KR20200062795A - Film with improved water repellency and oil elution properties and preparation method thereof - Google Patents

Abstract

The present invention relates to a film with improved water repellency and oil elution properties, which comprises: a base layer including polymer resin and oil; and a hydrophobic coating layer having surface roughness assigned thereto. According to the present invention, since oil is contained in the polymer resin of the base layer and the surface roughness and hydrophobic properties are assigned to a surface of the film, the film has the improved water repellency repelling water droplets without absorbing the same. Moreover, the present invention provides an advantage of providing a film having slip characteristics to prevent ice from being attached to the film when moisture is frozen by a certain cause regardless of such water repellency.

Description

FILM WITH IMPROVED WATER REPELLENCY AND OIL ELUTION PROPERTIES AND PREPARATION METHOD THEREOF}

The present invention relates to a film having improved water repellent properties and oil elution properties and a method for manufacturing the same, more specifically, it exhibits improved water repellency properties by imparting surface roughness and hydrophobicity, and in addition, exhibits oil elution properties. It relates to a film that can be represented together and a method for manufacturing the same.

An icepphobic coating technology that prevents freezing of moisture on an object surface or lowers the adhesion strength of formed ice has recently attracted attention.

It is necessary to provide the superhydrophobic property that repels water droplets without first absorbing them. It is known that such a super water-repellent property can be realized by a superhydrophobic treatment, and can be generally achieved when chemical surface treatment is performed to form a fine concavo-convex structure on the surface and to obtain hydrophobicity. That is, it is known that when the surface having a hydrophobic property increases surface roughness due to a micro nano pattern or the like, the surface has a contact angle with water of 150 degrees or more and exhibits super water repellency.

In relation to forming a surface structure for providing such super water repellency, a technique for forming a fine micro-nano pattern on a solid surface using an etching technique has been proposed, but the efficiency is low in cost and processability, and a large area coating has not yet been performed. There is a problem that is difficult to apply to the treatment.

Therefore, there is a need for research on improved technology in terms of economic efficiency and fairness with regard to surface roughness and hydrophobic treatment for super water repellency. In addition, in addition to the above-mentioned super water-repellent properties, considering the fact that ice may be formed on the surface for any reason despite the super-water-repellent properties, research and development of a technology capable of preventing the adhesion of the formed ice to the surface is necessary. .

Korea Patent Publication 10-2013-0082217

The present invention is to solve the problems of the prior art described above, by having an improved water repellent characteristics close to the super water repellent characteristics and at the same time having the oil elution characteristics, it is possible to primarily prevent the freezing of moisture, and nevertheless freezing occurs The purpose is to provide a film and a method of manufacturing the film, which can prevent ice from adhering to the surface.

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

In order to achieve the above object, a film having improved water repellency and oil elution properties according to the present invention basically includes a base layer comprising a polymer resin and oil and a hydrophobic coating layer provided with surface roughness. It consists of a structure.

Specifically, the film according to an aspect of the present invention, a base layer comprising a polymer resin and oil; And a coating layer comprising hydrophobic porous silica particles on the substrate layer.

In this way, by incorporating oil in the polymer resin of the base layer, the characteristics of the oil component being continuously eluted from the inside of the film can be realized, and at the same time, surface roughness and hydrophobicity are given to the film surface by including hydrophobic porous silica particles in the coating layer. It may exhibit improved water repellent properties. The hydrophobic porous silica particles may be silica particles having macropores having a pore size of 50 nm to 1 micrometer.

The polymer resin included in the base layer of the film is not particularly limited, but may include a hydrophobic polymer resin, and preferably may include a polydimethylsiloxane (PDMS) resin, a polyurethane resin, and the like.

In addition, there is no particular limitation on the mixing form of the polymer resin and the oil, as the oil mixed with the polymer resin is directly mixed with the polymer resin or the porous particles in the form of impregnating the pores with the polymer resin are mixed with the polymer resin. When oil is mixed in the substrate layer in the form of oil impregnation in the pores of the porous particles, the oil first elutes from the pores and then moves to the surface of the substrate layer and the coating layer and elutes to the film surface, so that when the oil is directly mixed, Compared, there is an advantage in that the oil elution duration can be adjusted so that it elutes slowly.

More specifically, the base layer may include PDMS resin and at least one oil of silicone oil 100CS or silicone oil 60CS in a mass ratio of 10:1 to 8.

In addition, the type of oil included in the base layer is not particularly limited, but may be selected from silicone oil, fluorine-based oil, vegetable oil and mineral oil, preferably, silicone oil may be included in the base layer. have.

Matters related to the polymer resin and oil content ratio, type, etc. of the base layer as described above may be applied in the same way to films of other aspects to be described later, and thus detailed description thereof will be omitted below.

The method of manufacturing a film according to an aspect of the present invention described above includes mixing a polymer resin and an oil to prepare a base layer precursor; Curing the base layer precursor to form a base layer; And forming a coating layer by applying and drying a coating solution containing hydrophobic porous silica particles on the substrate layer.

Here, the coating solution, mixing the porous silica particles and a silane coupling agent in a toluene solvent; Heating and stirring the mixed solution to perform hydrophobic surface treatment of the porous silica particles; Drying the heated and stirred mixed solution to obtain hydrophobic porous silica particles; And redispersing the hydrophobic porous silica particles in an alcohol solvent.

Specifically, the substrate layer precursor, a mixture of PDMS monomer and a curing agent in a mass ratio of 9:1, and at least one oil of silicone oil 100CS or silicone oil 60CS, so that the mass ratio of PDMS and oil is 10:1 to 8 It is prepared by mixing. The prepared base layer precursor is cured at 80 degrees for 2 hours to form a base layer.

The silane coupling agent may include triethoxyoctylsilane and trichlorododecylsilane. The alcohol solvent may be selected from ethanol, propanol, or butanol, and the hydrophobic porous silica particles may be included in a mass ratio of 0.1:2.5 with respect to ethanol, propanol, or butanol solvent to prepare a coating solution.

The prepared coating solution may be applied on the substrate layer by spray coating, drop coating, or the like, and is not particularly limited, but is preferably applied by spray coating in terms of processability. The spray-coated coating layer is dried for 1 to 4 hours upon drying to prepare the film of the present invention.

The film according to another aspect of the present invention includes a polymer resin, a base layer comprising oil and hydrophilic porous silica particles; And a coating layer comprising hydrophobic silica nanoparticles on the substrate layer. It may include.

In this way, by incorporating oil in the polymer resin of the base layer, the oil component is continuously eluted from the inside of the film, and at the same time, the hydrophilic functional group of the hydrophilic porous silica particles contained in the base layer protrudes to the surface of the base layer to protrude the surface of the base layer. It can function to provide a fine uneven structure. The coating layer formed on the surface of the substrate layer provided with such a fine concavo-convex structure expresses the concavo-convex structure corresponding to the fine concavo-convex structure on the surface of the substrate layer as it is on the surface of the coating layer. It becomes possible to provide surface roughness and hydrophobicity. As a result, surface roughness and hydrophobicity may be imparted to the film surface to exhibit improved water repellency. The hydrophilic porous silica particles may be silica particles having macropores of 1 micrometer at a pore size of 50 nm.

The method of manufacturing a film according to another aspect of the present invention described above comprises the steps of preparing a precursor of a base layer by mixing polymer resin, oil, and hydrophilic porous particles; Curing the base layer precursor to form a base layer; And forming a coating layer by applying and drying a coating solution containing hydrophobic silica nanoparticles on the substrate layer.

Here, the coating solution, mixing the silica nanoparticles and a silane coupling agent in a toluene solvent; Heating and stirring the mixed solution to perform hydrophobic surface treatment of the silica nanoparticles; Drying the heated and stirred mixed solution to obtain hydrophobic silica nanoparticles; And redispersing the hydrophobic silica nanoparticles in an alcohol solvent.

Specifically, the substrate layer precursor, a mixture of PDMS monomer and a curing agent in a mass ratio of 9:1, and at least one oil of silicone oil 100CS or silicone oil 60CS, so that the mass ratio of PDMS and oil is 10:1 to 8 It is prepared by mixing. In addition, the hydrophilic porous particles and PDMS may be mixed in a mass ratio of 0.05 to 0.4:2. The prepared base layer precursor is cured at 80 degrees for 2 hours to form a base layer.

The silane coupling agent may include triethoxyoctylsilane and trichlorododecylsilane. The alcohol solvent may be selected from ethanol, propanol, or butanol, and the hydrophobic silica nanoparticles may be included in a mass ratio of 0.1:2.5 with respect to ethanol, propanol, or butanol solvent to prepare a coating solution. The coating solution may be applied by a spray coating method, and dried for 1 to 4 hours during natural drying to prepare a film of the present invention.

The film according to still another aspect of the present invention includes a polymer resin and an oil, and a substrate layer on which a fine uneven structure transferred from paper is formed; And a coating layer comprising hydrophobic silica nanoparticles on the substrate layer.

In this way, by including oil in the polymer resin of the base layer, the oil component is continuously eluted from the inside of the film, and at the same time, the coating layer formed on the surface of the base layer provided with a fine uneven structure corresponds to the fine uneven structure on the surface of the base layer. The uneven structure described above is exposed on the surface of the coating layer as it is, and by including hydrophobic silica nanoparticles in the coating layer itself, it is possible to provide surface roughness and hydrophobicity to the film surface. The fine concavo-convex structure provided on the surface of the substrate layer is transferred from the paper surface, and is formed in a shape in which fine concavo-convex structures having a size of 1 to 100 micrometers on the paper surface are engraved.

The method for manufacturing a film according to another aspect of the present invention comprises the steps of preparing a base layer precursor comprising a polymer resin and an oil; Applying the substrate layer precursor on paper; Curing the base layer precursor to form a base layer; Separating the paper from the cured substrate layer and transferring the uneven structure of the paper surface to the surface of the substrate layer by engraving; And forming a coating layer by applying and drying a coating solution containing hydrophobic silica nanoparticles on the substrate layer.

Specifically, the substrate layer precursor, a mixture of PDMS monomer and a curing agent in a mass ratio of 9:1, and at least one oil of silicone oil 100CS or silicone oil 60CS, so that the mass ratio of PDMS and oil is 10:1 to 8 It is prepared by mixing. The prepared substrate layer precursor is poured onto paper before PDMS curing, cured for 2 hours at 80 degrees, and then the paper is removed from the cured substrate layer to prepare a substrate layer having a surface on which fine uneven structures transferred from the paper are formed.

In the step of preparing the coating solution and forming the coating layer, the same method as the method of manufacturing the film of the other aspect described above may be applied, so a detailed description thereof will be omitted.

According to the present invention constituted as described above, by containing oil in the polymer resin of the base layer and imparting surface roughness and hydrophobicity to the film surface, it has improved water repellency characteristics that does not absorb water droplets, and despite these water repellency characteristics There is an advantage in that a film exhibiting slip properties can be provided so that ice does not adhere when the moisture is frozen for some reason.

In addition, according to the present invention, there is an advantage in that surface roughness and hydrophobicity can be imparted to the film surface in an advantageous manner in terms of process and cost effectiveness.

In addition, according to the present invention, there is an effect that can provide a film capable of exhibiting oil repellency while exhibiting water repellency close to the super-water repellent property at a contact angle with water of 120 degrees or more on the film surface.

Figure 1a is a view showing the contact angle measurement data according to the type of silicone oil contained in the PDMS film,
Figure 1b is a view showing the contact angle measurement data according to the content of the fluorine-based oil 103 contained in the PDMS film,
2 is a view conceptually showing a cross-sectional structure of a film according to an aspect of the present invention,
3A is an SEM image of a hydrophobic porous silica powder prepared according to Example 1,
Figure 3b is FT-IR spectrum data before and after the hydrophobic surface treatment of the hydrophobic porous silica powder prepared according to Example 1,
4 is a view showing the results of measuring the contact angle of a film formed of a coating layer containing hydrophobic porous silica particles prepared according to Example 2,
5 is a view conceptually showing a cross-sectional structure of a film according to another aspect of the present invention,
6 is an SEM image of hydrophobic silica nanoparticles prepared according to Example 3,
7 is a view showing the results of measuring the contact angle of a film having a hydrophobic silica nanoparticle coating layer formed on a base layer containing hydrophilic porous silica particles prepared according to Example 4,
8 is a view showing the measurement results of the contact angle of Comparative Examples 1 to 3 for Example 4 film,
9 is a view conceptually showing a cross-sectional structure of a film according to another aspect of the present invention,
10 is an SEM image of a paper surface,
11 is a view conceptually showing a method of transferring a fine concavo-convex structure of a paper surface to a base layer;
12A is a SEM image of the surface of the PDMS substrate layer, on which the fine irregularities of the paper surface are transferred, in the process of manufacturing the film according to Example 5;
12B is an SEM image of a film surface on which a hydrophobic silica nanoparticle coating layer is formed on a substrate layer provided with an uneven structure transferred from paper prepared according to Example 5,
13A is a SEM image of the surface of a PDMS substrate layer on which a fine uneven structure of a paper surface is transferred in the process of manufacturing a film according to Comparative Example 4 for a film of Example 5;
13B is a SEM image of a film surface on which a hydrophobic silica nanoparticle coating layer is formed on a substrate layer provided with an uneven structure transferred from paper prepared according to Comparative Example 4;
14A is a view showing a result of measurement of a contact angle for a film of Example 5;
14B is a view showing a measurement result of contact angle of Comparative Example 4 for Example 5 film.

Hereinafter, the present invention will be described in more detail through examples. The objects, features, and advantages of the present invention will be readily understood through the following examples. The present invention is not limited to the embodiments described herein, and may be embodied in other forms. The embodiments introduced herein are provided to sufficiently convey the spirit of the present invention to those skilled in the art to which the present invention pertains. Therefore, the present invention should not be limited by the following examples.

In the present invention, in order to solve the freezing phenomenon caused by the adhesion of moisture at low temperatures, the polymer substrate layer contains oil, and surface roughness is provided to impart improved water repellency to the polymer film containing oil. A film comprising a hydrophobic coating layer is provided.

The oil contained in the base layer is not a component contributing to the improved water repellent properties of the film, but the oil component is ice when the water freezes at low temperatures despite the improved water repellent properties of the film due to the hydrophobic coating layer imparted with surface roughness The slip property is improved so as not to adhere to this surface.

First, in order to confirm the film surface properties according to the inclusion of oil in the base layer, the contact angle according to the type and content of the oil contained in the base layer was measured and the process and results will be described below.

Experiment of measuring the contact angle according to the type and content of oil contained in the base layer

Prepare 4 types of films cured for 2 hours at 80 degrees Celsius by including 0.4 g of silicone oil 6CS, 100CS, 350CS, and 1000CS in 1 g of PDMS resin, and measure the contact angle for each. It is shown in 1a.

In addition, six types of films prepared by curing the fluorine-based oil 103 in 0.1 g, 0.2 g, 0.3 g, 0.4 g, 0.5 g, and 0.6 g in 1 g of PDMS resin for 2 hours at 80 degrees Celsius are prepared. After measuring the contact angle for each, the results are shown in Figure 1b.

From the contact angle measurement results of FIGS. 1A and 1B, it was confirmed that there was a difference in the contact angle measurement value according to the type and content of the viscosity or component of the oil. When oil was added in small amounts, the contact angle tended to be measured high, and conversely, as the oil addition amount increased, surface hydrophobicity decreased and water repellency could be deteriorated. Therefore, it can be seen that in order to promote slip property through elution of surface oil as an iSPOBIC film material, oil addition should be made in consideration of the type and content of oil capable of promoting slip property without significantly degrading water repellency. .

The present invention provides an improved water repellency close to super water repellency by properly balancing the water repellent properties and oil elution properties of the film as described above, while preventing the ice from adhering when freezing occurs because water repellent properties are not properly expressed for any reason. Provided is a film that can be prevented.

2 conceptually illustrates a cross-sectional structure of a film according to an aspect of the present invention. As shown, the film according to an aspect of the present invention, a base layer 100 comprising a polymer resin 130 and an oil 110, and a coating layer comprising hydrophobic porous silica particles 230 on the base layer It is made of a configuration 200 is provided.

For the hydrophobic porous silica particles 230, the surface of the hydrophilic porous silica particles is surface-modified with a silane coupling agent having a hydrocarbon group, and a hydrophobic treatment is used. Such hydrophobic porous silica particles, when applied to the coating layer of the film in this embodiment, have a micrometer-unit particle size, and macroporous silica particles themselves having a large number of pores of 50 nm or more in size, with fine irregularities on the film surface. While providing a structure, the surface of the film is made hydrophobic by a hydrocarbon group by surface modification.

An example that can be applied to the film production of Figure 2 will be described below.

<Example 1>

Preparation of hydrophobic porous silica particles

First, porous silica powder was prepared by synthesis. The porous silica powder may be a commercially available one, and there is no particular limitation on the synthesis method, but in this embodiment, the porous silica powder having macropores is synthesized by a self-assembly technique as disclosed in Patent No. 1875454. Was prepared. That is, when heat is supplied at a fixed temperature, water and ethanol evaporate from an emulsion droplet composed of a dispersion medium containing polymer particles (eg, polystyrene particles) and a precursor (TEOS), thereby causing the droplets to shrink, and at this time, the droplets shrink A method was used in which the polymer particles and precursors inside the droplets were self-assembled by utilizing the force to be formed, and then porous ceramic particles were formed through continuous heat treatment such as calcination.

After mixing 0.4 g of the porous silica powder prepared as described above and 2.5 ml of a silane coupling agent (triethoxyoctylsilane) in 10 ml of a toluene solvent, the mixture was heated at 65 degrees Celsius and stirred for 3 hours to treat the porous silica particles with a hydrophobic surface. Next, the treated mixed solution was dried to obtain a hydrophobic porous silica powder having macropores.

The SEM image of the hydrophobic porous silica powder obtained by the above method is shown in Fig. 3A, and the FT-IR spectrum data is shown in Fig. 3B. Figure 3a shows that the hydrophobic porous silica powder is made of a structure in which a large number of macropores having a size of 550 nm is formed, whereby, when the porous silica powder is included in the coating layer of the film, the fine itself imparts surface roughness to the film surface. It can be confirmed that it can function as an uneven structure. In addition, Figure 3b shows the data before and after the hydrophobic surface treatment of the porous silica powder, the porous silica powder after the hydrophobic surface treatment has a characteristic peak derived from the hydrocarbon chain of the silane coupling agent used in the treatment is about 2,700 to 3,000 cm ^-1 It can be confirmed that it appears in the wave number of, it was confirmed that the porous silica powder can impart hydrophobic properties to the film surface.

Next, a specific example of manufacturing the film conceptually illustrated in FIG. 2 will be described. The examples described below have been specifically described for producing a film using a PDMS film base layer as a polymer resin, but the scope of application of the present invention is not limited thereto. Various polymer resins that can be applied within the scope of not impairing the features of the present invention may be applied as the base material of the present invention.

<Example 2>

Preparation of a film in which a coating layer containing hydrophobic porous silica particles is formed on a PDMS base layer containing oil

The PDMS monomer and the curing agent were mixed at a weight ratio of 9:1, and 0.4 g of silicone oil (100 CS) was uniformly mixed with 1 g of PDMS before curing, and then cured for 2 hours at 80 degrees Celsius to obtain a polymer base layer. It was prepared.

The hydrophobic porous silica powder prepared according to Example 1 was dispersed in butanol to prepare a coating solution, but 2.5 g of butanol per 0.1 g of hydrophobic porous silica powder was applied to prepare a coating solution.

After spraying the prepared coating solution on the surface of the substrate layer, it was naturally dried for several hours to prepare a film.

Characteristic evaluation

In order to evaluate the water repellent properties of the prepared film, a static water contact angle was measured for the film surface. As shown in FIG. 4, immediately after the film was prepared, the contact angle was 120.2°, which was confirmed to be larger than that of the PDMS film without forming a coating layer, 111.7°, and the contact angle after 1 day was 124.4° and the contact angle after 2 days was It was measured to be 121.2°. As described above, it was confirmed that the prepared film has a contact angle of 120° or more, and thus has oil elution characteristics and at the same time can exhibit water repellency characteristics close to super water repellency.

5 conceptually illustrates a cross-sectional structure of a film according to another aspect of the present invention. As shown, the film according to another aspect of the present invention, a polymer resin 130 and an oil 110, a base layer 100 comprising hydrophilic porous silica particles 150, and a hydrophobic silica on the base layer It is made of a configuration in which the coating layer 200 including the nanoparticles 210 is provided.

The hydrophilic functional group of the hydrophilic porous silica particles contained in the substrate layer may function to provide a fine uneven structure to the surface of the substrate layer by protruding to the surface of the substrate layer, and hydrophobic silica nano applied to the surface of the substrate layer provided with such a fine uneven structure The coating layer containing the particles can provide surface roughness and hydrophobicity to the film surface. As the hydrophilic porous silica particles, as in Example 1 described above, macropore silica particles synthesized by commercial or self-assembly techniques as disclosed in Patent No. 1875454 may be used.

Next, a specific example of manufacturing the film conceptually illustrated in FIG. 5 will be described.

<Example 3>

Preparation of hydrophobic silica nanoparticles

After preparing the commercial silica nanoparticles (Aldrich Chemical), 1 ml of the prepared silica nanoparticles (2 g) and a silane coupling agent (trichlorododecylsilane) were mixed in 40 ml of toluene solvent, and the mixture was heated at 70 degrees Celsius and stirred for 3 hours. The silica nanoparticles were treated with a hydrophobic surface. Next, the treated mixed solution was dried to obtain hydrophobic silica nanoparticle powder.

The SEM image of the hydrophobic silica nanoparticles obtained by the above method is shown in FIG. 6. Hydrophobic silica nanoparticles are approximately 10-20 nm in size, and when coated on the surface of a substrate layer on which hydrophilic porous silica particles and hydrophilic protrusions in a few micrometers are included in a coating solution, surface roughness corresponding to hydrophilic porous silica particles and hydrophilic protrusions Can be expressed as it is on the surface of the coating layer.

<Example 4>

Preparation of a film in which a hydrophobic silica nanoparticle coating layer is formed on a PDMS base layer containing oil and hydrophilic porous silica particles

The PDMS monomer and the curing agent are mixed at a mass ratio of 9:1, and before curing, 0.2 g of hydrophilic porous silica and 0.2 g of silicone oil (100 CS) are added to 2 g of PDMS, followed by uniform mixing, followed by curing for 2 hours at 80 degrees Celsius. A polymer base layer was prepared by treatment.

The coating solution was prepared by dispersing the hydrophobic silica nanoparticle powder prepared according to Example 3 in butanol, but applying 5 g of butanol per 0.2 g of the hydrophobic silica nanoparticle powder.

After spraying the prepared coating solution on the surface of the substrate layer, it was naturally dried for several hours to prepare a film.

Characteristic evaluation

In order to evaluate the water repellent properties of the prepared film, a static water contact angle was measured for the film surface. As shown in FIG. 7, the contact angle was 98° immediately after preparation of the film, and it was measured to be 97° after two spray coatings and 127° after the additional two spray coatings. As described above, it was confirmed that the prepared film has a contact angle of 120° or more, and thus has oil elution characteristics and at the same time can exhibit water repellency characteristics close to super water repellency.

<Comparative Examples 1 to 3>

Comparative Example for the film of Example 4: Preparation of a film in which hydrophobic silica nanoparticle coating layer is formed on the PDMS base layer containing no oil and hydrophilic porous silica particles

Three types of polymers are mixed by mixing PDMS monomer and curing agent in a mass ratio of 9:1, hydrophilic porous silica with respect to 2g of PDMS, 0.05g, 0.075g, and 0.2g, respectively, before curing, and then curing at 80°C for 2 hours. A base layer was prepared. At this time, no oil was added.

After preparing the coating liquid in the same manner as in Example 4, spraying the prepared coating liquid on each of the base layers, followed by natural drying for several hours to prepare Comparative Example 1 (hydrophilic porous silica 0.05 g), Comparative Example 2 (hydrophilic porous silica) 0.075g) and Comparative Example 3 (hydrophilic porous silica 0.2g) were prepared.

For each comparative example, the contact angle was measured after spraying and drying the coating solution twice, and the contact angle was measured after additional two spraying and drying, and the results are shown in FIG. 8.

In the case of the film to which the oil was added from the measurement result of the contact angle in FIG. 8 (Example 4), the synergistic effect of the contact angle was found to be slightly insignificant compared to the film to which the oil was not added (Comparative Examples 1 to 3), but improved water repellency of the film It can be understood that the film of Example 4 can be sufficiently applied as an iSPOBIC film material in that the property and the slip property through surface elution of oil can be realized.

9 conceptually illustrates a cross-sectional structure of a film according to another aspect of the present invention. As shown, the film according to another aspect of the present invention, the base layer 100 comprising a polymer resin 130 and an oil 110, and hydrophobic silica nanoparticles 210 on the base layer It includes a coating layer 200, characterized in that the surface of the substrate layer is provided with a fine uneven structure 170 transferred from paper.

The fine concavo-convex structure provided on the surface of the substrate layer is transferred from the paper surface, and the fine concavo-convex structure of the size of 1 to 100 micrometers of the paper surface as shown in FIG. 10 is confirmed by the SEM of the paper surface. It is made in a shape. The film of the present invention provides a surface roughness and hydrophobicity on the film surface by providing a coating layer containing hydrophobic silica nanoparticles capable of exposing the uneven structure to the surface on the substrate layer on which a fine uneven structure transferred from paper is formed. can do.

The following is a specific example of manufacturing the film conceptually illustrated in FIG. 9.

<Example 5>

The PDMS monomer and the curing agent are mixed at a mass ratio of 9:1, and 0.4 g of silicone oil (100 CS) is uniformly mixed with 1 g of PDMS before curing, poured over paper, and then cured for 2 hours at 80°C. Did. Thereafter, by removing the paper from the cured PDMS, a substrate layer having an uneven structure of the paper surface transferred to the cured PDMS surface was engraved was prepared. 11 schematically shows a method of transferring a fine concavo-convex structure of a paper surface to a substrate layer.

The coating solution was prepared by dispersing the hydrophobic silica nanoparticle powder prepared according to Example 3 in butanol, but applying 5 g of butanol per 0.2 g of the hydrophobic silica nanoparticle powder.

After spraying the prepared coating solution on the surface of the substrate layer, it was naturally dried for several hours to prepare a film.

FIG. 12A shows an SEM image of the surface of a PDMS substrate layer containing the oil with which the fine uneven structure of the paper surface has been transferred during the manufacturing process of the film according to Example 5, and FIG. 12B shows the uneven structure transferred from paper according to Example 5 Shows a SEM image of the film surface on which the hydrophobic silica nanoparticle coating layer is formed on the substrate layer provided with.

<Comparative Example 4>

Example 5 Comparative Example for Film: Preparation of a film having a hydrophobic silica nanoparticle coating layer formed on a PDMS polymer resin base layer that does not contain oil, provided with an uneven structure transferred from paper

A film was prepared under the same conditions as in Example 5, except that no oil was added at the time of manufacturing the base layer.

13A shows an SEM image of the surface of the PDMS substrate layer on which the fine uneven structure of the paper surface is transferred in the process of manufacturing the film according to Comparative Example 4, and FIG. 13B is a substrate provided with the uneven structure transferred from paper according to Comparative Example 4 The SEM image of the film surface on which the hydrophobic silica nanoparticle coating layer is formed is shown.

Characteristic evaluation

The contact angle was measured for Example 5 and Comparative Example 4, and the results are shown in FIGS. 14A and 14B. In the case of the film of Example 5 to which oil was added, it was observed from the electron microscope image shown in FIG. 12A that the oil eluted from the inside of the film to the surface. When the spray coating was performed once, the contact angle was only 87.4 degrees, but when the number of spray coatings was increased up to 5 times, it was confirmed that a high contact angle of 131.2 degrees was reached. The surface of the specimen subjected to spray coating on the surface of the PDMS containing oil is shown in the electron microscope image of FIG. 12B.

In addition, the film of Comparative Example 4, to which no oil was added, was measured at a contact angle of 134.7 degrees with one spray coating, and measurement of contact angle was impossible due to the phenomenon that water droplets rolled over two or more coatings.

Comparative Example 4 film has a higher contact angle synergistic effect than the film of Example 5 containing oil, which is due to the reason that the fine roughness of the surface of the coating layer is slightly offset by the oil component flowing out from the inside of the film of Example 5 It is understood that. Nevertheless, the film of Example 5 is expected to be able to be sufficiently utilized in implementing the iSpobic properties because it exhibits the surface dissolution properties of the oil in addition to the improved water repellency properties close to super water repellency.

As described above, according to the film of the present invention and a method for manufacturing the same, it is possible to provide a film capable of exhibiting oil repellency while exhibiting water repellency close to the super water repellent property at which the contact angle with water on the film surface is 120 degrees or more, In terms of process and cost effectiveness, it is possible to impart surface roughness and hydrophobicity to the film surface in an advantageous manner, and thus has a high commercialization potential. Therefore, it is expected that it can be used for various purposes, such as preventing contamination of optical lenses, automobile windows, electronic devices, fibers, preventing corrosion, preventing freezing, and preventing biological contamination.

100: base layer 110: oil
130: polymer resin 150: hydrophilic porous silica
170: uneven structure 200: coating layer
210: hydrophobic silica nanoparticles 230: hydrophobic porous silica
231: Qigong

Claims (5)

A base layer comprising a polymer resin and oil; And
A coating layer comprising hydrophobic porous silica particles on the substrate layer;
A film having improved water repellency and oil elution characteristics, including a.
A base layer comprising a polymer resin, oil and hydrophilic porous silica particles; And
A coating layer comprising hydrophobic silica nanoparticles on the substrate layer;
A film having improved water repellency and oil elution characteristics, including a.
The method according to claim 1 or 2,
The base layer is a film having improved water repellency and oil elution characteristics, characterized in that it comprises a PDMS resin and at least one oil of silicone oil 100CS or silicone oil 60CS at a mass ratio of 10:1 to 8,
Preparing a base layer precursor by mixing a polymer resin and an oil;
Curing the base layer precursor to form a base layer;
Including the step of applying a coating liquid containing hydrophobic porous silica particles on the base layer and drying to form a coating layer;
The coating solution,
Mixing porous silica particles and a silane coupling agent in a toluene solvent;
Heating and stirring the mixed solution to perform hydrophobic surface treatment of the porous silica particles;
Drying the heated and stirred mixed solution to obtain hydrophobic porous silica particles; And
A method for producing a film having improved water repellency and oil elution characteristics, characterized in that the hydrophobic porous silica particles are redispersed in an alcohol solvent.
Preparing a base layer precursor by mixing polymer resin, oil, and hydrophilic porous particles;
Curing the base layer precursor to form a base layer; And
Includes; coating and drying the coating solution containing the hydrophobic silica nanoparticles on the substrate layer to form a coating layer;
The coating solution,
Mixing silica nanoparticles and a silane coupling agent in a toluene solvent;
Heating and stirring the mixed solution to perform hydrophobic surface treatment of the silica nanoparticles;
Drying the heated and stirred mixed solution to obtain hydrophobic silica nanoparticles; And
A method for producing a film having improved water repellency and oil elution characteristics, characterized in that the hydrophobic silica nanoparticles are produced through a coating liquid production step comprising redispersing the result in an alcohol solvent.

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