Method for preparing hydrophilic light-curable polymer structures with slippery surfaces

Abstract

The present invention relates to a method for preparing hydrophilic light-curable polymer structures with slippery surfaces and, more specifically, to a method for preparing hydrophilic light-curable polymer structures with slippery surfaces, which mimic the surface structure of Nepenthes so as to have a low-viscosity silicone lubricant loaded on the surfaces of porous nanopores, and thus low-adhesion slippery surfaces are implemented.

Description

Method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface

[0001] The present invention relates to a method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface, and more particularly, to a method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface by imitating the surface structure of a bug-catching plant and loading a low-viscosity silicone lubricant on a porous nano-pore surface to realize a low-adhesion slippery surface.

[0002]

[0003] Controlling the adhesion and transport of materials in various states is crucial in many fields, including medicine, engineering, and energy. For example, in medical materials, chemical surface treatments and mimicking microscopic surface structures like cicada wings are used to prevent and control infection from infectious pathogens such as the novel coronavirus and superbugs. Furthermore, controlling surface treatments and surface structures to prevent ice adhesion is also a key issue in the aerospace and energy industries.

[0004] As described above, research on material attachment and transport control through the interaction of various materials and surfaces has had a significant impact on many fields, and thus the importance of research on this has greatly increased.

[0005] Nature has already evolved through a highly advanced process, developing the functions and structures of surfaces for survival. Emulating this wisdom of nature, various functional surface engineering technologies are rapidly developing.

[0006] A DLP (Digital light processing) 3D printer is a 3D printer that forms a model by projecting a mask onto a light-curing resin with high-resolution projection light. It forms a high-precision layered surface in units of planes, and is built around a transparent resin tank on the bottom and a build platform that descends into the resin tank, and builds parts by stacking layers upside down one by one.

[0007] When separating a model manufactured by the above DLP 3D printer from a tray, the release property of the tray is poor, making separation difficult. Therefore, a release agent such as silicone or film is coated and used in the past.

[0008] However, if the release agent is coated as described above, the release agent may be frequently peeled off by the cured resin, which may cause damage during the printing process. In addition, if the coating layer is used repeatedly, the release agent may gradually become contaminated with the release agent, which may cause a deterioration in the quality of the manufactured product.

[0009] Due to the above problems, there is a need for a polymer structure having a slippery surface that allows the sculpture to be easily separated from the tray without causing damage or contamination to the sculpture, and a method for manufacturing the same.

[0010]

[0011] The purpose of the present invention is to provide a method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface that allows the structure to be easily separated from a tray without causing damage or contamination to the structure, in order to solve the above problems.

[0012] In addition, the purpose of the present invention is to provide a method for manufacturing a hydrophilic photo-curable polymer structure having a slippery surface by imitating the surface structure of a bug-catching plant, loading a low-viscosity silicone lubricating material on a porous nano-pore surface, and implementing a low-adhesion slippery surface through surface treatment using light.

[0013] The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the art from the description of the present invention.

[0014]

[0015] In order to achieve the above object, the present invention provides a method for producing a hydrophilic photocurable polymer structure having a slippery surface, comprising the steps of: producing a porous nano-pore surface layer; functionalizing the porous nano-pore surface by forming -OH groups; forming a silane water-repellent coating layer; functionalizing the porous nano-pore surface by forming -OH groups; forming a low-viscosity silicone lubricating coating layer having a viscosity of 5 to 15 cS; and irradiating with light.

[0016] In the present invention, the step of manufacturing the porous nano-pore surface layer is characterized by including the steps of: mixing a hydrophilic photo-curable polymer and a water-soluble polymer; applying the mixture to a substrate; photo-curing the mixture applied to the substrate; and immersing the cured mixture in water to remove the water-soluble polymer.

[0017] In the present invention, the step of mixing the hydrophilic photocurable polymer and the water-soluble polymer is characterized in that the hydrophilic photocurable polymer and the water-soluble polymer are mixed in a weight ratio of 1: (0.5 to 1.5).

[0018] In the present invention, the photocuring step is characterized by UV photocuring with a wavelength of 320 to 400 nm.

[0019] In the present invention, the step of functionalizing the porous nano-pore surface layer by forming an -OH group on the surface is characterized by functionalizing the surface through light treatment.

[0020] In the present invention, the light treatment is characterized by performing ultraviolet ray cleaning (UV Ozone) treatment for 5 to 20 minutes.

[0021] In the present invention, the step of forming the silane water-repellent coating layer is characterized by including the steps of: applying a liquid silane series nanoparticle solution to a glass container; placing a substrate on the upper part of the glass container; heating the glass container to evaporate the silane series nanoparticle solution; and obtaining a substrate having the evaporated nanoparticle solution coated on the surface.

[0022] In the present invention, the silane series nanoparticle solution is characterized in that it is at least one selected from the group consisting of octadecyltrichloro silane (OTS), amino silane, vinyl silane, epoxy silane, methacryloxy silane, sulfide silane, ureide silane, alkyl silane, phenyl silane, oxime silane, isocyanato silane, fluoro silane, bis(trimethylsilyl)amine (HMDZ, hexamethyldisilazane), alkyl silane, and amino silane.

[0023] In the present invention, the step of evaporating the silane series nanoparticle solution is characterized by evaporating at 100 to 120°C for 40 to 60 minutes.

[0024] In the present invention, the step of functionalizing the surface by forming an -OH group on the surface of the silane water-repellent coating layer is characterized by functionalizing the surface by light treatment.

[0025] In the present invention, the light treatment is characterized by performing ultraviolet ray cleaning (UV Ozone) treatment for 5 to 20 minutes.

[0026] In the present invention, the step of forming the low-viscosity silicone lubricating coating layer is characterized by including the step of coating a low-viscosity silicone lubricating material having a viscosity of 5 to 15 cS on the functionalized silane water-repellent coating layer.

[0027] In the present invention, the step of coating the low viscosity silicone lubricating material having a viscosity of 5 to 15 cS on the functionalized silane water-repellent coating layer comprises coating the low viscosity silicone lubricating material at a viscosity of 10 to 20 μL / cm 2 It is characterized by coating with an amount of .

[0028] In the present invention, the light irradiating step is characterized by irradiating using a UV grafting method.

[0029] In the present invention, the light irradiating step is to irradiate ultraviolet rays (UV) with a wavelength of 320 to 400 nm at 5,000 to 14,000 mJ / cm 2 It is characterized by being investigated by the amount of investigation.

[0030]

[0031] By means of solving the above problem, the present invention can provide a method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface that allows the sculpture to be easily separated from a tray without causing damage or contamination to the sculpture.

[0032] In addition, the present invention can provide a method for manufacturing a hydrophilic photo-curable polymer structure having a slippery surface by imitating the surface structure of a bug-catching plant, loading a low-viscosity silicone lubricating material on a porous nano-pore surface, and implementing a low-adhesion slippery surface through surface treatment using light.

[0033] In addition, the present invention can provide a method for manufacturing a hydrophilic photo-curable polymer structure having a slippery surface capable of implementing a slippery low-adhesion surface through simple surface treatment using light.

[0034] In addition, the present invention can provide a method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface that can be applied as a self-cleaning surface by utilizing the slippery surface properties.

[0035] In addition, the present invention can provide a method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface that can be used as a waterproof, antifouling, and anti-icing material and a display material.

[0036] The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

[0037]

[0038] FIG. 1 is a drawing showing a manufacturing process of a hydrophilic photocurable polymer structure having a slippery surface according to the present invention.

[0039] Figure 2 is a drawing showing the results of SEM observation of a polymer according to the mixing ratio of a photocurable polymer and a water-soluble polymer according to the present invention.

[0040] FIG. 3 is a drawing showing the pore size and number of polymers according to the mixing ratio of the photocurable polymer and the water-soluble polymer according to the present invention.

[0041] FIG. 4 is a drawing showing the results of measuring the water contact angle of the surface at each stage of manufacturing a hydrophilic photocurable polymer structure having a slippery surface according to the present invention.

[0042] FIG. 5 is a diagram showing (a) contact angles for various droplets and (b) sliding angles for various droplets of a hydrophilic photocurable polymer structure having a slippery surface according to the present invention.

[0043] FIG. 6 is a diagram showing (a) a state in which a droplet is in contact with the surface of a polymer structure in which no pores are formed according to the present invention, (b) a surface from which the droplet has evaporated, (c) a contact radius over time, and (d) a contact angle over time.

[0044] FIG. 7 is a drawing showing (a) a state in which a droplet is in contact with the surface of a porous polymer structure according to the present invention, (b) a surface from which the droplet has evaporated, (c) a contact radius over time, and (d) a contact angle over time.

[0045] FIG. 8 is a diagram showing (a) a state in which a droplet is in contact with the surface of a hydrophilic photocurable polymer structure having a slippery surface according to the present invention, (b) a surface from which a droplet has evaporated, (c) a contact radius over time, and (d) a contact angle over time.

[0046] FIG. 9 is a drawing showing (a) a 3D printer using a hydrophilic photocurable polymer having a slippery surface according to the present invention and (b) a model manufactured using the 3D printer.

[0047] FIG. 10 is a diagram showing the transmittance according to wavelength of polymer structures manufactured in (a) examples and comparative examples according to the present invention and (b) a hydrophilic photocurable polymer structure having a slippery surface.

[0048] Figure 11 is a drawing showing an anti-fouling test device according to the present invention.

[0049] Figure 12 is a drawing showing the results of SEM observation of polymer structures manufactured in examples and comparative examples according to the present invention.

[0050] FIG. 13 is a diagram showing (a) the adhesive strength over time and (b) the average force per area of ​​polymer structures manufactured in examples and comparative examples according to the present invention.

[0051]

[0052] The terms used in this specification have been selected from widely used, current terms, taking into account the functions of the present invention. However, these terms may vary depending on the intentions of those skilled in the art, precedents, the emergence of new technologies, etc. Furthermore, in certain cases, terms may be arbitrarily selected by the applicant, in which case their meanings will be described in detail in the relevant description of the invention. Therefore, the terms used in this invention should not be defined simply as names, but rather based on their inherent meanings and the overall content of the present invention.

[0053] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and shall not be interpreted in an idealized or overly formal sense unless explicitly defined herein.

[0054] Numerical ranges are inclusive of the values ​​defined in the ranges above. Any maximum numerical limitation given throughout this specification includes any lower numerical limitation, as if that lower numerical limitation were explicitly stated. Any minimum numerical limitation given throughout this specification includes any higher numerical limitation, as if that higher numerical limitation were explicitly stated. Any numerical limitation given throughout this specification will include any better numerical range within the broader numerical range, as if that narrower numerical limitation were explicitly stated.

[0055]

[0056] Hydrophilic photocurable polymer structure with a slippery surface

[0057] The present invention relates to a hydrophilic photocurable polymer structure having a slippery surface.

[0058] The present invention relates to a hydrophilic photocurable polymer structure having a slippery surface, which is fixed by light irradiation, and which comprises a functionalized porous nanoporous surface layer; a functionalized silane water-repellent coating layer; and a low-viscosity silicone lubricating coating layer.

[0059] The hydrophilic photocurable polymer structure having the above slippery surface may include a porous nano-pore surface that effectively retains a relatively large amount of low-viscosity silicone lubricant material compared to a flat surface.

[0060] In the present invention, the functionalized porous nano-pore surface layer may include a porous polymer obtained by immersing a mixture of a hydrophilic photo-curable polymer and a water-soluble polymer in water after photo-curing to remove the water-soluble polymer.

[0061] In the present invention, the hydrophilic photocurable polymer and water-soluble polymer mixture may be a mixture of the hydrophilic photocurable polymer and the water-soluble polymer in a weight ratio of 1:0.5 to 1.5, and preferably a mixture of the hydrophilic photocurable polymer and the water-soluble polymer in a weight ratio of 1:1.

[0062] When mixed in the above weight ratio, a dense nano-pore structure that can contain the most low-viscosity silicone lubricating material may be formed. When the hydrophilic tubular curing polymer and the water-soluble polymer are mixed in a weight ratio of 1:0.5, a problem of reduced durability of the polymer may occur due to the large number of pores, and when mixed in a weight ratio of 1:1.5, pores may not be sufficiently formed, so the low-viscosity silicone lubricating material may not be contained, and thus slippery properties may not be expressed.

[0063] In the present invention, the photocuring may be UV photocuring.

[0064] In the present invention, the photocuring may be curing using light having a wavelength of 320 to 400 nm.

[0065] In the present invention, the functionalized porous nano-pore surface layer may have a pore size of 0.1 to 60 nm. If the pore size is less than 0.1 nm, the low-viscosity silicone lubricant may not be introduced into the pores, and if it exceeds 60 nm, the durability of the polymer structure may be reduced.

[0066] In the present invention, the functionalized porous nano-pore surface layer may have an average pore size of 11 to 18 nm.

[0067] In the present invention, the functionalized porous nano-porous surface layer may have a porosity of 40 to 60% relative to 100% of the surface layer area. If the porosity is less than 40%, the amount of the low-viscosity silicone lubricant contained in the polymer structure may not be sufficient, resulting in a failure to exhibit slippery surface performance. If the porosity exceeds 60%, the durability of the polymer structure may deteriorate.

[0068] In the present invention, the functionalized porous nanoporous surface layer may be surface-functionalized by light treatment. The functionalization may be a water-repellent coating to prevent water droplets from pinning and slipping, as the nanoporous surface becomes hydrophilic.

[0069] In the present invention, the light treatment may be ultraviolet (UV) ozone treatment. The ultraviolet (UV) ozone treatment may be a pretreatment step for surface functionalization prior to water-repellent coating. The ultraviolet (UV) ozone treatment may induce chemical bonding with silane (-Silane) nanoparticles to form -OH groups.

[0070] In the present invention, the light treatment may be performed for 5 to 20 minutes. If the light treatment is performed for less than 5 minutes, -OH groups may not be formed on the surface layer, and if the light treatment is performed for more than 20 minutes, the shape of the surface may be deformed due to strong heat and light energy.

[0071] In the present invention, the functionalized porous nano-pore surface layer may have an -OH group formed thereon.

[0072] In the present invention, the functionalized silane water-repellent coating layer may include silane-based nanoparticles.

[0073] The above silane water-repellent coating layer may be formed by applying a liquid silane series nanoparticle solution to a beaker, placing a specimen on the upper part of the beaker, and then evaporating the nanoparticles in a temperature environment of 100 to 120°C for 40 to 60 minutes to coat the nanoparticles on the surface.

[0074] In the present invention, the silane-based nanoparticles may be at least one selected from the group consisting of octadecyltrichloro silane (OTS), amino silane, vinyl silane, epoxy silane, methacryloxy silane, sulfide silane, ureide silane, alkyl silane, phenyl silane, oxime silane, isocyanato silane, fluoro silane, bis(trimethylsilyl)amine (HMDZ, hexamethyldisilazane), alkyl silane, and amino silane, but are not limited thereto.

[0075] In the present invention, the functionalized silane water-repellent coating layer may have a surface functionalized by light treatment.

[0076] The above functionalization may be a secondary functionalization treatment on the water-repellent coated surface to form -OH groups for chemical bonding with a low-viscosity silicone lubricant material to be coated later.

[0077] In the present invention, the light treatment may be an ultraviolet cleaning (UV Ozone) treatment.

[0078] In the present invention, the light treatment may be performed for 5 to 20 minutes. If the light treatment is performed for less than 5 minutes, -OH groups may not be formed on the surface layer, and if the light treatment is performed for more than 20 minutes, the shape of the surface may be deformed due to strong heat and light energy.

[0079] In the present invention, the functionalized silane water-repellent coating layer may have an -OH group formed thereon.

[0080] In the present invention, the low-viscosity silicone lubricating coating layer may include a low-viscosity silicone lubricating material of 5 to 15 cS. If the viscosity exceeds 15 cS, slippery surface properties may not be realized due to high viscosity, and if it is less than 5 cS, viscosity may not appear, so slippery surface properties exhibiting effects such as a low sliding angle on water and droplet aggregation may not be realized.

[0081] In the present invention, the low viscosity silicone lubricating coating layer may have a surface tension of 18 to 23 mN / m.

[0082] In the present invention, the light irradiation may be UV grafting. Through the UV grafting light irradiation, the porous surface layer and the low-viscosity silicone lubricating coating layer may be chemically bonded to form a polymer brush on the porous surface layer. The polymer brush formed as described above may exhibit excellent slipperiness and thereby exhibit a coagulation phenomenon of droplets.

[0083] In the present invention, the light irradiation is ultraviolet (UV) rays of 5,000 to 14,000 mJ / cm 2 It may have been investigated with a dose of 5,000 mJ / cm of the above ultraviolet rays. 2 If the irradiation dose is less than 14,000 mJ / cm, -OH groups for polymer brush formation may not be formed on the surface layer. 2 If the irradiation exceeds the irradiation amount, the shape of the surface layer may be deformed due to strong heat and light energy.

[0084] In the present invention, the light irradiation is 5,000 to 14,000 mJ / cm of light having a wavelength of 320 to 400 nm. 2 It may have been investigated by the amount of investigation.

[0085] In the present invention, the surface of the polymer structure may exhibit a water contact angle of 80 to 100°.

[0086] In the present invention, the surface of the polymer structure may exhibit a water sliding angle of 0.4 to 1.2 °.

[0087] In the present invention, the surface of the polymer structure may exhibit an oil contact angle of 21 to 32°. The polymer structure may exhibit high contact angles and sliding angles for various droplets including milk, FC oil, olive oil, and honey.

[0088] The hydrophilic photocurable polymer structure having the above-described slippery surface may be capable of digital patterning, as shown in Fig. 9, because it includes a photocurable material. The digitally patterned polymer structure may exhibit a liquid pattern only on its surface, preventing water from wetting. As described above, a desired shape can be created, and the flow control of the droplets may be possible.

[0089] The present invention relates to a release film for 3D printing, comprising a hydrophilic photocurable polymer structure having the slippery surface.

[0090] In the present invention, the 3D printing may be a DLP print.

[0091] The present invention relates to a waterproof, anti-fouling, and anti-icing material comprising a hydrophilic photo-curable polymer structure having the slippery surface described above. The waterproof, anti-fouling, and anti-icing material may exhibit properties that allow ice formed on the surface to slide smoothly. The material may be applicable as an anti-icing surface in extreme environments.

[0092] The present invention relates to a display material comprising a hydrophilic photocurable polymer structure having the slippery surface.

[0093] The above polymer structure may be utilized in a QR code exposed to an external environment, such as a channel structure required for drug delivery and a self-cleaning property.

[0094]

[0095] Method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface

[0096] The present invention relates to a method for producing a hydrophilic photocurable polymer structure having a slippery surface.

[0097] The present invention relates to a method for producing a hydrophilic photocurable polymer structure having a slippery surface, comprising the steps of: producing a porous nanoporous surface layer; functionalizing the porous nanoporous surface layer; forming a silane water-repellent coating layer; functionalizing the silane water-repellent coating layer; forming a low-viscosity silicone lubricating coating layer; and irradiating with light.

[0098] The method for manufacturing a hydrophilic photocurable polymer structure having the above slippery surface may include manufacturing a porous nano-pore surface that effectively retains a relatively large amount of a low-viscosity silicone lubricant material compared to a flat surface.

[0099] In the present invention, the step of manufacturing the porous nano-pore surface layer may include the steps of: mixing a hydrophilic photo-curable polymer and a water-soluble polymer; applying the mixture to a substrate; photo-curing the mixture applied to the substrate; and immersing the cured mixture in water to remove the water-soluble polymer.

[0100] In the present invention, the step of mixing the hydrophilic photocurable polymer and the water-soluble polymer may be to mix the hydrophilic photocurable polymer and the water-soluble polymer in a weight ratio of 1:0.5 to 1.5.

[0101] When mixed in the above weight ratio, a dense nano-pore structure that can contain the most low-viscosity silicone lubricating material may be formed. When the hydrophilic tubular curing polymer and the water-soluble polymer are mixed in a weight ratio of 1:0.5, a problem of reduced durability of the polymer may occur due to the large number of pores, and when mixed in a weight ratio of 1:1.5, pores may not be sufficiently formed, so the low-viscosity silicone lubricating material may not be contained, and thus slippery properties may not be expressed.

[0102] In the present invention, the photocuring step may be UV photocuring.

[0103] In the present invention, the photocuring step may be curing using light having a wavelength of 320 to 400 nm.

[0104] In the present invention, the step of functionalizing the porous nanopore surface layer may be functionalizing the surface through light treatment. The functionalization may be a water-repellent coating to prevent water droplets from pinning and slipping by making the nanopore surface hydrophilic.

[0105] In the present invention, the light treatment may be ultraviolet (UV) ozone treatment. The ultraviolet (UV) ozone treatment may be a pretreatment step for surface functionalization prior to water-repellent coating. The ultraviolet (UV) ozone treatment may induce chemical bonding with silane (-Silane) nanoparticles to form -OH groups.

[0106] In the present invention, the light treatment may be performed for 5 to 20 minutes. If the light treatment is performed for less than 5 minutes, -OH groups may not be formed on the surface layer, and if the light treatment is performed for more than 20 minutes, the shape of the surface may be deformed due to strong heat and light energy.

[0107] In the present invention, the step of forming the silane water-repellent coating layer may include the steps of: applying a liquid silane series nanoparticle solution to a glass container; placing the substrate on the upper part of the glass container; heating the glass container to evaporate the silane series nanoparticle solution; and obtaining a substrate having the evaporated nanoparticle solution coated on the surface.

[0108] In the present invention, the silane series nanoparticle solution may be at least one selected from the group consisting of octadecyltrichloro silane (OTS), amino silane, vinyl silane, epoxy silane, methacryloxy silane, sulfide silane, ureide silane, alkyl silane, phenyl silane, oxime silane, isocyanato silane, fluoro silane, bis(trimethylsilyl)amine (HMDZ, hexamethyldisilazane), alkyl silane, and amino silane.

[0109] In the present invention, the step of evaporating the silane series nanoparticle solution may be evaporating at 100 to 120°C for 40 to 60 minutes.

[0110] In the present invention, the step of functionalizing the silane water-repellent coating layer may be to functionalize the surface by light treatment. The functionalization may be to form -OH groups for chemical bonding with a low-viscosity silicone lubricating material to be coated later by performing a secondary functionalization treatment on the water-repellent coated surface.

[0111] In the present invention, the light treatment may be an ultraviolet cleaning (UV Ozone) treatment.

[0112] In the present invention, the light treatment may be performed for 5 to 20 minutes. In the present invention, the light treatment may be performed for 5 to 20 minutes. If the light treatment is performed for less than 5 minutes, -OH groups may not be formed on the surface layer, and if it is performed for more than 20 minutes, the shape of the surface may be deformed due to strong heat and light energy. Through the functionalization, -OH groups may be formed on the silane water-repellent coating layer.

[0113] In the present invention, the step of forming the low-viscosity silicone lubricating coating layer may include a step of coating a low-viscosity silicone lubricating material on the functionalized silane water-repellent coating layer.

[0114] In the present invention, the low viscosity silicone lubricating material may have a viscosity of 5 to 15 cS. If the viscosity exceeds 15 cS, slippery surface properties may not be realized due to high viscosity, and if it is less than 5 cS, viscosity may not be displayed, so slippery surface properties such as a low sliding angle on water and droplet aggregation may not be realized.

[0115] In the present invention, the step of coating the low-viscosity silicone lubricating material is to coat the low-viscosity silicone lubricating material at 10 to 20 μL / cm 2 It may be coated with an amount of 10 μL / cm of the silicone lubricating material. 2 If the coating amount is less than 20 μL / cm, the slippery surface properties may not be realized. 2 If the coating is applied in an amount exceeding , the problem of contaminating the surface of the porous surface layer may occur.

[0116] In the present invention, the light irradiation step may be performed using an ultraviolet (UV) grafting method. Through the UV grafting light irradiation, the porous surface layer and the low-viscosity silicone lubricating coating layer may be chemically bonded to form a polymer brush on the porous surface layer. The polymer brush formed as described above may exhibit excellent slipperiness and thereby exhibit a coagulation phenomenon of droplets.

[0117] In the present invention, the light irradiating step is to irradiate ultraviolet rays (UV) at 5,000 to 14,000 mJ / cm 2 It may be investigated with a dose of 5,000 mJ / cm of the above ultraviolet rays. 2 If the irradiation dose is less than 14,000 mJ / cm, -OH groups for polymer brush formation may not be formed on the surface layer. 2 If the irradiation exceeds the irradiation amount, the shape of the surface layer may be deformed due to strong heat and light energy.

[0118] In the present invention, the light irradiating step is irradiating light with a wavelength of 320 to 400 nm at 5,000 to 14,000 mJ / cm 2 It may be investigated by the amount of investigation.

[0119]

[0120] Example

[0121] Hereinafter, examples of the present invention will be described in detail, but it is obvious that the present invention is not limited to the following examples.

[0122] The advantages and features of the present invention, and the methods for achieving them, will become clearer with reference to the embodiments described in detail below. However, the present invention is not limited to the embodiments disclosed below and may be implemented in various different forms. The embodiments are provided solely to ensure that the disclosure of the present invention is complete and to fully inform those skilled in the art of the scope of the invention. The present invention is defined solely by the scope of the claims.

[0123]

[0124] <Example 1> Porous polymer structure

[0125] Polyethylene glycol (PEG), a water-soluble material, was mixed with a photocurable resin of the polyurethane acrylate series, a photocurable material, at a weight ratio (wt%) of 1:1. After curing the resin, it was immersed in water for 1 hour, and then dried in an oven at 70°C for 1 hour to produce a polymer structure with formed nanopores. (Step 1)

[0126]

[0127] <Example 2> Hydrophilic photocurable polymer structure having a slippery surface

[0128] The polymer structure manufactured in Example 1 was irradiated with UV-B light having a wavelength of 184 to 255 nm for 15 minutes to form a hydroxyl group (step 2).

[0129] Afterwards, octadecyltrichloro silane (OTS) was vapor-deposited on a heating plate at 120°C for 40 minutes to form a water-repellent coating layer in which the hydroxyl group formed on the surface of the polymer structure and the OTS were combined. (step 3)

[0130] The water-repellent coating layer was treated with UV ozone for 20 minutes to form hydroxyl groups on the surface once more (step 4).

[0131] 10 μL / cm of silicone oil was applied on the above coating layer. 2 Drop coating was performed with the capacity of (step 5).

[0132] Afterwards, UV-B light with a wavelength of 205 to 340 nm was applied at 20 mJ / cm 2 A hydrophilic photo-curable polymer structure having a slippery surface formed by irradiating the porous surface with the silicone oil for 15 minutes to induce bonding between the porous surface and the silicone oil, thereby forming a PDMS brush filled with the silicone oil in the surface layer was manufactured (step 6).

[0133]

[0134] <Comparative Example 1-1>

[0135] It was manufactured in the same manner as Example 1, except that the water-soluble material, polyethylene glycol, and the photocurable resin of the polyurethane acrylate series were mixed in a weight ratio (wt%) of 10:1.

[0136]

[0137] <Comparative Example 1-2>

[0138] It was manufactured in the same manner as Example 1, except that the water-soluble material, polyethylene glycol, and the photocurable resin of the polyurethane acrylate series were mixed in a weight ratio (wt%) of 2:1.

[0139]

[0140] Comparative Example 2

[0141] A polymer structure having a conventional flat surface was manufactured.

[0142]

[0143] <Experimental Example 1> SEM Analysis

[0144] The surface of the polymer structure manufactured in Example 1 and Comparative Examples 1-1 to 1-2 was analyzed by SEM, and the results are shown in Fig. 2.

[0145] As shown in Fig. 2, no nanopores were formed on the surface of the polymer structure manufactured by mixing the water-soluble material and photocurable resin of Comparative Example 1-1 at a weight ratio of 10:1. Very small-sized nanopores were formed on the surface of the polymer structure manufactured by mixing the water-soluble material and photocurable resin of Comparative Example 1-2 at a weight ratio of 2:1.

[0146] On the other hand, on the surface of the polymer structure manufactured by mixing the water-soluble material and photocurable resin of Example 1 in a weight ratio of 1:1, nanopores of a larger size were formed compared to the nanopores formed in Comparative Example 1-2.

[0147] Through the above results, it was confirmed that when a polymer structure was manufactured by mixing a water-soluble material and a photocurable resin in a weight ratio of 1:1 according to the conditions limited to the method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface according to the present invention, large-sized nanopores were formed at a high density and a low-viscosity silicone lubricating material could be included.

[0148]

[0149] <Experimental Example 2> Measurement of formed nanopores

[0150] The size and number of nanopores formed on the surface of the polymer structures manufactured in Example 1 and Comparative Examples 1-2 were measured, and the results are shown in Fig. 3.

[0151] As shown in Fig. 3, the polymer structure of Comparative Example 1-2 contained the largest number of nanopores with a size of 0 to 10 nm, and some nanopores with a size of 11 to 20 nm.

[0152] In contrast, the polymer structure of Example 1 was found to contain the largest number of nanopores with a size of 11 to 20 nm. It contained relatively few nanopores with a size of 0 to 10 nm, and also contained some nanopores with a size of 21 to 60 nm.

[0153] Through the above results, it was confirmed that when a polymer structure was manufactured by mixing a water-soluble material and a photocurable resin in a weight ratio of 1:1 according to the conditions limited to the method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface according to the present invention, large-sized nanopores were formed at a high density and a low-viscosity silicone lubricating material could be included.

[0154]

[0155] <Experimental Example 3> Measurement of water contact angle on the surface at each manufacturing stage

[0156] The water contact angle of the surface formed in each manufacturing step of the above Examples 1 and 2 was measured, and the results are shown in Fig. 4.

[0157] As shown in Fig. 4, the water contact angle was found to increase from step 1 of the above-described Example 1 until the silane water-repellent coating layer was formed in step 3 of the above-described Example 2. When the water-repellent coating layer in step 4 of the above-described Example 2 was functionalized, the water contact angle was found to decrease significantly, but after step 5 of forming a lubricating coating layer on the water-repellent coating layer and step 6 of irradiating with light, the water contact angle was found to increase.

[0158] Through the above results, it was confirmed that a slippery surface appears in the manufactured polymer structure only when the manufacturing process is carried out including all the steps limited in the method for manufacturing a hydrophilic photocurable polymer structure having a slippery surface according to the present invention.

[0159]

[0160] <Experimental Example 4> Measurement of contact angle and sliding angle of various droplets

[0161] Water, milk, FC oil, olive oil, and honey were dropped on the surface of the polymer structure manufactured in Example 2, and the contact angle and sliding angle for each droplet were measured, and the results are shown in Fig. 5.

[0162] As shown in Fig. 5, the polymer structure of Example 2 was confirmed to exhibit excellent water repellency with a contact angle of 97.0 ± 2.2 ° and a sliding angle of 0.8 ± 0.4 ° for water. In addition, when considering the characteristics of each droplet, it exhibited superior water repellency to milk, FC oil, olive oil, and honey compared to a conventional film.

[0163] Through the above results, it was confirmed that the hydrophilic photocurable polymer structure having a slippery surface according to the present invention has low adhesion and slipperiness, exhibiting excellent water repellency for various droplets.

[0164]

[0165] <Experimental Example 5> Analysis of sliding performance

[0166] After dropping 2 μL of colloidal solution onto the polymer structures manufactured in Comparative Example 2 and Examples 1 to 2, it was evaporated, and the contact area and contact angle were repeatedly measured over time until complete evaporation, and the results are shown in Figures 6 to 8.

[0167] As shown in Fig. 6, the polymer structure of Comparative Example 2 exhibited a contact area of ​​1.2 to 0.4 mm and a contact angle of 100 to 25° until the solution completely evaporated, and the solution appeared to evaporate without slipping.

[0168] In addition, as shown in Fig. 7, the porous polymer structure of Example 1 exhibited a high contact area and low contact angle of 1.2 to 1.6 mm and 45 to 10°, respectively, compared to Comparative Example 2, until the solution completely evaporated, and the solution was found to evaporate without slipping.

[0169] In addition, as shown in Fig. 8, the polymer structure having the slippery surface of Example 2 exhibited a contact area of ​​1.2 to 0.4 mm and a contact angle of 110 to 30° until the solution completely evaporated, and the phenomenon of the solution slipping and coagulating as it evaporated on the slippery surface was dramatically observed.

[0170] Through the above results, it was confirmed that the hydrophilic photocurable polymer structure having a slippery surface according to the present invention forms polymer brushes on the surface layer through light irradiation, and exhibits slipperiness and a coagulation phenomenon of droplets through this, which are not observed in conventional planar polymer structures and porous polymer structures.

[0171]

[0172] <Experimental Example 6> Permeability Analysis

[0173] The transmittance according to wavelength of the polymer structures manufactured in Comparative Example 2 and Examples 1 to 2 was analyzed, and the results are shown in Fig. 10.

[0174] As shown in Fig. 10 (a), the polymer structure having a slippery surface of Example 2 exhibited high transmittance over a wide wavelength range compared to the polymer structures of Comparative Example 2 and Example 1.

[0175] In addition, as shown in Fig. 10 (b), the polymer structure having a slippery surface of Example 2 exhibited high transparency when visually observed in an outdoor environment.

[0176] Through the above results, it was confirmed that the hydrophilic photocurable polymer structure having a slippery surface according to the present invention exhibits high transmittance over a wide wavelength range, and thus exhibits high transparency, and thus can be utilized as a display surface, etc.

[0177]

[0178] <Experimental Example 7> SEM analysis of the surface after the anti-icing experiment

[0179] After conducting an anti-icing experiment as shown in Fig. 11 using the polymer structures manufactured in Comparative Example 2 and Examples 1 to 2, the structures were analyzed using SEM, and the results thereof are shown in Fig. 12.

[0180] As shown in Fig. 12, on the surface of the polymer structure having the slippery surface of Example 2, a slipping trace of ice formed on the surface was observed, which did not appear on the surfaces of the polymer structures of Comparative Example 2 and Example 1.

[0181] Through the above results, it was confirmed that the hydrophilic photocurable polymer structure having a slippery surface according to the present invention exhibits high slipperiness even on solids such as ice, and thus can be utilized as an anti-icing material, etc.

[0182]

[0183] <Experimental Example 8> Measurement of adhesive strength and force per area after anti-icing experiment

[0184] After conducting an anti-icing experiment as shown in Fig. 11 using the polymer structures manufactured in Comparative Example 2 and Examples 1 to 2, the adhesive strength and force per area of ​​the structures over time were measured, and the results thereof are shown in Fig. 13.

[0185] As shown in Fig. 13 (a), the polymer structure having a slippery surface of Example 2 exhibited very low adhesion compared to the polymer structures of Comparative Example 2 and Example 1 due to slipperiness on ice.

[0186] In addition, as shown in Fig. 13 (b), the force per area of ​​the polymer structure having the slippery surface of Example 2 was found to be 4.99 ± 2.82 kPa, which was very low compared to the force per area of ​​the polymer structures of Comparative Example 2 and Example 1.

[0187] Through the above results, it was confirmed that the hydrophilic photocurable polymer structure with a slippery surface according to the present invention exhibits high slipperiness even on solids such as ice and is easy to process with low force per area. Accordingly, it was confirmed that it can be utilized as an anti-icing material in various fields.

Claims

1. A step of manufacturing a porous nano-pore surface layer; A step of functionalizing the porous nanopore surface by forming an -OH group; Step of forming a silane water-repellent coating layer; A step of functionalizing the surface of the silane water-repellent coating layer by forming an -OH group; A step of forming a low viscosity silicone lubricating coating layer having a viscosity of 5 to 15 cS; and A method for producing a hydrophilic photocurable polymer structure having a slippery surface, comprising a step of irradiating light.

2. In paragraph 1, The step of manufacturing the above porous nano-pore surface layer is: A step of mixing a hydrophilic photocurable polymer and a water-soluble polymer; A step of applying the above mixture to a substrate; A step of photo-curing the mixture applied to the substrate; and A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by comprising a step of immersing the cured mixture in water to remove a water-soluble polymer.

3. In paragraph 2, The step of mixing the above hydrophilic photocurable polymer and water-soluble polymer is: A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by mixing the hydrophilic photocurable polymer and the water-soluble polymer in a weight ratio of 1: (0.5 to 1.5).

4. In paragraph 2, The above photo-curing step is: A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by being cured with UV light having a wavelength of 320 to 400 nm.

5. In paragraph 1, The step of functionalizing the porous nano-pore surface layer by forming -OH groups on the surface is as follows. A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by functionalizing the surface through phototreatment.

6. In paragraph 5, The above light treatment is, A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by performing ultraviolet irradiation (UV ozone) treatment for 5 to 20 minutes.

7. In paragraph 1, The step of forming the above silane water-repellent coating layer is: A step of applying a liquid silane series nano particle solution to a glass container; A step of placing a substrate on the upper part of the glass container; A step of heating the glass container to evaporate the silane series nano particle solution; and A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by comprising a step of obtaining a substrate having the evaporated nanoparticle solution coated on the surface.

8. In paragraph 7, The above silane series nano particle solution is, A method for producing a hydrophilic photo-curable polymer structure having a slippery surface, characterized in that the polymer is at least one selected from the group consisting of octadecyltrichloro silane (OTS), amino silane, vinyl silane, epoxy silane, methacryloxy silane, sulfide silane, ureide silane, alkyl silane, phenyl silane, oxime silane, isocyanato silane, fluoro silane, bis(trimethylsilyl)amine (HMDZ, hexamethyldisilazane), alkyl silane, and amino silane.

9. In paragraph 7, The step of evaporating the above silane series nano particle solution is: A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by evaporating at 100 to 120° C. for 40 to 60 minutes.

10. In paragraph 1, The step of functionalizing the surface of the silane water-repellent coating layer by forming an -OH group is as follows. A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized in that the surface is functionalized by phototreatment.

11. In paragraph 10, The above light treatment is, A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by performing ultraviolet irradiation (UV ozone) treatment for 5 to 20 minutes.

12. In paragraph 1, The step of forming the above low viscosity silicone lubricating coating layer is: A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by comprising a step of coating a low-viscosity silicone lubricating material having a viscosity of 5 to 15 cS on the functionalized silane water-repellent coating layer.

13. In paragraph 12, The step of coating a low viscosity silicone lubricating material having a viscosity of 5 to 15 cS on the functionalized silane water-repellent coating layer is as follows. The above low viscosity silicone lubricating material is 10 to 20 μL / cm 2 A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by coating it with an amount of .

14. In paragraph 1, The above light irradiating step is: A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by irradiating with UV grafting.

15. In paragraph 1, The above light irradiating step is: Ultraviolet (UV) rays with a wavelength of 320 to 400 nm at 5,000 to 14,000 mJ / cm 2 A method for producing a hydrophilic photocurable polymer structure having a slippery surface, characterized by being irradiated with a radiation dose.

Images