-repellent particles ha

According to one embodiment, the polymer resin may include polyurethane (Poly Urethane).

According to an embodiment, the base nanoparticles may include at least one of _{SiO 2} , TiO ₂ , ZnO, CaCO ₃ , Al ₂ O ₃ , or ZrO _{2 .}

According to an embodiment, the self-assembled monolayer forming material may include at least one of a silane-based material, a fatty acid-based material, or a thiol-based material.

According to an embodiment, in the source solution preparation step, the -OH group of the base nanoparticles reacts with the functional group of the self-assembled monolayer forming material to form the self-assembled monolayer surrounding the base nanoparticles. can

In order to solve the above technical problems, the present invention provides a super water-repellent structure.

According to an embodiment, the super water-repellent structure includes a substrate, and a super water-repellent pattern disposed on the substrate, wherein the super water-repellent pattern is, a plurality of super water-repellent particles, and an empty space between the plurality of super water-repellent particles (empty space) may include a polymer resin filling at least a portion.

According to an embodiment, the super water-repellent particle may include a base nanoparticle and a self-assembled monolayer (SAM) surrounding the base nanoparticle.

According to an embodiment, the base nanoparticles may exhibit hydrophilicity, and the super water-repellent particles may exhibit hydrophobicity.

The super water-repellent coating method according to an embodiment of the present invention comprises the steps of preparing a source solution by mixing the base nanoparticles, the self-assembled monomolecular film forming material, and the first solvent, and drying the source solution, from the source solution to the base nano Extracting the super water-repellent particles comprising the particles, and a self-assembled monomolecular film surrounding the base nanoparticles, mixing the super water-repellent particles with a second solvent to prepare the super water-repellent coating solution, and the super water-repellent coating The solution may be provided on the substrate provided with the polymer resin to form a super water-repellent pattern on the substrate.

In addition, the super water-repellent pattern forming step, by providing the super water-repellent coating solution on the substrate provided with the polymer resin, a preliminary super water-repellent pattern comprising a concave portion and a convex portion formed by aggregation of the plurality of super water-repellent particles forming a, and curing the preliminary super-repellent pattern, wherein the polymer resin penetrates into the empty space formed between the plurality of super-repellent particles to fill at least a portion of the empty space have. Accordingly, after coating the polymer resin on the substrate, a super water-repellent coating method having improved durability, improved abrasion resistance, and improved super water-repellent properties can be provided by a simple process of coating the super water-repellent coating solution once more.

1 is a flowchart illustrating a super water-repellent coating method according to an embodiment of the present invention.
Figure 2 is a view showing the super water-repellent particles used in the super water-repellent coating method according to an embodiment of the present invention.
3 and 4 are views showing the step of forming a preliminary super water-repellent pattern of the super water-repellent coating method according to an embodiment of the present invention.
FIG. 5 is an enlarged view of A of FIG. 4 .
6 is a view showing a step of forming a super water-repellent pattern in the super water-repellent coating method according to an embodiment of the present invention.
7 is an optical photograph of a cross-section of a super water-repellent structure according to an embodiment of the present invention.
8 to 11 are photographs and graphs showing the surface properties according to the ratio of the super water-repellent particles and the polymer resin included in the super water-repellent structure according to an embodiment of the present invention.
12 to 15 are photographs showing abrasion resistance according to the ratio of the super water-repellent particles and the polymer resin included in the super water-repellent structure according to an embodiment of the present invention.
16 to 19 are photographs and graphs illustrating changes in roughness according to an abrasion resistance test of a super water-repellent structure according to an embodiment of the present invention.
20 is a graph showing the contact angle according to the ratio of the super water-repellent particles and the polymer resin included in the super water-repellent structure according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical spirit of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In this specification, when a component is referred to as being on another component, it means that it may be directly formed on the other component or a third component may be interposed therebetween. In addition, in the drawings, thicknesses of films and regions are exaggerated for effective description of technical content.

In addition, in various embodiments of the present specification, terms such as first, second, third, etc. are used to describe various components, but these components should not be limited by these terms. Accordingly, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.

Each embodiment described and illustrated herein also includes a complementary embodiment thereof. In addition, in the present specification, 'and/or' is used to mean including at least one of the elements listed before and after.

In the specification, the singular expression includes the plural expression unless the context clearly dictates otherwise. In addition, terms such as "comprise" or "have" are intended to designate that a feature, number, step, element, or a combination thereof described in the specification is present, and one or more other features, numbers, steps, configuration It should not be construed as excluding the possibility of the presence or addition of elements or combinations thereof.

In addition, in the following description of the present invention, if it is determined that a detailed description of a related well-known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted.

1 is a flowchart illustrating a super water-repellent coating method according to an embodiment of the present invention, and FIG. 2 is a view showing super water-repellent particles used in a super water-repellent coating method according to an embodiment of the present invention. The super water-repellent structure according to an embodiment of the present invention means a structure formed through the super water-repellent coating method according to the embodiment. However, the manufacturing method of the super water-repellent structure according to the embodiment is not limited to the super water-repellent coating method according to the embodiment.

Referring to FIG. 1 , a source solution may be prepared by mixing the base nanoparticles 12 , the self-assembled monolayer forming material, and the first solvent ( S100 ). When the base nanoparticles 12 and the self-assembled monomolecular film-forming material are mixed, the -OH group of the base nanoparticle 12 may react with the functional group of the self-assembled monomolecular film forming material. Accordingly, a self-assembled monolayer (SAM) 14 surrounding the base nanoparticles 12 may be formed. As a result, the base nanoparticles 12 and the material forming the self-assembled monolayer 14 may react to form the super water-repellent particles 10 . That is, the superhydrophobic particles 10 may include the base nanoparticles 12 and the self-assembled monolayer 14 surrounding the base nanoparticles 12 . In this case, the base nanoparticles 12 may have hydrophilicity, and the super water-repellent particles 10 may have hydrophobicity. That is, by modifying the surface of the base nanoparticles 12 having hydrophilicity, it can be changed to hydrophobicity.

For example, the base nanoparticles 12 may include at least one _{of SiO 2} , TiO ₂ , ZnO, CaCO ₃ , Al ₂ O ₃ , and ZrO _{2 .} In addition, the base nanoparticles 12 may have a size of 5 to 100 nm, preferably 5 to 25 nm.

According to an embodiment, the self-assembled monolayer forming material may include at least one of a silane-based material, a fatty acid-based material, and a thiol-based material. More specifically, the self-assembled monolayer forming material is trimethoxy(ocradecyl)silane, octadecyltrichlorosilane (OTS), perfluorodecyltrichlorosilane, perfluorodecyltrichlorosilane, perfluoro Trichlorosilane or triethoxysilane with 13 or more F groups, such as perfluorodecyltriethoxysilane and perfluorooctyltriethoxysilane, is a fatty acid family with 12 or more carbons. Cano acid (dodecanoic acid), tetradecanoic acid (tetradecanoic acid), hexadecanoic acid (hexadecanoic acid), stearic acid (stearicacid), it may be exemplified that at least one is selected from the group consisting of octadecanoic acid (octadecanoic acid) , but is not limited thereto.

According to an embodiment, the first solvent may be a non-polar solvent so that the self-assembled monolayer 14 surrounding the base nanoparticles 12 is easily formed. For example, the first solvent may be toluene, hexane, pentane, ethyl alcohol, or the like. On the other hand, when a polar solvent is used as the first solvent, the self-assembled monolayer 14 is formed because polymer polymerization between the self-assembled monomolecular film-forming materials, for example, perfluorooctyltriethoxysilane, occurs. It may not be easily formed.

The source solution may be dried, and the super water-repellent particles 10 may be extracted from the source solution (S200). In this case, the super water-repellent particles 10 may be formed in the form of clusters of the base nanoparticles 12 on which the self-assembled monolayer 14 is formed. For example, as described above, while the base nanoparticles 12 have an average size of 5 to 25 nm, the super water-repellent particles 10 in which a plurality of base nanoparticles 12 are aggregated are 1 to 20 μm. may have an average particle diameter of That is, when the base nanoparticles 12 are aggregated and grown into the super water-repellent particles 10 in micro units, the surface roughness is significantly increased compared to the individual base nanoparticles 12, so that the super water-repellent properties can be greatly improved. have.

More specifically, in the step (S200) of extracting the super water-repellent particles (10), a portion of the first solvent and a portion of the first solvent through a centrifugal separation or precipitation separation method of the surface treatment solution that has undergone the source solution preparation step (S100), the It may include removing the unreacted self-assembled monolayer forming material that is not bound to the base nanoparticles 12 (S210), and drying the source solution after the step S210 (S220).

In step S210, a portion of the first solvent contained in excess may be primarily removed, and may serve to remove the unreacted self-assembled monomolecular film forming material acting as an impurity in the super water-repellent coating solution to be described later.

The step S220 serves to remove the residual amount of the first solvent and induce aggregation between the base nanoparticles 12, and is preferably made at room temperature (eg, 15 to 25° C.), S220 step When the drying is made at a high temperature, it is difficult to ensure the uniformity of the size of the super water-repellent particles 10, and it may cause deterioration of the super water-repellent performance.

The super water-repellent particles 10 may be mixed with a second solvent to prepare a super water-repellent coating solution (S300). According to an embodiment, the second solvent may be an eco-friendly polar solvent with high volatility. For example, the second solvent may be ethyl alcohol.

The super water-repellent coating solution may be provided on the substrate provided with the polymer resin to form a super water-repellent pattern on the substrate 100 (S400). More specifically, the super water-repellent pattern forming step (S400) provides the super water-repellent coating solution on the substrate 100 provided with the polymer resin 110, and the super water-repellent particles 10 are formed with the polymer resin ( The step (S410) of penetrating into the 110), the step of stacking the super water-repellent particles 10 permeated in the polymer resin 110 (S420), the polymer resin along the shape of the super-repellent particles 10 stacked Forming the preliminary super water-repellent pattern 200 of which the shape of ( 110 ) is deformed ( S430 ), and curing the preliminary super water-repellent pattern 200 ( S440 ) may be included. Hereinafter, each step will be described in more detail.

3 and 4 are views showing the steps of forming a preliminary super water-repellent pattern in the super water-repellent coating method according to an embodiment of the present invention, FIG. 5 is an enlarged view of FIG. 4 A, and FIG. 6 is a view of the present invention It is a view showing the formation step of the super water-repellent pattern of the super water-repellent coating method according to an embodiment.

3 to 5 , the substrate 100 provided with the polymer resin 110 may be prepared. According to an embodiment, the polymer resin 110 may be in a liquid state. In addition, the polymer resin 110 may be provided on the substrate 100 by a spin coating method. Accordingly, the substrate 100 coated with the liquid polymer resin 100 may be prepared. According to an embodiment, the polymer resin 110 may be an organic, non-polar solvent. On the other hand, the polymer resin 110 may not use an aqueous binder. For example, the polymer resin 110 may include polyurethane (poly urethane).

In the step S410, when the super water-repellent coating solution is provided on the polymer resin 110, the super water-repellent particles 10 included in the super water repellent coating solution may permeate into the polymer resin 110. . According to an embodiment, it may be provided by a method of spraying the super water-repellent coating solution on the polymer resin 110 . In this case, according to the thickness of the polymer resin 110, the injection amount and the injection intensity of the super water-repellent coating solution may be controlled. Specifically, as the thickness of the polymer resin 110 increases, the amount of spraying of the super water-repellent coating solution increases, and the spraying intensity may be increased.

In the step S420, when the super water-repellent coating solution is continuously provided on the polymer resin 110, the super water-repellent particles 10 may be laminated. Thereafter, in the step S430, the preliminary super water-repellent pattern 200 in which the shape of the polymer resin 110 is deformed according to the shape of the super-water-repellent particles 10 stacked may be formed. For example, the size of the super water-repellent particles 10 agglomerated in step S420 may be 1 to 20 μm. In addition, the thickness of the preliminary super water-repellent pattern 200 formed in step S430 may be 1 to 10 μm.

According to an embodiment, the preliminary super water-repellent pattern 200 may include an empty space (EP) formed between the plurality of super water-repellent particles 10 . In addition, in the step of forming the preliminary super water-repellent pattern 200 , the polymer resin 110 may permeate into the empty space EP. Accordingly, the polymer resin 110 may fill at least a portion of the empty space EP, and the shape of the polymer resin 110 may be deformed according to the shape of the superhydrophobic particles 10 stacked.

Specifically, when the super water-repellent particles 10 having hydrophobicity are provided on the polymer resin 110 in a liquid state as described above, between the polymer resin 110 and the super water-repellent particles 10 is a capillary tube. Capillarity may occur, and the polymer resin 110 may cover the surface of the super water-repellent particle 10 . The polymer resin 110 covering the surface of the super water-repellent particle 10 may penetrate into the empty space EP and fill the empty space EP. This may be generated in order to lower the surface energy of the polymer resin 110 with the surface of the super water-repellent particle 10 .

That is, when the super water-repellent coating solution is continuously provided on the polymer resin 110 , a plurality of the super water-repellent particles 10 are stacked to form a structure having a specific shape, and the polymer resin 110 is a plurality of The super water-repellent particles 10 of the are not only deformed according to the shape of the structure formed by stacking, but also can penetrate into the empty space EP formed in the structure. Accordingly, the preliminary super water-repellent pattern 200 may include the plurality of super water-repellent particles 10 and the polymer resin 110 filling at least a portion of the empty space between the super water-repellent particles 10 . .

According to an embodiment, the preliminary super water-repellent pattern 200 may include a concave portion 200a and a convex portion 200b. That is, in the process in which the super water-repellent particles 10 are stacked, a region in which a relatively large amount of the super water-repellent particles 10 are stacked to protrude from the substrate 100 is formed as a convex portion 200b, and a plurality of A region between the convex portions 200b of the convex portion 200b may be formed as a concave portion 200a. In other words, a structure including the super water-repellent particles 10 and the polymer resin 110 and having a roughness may be formed on the substrate 100 .

According to an embodiment, the polymer resin 110 may improve adhesion between the substrate 100 and the super water-repellent particle 10 . Accordingly, the plurality of super water-repellent particles 10 are easily adhered to the substrate 100 , so that the formation efficiency of the preliminary super water-repellent pattern 200 can be improved. In contrast, when the super water-repellent coating solution is provided on the substrate 100 in a state in which the polymer resin 110 is not provided, the super water-repellent particles 10 are not adhered to the substrate 100 . This may cause a problem in that the formation efficiency of the preliminary super water-repellent pattern 200 is lowered.

In the step S440 , the preliminary super water-repellent pattern 200 may be cured to form the super water-repellent pattern 300 . Specifically, when the preliminary super water-repellent pattern 200 is cured, the polymer resin 10 filled between the super water-repellent particles 10 may be cured to form the super water-repellent pattern 300 . Accordingly, the super water-repellent structure according to the embodiment can be manufactured. That is, the super water-repellent structure according to the embodiment includes the substrate 100 and the super water-repellent pattern 300 disposed on the substrate 100, wherein the super water-repellent pattern 300 includes the plurality of The super water-repellent particle 10 and the polymer resin 110 filling at least a portion of the empty space EP between the plurality of super water-repellent particles 10 may be included. In this case, the polymer resin 110 filling the empty space EP may improve the bonding force between the plurality of super water-repellent particles 10 . Accordingly, a super water-repellent structure having improved mechanical strength can be formed. In addition, as the mechanical strength of the super water-repellent structure is improved, durability and abrasion resistance may be improved.

According to an embodiment, by controlling the ratio of the super water-repellent particles 10 and the polymer resin 110 in the super water-repellent structure, the surface roughness value of the super water-repellent structure can be controlled. Specifically, so that the value obtained by dividing the mass of the super water-repellent particles 10 in the super water-repellent structure by the mass of the polymer resin 110 has 0.7 to 1.1, the super water-repellent particles 10 and the polymer resin 110 When controlling the ratio of, the surface roughness of the super water-repellent structure may be 5.0 μm or more based on Ra and 1.0 or less based on Rsk. In this case, the super water-repellent structure may have improved durability, improved abrasion resistance, and improved super water-repellent properties.

On the other hand, when the value obtained by dividing the mass of the super water-repellent particles 10 in the super water-repellent structure by the mass of the polymer resin 110 is less than 0.7, the surface roughness of the super water-repellent structure cannot be sufficiently secured, super water-repellent properties may not appear. On the other hand, when the value obtained by dividing the mass of the super water-repellent particles 10 in the super water-repellent structure by the mass of the polymer resin 110 is more than 1.1, the polymer resin 110 easily enters the empty space EP. Failure to penetrate, the bonding force between the plurality of super water-repellent particles (10) may be reduced. Accordingly, the durability of the super water-repellent structure is lowered, and consequently, a problem that the super water-repellent property is lowered may occur.

Super water-repellent coating method according to an embodiment of the present invention, preparing the source solution by mixing the base nanoparticles 12, the self-assembled monolayer forming material, and the first solvent, drying the source solution , extracting the super water-repellent particles 10 including the base nanoparticles 12, and the self-assembled monolayer 14 surrounding the base nanoparticles 12 from the source solution, the super water-repellent particles Mixing with the second solvent to prepare the super water-repellent coating solution, and providing the super water-repellent coating solution on the substrate 100 provided with the polymer resin 110, on the substrate 100 It may include forming the super water-repellent pattern 300 on the.

In addition, the super water-repellent pattern forming step provides the super water-repellent coating solution on the substrate 100 on which the polymer resin 110 is provided, and the plurality of super water-repellent particles 10 are agglomerated to form a concave portion. and forming the preliminary super water-repellent pattern 200 including a convex portion, and curing the preliminary super water-repellent pattern 200, wherein the polymer resin 110 is the plurality of super water-repellent particles 10 ) may penetrate into the empty space EP formed between them, and may fill at least a part of the empty space EP. Accordingly, after coating the polymer resin on the substrate, a super water-repellent coating method having improved durability, improved abrasion resistance, and improved super water-repellent properties can be provided by a simple process of coating the super water-repellent coating solution once more.

Above, the super water-repellent coating method and the super water-repellent structure according to an embodiment of the present invention have been described. Hereinafter, various methods of forming the concave portion and the convex portion included in the preliminary super water-repellent pattern will be described through the super water-repellent coating method according to the first to fifth modified examples of the present invention.

The super water-repellent coating method according to the first modified example of the present invention may be the same as the super water-repellent coating method according to the embodiment described with reference to FIGS. 1 to 6 . However, in the super water-repellent coating method according to the first modified example, the material included in the super water-repellent coating solution may be different from that of the super water-repellent coating method according to the embodiment. Specifically, the super water-repellent coating solution of the super water-repellent coating method according to the first modification may include the super water-repellent particles, the third solvent, and the fourth solvent.

According to an embodiment, the third solvent and the fourth solvent may have different vapor tensions. For example, the third solvent may have a lower vapor tension than that of the fourth solvent. Also, the third solvent and the fourth solvent may not be mixed with each other. For example, the third solvent may include at least one of a-terpineol, cyclohexanol, and 1-dodecanol. The fourth solvent may be distilled water.

Accordingly, when the super water-repellent coating solution is provided on the substrate to form the preliminary super water-repellent pattern, a region having a high ratio of the fourth solvent in the super water-repellent coating solution is formed as a recess, and the third solvent A region having a high ratio of may be formed as a convex portion. Specifically, when the super water-repellent coating solution is provided on the substrate, as the third solvent and the fourth solvent are not mixed with each other, the source solution provided on the substrate has a ratio of the third solvent A high region may be divided into a region having a high ratio of the fourth solvent. In this case, as the vapor tension of the fourth solvent is higher than that of the third solvent, the fourth solvent may be evaporated before the third solvent. Accordingly, in the super water-repellent coating solution provided on the substrate, a region having a high proportion of the fourth solvent may be formed as a concave portion, and a region having a high proportion of the third solvent may be formed as a convex portion.

That is, in the super water-repellent coating method according to the first modification, in the step of preparing the super water-repellent coating solution, as preparing the super water-repellent coating solution comprising a third solvent and a fourth solvent having different vapor tensions, The preliminary super water-repellent pattern including a concave portion and a convex portion may be easily formed.

The super water-repellent coating method according to the second modified example of the present invention may be the same as the super water-repellent coating method according to the embodiment described with reference to FIGS. 1 to 6 . However, in the super water-repellent coating method according to the second modification, the step of forming the preliminary super water-repellent pattern includes providing the super water-repellent coating solution at a first rate on the substrate, and on the substrate It may include providing the super water-repellent coating solution at two rates. For example, the first speed may be slower than the second speed. That is, the preliminary super water-repellent pattern included in the super water-repellent structure according to the second modification is, after spraying the super water-repellent coating solution at a relatively slow speed on the substrate, the super water-repellent coating solution at a relatively high speed It can be formed by spraying once more. Accordingly, the concave portion and the convex portion of the super water-repellent pattern can be easily formed.

Specifically, when the super water-repellent coating solution is provided on the substrate at the first rate, a base film with a flat upper surface is formed, and when the super water-repellent coating solution is provided at the second rate, The preliminary super water-repellent pattern including a concave portion and a convex portion may be formed.

That is, in the super water-repellent coating method according to the second modification, in the step of forming the preliminary super water-repellent pattern, by spraying the super water-repellent coating solution twice at different speeds, the super water-repellent coating solution including concave and convex parts A water-repellent pattern can be easily formed.

The super water-repellent coating method according to the third modified example of the present invention may be the same as the super water-repellent coating method according to the embodiment described with reference to FIGS. 1 to 6 . However, in the super water-repellent coating method according to the third modified example, in the step of forming the preliminary super water-repellent pattern, while the super water-repellent coating solution is provided on the substrate, the substrate may be heat-treated. Accordingly, the concave portion and the convex portion of the super water-repellent pattern can be easily formed.

Specifically, when the substrate is heat-treated while the super-water-repellent coating solution is provided, the rate at which the solvent included in the super water-repellent coating solution is evaporated may be increased. However, as described in the super water-repellent coating method according to the embodiment, as the super water-repellent particles are non-uniformly dispersed in the solvent, concave portions and convex portions may be formed due to a fast evaporation rate.

That is, in the super water-repellent coating method according to the third modification, in the step of forming the preliminary super water-repellent pattern, as the substrate is heat-treated while the super water-repellent coating solution is provided, the preliminary including concave and convex parts A super water-repellent pattern can be easily formed.

The super water-repellent coating method according to the fourth modification of the present invention may be the same as the super water-repellent coating method according to the embodiment described with reference to FIGS. 1 to 6 . However, in the super water-repellent coating method according to the fourth modification, the step of forming the preliminary super water-repellent pattern is a step of providing the super water-repellent coating solution on the substrate at a relatively low first temperature, and a relatively high It may include providing the super water-repellent coating solution on the substrate at a second temperature. Accordingly, the concave portion and the convex portion of the preliminary super water-repellent pattern may be easily formed.

Specifically, when the super water-repellent coating solution is provided on the substrate cooled to the first temperature, a base film having a flat upper surface may be formed as the evaporation rate of the solvent is lowered. In this state, when the super water-repellent coating solution is provided on the substrate at a relatively high second temperature, as the evaporation rate of the solvent increases, concave portions and convex portions may be formed on the base film.

That is, in the super water-repellent coating method according to the fourth modification, in the step of forming the preliminary super water-repellent pattern, the super water-repellent coating solution is provided on the substrate at a relatively low temperature, and then at a relatively high temperature. By providing the super water-repellent coating solution again on the substrate, the preliminary super water-repellent pattern including concave parts and convex parts can be easily formed.

The super water-repellent coating method according to the fifth modification of the present invention may be the same as the super water-repellent coating method according to the embodiment described with reference to FIGS. 1 to 6 . However, in the super water-repellent coating method according to the fifth modification, the material included in the super water-repellent coating solution may be different from that of the super water-repellent coating method according to the embodiment. Specifically, the super water-repellent coating solution of the super water-repellent coating method according to the fifth modification may include a first super water-repellent particle, a second super water-repellent particle, a third super water-repellent particle, and a solvent.

According to an embodiment, the first to the third super-repellent particles may be charged with different polarities. For example, the first super water-repellent particle may be charged with (+), and the second super water-repellent particle may be charged with (-). On the other hand, the third super water-repellent particle may be neutral. Accordingly, when the super water-repellent coating solution is provided on the substrate to form the preliminary super water repellent pattern, the first and second super water repellent particles are combined with each other to easily form concave and convex portions. Specifically, as the first and second super water-repellent particles are combined with each other in the super water repellent coating solution, aggregates of super water repellent particles having different sizes may be irregularly dispersed in the super water repellent coating solution. Accordingly, concave portions and convex portions may be formed in the process of evaporating the solvent of the super water-repellent coating solution.

That is, in the super water-repellent coating method according to the fifth modification, in the step of preparing the super water-repellent coating solution, the source solution comprising the first to third super water-repellent particles charged with different polarities is prepared. , the super water-repellent pattern including a concave portion and a convex portion can be easily formed.

Hereinafter, a super water-repellent coating method according to a sixth modification of the present invention in which the super water repellent pattern is formed of super water repellent particles of different sizes will be described.

The super water-repellent coating method according to the sixth modification of the present invention may be the same as the super water-repellent coating method according to the embodiment described with reference to FIGS. 1 to 6 . However, in the super water repellent coating method according to the sixth modification, in the step of forming the preliminary super water repellent pattern, the super water repellent coating solution provided on the substrate is a first super water repellent coating solution and a second super water repellent coating solution A coating solution may be included. According to an embodiment, the first super water-repellent coating solution may include a first super water-repellent particle and a solvent, and the second super water-repellent coating solution may include a second super water repellent particle and a solvent. The first and second super water-repellent particles may have different particle sizes. For example, the first super-repellent particles may have a larger size than the second super-repellent particles.

In addition, the step of forming the preliminary super water-repellent pattern, providing the first super water-repellent coating solution, and providing the second super water-repellent coating solution after the first super water-repellent coating solution is provided can That is, in the super water-repellent coating method according to the sixth modification, after the first super water-repellent coating solution having a relatively large particle size is provided, the second super water-repellent coating solution having a relatively small particle size is provided. , the preliminary super water-repellent pattern may be formed.

In this case, the lower portion of the preliminary super water-repellent pattern is composed of the first super-repellent particles having a relatively large particle size, and the upper portion of the preliminary super-water-repellent pattern is the second super water-repellent particle size is relatively small. It may be composed of particles. Accordingly, the size of the empty space formed under the preliminary super water-repellent pattern may be larger than the size of the empty space formed above the preliminary super water-repellent pattern.

In the lower portion of the preliminary super water-repellent pattern in which the size of the empty space is formed to be relatively large, a relatively large amount of the polymer resin permeates to improve the bonding force between the first super water-repellent particles. On the other hand, in the upper part of the preliminary super water-repellent pattern in which the size of the empty space is formed to be relatively small, as the radius of the capillary tube becomes smaller, as shown in Equation 1 below, the penetration of the polymer resin is easier can be done

<Equation 1>

(h: height of meniscus, R: radius of capillary tube, γ: specific weight of water, T: surface tension, θ: slope from tube wall)

As a result, the preliminary super water-repellent pattern according to the sixth modification may be composed of particles of different sizes and may include empty spaces of different sizes. Accordingly, in the super water-repellent pattern formed by curing the preliminary super-repellent pattern, the bonding force between the super-repellent particles is improved due to a relatively large amount of polymer resin in the lower part, and the capillary phenomenon is improved in the upper part of the polymer resin. As penetration becomes easier, overall durability can be improved.

Hereinafter, the super water-repellent coating method according to the seventh modification of the present invention with improved efficiency of penetrating the super water-repellent particles into the polymer resin will be described.

The super water-repellent coating method according to the seventh modification of the present invention may be the same as the super water-repellent coating method according to the embodiment described with reference to FIGS. 1 to 6 . However, in the super water-repellent coating method according to the seventh modification, the super water-repellent coating solution is provided on the substrate 100 on which the polymer resin 110 is provided, and the super water-repellent particles 10 are coated with the polymer resin The polymer resin 110 provided with the super water-repellent particles 10 before the step (S420) of stacking the super water-repellent particles 10 permeated in the polymer resin 110 after the step (S410) of infiltrating (110) ) may further comprise a step of heat-treating. Accordingly, the super water-repellent particles 10 may easily penetrate into the polymer resin 110 .

Above, the super water-repellent coating method and super water-repellent structure according to the embodiments and modifications of the present invention have been described. Hereinafter, specific experimental examples and characteristic evaluation results of the super water-repellent structure according to an embodiment of the present invention will be described.

according to the embodiment super water repellent structure manufacturing

_{SiO 2} nanoparticles with a size of 1 to 15 nm, Trimethoxy(ocradecyl)silane, and Ethyl alcohol anhydrous (99.5%) were mixed and dried to extract super water-repellent particles in which a self-assembled monolayer (SAM) was formed on _{SiO 2 nanoparticles.} . The extracted super water-repellent particles were put in ethyl alcohol and stirred to prepare a super water-repellent coating solution.

After spin-coating polyurethane (PU) on a substrate, spraying the super water-repellent coating solution at a spray pressure of 0.3 mpa at a distance of 15 cm on the polyurethane to form a preliminary super water-repellent pattern, then preliminary super water repellency The pattern was cured to form a super water-repellent pattern. Accordingly, the super water-repellent structure according to the above embodiment was manufactured.

7 is an optical photograph of a cross-section of a super water-repellent structure according to an embodiment of the present invention.

Referring to FIG. 7 , a schematic diagram of the super water-repellent structure and a cross-section of the super water-repellent structure according to the embodiment were shown by taking a scanning electron microscope (SEM) photographing. As can be seen in FIG. 7 , in the super water-repellent structure according to the embodiment, it was confirmed that the polymer resin 110 penetrated between the super water-repellent particles 10 in the process of forming the super water-repellent pattern.

8 to 11 are photographs and graphs showing the surface characteristics according to the ratio of the super water-repellent particles and the polymer resin included in the super water-repellent structure according to an embodiment of the present invention.

Referring to (a) to (c) of Figure 8, the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 0.03. The surface SEM photograph of the structure is shown in FIGS. 8 (a) and (b) at different magnifications, and the surface characteristics of the super water-repellent structure are shown in FIG. 8 (c).

As can be seen from (a) and (b) of Figure 8, the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 0.03. It was confirmed that the rough structure of the surface of the super water-repellent structure was hardly formed. In addition, as can be seen in FIG. 8(c), the super water-repellent structure confirmed in FIGS. 8(a) and (b) is R _a (μm): 0.116, R _sk : 0.64, CA (contact angel, degree) : It was confirmed that the surface characteristics appeared as 74.7.

9 (a) to (c), the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 0.15 The surface SEM photograph of the structure is shown in FIGS. 9 (a) and (b) at different magnifications, and the surface characteristics of the super water-repellent structure are shown in FIG. 9 (c).

As can be seen from (a) and (b) of Figure 9, the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 0.15. It was also confirmed that the rough structure of the surface of the super water-repellent structure was hardly formed. In addition, as can be seen in FIG. 9(c), the super water-repellent structure confirmed in FIGS. 9(a) and (b) is R _a (μm): 3.921, R _sk : 2.8, CA (contact angel, degree) : It was confirmed that the surface characteristics appeared as 90.8.

Referring to FIG. 10 (a) to (c), the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super-repellent particles by the mass of the polymer resin is 0.3. The surface SEM photograph of the structure was shown in FIGS. 10 (a) and (b) at different magnifications, and the surface characteristics of the super water-repellent structure were shown in FIG. 10 (c).

As can be seen in (a) and (b) of Figure 10, the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 0.3. Although the surface rough structure was formed in the super water-repellent structure, it was confirmed that the roughness was low. In addition, as can be seen in FIG. 10 (c), the super water-repellent structure confirmed in FIGS. 10 (a) and (b) is R _a (μm): 13.165, R _sk : 0.59, CA (contact angel, degree) : 148.2, it was confirmed that the surface characteristics appeared.

11 (a) to (c), the ratio of the super water-repellent particle and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particle by the mass of the polymer resin is 0.9. The surface SEM photograph of the structure is shown in FIGS. 11 (a) and (b) at different magnifications, and the surface characteristics of the super water-repellent structure are shown in FIG. 11 (c).

11 (a) and (b), the ratio of the super water-repellent particle and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particle by the mass of the polymer resin is 0.9. It was confirmed that the super water-repellent structure was formed to have high roughness characteristics on the surface. In addition, as can be seen in FIG. 11(c), the super water-repellent structure confirmed in FIGS. 11(a) and (b) is R _a (μm): 15.517, R _sk : -0.17, CA (contact angel, degree) ): It was confirmed that the surface characteristics appeared as 158.

12 to 15 are photographs showing abrasion resistance according to the ratio of the super water-repellent particles and the polymer resin included in the super water-repellent structure according to an embodiment of the present invention.

Referring to (a) and (b) of Figure 12, the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin becomes 0 After the abrasion rubbing test was performed under the conditions of load 60g, 25RPM, and 30 round trips, it was photographed to confirm the abrasion resistance. Fig. 12(a) shows before the test, and Fig. 12(b) shows after the test.

As can be seen from (a) and (b) of Figure 12, the super water-repellent particle and the ratio of the polymer resin are controlled so that the value obtained by dividing the mass of the super water-repellent particle by the mass of the polymer resin becomes 0. As for the water-repellent structure, it was confirmed that roughness was not formed on the surface, and the super water-repellent property did not appear.

13 (a) and (b), the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 0.9 After the abrasion rubbing test was performed under the conditions of load 60g, 25RPM, and 30 round trips, it was photographed to confirm the abrasion resistance. Fig. 13 (a) shows before the test, and Fig. 13 (b) shows after the test.

Referring to (a) and (b) of Figure 14, the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 1.1 After the abrasion rubbing test was performed under the conditions of load 60g, 25RPM, and 30 round trips, it was photographed to confirm the abrasion resistance. Fig. 14(a) shows before the test, and Fig. 14(b) shows after the test.

As can be seen in FIGS. 13 and 14 , the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin is controlled so that the values obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin are 0.9 and 1.1, It was confirmed that the roughness of the surface was easily formed to exhibit excellent super water-repellent properties as well as excellent abrasion resistance.

Referring to (a) and (b) of Figure 15, the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 2.1 After the abrasion rubbing test was performed under the conditions of load 60g, 25RPM, and 30 round trips, it was photographed to confirm the abrasion resistance. Fig. 15 (a) shows before the test, and Fig. 15 (b) shows after the test.

As can be seen from (a) and (b) of Figure 15, the super water repellent according to the embodiment in which the ratio of the super water repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water repellent particles by the mass of the polymer resin is 2.1. In the structure, it was confirmed that the polymer resin did not sufficiently penetrate into the super water-repellent particles, and the abrasion resistance was significantly reduced.

16 to 19 are photographs and graphs illustrating a change in roughness according to a wear resistance test of a super water-repellent structure according to an embodiment of the present invention.

16 (a) and (b), the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 0.9 After the abrasion rubbing test was performed under the conditions of load 60g, 25RPM, and reciprocating 30 times, the surface of the super water-repellent structure was photographed by SEM to confirm abrasion resistance. Fig. 16 (a) shows before the test, and Fig. 16 (b) shows after the test. Referring to FIG. 17 , the surface roughness value of FIG. 16(a) and the surface roughness value of FIG. 16(b) are graphed.

16 and 17, the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particle and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particle by the mass of the polymer resin is 0.9, the Abrasion Rubbing Test Before (Pre-rubbing test), the surface properties showed as R _a (μm): 15.517, R _sk : -0.17, and after the abrasion rubbing test (After-rubbing test), the surface properties were R _a (μm): 5.842, R _sk : It was confirmed that it appeared as -0.32.

Referring to (a) and (b) of Figure 18, the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particles by the mass of the polymer resin is 2.1 After the abrasion rubbing test was performed under the conditions of load 60g, 25RPM, and reciprocating 30 times, the surface of the super water-repellent structure was photographed by SEM to confirm abrasion resistance. Figure 18 (a) shows before the test, and Figure 18 (b) shows after the test. Referring to FIG. 19 , the surface roughness value of FIG. 18 (a) and the surface roughness value of FIG. 18 (b) are graphed.

18 and 19, the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particle and the polymer resin is controlled so that the value obtained by dividing the mass of the super water-repellent particle by the mass of the polymer resin is 2.1, the Abrasion Rubbing Test Before (Pre-rubbing test), the surface properties were R _a (μm): 10.724, R _sk : 0.23, and after the abrasion rubbing test (After-rubbing test), the surface properties were R _a (μm): 3.175 , R _sk : It was confirmed that it appeared as -2.74.

20 is a graph showing the contact angle according to the ratio of the super water-repellent particles and the polymer resin included in the super water-repellent structure according to an embodiment of the present invention.

Referring to FIG. 20 , the abrasion rubbing test was performed under the conditions of 60 g, 25 RPM, and 30 round trips in the super water-repellent structure according to the embodiment in which the ratio of super water-repellent particles and polymer resin was controlled, and before proceeding (Pre-rubbing) Water contact angle (degree) was shown for each and after rubbing.

As can be seen in FIG. 20 , the super water-repellent structure according to the embodiment in which the ratio of the super water-repellent particles and the polymer resin was controlled to 0.7 to 1.1 exhibited a high contact angle, thereby confirming that it had excellent super water-repellent properties. In addition, the super water-repellent structure according to the embodiment, in which the ratio of the super water-repellent particles and the polymer resin was controlled to 0.7 to 1.1, showed that the contact angle difference before and after the abrasion rubbing test was small, so it was confirmed that the abrasion resistance was also excellent.

As mentioned above, although the present invention has been described in detail using preferred embodiments, the scope of the present invention is not limited to specific embodiments and should be construed according to the appended claims. In addition, those skilled in the art will understand that many modifications and variations are possible without departing from the scope of the present invention.

10: super water-repellent particles
12: base nanoparticles
14: self-assembled monolayer
100: substrate
110: polymer resin
200: preliminary super water-repellent pattern
300: super water-repellent pattern

Claims (11)

SiO2, TiO2, ZnO, CaCO3, Al2O3, and a self-assembled monolayer film-forming material comprising at least one of a base nanoparticle, a silane-based material, a fatty acid-based material, or a thiol-based material comprising at least any one of, and preparing a source solution by mixing a first solvent;
Drying the source solution, extracting super water-repellent particles comprising the base nanoparticles, and a self-assembled monolayer (SAM) surrounding the base nanoparticles from the source solution;
preparing a super water-repellent coating solution by mixing the super water-repellent particles with a second solvent; and
Providing the super water-repellent coating solution on a substrate provided with a polymer resin, comprising the step of forming a super water-repellent structure comprising a super water-repellent pattern on the substrate,
In the super water-repellent structure, a value obtained by dividing the mass of the super water-repellent structure particles by the mass of the polymer resin is 0.7 or more and 1.1 or less.
According to claim 1,
The super water-repellent pattern forming step,
providing the super water-repellent coating solution on the substrate provided with the polymer resin, and permeating the super water-repellent particles into the polymer resin;
stacking the super water-repellent particles permeated into the polymer resin;
Forming a preliminary super water-repellent pattern in which the shape of the polymer resin is deformed according to the shape of the laminated super water-repellent particles; and
Super water-repellent coating method comprising the step of curing the preliminary super water-repellent pattern.
3. The method of claim 2,
The preliminary super-repellent pattern includes an empty space formed between the plurality of super-repellent particles,
In the step of forming the preliminary super water-repellent pattern, the polymer resin penetrates into the empty space, and the super water-repellent coating method comprising filling at least a portion of the empty space.
4. The method of claim 3,
The polymer resin filling the empty space, super water-repellent coating method comprising improving the bonding force between the plurality of super water-repellent particles.
According to claim 1,
The polymer resin is a super water-repellent coating method comprising polyurethane (Poly Urethane).
delete delete According to claim 1,
In the source solution preparation step,
Super water-repellent coating method comprising the -OH group of the base nanoparticles reacting with the functional group of the self-assembled monomolecular film-forming material to form the self-assembled monomolecular film surrounding the base nanoparticles.
Board; and
Including a super water-repellent pattern disposed on the substrate,
The super water-repellent pattern,
A plurality of super water-repellent particles, and a polymer resin filling at least a portion of an empty space between the plurality of super water-repellent particles,
The value obtained by dividing the mass of the super water-repellent particles disposed on the substrate by the mass of the polymer resin includes those of 0.7 or more and 1.1 or less,
The super water-repellent particles, SiO2, TiO2, ZnO, CaCO3, Al2O3, or a base nanoparticle comprising at least one of ZrO2, and a silane-based material, a fatty acid-based material, or at least one of a thiol-based material comprising A super water-repellent structure comprising a self-assembled monolayer (SAM) surrounding the base nanoparticles.
delete 10. The method of claim 9,
The base nanoparticles represent hydrophilicity, and the super water-repellent particles exhibit hydrophobicity.

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