WO2023195625A1 - Antifouling coating film and manufacturing method therefor - Google Patents

Antifouling coating film and manufacturing method therefor Download PDF

Info

Publication number
WO2023195625A1
WO2023195625A1 PCT/KR2023/002104 KR2023002104W WO2023195625A1 WO 2023195625 A1 WO2023195625 A1 WO 2023195625A1 KR 2023002104 W KR2023002104 W KR 2023002104W WO 2023195625 A1 WO2023195625 A1 WO 2023195625A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
hydrophilic
hydrophobic
coating film
antifouling coating
Prior art date
Application number
PCT/KR2023/002104
Other languages
French (fr)
Korean (ko)
Inventor
이민경
고영덕
김광주
김진주
임명혁
Original Assignee
삼성전자주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 삼성전자주식회사 filed Critical 삼성전자주식회사
Publication of WO2023195625A1 publication Critical patent/WO2023195625A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
    • B05D3/0453—After-treatment
    • B05D3/046—Curing or evaporating the solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives

Definitions

  • the present invention relates to an antifouling coating film and a method of manufacturing the same, and more specifically, to a hybrid coating film having both hydrophilic and hydrophobic properties and a method of manufacturing the same.
  • a coating film that has both a hydrophilic and hydrophobic surface can improve cleaning properties because contaminants attached to the surface of the substrate become unstable.
  • hydrophobic fine particles are impregnated into a hydrophilic coating film.
  • hydrophobic fine particles are not easy to float on the surface and are randomly distributed, making it difficult to create a uniform surface.
  • the purpose of the present invention to solve the above problems is to provide an antifouling coating film that maximizes cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment.
  • the aim is to provide a solution-based, simple and economical method of manufacturing an antifouling coating film.
  • a method for manufacturing an antifouling coating film includes preparing an emulsion mixed coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution; A coating solution application step of applying the emulsion mixed coating solution to the surface of the substrate; Inducing a phase change by natural evaporation; and a drying step.
  • the method of manufacturing an antifouling coating film according to an embodiment of the present invention may further include a primer application step of applying a primer to the surface of the substrate before the step of applying the coating solution.
  • the hydrophilic solution includes a hydrophilic polymer
  • the hydrophilic polymer is polyvinyl alcohol (PVA), polyvinylpyridine (PVP), , polyacrylic acid (PAA), polyacrylamide, polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine. You can.
  • the hydrophilic solution includes a hydrophilic solvent
  • the hydrophilic solvent may include at least one of water, alcohol, acetone, and methanol.
  • the hydrophobic solution includes a hydrophobic polymer, and the hydrophobic polymer is fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, and polytetra. It may include at least one of fluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
  • the hydrophobic solution includes a hydrophobic solvent
  • the hydrophobic solvent is hydrofluoroether (HFE), fluoroethylene vinyl ether (FEVE), It may contain at least one of hexane, benzene, and toluene.
  • the emulsion mixed coating solution may include, in weight percent, a hydrophilic solution: 90 to 99%, the remaining hydrophobic solution, and other unavoidable impurities.
  • the emulsion mixed coating solution may further include at least one of SiO 2 nanoparticles and an antistatic agent.
  • the substrate may include at least one of electrogalvanized steel sheet (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). there is.
  • EMI electrogalvanized steel sheet
  • PP polypropylene
  • SAN styrene-acrylonitrile
  • the coating liquid application step may be performed by a wet-on-wet or dry-on-dry method.
  • the drying step may be performed at 60 to 150° C. for 10 to 30 minutes.
  • the antifouling coating film according to an embodiment of the present invention includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
  • the hydrophilic polymer is polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide ( It may include at least one of polyacrylamide), polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine.
  • the hydrophobic polymer is at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane. It can contain one.
  • the antifouling coating film according to an embodiment of the present invention may further include at least one of SiO 2 nanoparticles and an antistatic agent.
  • a panel for home appliances includes: a substrate; and an antifouling coating film provided on the top of the substrate, wherein the antifouling coating film includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
  • the substrate may include at least one of electrogalvanized steel sheet (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). .
  • EMI electrogalvanized steel sheet
  • PP polypropylene
  • SAN styrene-acrylonitrile
  • the hydrophilic polymer is polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), and polyacrylic acid. It may include at least one of amide, polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine.
  • the hydrophobic polymer is fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane. It may include at least one of:
  • the antifouling coating film may further include at least one of SiO 2 nanoparticles and an antistatic agent.
  • an antifouling coating film that maximizes cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment.
  • FIG. 1 is a flowchart of a method for manufacturing an antifouling coating film according to an example of the present invention.
  • Figure 2 is a schematic diagram of an emulsion mixed coating solution according to an example of the present invention.
  • Figure 3 is a flowchart showing the process of forming an antifouling coating film according to an example of the present invention.
  • Figure 4 is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared by the Dry on Dry method with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
  • SEM scanning electron microscope
  • Figure 5 is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared by the Wet on Wet method as an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
  • SEM scanning electron microscope
  • Figure 6 is a photograph taken at 10,000 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
  • SEM scanning electron microscope
  • Figure 7 is a photograph imaged with a 3D microscope of an uncoated substrate after contamination in an environment of 10°C and 80% humidity.
  • Figure 8 is a photograph imaged with a 3D microscope of a contaminated uncoated substrate in an environment of 10°C and 80% humidity after cleaning it with a cotton cloth.
  • Figure 9 is a photograph imaged with a 3D microscope of an antifouling coating substrate after contamination in an environment of 10°C and 80% humidity.
  • Figure 10 is a photograph imaged with a 3D microscope of a contaminated antifouling coating substrate in an environment of 10°C and 80% humidity after cleaning it with a cotton cloth.
  • a method for manufacturing an antifouling coating film includes preparing an emulsion mixed coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution; A coating solution application step of applying the emulsion mixed coating solution to the surface of the substrate; Inducing a phase change by natural evaporation; and a drying step.
  • the present invention relates to a polymer or polymer composite coating film having both a hydrophilic and hydrophobic surface.
  • a coating film that has both a hydrophilic and hydrophobic surface has excellent cleaning properties. This is because when contaminants come into contact with both the hydrophilic and hydrophobic parts of the coating film, they become unstable and can easily be removed by air currents, moisture, vibration, etc. In addition, since the hydrophilic material on the surface of the coating film removes static electricity, the adhesion of contaminants due to electrification is suppressed and the contamination prevention effect is excellent. Therefore, the antifouling coating film according to the present invention can be applied to parts that can be easily contaminated, such as panels of home appliances such as air conditioners, air purifiers, and cross fans.
  • a hybrid coating film having both hydrophilic and hydrophobic properties is implemented by applying an emulsion mixed coating solution to the surface of the substrate and then inducing a phase change in the internal particles. Therefore, it is a different technique from the phase-inversion method, in which a polymer solution is applied on a substrate, the solvent is evaporated, and then the polymer solution is immersed in a non-solvent.
  • the phase inversion method uses a method in which the structure of the film is formed through the difference in substitution rate between the solvent and the non-solvent.
  • a method for manufacturing an antifouling coating film includes preparing an emulsion mixed coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution; A coating solution application step of applying the emulsion mixed coating solution to the surface of the substrate; Inducing a phase change by natural evaporation; and a drying step.
  • the method of manufacturing an antifouling coating film according to an embodiment of the present invention may further include a primer application step of applying a primer to the surface of the substrate before the step of applying the coating solution.
  • FIG. 1 is a flowchart of a method for manufacturing an antifouling coating film according to an example of the present invention.
  • the method of manufacturing an antifouling coating film according to an example of the present invention may include a series of steps for preparing a coating solution, applying the coating solution, inducing a phase change, and drying.
  • an emulsion mixed coating solution in which a hydrophobic solution is dispersed in a hydrophilic solution can be prepared.
  • the hydrophilic solution can be prepared by dissolving a hydrophilic polymer in a hydrophilic solvent
  • the hydrophobic solution can be prepared by dissolving a hydrophobic polymer in a hydrophobic solvent.
  • Figure 2 is a schematic diagram of an emulsion mixed coating solution according to an example of the present invention.
  • the emulsion mixed coating solution according to an example of the present invention has hydrophobic solution particles uniformly dispersed in a hydrophilic solution.
  • mixing equipment such as sonication or homogenizer can be applied so that the hydrophobic solution particles can be uniformly dispersed in the hydrophilic solution.
  • Sonication can perform the role of mixing hydrophobic solution particles in a hydrophilic solution and splitting hydrophobic solution particles that are to be fused using ultrasonic waves.
  • the homogenizer may serve to mechanically mix hydrophobic solution particles.
  • the hydrophilic solution includes a hydrophilic polymer, and the hydrophilic polymer includes polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, It may include at least one of polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine. However, it is not limited to this, and polar polymers can also be used. Meanwhile, considering that the upper limit of the hydrophilic solution concentration is 15%, it is desirable to select a hydrophilic polymer with a solubility in the hydrophilic solvent of 15% or more. Here, solubility means the maximum amount of solute that can be dissolved in a solvent.
  • the hydrophilic solution includes a hydrophilic solvent, and the hydrophilic solvent may include at least one of water, alcohol, acetone, and methanol. However, it is not limited to this, and a polar solvent may be used. At this time, it is desirable to select a hydrophilic solvent in which more than 15% of the hydrophilic polymer can be dissolved.
  • the hydrophilic solution is preferably prepared at a concentration of 3 to 15%.
  • the concentration of the hydrophilic solution is too low, the area fraction of the hydrophilic region of the antifouling coating film may become too low, resulting in poor cleaning properties. However, if the concentration of the hydrophilic solution is too high, the viscosity of the solution may increase and productivity may decrease.
  • the hydrophobic solution includes a hydrophobic polymer, and the hydrophobic polymer includes at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane. can do. However, it is not limited to this, and non-polar polymers can also be used. Meanwhile, considering that the upper limit of the hydrophobic solution concentration is 15%, it is desirable to select a hydrophobic polymer with a solubility in the hydrophobic solvent of 15% or more. Here, solubility means the maximum amount of solute that can be dissolved in a solvent.
  • the hydrophobic solution includes a hydrophobic solvent
  • the hydrophobic solvent may include at least one of hydrofluoroether (HFE), fluoroethylene vinyl ether (FEVE), hexane, benzene, and toluene.
  • HFE hydrofluoroether
  • FEVE fluoroethylene vinyl ether
  • hexane benzene
  • toluene toluene
  • a non-polar solvent may be used.
  • the hydrophobic solution is preferably prepared at a concentration of 3 to 15%.
  • the concentration of the hydrophobic solution is too low, it may be difficult to distinguish phases within the emulsion mixed coating solution. However, if the concentration of the hydrophobic solution is too high, the coating film may appear uneven due to emulsion instability.
  • the emulsion mixed coating solution may include, in weight percent, a hydrophilic solution: 90 to 99%, the remaining hydrophobic solution, and other unavoidable impurities.
  • the main feature of the present invention is to maximize cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment. Therefore, the contents of the hydrophilic solution and the hydrophobic solution can be adjusted to control the hydrophilic and hydrophobic regions of the surface of the antifouling coating film.
  • hydrophilic solution Since a large amount of hydrophilic solution is required to allow the hydrophobic solution particles to be dispersed within the hydrophilic solution, it is preferable to add the hydrophilic solution in an amount of 90% by weight or more. However, if the content of the hydrophilic solution exceeds 99%, the hydrophobic solution particles may be trapped in the hydrophilic solution.
  • the content of the hydrophobic solution is too low, the particle size of the hydrophobic solution in the emulsion mixed coating solution becomes too small, making it difficult for phase change to occur by natural drying. If phase change does not occur, the hydrophobic solution particles are trapped inside the hydrophilic solution, making it difficult to manufacture a hybrid coating film that has both hydrophilic and hydrophobic properties. However, if the content of the hydrophobic solution is too high, it may be difficult for the hydrophobic solution particles to float to the surface, making it difficult to implement a hybrid coating film.
  • the emulsion mixed coating solution may further include at least one of SiO 2 nanoparticles and an antistatic agent.
  • SiO 2 nanoparticles have the effect of reinforcing the strength of the antifouling coating film, and antistatic agents can maximize the effect of suppressing the attachment of contaminants due to charging.
  • ZOT (Zn-Sn-O) particles can be used as an antistatic agent, but are not limited to this.
  • a coating solution application step can be performed in which the prepared emulsion mixed coating solution is applied to the surface of the substrate.
  • a primer application step of applying a primer to the surface of the substrate may be further included.
  • the primer application step may be additionally performed if necessary depending on the type of substrate.
  • Substrates requiring a primer application step may include, but are not limited to, polypropylene (PP) and styrene-acrylonitrile (SAN).
  • the substrate may include at least one of electrogalvanized steel (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). However, it is not limited to this, and a more suitable substrate may be selected depending on the purpose and use.
  • EGI electrogalvanized steel
  • PP polypropylene
  • SAN styrene-acrylonitrile
  • the coating liquid application step may be performed by Wet-on-Wet or Dry-on-Dry method.
  • the Wet-on-Wet method is a method of applying an emulsion mixed coating solution when the primer or base coat is not sufficiently dried. Wet-on-Wet method has excellent productivity.
  • the Dry-on-Dry method is a method of applying an emulsion mixed coating solution after sufficiently drying the primer or base coat.
  • the Dry-on-Dry method can create a coating film with excellent uniformity.
  • the concentration of hydrophobic polymer may decrease as the primer or base coat is partially mixed with the coating agent. Accordingly, the formation of hydrophilic regions on the surface can be advantageous. That is, in the case of the Wet-on-Wet method, as the content of the hydrophilic solution increases, the area fraction of the hydrophilic region on the surface of the antifouling coating film increases, and as the content of the hydrophobic solution increases, the area fraction of the minority region on the surface of the antifouling coating film increases. do.
  • a suitable coating solution application method can be selected depending on the type of substrate, weight percent of hydrophobic solution in the emulsion mixed coating solution, etc.
  • a step of inducing a phase change and a drying step can be performed by natural evaporation.
  • Figure 3 is a flowchart showing the process of forming an antifouling coating film according to an example of the present invention.
  • a phase change can be induced by first drying the substrate to which the coating solution has been applied at room temperature. During the room temperature drying process, the solvent in the coating solution naturally evaporates. At this time, the particle interface between the hydrophilic solution and the hydrophobic solution reaches a critical concentration where instability occurs from a thermodynamic point of view. When the critical concentration is reached, a phase change such as coalescence or creaming of hydrophobic solution particles occurs in the direction of decreasing interfacial energy. Through this phase change, the hydrophobic solution particles float to the upper surface of the coating solution.
  • a drying step may be performed in which the coating liquid applied to the surface of the substrate is dried at high temperature.
  • the drying step may be performed at 60 to 150° C. for 10 to 30 minutes.
  • the drying temperature is too high, the evaporation rate is too fast and cracks may occur in the coating film. However, if the drying temperature is too low, the uniformity of the coating film may decrease and the process time may increase, thereby reducing productivity.
  • drying time is too short, complete drying does not occur and the coating film is not properly formed. However, if the drying time is too long, cracks in the coating film may occur due to overcuring.
  • the antifouling coating film according to an embodiment of the present invention includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
  • the main feature of the present invention is to maximize cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment.
  • the hydrophilic and hydrophobic areas can be controlled.
  • the wider the hydrophilic area the more advantageous it can be in environments with high humidity.
  • moisture in the air first attaches to the antifouling coating film, and then contaminants accumulate. Therefore, it is effective to increase cleaning properties by using a coating film with a large hydrophilic area.
  • the contamination prevention function that prevents contaminants from sticking to the coating film can be improved.
  • an antifouling coating film containing 3.3 to 31% of the hydrophilic region and the remaining minority region in terms of area fraction can be implemented.
  • Figure 4 is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared by the Dry on Dry method with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution
  • Figure 5 is an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution, and is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film manufactured by the Wet on Wet method.
  • SEM scanning electron microscope
  • the area fraction of the hydrophilic region was controlled to be wide by reducing the content of the hydrophilic solution and applying the coating solution using a dry on dry method. Additionally, referring to Figure 5, it can be seen that the area fraction of the hydrophilic region was controlled to be narrow by lowering the content of the hydrophilic solution and applying the coating solution in a wet-on-wet manner.
  • hydrophilic and hydrophobic regions can be controlled by adjusting the size of the pores in the hydrophobic region depending on the drying temperature, type of solvent, etc.
  • Figure 6 is a photograph taken at 10,000 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
  • SEM scanning electron microscope
  • the size of the pores in the hydrophobic region can be controlled depending on the drying temperature of the drying step and the type of hydrophobic solvent.
  • the drying temperature is low or a hydrophobic solvent with a slow evaporation rate is used, the size of the pores in the hydrophobic region may become small. If the size of the pores in the minority area becomes smaller, the antifouling effect according to the minority area can be further increased.
  • hydrophilic and hydrophobic regions are controlled depending on the content of the hydrophilic solution and the hydrophobic solution, the coating solution application method, drying temperature, type of solvent, etc. Therefore, according to an example of the present invention, an antifouling coating film having both hydrophilic and hydrophobic regions can be implemented simply and economically based on a solution. Additionally, according to an example of the present invention, the hydrophilic and hydrophobic regions can be controlled without complex equipment or separate material synthesis.
  • hydrophilic polymers include polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, polyallylamine, and polyethyleneimine. It may include at least one of (polyethyleneimine), polyalkyloxazoline, and polyalkylamine.
  • the hydrophobic polymer may include at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
  • the antifouling coating film according to an embodiment of the present invention may further include at least one of SiO 2 nanoparticles and an antistatic agent.
  • SiO 2 nanoparticles have the effect of reinforcing the strength of the antifouling coating film, and the antistatic agent can maximize the effect of suppressing the attachment of contaminants due to charging.
  • ZOT (Zn-Sn-O) particles can be used as an antistatic agent, but are not limited to this.
  • a panel for home appliances includes: a substrate; and an antifouling coating film provided on the top of the substrate, wherein the antifouling coating film includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
  • the area fraction of the hydrophilic and hydrophobic regions of the antifouling coating film can be controlled.
  • cleaning efficiency can be effectively improved by using panels for home appliances that utilize an antifouling coating film with a large hydrophilic area.
  • the substrate may include at least one of electrogalvanized steel (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). However, it is not limited to this, and a more suitable substrate may be selected depending on the purpose and use of the home appliance.
  • EGI electrogalvanized steel
  • PP polypropylene
  • SAN styrene-acrylonitrile
  • the hydrophilic polymers include polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, polyallylamine, and polyethyleneimine. ), polyalkyloxazoline, and polyalkylamine.
  • the hydrophobic polymer may include at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
  • the home appliance panel may further include at least one of SiO 2 nanoparticles and an antistatic agent.
  • SiO 2 nanoparticles have the effect of reinforcing the strength of the antifouling coating film, and the antistatic agent can maximize the effect of suppressing the attachment of contaminants due to charging.
  • ZOT (Zn-Sn-O) particles can be used as an antistatic agent, but are not limited to this.
  • Table 1 below shows the area fractions of hydrophilic and hydrophobic regions measured using a scanning electron microscope (SEM) for the antifouling coating film according to an example of the present invention.
  • SEM scanning electron microscope
  • the specimen was manufactured using an electroplated steel sheet (EGI) substrate, a hydrophilic solution of polyvinyl alcohol (PVA) dissolved in water, and a hydrophobic solution of fluorinated silicon dissolved in hydrofluoroether (HFE).
  • the drying step was performed at 150°C for 20 minutes.
  • the hydrophilic region area fraction was controlled depending on the contents of the hydrophilic solution and hydrophobic solution and the coating solution application method.
  • the area fraction of the hydrophilic region decreases, and in the case of the Wet on Wet method, it can be seen that the area fraction of the hydrophilic region increases as the content of the hydrophilic solution increases. there was.
  • the cleanability test was performed by measuring the degree of contamination of each specimen in a low-temperature and high-humidity environment of 10°C and 80% humidity, based on photographs imaged with a 3D microscope.
  • Each specimen was left in an environment of 10°C and 80% humidity for 5 days to become contaminated, and was cleaned by rubbing with the same cotton cloth.
  • the bright part is the contaminated part with dust attached, and the dark part is the clean part.
  • the degree of contamination refers to the area to which dust is attached compared to the total area of the specimen.
  • Figure 7 is a photograph imaged with a 3D microscope of an uncoated substrate after being contaminated in an environment of 10°C and 80% humidity
  • Figure 8 is a photograph of an uncoated substrate contaminated in an environment of 10°C and 80% humidity.
  • This is a photo imaged with a 3D microscope of the appearance after cleaning with a cotton cloth.
  • the specimens in FIGS. 7 and 8 used an electro-galvanized steel sheet (EGI) substrate.
  • EPI electro-galvanized steel sheet
  • Figure 9 is a photograph imaged with a 3D microscope of an antifouling coating substrate after it was contaminated in an environment of 10°C and 80% humidity
  • Figure 10 is a photograph of an antifouling coating substrate contaminated in an environment of 10°C and 80% humidity.
  • This is a photo imaged with a 3D microscope of the appearance after cleaning with a cotton cloth.
  • the specimens in Figures 9 and 10 are electroplated steel sheet (EGI) substrate, a hydrophilic solution obtained by dissolving polyvinyl alcohol (PVA) in water, and a hydrophobic solution obtained by dissolving fluorinated silicon in hydrofluoroether (HFE).
  • EGI electroplated steel sheet
  • PVA polyvinyl alcohol
  • HFE hydrofluoroether
  • the uncoated substrate in the case of the uncoated substrate, the degree of contamination after contamination in an environment of 10°C and 80% humidity was found to be 94.8%, and the degree of contamination after cleaning with a cotton cloth was found to be 71.9%. In other words, the uncoated substrate not only did little to prevent contamination, but also had poor cleaning properties.
  • the contamination level after contamination in an environment of 10°C and 80% humidity was found to be 13.5%, and the contamination level after cleaning with a cotton cloth was 0.1%.
  • the anti-fouling coating substrate not only had an excellent anti-fouling effect, but also significantly improved cleaning properties.
  • an antifouling coating film that maximizes cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment.
  • a simple and economical method of manufacturing an antifouling coating film based on a solution can be provided.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Disclosed herein are a hybrid antifouling coating film with both hydrophilic and hydrophobic functions and a manufacturing method therefor. A method for manufacturing an antifouling coating film according to an embodiment of the present invention may comprise: a step of preparing an emulsion mixture coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution; a coating solution-coating step of applying the emulsion mixture coating solution onto a substrate surface; a step of inducing a phase change through natural evaporation; and a drying step.

Description

방오 코팅막 및 그 제조방법Antifouling coating film and manufacturing method thereof
본 발명은 방오 코팅막 및 그 제조방법에 관한 것으로, 보다 상세하게는, 친수 및 소수 성능을 동시에 갖는 하이브리드 코팅막 및 그 제조방법에 관한 것이다.The present invention relates to an antifouling coating film and a method of manufacturing the same, and more specifically, to a hybrid coating film having both hydrophilic and hydrophobic properties and a method of manufacturing the same.
친수성과 소수성 표면을 동시에 갖는 코팅막은, 기재 표면에 부착된 오염물질이 불안정한 상태가 되기 때문에 청소성이 향상될 수 있다. A coating film that has both a hydrophilic and hydrophobic surface can improve cleaning properties because contaminants attached to the surface of the substrate become unstable.
통상적으로, 친수성과 소수성을 동시에 가지는 표면을 형성하기 위해, 친수 코팅막에 소수성 미세입자가 함침되는 방식을 활용한다. 다만, 소수성 미세입자가 표면에 부상하기 쉽지 않고, 랜덤하게 분포하여 균일한 표면을 구현하기 어려운 점이 있다. Typically, in order to form a surface that has both hydrophilic and hydrophobic properties, a method in which hydrophobic fine particles are impregnated into a hydrophilic coating film is utilized. However, hydrophobic fine particles are not easy to float on the surface and are randomly distributed, making it difficult to create a uniform surface.
균일한 표면 구조를 형성하기 위한 방법으로는, 친수성-소수성 블록 공중합체를 기재 상부에 스핀-코팅하여 하이브리드 나노구조를 구현하는 방식이 있다. 그러나, 이러한 방법은 친수성-소수성 고분자 공중합체를 합성하는 단계가 별도로 필요하므로, 제조방법이 복잡하고 가격이 비싸다. 또한, 이러한 방법은 나노 단위의 막과 구조 형성으로 제한된다는 제약이 있다.As a method to form a uniform surface structure, there is a method of implementing a hybrid nanostructure by spin-coating a hydrophilic-hydrophobic block copolymer on the top of the substrate. However, this method requires a separate step of synthesizing a hydrophilic-hydrophobic polymer copolymer, so the manufacturing method is complicated and expensive. Additionally, this method has the limitation of being limited to the formation of nanoscale films and structures.
또한, 포토 리소그래피 공정으로 요철 구조의 표면을 형성한 후, 특정 표면을 불소 혹은 실리콘화합물을 이용해 소수성으로 개질하는 방식도 활용된다. 그러나, 이러한 방식은, 장비가 매우 고가이고, 패턴 형성에 소요되는 시간이 길다는 단점이 있다. 또한, 이러한 방식은, 패턴의 형상이 대면적에 접합하지 않으므로, 산업체에서 실제로 응용되는 데에는 많은 제약이 따른다. In addition, a method of forming a surface with a concavo-convex structure through a photolithography process and then modifying the specific surface to be hydrophobic using a fluorine or silicon compound is also used. However, this method has the disadvantage that the equipment is very expensive and the time required to form the pattern is long. In addition, since this method does not fit the shape of the pattern to a large area, there are many limitations in its actual application in industry.
따라서, 복잡한 장비나 별도의 물질 합성 없이, 단순하고 경제적으로 친수성과 소수성 표면을 동시에 갖는 코팅막을 제조하는 방법이 요구되고 있다.Therefore, there is a need for a simple and economical method of manufacturing a coating film that has both hydrophilic and hydrophobic surfaces without complex equipment or separate material synthesis.
상기와 같은 문제점을 해결하기 위한 본 발명의 목적은, 사용 환경에 따라 친수 및 소수 영역을 제어하여 청소성을 극대화시킨, 방오 코팅막을 제공하는데 있다.The purpose of the present invention to solve the above problems is to provide an antifouling coating film that maximizes cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment.
또한, 용액 기반으로 단순하고 경제적인, 방오 코팅막의 제조방법을 제공하는데 있다.In addition, the aim is to provide a solution-based, simple and economical method of manufacturing an antifouling coating film.
본 발명의 일 실시예에 따른 방오 코팅막의 제조방법은, 친수성 용액이 소수성 용액에 분산된, 에멀젼 혼합 코팅액을 제조하는 단계; 기재 표면에 상기 에멀젼 혼합 코팅액을 도포하는, 코팅액 도포 단계; 자연 증발에 의하여, 상 변화를 유도하는 단계; 및 건조 단계를 포함할 수 있다.A method for manufacturing an antifouling coating film according to an embodiment of the present invention includes preparing an emulsion mixed coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution; A coating solution application step of applying the emulsion mixed coating solution to the surface of the substrate; Inducing a phase change by natural evaporation; and a drying step.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법은, 상기 코팅액 도포 단계 이전에, 기재 표면에 프라이머를 도포하는, 프라이머 도포 단계를 더 포함할 수 있다.In addition, the method of manufacturing an antifouling coating film according to an embodiment of the present invention may further include a primer application step of applying a primer to the surface of the substrate before the step of applying the coating solution.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 친수성 용액은, 친수성 고분자를 포함하고, 상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함할 수 있다.In addition, in the method for producing an antifouling coating film according to an embodiment of the present invention, the hydrophilic solution includes a hydrophilic polymer, and the hydrophilic polymer is polyvinyl alcohol (PVA), polyvinylpyridine (PVP), , polyacrylic acid (PAA), polyacrylamide, polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine. You can.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 친수성 용액은, 친수성 용매를 포함하고, 상기 친수성 용매는, 물, 알코올, 아세톤 및 메탄올 중 적어도 하나를 포함할 수 있다.Additionally, in the method for producing an antifouling coating film according to an embodiment of the present invention, the hydrophilic solution includes a hydrophilic solvent, and the hydrophilic solvent may include at least one of water, alcohol, acetone, and methanol.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 소수성 용액은, 소수성 고분자를 포함하고, 상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함할 수 있다.In addition, in the method for producing an antifouling coating film according to an embodiment of the present invention, the hydrophobic solution includes a hydrophobic polymer, and the hydrophobic polymer is fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, and polytetra. It may include at least one of fluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 소수성 용액은, 소수성 용매를 포함하고, 상기 소수성 용매는, 하이드로플루오로에테르 (HFE), 플루오로에틸렌비닐에테르 (FEVE), 헥세인, 벤젠 및 톨루엔 중 적어도 하나를 포함할 수 있다.In addition, in the method for producing an antifouling coating film according to an embodiment of the present invention, the hydrophobic solution includes a hydrophobic solvent, and the hydrophobic solvent is hydrofluoroether (HFE), fluoroethylene vinyl ether (FEVE), It may contain at least one of hexane, benzene, and toluene.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 에멀젼 혼합 코팅액은, 중량%로, 친수성 용액: 90 내지 99%, 나머지 소수성 용액 및 기타 불가피한 불순물을 포함할 수 있다.In addition, in the method for producing an antifouling coating film according to an embodiment of the present invention, the emulsion mixed coating solution may include, in weight percent, a hydrophilic solution: 90 to 99%, the remaining hydrophobic solution, and other unavoidable impurities.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 에멀젼 혼합 코팅액은, SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함할 수 있다.Additionally, in the method for manufacturing an antifouling coating film according to an embodiment of the present invention, the emulsion mixed coating solution may further include at least one of SiO 2 nanoparticles and an antistatic agent.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 기재는, 전기아연도금강판 (EGI), 폴리 프로필렌 (PP) 및 스티렌-아크릴로니트릴(SAN) 중 적어도 하나를 포함할 수 있다.In addition, in the method of manufacturing an antifouling coating film according to an embodiment of the present invention, the substrate may include at least one of electrogalvanized steel sheet (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). there is.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 코팅액 도포 단계는, Wet-on-Wet 또는 Dry-on-Dry 방식으로 수행될 수 있다.Additionally, in the method of manufacturing an antifouling coating film according to an embodiment of the present invention, the coating liquid application step may be performed by a wet-on-wet or dry-on-dry method.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법에서, 상기 건조 단계는, 60 내지 150℃에서, 10 내지 30분간 수행될 수 있다.Additionally, in the method for manufacturing an antifouling coating film according to an embodiment of the present invention, the drying step may be performed at 60 to 150° C. for 10 to 30 minutes.
또한, 본 발명의 일 실시예에 따른 방오 코팅막은, 친수성 고분자와 소수성 고분자를 모두 포함하고, 면적분율로, 친수 영역 3.3 내지 31% 및 나머지 소수 영역을 포함할 수 있다.In addition, the antifouling coating film according to an embodiment of the present invention includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
또한, 본 발명의 일 실시예에 따른 방오 코팅막에서, 상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함할 수 있다.In addition, in the antifouling coating film according to an embodiment of the present invention, the hydrophilic polymer is polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide ( It may include at least one of polyacrylamide), polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine.
또한, 본 발명의 일 실시예에 따른 방오 코팅막에서, 상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함할 수 있다.Additionally, in the antifouling coating film according to an embodiment of the present invention, the hydrophobic polymer is at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane. It can contain one.
또한, 본 발명의 일 실시예에 따른 방오 코팅막은, SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함할 수 있다.Additionally, the antifouling coating film according to an embodiment of the present invention may further include at least one of SiO 2 nanoparticles and an antistatic agent.
또한, 본 발명의 일 실시예에 따른 가전기기용 패널은, 기재; 및 상기 기재 상부에 마련된 방오 코팅막을 포함하고, 상기 방오 코팅막은, 친수성 고분자와 소수성 고분자를 모두 포함하고, 면적분율로, 친수 영역 3.3 내지 31% 및 나머지 소수 영역을 포함할 수 있다.In addition, a panel for home appliances according to an embodiment of the present invention includes: a substrate; and an antifouling coating film provided on the top of the substrate, wherein the antifouling coating film includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
또한, 본 발명의 일 실시예에 따른 가전기기용 패널에서, 상기 기재는, 전기아연도금강판 (EGI), 폴리 프로필렌 (PP) 및 스티렌-아크릴로니트릴(SAN) 중 적어도 하나를 포함할 수 있다.Additionally, in the panel for home appliances according to an embodiment of the present invention, the substrate may include at least one of electrogalvanized steel sheet (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). .
또한, 본 발명의 일 실시예에 따른 가전기기용 패널에서, 상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함할 수 있다.In addition, in the home appliance panel according to an embodiment of the present invention, the hydrophilic polymer is polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), and polyacrylic acid. It may include at least one of amide, polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine.
또한, 본 발명의 일 실시예에 따른 가전기기용 패널에서, 상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함할 수 있다.In addition, in the home appliance panel according to an embodiment of the present invention, the hydrophobic polymer is fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane. It may include at least one of:
또한, 본 발명의 일 실시예에 따른 가전기기용 패널에서, 상기 방오 코팅막은, SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함할 수 있다.Additionally, in the home appliance panel according to an embodiment of the present invention, the antifouling coating film may further include at least one of SiO 2 nanoparticles and an antistatic agent.
본 발명의 일 예에 의하면, 사용 환경에 따라 친수 및 소수 영역을 제어하여 청소성을 극대화시킨 방오 코팅막을 제공할 수 있다.According to an example of the present invention, it is possible to provide an antifouling coating film that maximizes cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment.
또한, 본 발명의 일 예에 의하면, 용액 기반으로 단순하고 경제적인, 방오 코팅막의 제조방법을 제공할 수 있다.In addition, according to an example of the present invention, a simple and economical method of manufacturing an antifouling coating film based on a solution can be provided.
다만, 본 발명의 실시예 들에 따른 방오 코팅막 및 그 제조방법이 달성할 수 있는 효과는 이상에서 언급한 것들로 제한되지 않으며, 언급하지 않은 또 다른 효과들은 아래의 기재로부터 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.However, the effects that can be achieved by the antifouling coating film and its manufacturing method according to the embodiments of the present invention are not limited to those mentioned above, and other effects not mentioned can be found in the technical field to which the present invention belongs from the description below. It will be clearly understandable to those with ordinary knowledge.
도 1은, 본 발명의 일 예에 따른 방오 코팅막 제조방법의 흐름도이다.1 is a flowchart of a method for manufacturing an antifouling coating film according to an example of the present invention.
도 2는, 본 발명의 일 예에 따른 에멀젼 혼합 코팅액의 모식도이다.Figure 2 is a schematic diagram of an emulsion mixed coating solution according to an example of the present invention.
도 3은, 본 발명의 일 예에 따른 방오 코팅막 형성 과정을 나타내는 흐름도이다.Figure 3 is a flowchart showing the process of forming an antifouling coating film according to an example of the present invention.
도 4는, 친수성 용액 90 중량%를 포함하는 에멀젼 혼합 코팅액으로, Dry on Dry 방식에 의해 제조된 방오 코팅막을, 주사전자현미경(Scanning Electrone Microscope, SEM)으로 500배 확대 촬영한 사진이다.Figure 4 is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared by the Dry on Dry method with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
도 5는, 친수성 용액 90 중량%를 포함하는 에멀젼 혼합 코팅액으로, Wet on Wet 방식에 의해 제조된 방오 코팅막을 주사전자현미경(Scanning Electrone Microscope, SEM)으로 500배 확대 촬영한 사진이다.Figure 5 is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared by the Wet on Wet method as an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
도 6은, 친수성 용액 90 중량%를 포함하는 에멀젼 혼합 코팅액으로 제조된 방오 코팅막을 주사전자현미경(Scanning Electrone Microscope, SEM)으로 10000배 확대 촬영한 사진이다.Figure 6 is a photograph taken at 10,000 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
도 7은, 미코팅 기재를, 10℃ 및 습도 80%인 환경에서 오염시킨 후의 모습을 3D 현미경으로 이미지화한 사진이다.Figure 7 is a photograph imaged with a 3D microscope of an uncoated substrate after contamination in an environment of 10°C and 80% humidity.
도 8은, 10℃ 및 습도 80%인 환경에서 오염된 미코팅 기재를, 면포로 청소한 후의 모습을 3D 현미경으로 이미지화한 사진이다.Figure 8 is a photograph imaged with a 3D microscope of a contaminated uncoated substrate in an environment of 10°C and 80% humidity after cleaning it with a cotton cloth.
도 9는, 방오 코팅 기재를, 10℃ 및 습도 80%인 환경에서 오염시킨 후의 모습을 3D 현미경으로 이미지화한 사진이다.Figure 9 is a photograph imaged with a 3D microscope of an antifouling coating substrate after contamination in an environment of 10°C and 80% humidity.
도 10은, 10℃ 및 습도 80%인 환경에서 오염된 방오 코팅 기재를, 면포로 청소한 후의 모습을 3D 현미경으로 이미지화한 사진이다.Figure 10 is a photograph imaged with a 3D microscope of a contaminated antifouling coating substrate in an environment of 10°C and 80% humidity after cleaning it with a cotton cloth.
본 발명의 일 실시예에 따른 방오 코팅막의 제조방법은, 친수성 용액이 소수성 용액에 분산된, 에멀젼 혼합 코팅액을 제조하는 단계; 기재 표면에 상기 에멀젼 혼합 코팅액을 도포하는, 코팅액 도포 단계; 자연 증발에 의하여, 상 변화를 유도하는 단계; 및 건조 단계를 포함할 수 있다.A method for manufacturing an antifouling coating film according to an embodiment of the present invention includes preparing an emulsion mixed coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution; A coating solution application step of applying the emulsion mixed coating solution to the surface of the substrate; Inducing a phase change by natural evaporation; and a drying step.
이하에서는 본 발명의 실시 예를 첨부 도면을 참고하여 상세히 설명한다. 이하의 실시 예는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 본 발명의 사상을 충분히 전달하기 위해 제시하는 것이다. 본 발명은 여기서 제시한 실시 예만으로 한정되지 않고 다른 형태로 구체화될 수도 있다. 도면은 본 발명을 명확히 하기 위해 설명과 관계 없는 부분의 도시를 생략하고, 이해를 돕기 위해 구성요소의 크기를 다소 과장하여 표현할 수 있다.Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The following examples are presented to sufficiently convey the idea of the present invention to those skilled in the art. The present invention is not limited to the embodiments presented herein and may be embodied in other forms. In order to clarify the present invention, the drawings may omit illustrations of parts unrelated to the description and may slightly exaggerate the sizes of components to aid understanding.
명세서 전체에서, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있는 것을 의미한다.Throughout the specification, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.
단수의 표현은 문맥상 명백하게 예외가 있지 않는 한, 복수의 표현을 포함한다.Singular expressions include plural expressions unless the context clearly makes an exception.
본 발명은 친수성과 소수성 표면을 동시에 갖는 고분자 또는 고분자 복합재료 코팅막에 대한 것이다. The present invention relates to a polymer or polymer composite coating film having both a hydrophilic and hydrophobic surface.
친수성과 소수성 표면을 동시에 갖는 코팅막은 청소성이 매우 우수하다. 오염물질이 코팅막의 친수성 부분과 소수성 부분 모두에 접하게되면 불안정한 상태가 되므로, 기류, 수분, 진동 등에 의해 오염물이 쉽게 탈락될 수 있기 때문이다. 또한, 코팅막 표면의 친수성 물질이 정전기를 제거하므로, 대전에 의한 오염물의 부착도 억제되어 오염 방지 효과도 우수하다. 따라서, 본 발명에 의한 방오 코팅막은, 에어컨, 공기청정기, 크로스 팬 등 가전기기의 패널과 같이, 쉽게 오염될 수 있는 부품에 적용될 수 있다.A coating film that has both a hydrophilic and hydrophobic surface has excellent cleaning properties. This is because when contaminants come into contact with both the hydrophilic and hydrophobic parts of the coating film, they become unstable and can easily be removed by air currents, moisture, vibration, etc. In addition, since the hydrophilic material on the surface of the coating film removes static electricity, the adhesion of contaminants due to electrification is suppressed and the contamination prevention effect is excellent. Therefore, the antifouling coating film according to the present invention can be applied to parts that can be easily contaminated, such as panels of home appliances such as air conditioners, air purifiers, and cross fans.
본 발명에서는, 에멀젼 혼합 코팅액을 기재 표면에 도포한 후 내부 입자의 상변화를 유도하여, 친수 및 소수 성능을 동시에 갖는 하이브리드 코팅막을 구현하고 있다. 따라서, 고분자 용액을 기재 위에 도포한 후 용매를 증발시킨 다음 비용매에 담그는, 상전환법(Phase-inversion method)과 상이한 기술이다. 상전환법은, 용매와 비용매간 치환 속도차를 통해 막의 구조가 형성되는 방식을 취한다.In the present invention, a hybrid coating film having both hydrophilic and hydrophobic properties is implemented by applying an emulsion mixed coating solution to the surface of the substrate and then inducing a phase change in the internal particles. Therefore, it is a different technique from the phase-inversion method, in which a polymer solution is applied on a substrate, the solvent is evaporated, and then the polymer solution is immersed in a non-solvent. The phase inversion method uses a method in which the structure of the film is formed through the difference in substitution rate between the solvent and the non-solvent.
본 발명의 일 실시예에 따른 방오 코팅막의 제조방법은, 친수성 용액이 소수성 용액에 분산된, 에멀젼 혼합 코팅액을 제조하는 단계; 기재 표면에 상기 에멀젼 혼합 코팅액을 도포하는, 코팅액 도포 단계; 자연 증발에 의하여, 상 변화를 유도하는 단계; 및 건조 단계를 포함할 수 있다.A method for manufacturing an antifouling coating film according to an embodiment of the present invention includes preparing an emulsion mixed coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution; A coating solution application step of applying the emulsion mixed coating solution to the surface of the substrate; Inducing a phase change by natural evaporation; and a drying step.
또한, 본 발명의 일 실시예에 따른 방오 코팅막의 제조방법은, 상기 코팅액 도포 단계 이전에, 기재 표면에 프라이머를 도포하는, 프라이머 도포 단계를 더 포함할 수 있다.In addition, the method of manufacturing an antifouling coating film according to an embodiment of the present invention may further include a primer application step of applying a primer to the surface of the substrate before the step of applying the coating solution.
도 1은, 본 발명의 일 예에 따른 방오 코팅막 제조방법의 흐름도이다.1 is a flowchart of a method for manufacturing an antifouling coating film according to an example of the present invention.
도 1을 참고하면, 본 발명의 일 예에 따른 방오 코팅막 제조방법은, 일련의 코팅액 제조, 코팅액 도포, 상 변화 유도 및 건조 단계를 포함할 수 있다.Referring to FIG. 1, the method of manufacturing an antifouling coating film according to an example of the present invention may include a series of steps for preparing a coating solution, applying the coating solution, inducing a phase change, and drying.
상기 코팅액 제조 단계에서는, 소수성 용액이 친수성 용액에 분산된, 에멀젼 혼합 코팅액을 제조할 수 있다. 상기 친수성 용액은, 친수성 고분자를 친수성 용매에 용해시켜 제조할 수 있고, 상기 소수성 용액은, 소수성 고분자를 소수성 용매에 용해시켜 제조할 수 있다.In the coating solution preparation step, an emulsion mixed coating solution in which a hydrophobic solution is dispersed in a hydrophilic solution can be prepared. The hydrophilic solution can be prepared by dissolving a hydrophilic polymer in a hydrophilic solvent, and the hydrophobic solution can be prepared by dissolving a hydrophobic polymer in a hydrophobic solvent.
도 2는, 본 발명의 일 예에 따른 에멀젼 혼합 코팅액의 모식도이다.Figure 2 is a schematic diagram of an emulsion mixed coating solution according to an example of the present invention.
도 2를 참고하면, 본 발명의 일 예에 따른 에멀젼 혼합 코팅액은, 친수성 용액 내에 소수성 용액 입자가 균일하게 분산되어 있는 형태임을 알 수 있다.Referring to Figure 2, it can be seen that the emulsion mixed coating solution according to an example of the present invention has hydrophobic solution particles uniformly dispersed in a hydrophilic solution.
한편, 소수성 용액 입자가 친수성 용액에 균일하게 분산될 수 있도록, 소니케이션(sonication), 호모게나이저(homogenizer) 등의 혼합 설비를 적용할 수 있다. 소니케이션은, 초음파를 이용하여 친수성 용액 내의 소수성 용액 입자를 섞어주고, 융합하려는 소수성 용액 입자들을 쪼개는 역할을 수행할 수 있다. 호모게나이저는, 기계적으로 소수성 용액 입자들을 혼합해주는 역할을 수행할 수 있다.Meanwhile, mixing equipment such as sonication or homogenizer can be applied so that the hydrophobic solution particles can be uniformly dispersed in the hydrophilic solution. Sonication can perform the role of mixing hydrophobic solution particles in a hydrophilic solution and splitting hydrophobic solution particles that are to be fused using ultrasonic waves. The homogenizer may serve to mechanically mix hydrophobic solution particles.
상기 친수성 용액은, 친수성 고분자를 포함하고, 상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함할 수 있다. 다만, 이에 한정되지는 않고, 극성을 띄는 고분자를 활용할 수도 있다. 한편, 친수성 용액 농도의 상한이 15%인 점을 고려할 때, 친수성 용매에 대한 용해도가 15% 이상인 친수성 고분자를 선택하는 것이 바람직하다. 여기서 용해도란, 용매에 대해 용해될 수 있는 용질의 최대량을 의미한다. The hydrophilic solution includes a hydrophilic polymer, and the hydrophilic polymer includes polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, It may include at least one of polyallylamine, polyethyleneimine, polyalkyloxazoline, and polyalkylamine. However, it is not limited to this, and polar polymers can also be used. Meanwhile, considering that the upper limit of the hydrophilic solution concentration is 15%, it is desirable to select a hydrophilic polymer with a solubility in the hydrophilic solvent of 15% or more. Here, solubility means the maximum amount of solute that can be dissolved in a solvent.
상기 친수성 용액은, 친수성 용매를 포함하고, 상기 친수성 용매는, 물, 알코올, 아세톤 및 메탄올 중 적어도 하나를 포함할 수 있다. 다만, 이에 한정되지는 않고, 극성을 띄는 용매를 활용할 수도 있다. 이 때, 친수성 고분자가 15% 이상 용해될 수 있는 친수성 용매를 선택하는 것이 바람직하다. The hydrophilic solution includes a hydrophilic solvent, and the hydrophilic solvent may include at least one of water, alcohol, acetone, and methanol. However, it is not limited to this, and a polar solvent may be used. At this time, it is desirable to select a hydrophilic solvent in which more than 15% of the hydrophilic polymer can be dissolved.
또한, 친수성 용매의 증발속도가 빠를수록 코팅막 표면의 균일도가 증가하므로, 증기압이 높은 친수성 용매를 선택하는 것이 유리할 수 있다.Additionally, the faster the evaporation rate of the hydrophilic solvent, the greater the uniformity of the surface of the coating film, so it may be advantageous to select a hydrophilic solvent with a high vapor pressure.
한편, 친수성 용액은, 농도가 3 내지 15%로 제조하는 것이 바람직하다.Meanwhile, the hydrophilic solution is preferably prepared at a concentration of 3 to 15%.
친수성 용액의 농도가 너무 낮은 경우에는, 방오 코팅막의 친수영역 면적분율이 지나치게 낮아져 청소성이 열위해질 수 있다. 그러나, 친수성 용액의 농도가 너무 높은 경우에는, 용액의 점성이 증가하여, 생산성이 떨어질 수 있다.If the concentration of the hydrophilic solution is too low, the area fraction of the hydrophilic region of the antifouling coating film may become too low, resulting in poor cleaning properties. However, if the concentration of the hydrophilic solution is too high, the viscosity of the solution may increase and productivity may decrease.
상기 소수성 용액은, 소수성 고분자를 포함하고, 상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함할 수 있다. 다만, 이에 한정되지는 않고, 무극성을 띄는 고분자를 활용할 수도 있다. 한편, 소수성 용액 농도의 상한이 15%인 점을 고려할 때, 소수성 용매에 대한 용해도가 15% 이상인 소수성 고분자를 선택하는 것이 바람직하다. 여기서 용해도란, 용매에 대해 용해될 수 있는 용질의 최대량을 의미한다.The hydrophobic solution includes a hydrophobic polymer, and the hydrophobic polymer includes at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane. can do. However, it is not limited to this, and non-polar polymers can also be used. Meanwhile, considering that the upper limit of the hydrophobic solution concentration is 15%, it is desirable to select a hydrophobic polymer with a solubility in the hydrophobic solvent of 15% or more. Here, solubility means the maximum amount of solute that can be dissolved in a solvent.
상기 소수성 용액은, 소수성 용매를 포함하고, 상기 소수성 용매는, 하이드로플루오로에테르 (HFE), 플루오로에틸렌비닐에테르 (FEVE), 헥세인, 벤젠 및 톨루엔 중 적어도 하나를 포함할 수 있다. 다만, 이에 한정되지는 않고, 무극성을 띄는 용매를 활용할 수도 있다. 이 때, 소수성 고분자가 15% 이상 용해될 수 있는 소수성 용매를 선택하는 것이 바람직하다.The hydrophobic solution includes a hydrophobic solvent, and the hydrophobic solvent may include at least one of hydrofluoroether (HFE), fluoroethylene vinyl ether (FEVE), hexane, benzene, and toluene. However, it is not limited to this, and a non-polar solvent may be used. At this time, it is desirable to select a hydrophobic solvent in which more than 15% of the hydrophobic polymer can be dissolved.
한편, 소수성 용액은, 농도가 3 내지 15%로 제조하는 것이 바람직하다.Meanwhile, the hydrophobic solution is preferably prepared at a concentration of 3 to 15%.
소수성 용액의 농도가 너무 낮은 경우에는, 에멀젼 혼합 코팅액 내에서 상 구분이 어려울 수 있다. 그러나, 소수성 용액의 농도가 너무 높은 경우에는, 에멀젼 불안정으로 인해 코팅막이 불균일하게 나타날 수 있다.If the concentration of the hydrophobic solution is too low, it may be difficult to distinguish phases within the emulsion mixed coating solution. However, if the concentration of the hydrophobic solution is too high, the coating film may appear uneven due to emulsion instability.
상기 에멀젼 혼합 코팅액은, 중량%로, 친수성 용액: 90 내지 99%, 나머지 소수성 용액 및 기타 불가피한 불순물을 포함할 수 있다. The emulsion mixed coating solution may include, in weight percent, a hydrophilic solution: 90 to 99%, the remaining hydrophobic solution, and other unavoidable impurities.
본 발명은 사용 환경에 따라 친수 및 소수 영역을 제어하여 청소성을 극대화시키고자 하는 것이 주요한 일 특징이다. 따라서, 방오 코팅막 표면의 친수 및 소수 영역을 제어하기 위해 친수성 용액 및 소수성 용액의 함량을 조절할 수 있다.The main feature of the present invention is to maximize cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment. Therefore, the contents of the hydrophilic solution and the hydrophobic solution can be adjusted to control the hydrophilic and hydrophobic regions of the surface of the antifouling coating film.
친수성 용액 내부에 소수성 용액 입자가 분산될 수 있도록 하기 위해 친수성 용액이 다량 필요하므로, 친수성 용액의 함량은 90 중량% 이상 첨가하는 것이 바람직하다. 다만, 친수성 용액의 함량이 99% 초과하는 경우에는, 소수성 용액 입자가 친수성 용액 내에 갇힐 수 있다.Since a large amount of hydrophilic solution is required to allow the hydrophobic solution particles to be dispersed within the hydrophilic solution, it is preferable to add the hydrophilic solution in an amount of 90% by weight or more. However, if the content of the hydrophilic solution exceeds 99%, the hydrophobic solution particles may be trapped in the hydrophilic solution.
소수성 용액의 함량이 너무 낮으면, 에멀젼 혼합 코팅액 내의 소수성 용액 입자 크기가 너무 작아져서, 자연건조에 의한 상변화가 일어나기 어렵다. 상변화가 일어나지 않는다면, 소수성 용액 입자가 친수성 용액 내부에 갇히므로, 친수 및 소수 성능을 동시에 갖는 하이브리드 코팅막을 제조하기 어렵게 된다. 그러나, 소수성 용액의 함량이 너무 높은 경우에는, 소수성 용액 입자가 표면으로 부상하기 힘들어 하이브리드 코팅막 구현이 어려울 수 있다.If the content of the hydrophobic solution is too low, the particle size of the hydrophobic solution in the emulsion mixed coating solution becomes too small, making it difficult for phase change to occur by natural drying. If phase change does not occur, the hydrophobic solution particles are trapped inside the hydrophilic solution, making it difficult to manufacture a hybrid coating film that has both hydrophilic and hydrophobic properties. However, if the content of the hydrophobic solution is too high, it may be difficult for the hydrophobic solution particles to float to the surface, making it difficult to implement a hybrid coating film.
통상의 제조과정에서는 원료 또는 주위 환경으로부터 의도되지 않는 불순물들이 불가피하게 혼입될 수 있으므로, 이를 배제할 수는 없다. 이들 불순물들은 통상의 제조과정의 기술자라면 누구라도 알 수 있는 것이기 때문에 그 모든 내용을 특별히 본 명세서에서 언급하지는 않는다.In normal manufacturing processes, unintended impurities may inevitably be introduced from raw materials or the surrounding environment, so this cannot be ruled out. Since these impurities are known to anyone skilled in the ordinary manufacturing process, all of them are not specifically mentioned in this specification.
상기 에멀젼 혼합 코팅액은, SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함할 수 있다. The emulsion mixed coating solution may further include at least one of SiO 2 nanoparticles and an antistatic agent.
SiO2 나노입자는 방오 코팅막의 강도를 보강하는 효과가 있고, 대전방지제는 대전에 의한 오염물 부착을 억제하는 효과를 극대화할 수 있다. 한편, 대전방지제로써 ZOT(Zn-Sn-O) 입자를 활용할 수 있으나, 이에 한정되지는 않는다.SiO 2 nanoparticles have the effect of reinforcing the strength of the antifouling coating film, and antistatic agents can maximize the effect of suppressing the attachment of contaminants due to charging. Meanwhile, ZOT (Zn-Sn-O) particles can be used as an antistatic agent, but are not limited to this.
다음으로, 제조된 에멀젼 혼합 코팅액을 기재 표면에 도포하는, 코팅액 도포 단계를 수행할 수 있다.Next, a coating solution application step can be performed in which the prepared emulsion mixed coating solution is applied to the surface of the substrate.
한편, 상기 코팅액 도포 단계 이전에, 기재 표면에 프라이머를 도포하는, 프라이머 도포 단계를 더 포함할 수 있다. 상기 프라이머 도포 단계는, 기재의 종류에 따라 필요 시 추가로 수행될 수 있다. 프라이머 도포 단계가 필요한 기재는, 폴리 프로필렌 (PP) 및 스티렌-아크릴로니트릴(SAN)일 수 있으나, 이에 한정되지는 않는다.Meanwhile, before the coating solution application step, a primer application step of applying a primer to the surface of the substrate may be further included. The primer application step may be additionally performed if necessary depending on the type of substrate. Substrates requiring a primer application step may include, but are not limited to, polypropylene (PP) and styrene-acrylonitrile (SAN).
상기 기재는, 전기아연도금강판 (EGI), 폴리 프로필렌 (PP) 및 스티렌-아크릴로니트릴(SAN) 중 적어도 하나를 포함할 수 있다. 다만 이에 한정되지 않고, 목적 및 용도에 따라 보다 적합한 기재를 선택할 수도 있다.The substrate may include at least one of electrogalvanized steel (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). However, it is not limited to this, and a more suitable substrate may be selected depending on the purpose and use.
상기 코팅액 도포 단계는, Wet-on-Wet 또는 Dry-on-Dry 방식으로 수행될 수 있다.The coating liquid application step may be performed by Wet-on-Wet or Dry-on-Dry method.
Wet-on-Wet 방식은, 프라이머나 하도막이 충분히 건조되지 않은 상태에서 에멀젼 혼합 코팅액을 도포하는 방식이다. Wet-on-Wet 방식은 생산성이 우수하다.The Wet-on-Wet method is a method of applying an emulsion mixed coating solution when the primer or base coat is not sufficiently dried. Wet-on-Wet method has excellent productivity.
Dry-on-Dry 방식은, 프라이머나 하도막을 충분히 건조시킨 후 에멀젼 혼합 코팅액을 도포하는 방식이다. Dry-on-Dry 방식은, 코팅막의 균일도가 우수한 코팅막을 구현할 수 있다.The Dry-on-Dry method is a method of applying an emulsion mixed coating solution after sufficiently drying the primer or base coat. The Dry-on-Dry method can create a coating film with excellent uniformity.
Wet-on-Wet 방식의 경우에는, 프라이머나 하도막이 코팅제와 일부 섞이면서 소수성 고분자의 농도가 감소할 수 있다. 따라서, 표면의 친수 영역 형성이 유리해질 수 있다. 즉, Wet-on-Wet 방식의 경우에는, 친수성 용액의 함량이 증가할수록 방오 코팅막 표면의 친수 영역의 면적분율이 증가하고, 소수성 용액의 함량이 증가할수록 방오 코팅막 표면의 소수 영역의 면적분율이 증가한다.In the case of the wet-on-wet method, the concentration of hydrophobic polymer may decrease as the primer or base coat is partially mixed with the coating agent. Accordingly, the formation of hydrophilic regions on the surface can be advantageous. That is, in the case of the Wet-on-Wet method, as the content of the hydrophilic solution increases, the area fraction of the hydrophilic region on the surface of the antifouling coating film increases, and as the content of the hydrophobic solution increases, the area fraction of the minority region on the surface of the antifouling coating film increases. do.
그러나, Dry-on-Dry 방식의 경우에는, 친수성 용액의 함량이 증가할수록 친수성 용액과 소수성 용액의 상 분리 및 상 변화가 발생하기 어려울 수 있다. 따라서, 친수성 용액의 함량이 증가할수록 방오 코팅막 표면의 친수 영역의 면적분율이 감소하게 된다.However, in the case of the dry-on-dry method, as the content of the hydrophilic solution increases, it may be difficult for phase separation and phase change between the hydrophilic solution and the hydrophobic solution to occur. Therefore, as the content of the hydrophilic solution increases, the area fraction of the hydrophilic region on the surface of the antifouling coating film decreases.
본 발명에서는, 기재 종류, 에멀젼 혼합 코팅액 내 소수성 용액의 중량% 등에 따라 적합한 코팅액 도포 방식을 선택할 수 있다.In the present invention, a suitable coating solution application method can be selected depending on the type of substrate, weight percent of hydrophobic solution in the emulsion mixed coating solution, etc.
다음으로, 자연 증발에 의하여, 상 변화를 유도하는 단계 및 건조 단계를 수행할 수 있다.Next, a step of inducing a phase change and a drying step can be performed by natural evaporation.
도 3은, 본 발명의 일 예에 따른 방오 코팅막 형성 과정을 나타내는 흐름도이다.Figure 3 is a flowchart showing the process of forming an antifouling coating film according to an example of the present invention.
도 3을 참고하면, 먼저 코팅액을 도포한 기재를 상온에서 건조시켜 상변화를 유도할 수 있다. 상온 건조 과정에서 코팅액 내 용매는 자연 증발이 일어나게 된다. 이때, 친수성 용액과 소수성 용액 입자 계면은 열역학적인 관점에서 불안정이 일어나는 임계 농도에 도달하게 된다. 임계 농도에 도달하게 되면, 계면 에너지가 감소하는 방향으로 소수성 용액 입자의 합체(Coalescence) 혹은 크리밍(Creaming) 등의 상변화가 일어난다. 이러한 상변화를 통해 소수성 용액 입자는 코팅액 상부 표면으로 부상하게 된다.Referring to Figure 3, a phase change can be induced by first drying the substrate to which the coating solution has been applied at room temperature. During the room temperature drying process, the solvent in the coating solution naturally evaporates. At this time, the particle interface between the hydrophilic solution and the hydrophobic solution reaches a critical concentration where instability occurs from a thermodynamic point of view. When the critical concentration is reached, a phase change such as coalescence or creaming of hydrophobic solution particles occurs in the direction of decreasing interfacial energy. Through this phase change, the hydrophobic solution particles float to the upper surface of the coating solution.
한편, 소수성 용액 입자의 상변화가 충분히 이루어지지 않은 상태에서 고온 건조를 수행하면, 소수성 용액 입자가 코팅액 상부 표면으로 부상하지 못하고 친수성 용액 내부에 갇히므로, 친수 및 소수 성능을 동시에 갖는 하이브리드 코팅막 구현이 어려울 수 있다.On the other hand, if high-temperature drying is performed without sufficient phase change of the hydrophobic solution particles, the hydrophobic solution particles cannot float to the upper surface of the coating solution and are trapped inside the hydrophilic solution, making it possible to implement a hybrid coating film that has both hydrophilic and hydrophobic performance. It can be difficult.
다음으로, 기재 표면에 도포된 코팅액을 고온 건조시키는, 건조 단계를 수행할 수 있다.Next, a drying step may be performed in which the coating liquid applied to the surface of the substrate is dried at high temperature.
상기 건조 단계는, 60 내지 150℃에서, 10 내지 30분간 수행될 수 있다.The drying step may be performed at 60 to 150° C. for 10 to 30 minutes.
건조 온도가 너무 높으면, 증발속도가 지나치게 빨라 코팅막에 크랙이 발생할 수 있다. 그러나, 건조 온도가 너무 낮으면, 코팅막의 균일도가 떨어지고, 공정시간이 늘어나므로 생산성이 저하될 수 있다.If the drying temperature is too high, the evaporation rate is too fast and cracks may occur in the coating film. However, if the drying temperature is too low, the uniformity of the coating film may decrease and the process time may increase, thereby reducing productivity.
건조 시간이 너무 짧으면, 완전 건조가 이루어지지 않아 코팅막이 제대로 형성되지 못한다. 그러나, 건조 시간이 너무 길면, 과경화에 의한 코팅막 크랙이 발생할 수 있다.If the drying time is too short, complete drying does not occur and the coating film is not properly formed. However, if the drying time is too long, cracks in the coating film may occur due to overcuring.
한편, 상 변화 이후에는 용매가 빠르게 증발할수록 코팅막 균일도가 증가하므로, 건조 온도가 높은 것이 유리할 수 있다. 다만, 코팅액 조성 및 기재 종류에 따라 건조 온도를 다르게 선택하는 것이 바람직하다.On the other hand, after the phase change, the faster the solvent evaporates, the more uniform the coating film is, so it may be advantageous to have a high drying temperature. However, it is desirable to select a different drying temperature depending on the coating liquid composition and type of substrate.
다음으로, 본 발명의 다른 일 측면에 따른 방오 코팅막에 대하여 설명한다.Next, an antifouling coating film according to another aspect of the present invention will be described.
본 발명의 일 실시예에 따른 방오 코팅막은, 친수성 고분자와 소수성 고분자를 모두 포함하고, 면적분율로, 친수 영역 3.3 내지 31% 및 나머지 소수 영역을 포함할 수 있다.The antifouling coating film according to an embodiment of the present invention includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
상술한 바와 같이, 본 발명은 사용 환경에 따라 친수 및 소수 영역을 제어하여 청소성을 극대화시키고자 하는 것이 주요한 일 특징이다. 친수성 용액 및 소수성 용액의 함량과 코팅액 도포 방식을 조절함으로써, 친수 및 소수 영역을 제어할 수 있다.As described above, the main feature of the present invention is to maximize cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment. By adjusting the content of the hydrophilic solution and the hydrophobic solution and the method of applying the coating solution, the hydrophilic and hydrophobic areas can be controlled.
친수 영역이 넓을수록, 습도가 높은 환경에서 유리할 수 있다. 습도가 높은 환경에서는, 먼저 대기중의 수분이 방오 코팅막에 부착되고, 그 후 오염물이 쌓이게 된다. 따라서, 친수 영역이 넓은 코팅막을 활용하여 청소성을 높이는 것이 효과적이다. 한편, 소수 영역이 넓은 경우에는, 오염물이 코팅막에 달라붙지 않도록 하는 오염 방지 기능이 향상될 수 있다.The wider the hydrophilic area, the more advantageous it can be in environments with high humidity. In a high humidity environment, moisture in the air first attaches to the antifouling coating film, and then contaminants accumulate. Therefore, it is effective to increase cleaning properties by using a coating film with a large hydrophilic area. On the other hand, when the minority area is large, the contamination prevention function that prevents contaminants from sticking to the coating film can be improved.
본 발명에서 제시하는, 친수성 용액 및 소수성 용액의 함량과 코팅액 도포 방식을 조절함으로써, 면적분율로, 친수 영역 3.3 내지 31% 및 나머지 소수 영역을 포함하는 방오 코팅막을 구현할 수 있다.By adjusting the content of the hydrophilic solution and the hydrophobic solution and the coating solution application method presented in the present invention, an antifouling coating film containing 3.3 to 31% of the hydrophilic region and the remaining minority region in terms of area fraction can be implemented.
도 4는, 친수성 용액 90 중량%를 포함하는 에멀젼 혼합 코팅액으로, Dry on Dry 방식에 의해 제조된 방오 코팅막을, 주사전자현미경(Scanning Electrone Microscope, SEM)으로 500배 확대 촬영한 사진이고, 도 5는, 친수성 용액 90 중량%를 포함하는 에멀젼 혼합 코팅액으로, Wet on Wet 방식에 의해 제조된 방오 코팅막을 주사전자현미경(Scanning Electrone Microscope, SEM)으로 500배 확대 촬영한 사진이다.Figure 4 is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared by the Dry on Dry method with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution, and Figure 5 is an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution, and is a photograph taken at 500 times magnification using a scanning electron microscope (SEM) of an antifouling coating film manufactured by the Wet on Wet method.
도 4를 참고하면, 친수성 용액 함량을 낮추고, 코팅액을 Dry on Dry 방식으로 도포함으로써, 친수 영역의 면적분율이 넓게 나타나도록 제어했다는 것을 확인할 수 있다. 또한, 도 5를 참고하면, 친수성 용액 함량을 낮추고, 코팅액을 Wet on Wet 방식으로 도포함으로써, 친수 영역의 면적분율이 좁게 나타나도록 제어했다는 것을 확인할 수 있다.Referring to FIG. 4, it can be seen that the area fraction of the hydrophilic region was controlled to be wide by reducing the content of the hydrophilic solution and applying the coating solution using a dry on dry method. Additionally, referring to Figure 5, it can be seen that the area fraction of the hydrophilic region was controlled to be narrow by lowering the content of the hydrophilic solution and applying the coating solution in a wet-on-wet manner.
추가적으로, 건조 온도, 용매 종류 등에 따라 소수 영역 내 기공의 크기를 조절함으로써, 친수 및 소수 영역을 제어할 수도 있다.Additionally, the hydrophilic and hydrophobic regions can be controlled by adjusting the size of the pores in the hydrophobic region depending on the drying temperature, type of solvent, etc.
도 6은, 친수성 용액 90 중량%를 포함하는 에멀젼 혼합 코팅액으로 제조된 방오 코팅막을 주사전자현미경(Scanning Electrone Microscope, SEM)으로 10000배 확대 촬영한 사진이다.Figure 6 is a photograph taken at 10,000 times magnification using a scanning electron microscope (SEM) of an antifouling coating film prepared with an emulsion mixed coating solution containing 90% by weight of a hydrophilic solution.
도 6을 참고하면, 소수 영역 내 미세 기공이 형성되어 있는 것을 확인할 수 있다. 소수성 용액의 용매는 대부분 코팅막 표면에 존재하므로, 증발이 비교적 빠르게 발생할 수 있다. 따라서, 소수 영역의 경우에는, 미세 기공이 형성될 수 있다.Referring to Figure 6, it can be seen that fine pores are formed in the minority area. Since most of the solvent in the hydrophobic solution exists on the surface of the coating film, evaporation can occur relatively quickly. Therefore, in the case of few regions, fine pores may be formed.
한편, 소수 영역 내 기공의 크기는, 상기 건조 단계의 건조 온도 및 소수성 용매의 종류에 따라 제어될 수 있다. 건조 온도가 낮거나, 증발 속도가 느린 소수성 용매를 사용할 경우에는, 소수 영역 내 기공의 크기가 작아질 수 있다. 소수 영역 내 기공의 크기가 작아지면, 소수 영역에 따른 방오 효과를 더욱 높일 수 있다.Meanwhile, the size of the pores in the hydrophobic region can be controlled depending on the drying temperature of the drying step and the type of hydrophobic solvent. When the drying temperature is low or a hydrophobic solvent with a slow evaporation rate is used, the size of the pores in the hydrophobic region may become small. If the size of the pores in the minority area becomes smaller, the antifouling effect according to the minority area can be further increased.
즉, 친수성 용액 및 소수성 용액의 함량, 코팅액 도포 방식, 건조 온도, 용매 종류 등에 따라 친수 및 소수 영역을 제어한다는 것을 확인할 수 있다. 따라서, 본 발명의 일 예에 의하면, 용액 기반으로 단순하고 경제적으로 친수 및 소수 영역을 동시에 갖는 방오 코팅막을 구현할 수 있다. 또한, 본 발명의 일 예에 의하면, 복잡한 장비나 별도의 물질 합성 없이, 친수 및 소수 영역을 제어할 수 있다.In other words, it can be confirmed that the hydrophilic and hydrophobic regions are controlled depending on the content of the hydrophilic solution and the hydrophobic solution, the coating solution application method, drying temperature, type of solvent, etc. Therefore, according to an example of the present invention, an antifouling coating film having both hydrophilic and hydrophobic regions can be implemented simply and economically based on a solution. Additionally, according to an example of the present invention, the hydrophilic and hydrophobic regions can be controlled without complex equipment or separate material synthesis.
한편, 상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함할 수 있다.Meanwhile, the hydrophilic polymers include polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, polyallylamine, and polyethyleneimine. It may include at least one of (polyethyleneimine), polyalkyloxazoline, and polyalkylamine.
또한, 상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함할 수 있다.Additionally, the hydrophobic polymer may include at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
본 발명의 일 실시예에 따른 방오 코팅막은, SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함할 수 있다.The antifouling coating film according to an embodiment of the present invention may further include at least one of SiO 2 nanoparticles and an antistatic agent.
상술한 것처럼, SiO2 나노입자는 방오 코팅막의 강도를 보강하는 효과가 있고, 대전방지제는 대전에 의한 오염물 부착을 억제하는 효과를 극대화할 수 있다. 한편, 대전방지제로써 ZOT(Zn-Sn-O) 입자를 활용할 수 있으나, 이에 한정되지는 않는다.As described above, SiO 2 nanoparticles have the effect of reinforcing the strength of the antifouling coating film, and the antistatic agent can maximize the effect of suppressing the attachment of contaminants due to charging. Meanwhile, ZOT (Zn-Sn-O) particles can be used as an antistatic agent, but are not limited to this.
다음으로, 본 발명의 또 다른 일 측면에 따른 가전기기용 패널에 대하여 설명한다.Next, a panel for home appliances according to another aspect of the present invention will be described.
본 발명의 일 실시예에 따른 가전기기용 패널은, 기재; 및 상기 기재 상부에 마련된 방오 코팅막을 포함하고, 상기 방오 코팅막은, 친수성 고분자와 소수성 고분자를 모두 포함하고, 면적분율로, 친수 영역 3.3 내지 31% 및 나머지 소수 영역을 포함할 수 있다.A panel for home appliances according to an embodiment of the present invention includes: a substrate; and an antifouling coating film provided on the top of the substrate, wherein the antifouling coating film includes both hydrophilic polymers and hydrophobic polymers, and may include 3.3 to 31% of the hydrophilic region and the remaining hydrophobic region in terms of area fraction.
가전기기의 사용 환경에 따라 상기 방오 코팅막의 친수 및 소수 영역의 면적분율을 제어할 수 있다. 예를 들면, 에어컨, 가습기 등 습도가 높은 환경에서 사용되는 가전기기의 경우에는, 친수 영역이 넓은 방오 코팅막을 활용한 가전기기용 패널을 사용함으로써, 효과적으로 청소성을 향상시킬 수 있다.Depending on the usage environment of the home appliance, the area fraction of the hydrophilic and hydrophobic regions of the antifouling coating film can be controlled. For example, in the case of home appliances used in environments with high humidity, such as air conditioners and humidifiers, cleaning efficiency can be effectively improved by using panels for home appliances that utilize an antifouling coating film with a large hydrophilic area.
상기 기재는, 전기아연도금강판 (EGI), 폴리 프로필렌 (PP) 및 스티렌-아크릴로니트릴(SAN) 중 적어도 하나를 포함할 수 있다. 다만 이에 한정되지 않고, 가전기기의 목적 및 용도에 따라 보다 적합한 기재를 선택할 수도 있다.The substrate may include at least one of electrogalvanized steel (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN). However, it is not limited to this, and a more suitable substrate may be selected depending on the purpose and use of the home appliance.
상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함할 수 있다.The hydrophilic polymers include polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, polyallylamine, and polyethyleneimine. ), polyalkyloxazoline, and polyalkylamine.
또한, 상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함할 수 있다.Additionally, the hydrophobic polymer may include at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
상기 가전기기용 패널은, SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함할 수 있다.The home appliance panel may further include at least one of SiO 2 nanoparticles and an antistatic agent.
상술한 것처럼, SiO2 나노입자는 방오 코팅막의 강도를 보강하는 효과가 있고, 대전방지제는 대전에 의한 오염물 부착을 억제하는 효과를 극대화할 수 있다. 한편, 대전방지제로써 ZOT(Zn-Sn-O) 입자를 활용할 수 있으나, 이에 한정되지는 않는다.As described above, SiO 2 nanoparticles have the effect of reinforcing the strength of the antifouling coating film, and the antistatic agent can maximize the effect of suppressing the attachment of contaminants due to charging. Meanwhile, ZOT (Zn-Sn-O) particles can be used as an antistatic agent, but are not limited to this.
이하에서, 본 발명에 대한 이해를 돕기 위하여 실시예 및 비교예를 기재한다. 다만, 하기 기재는 본 발명의 내용 및 효과에 관한 일 예에 해당할 뿐, 본 발명의 권리범위 및 효과가 반드시 이에 한정되는 것은 아니다.Below, examples and comparative examples are described to aid understanding of the present invention. However, the following description only corresponds to an example of the content and effects of the present invention, and the scope and effects of the present invention are not necessarily limited thereto.
{실시예}{Example}
<친수 및 소수 영역 면적분율 측정 시험><Hydrophilic and hydrophobic region area fraction measurement test>
아래 표 1에는, 본 발명의 일 예에 따른 방오 코팅막에 대해, 주사전자현미경(Scanning Electrone Microscope, SEM)을 이용하여, 친수 및 소수 영역의 면적분율을 측정해 나타냈다. 특히, 친수성 및 소수성 용액의 함량과 도포 방식에 따른, 친수 및 소수 영역의 면적분율을 나타냈다.Table 1 below shows the area fractions of hydrophilic and hydrophobic regions measured using a scanning electron microscope (SEM) for the antifouling coating film according to an example of the present invention. In particular, the area fractions of hydrophilic and hydrophobic regions according to the content of hydrophilic and hydrophobic solutions and application method were shown.
시편은, 전기이연도금강판(EGI) 기재, 폴리비닐알코올 (polyvinylalcohol, PVA)을 물에 용해시킨 친수성 용액 및 불소실리콘을 하이드로플루오로에테르 (HFE)에 용해시킨 소수성 용액을 사용하여 제조하였다. 건조 단계는, 150℃에서 20분간 수행했다.The specimen was manufactured using an electroplated steel sheet (EGI) substrate, a hydrophilic solution of polyvinyl alcohol (PVA) dissolved in water, and a hydrophobic solution of fluorinated silicon dissolved in hydrofluoroether (HFE). The drying step was performed at 150°C for 20 minutes.
코팅액 도포 방식Coating liquid application method Dry on DryDry on Dry Wet on WetWet on Wet
친수성 용액 함량
(중량%)Hydrophilic solution content
(weight%) 		9090 9595 9090 9999
친수 영역 면적분율(%)Hydrophilic area area fraction (%) 1717 99 3.53.5 3131
표 1을 참고하면, 친수 영역 면적분율은, 친수성 용액 및 소수성 용액의 함량과 코팅액 도포 방식에 따라 제어된다는 것을 확인할 수 있었다. 또한, Dry on Dry 방식의 경우에는 친수성 용액의 함량이 증가할수록 친수 영역의 면적분율이 감소하고, Wet on Wet 방식의 경우에는 친수성 용액의 함량이 증가할수록 친수 영역의 면적분율이 증가한다는 것을 확인할 수 있었다.Referring to Table 1, it was confirmed that the hydrophilic region area fraction was controlled depending on the contents of the hydrophilic solution and hydrophobic solution and the coating solution application method. In addition, in the case of the Dry on Dry method, as the content of the hydrophilic solution increases, the area fraction of the hydrophilic region decreases, and in the case of the Wet on Wet method, it can be seen that the area fraction of the hydrophilic region increases as the content of the hydrophilic solution increases. there was.
<청소성 시험><Cleanability test>
청소성 시험은, 10℃ 및 습도 80%인 저온 다습한 환경에서, 각 시편에 대해, 3D 현미경으로 이미지화한 사진을 바탕으로, 오염도를 측정함으로써 수행했다.The cleanability test was performed by measuring the degree of contamination of each specimen in a low-temperature and high-humidity environment of 10°C and 80% humidity, based on photographs imaged with a 3D microscope.
각 시편은, 10℃ 및 습도 80%인 환경에서 5일간 방치하여 오염시켰고, 동일한 면포로 문질러 청소했다.Each specimen was left in an environment of 10°C and 80% humidity for 5 days to become contaminated, and was cleaned by rubbing with the same cotton cloth.
3D 현미경으로 이미지화한 사진에서, 밝은 부분은 먼지가 부착되어 오염된 부분이고, 어두운 부분은 깨끗한 부분이다.In the photo imaged with a 3D microscope, the bright part is the contaminated part with dust attached, and the dark part is the clean part.
오염도는, 시편 전체 면적 대비 먼지가 부착되어 있는 면적을 의미한다.The degree of contamination refers to the area to which dust is attached compared to the total area of the specimen.
도 7은, 미코팅 기재를, 10℃ 및 습도 80%인 환경에서 오염시킨 후의 모습을 3D 현미경으로 이미지화한 사진이고, 도 8은, 10℃ 및 습도 80%인 환경에서 오염된 미코팅 기재를, 면포로 청소한 후의 모습을 3D 현미경으로 이미지화한 사진이다.Figure 7 is a photograph imaged with a 3D microscope of an uncoated substrate after being contaminated in an environment of 10°C and 80% humidity, and Figure 8 is a photograph of an uncoated substrate contaminated in an environment of 10°C and 80% humidity. , This is a photo imaged with a 3D microscope of the appearance after cleaning with a cotton cloth.
한편, 도 7 및 도 8의 시편은, 전기이연도금강판(EGI) 기재를 사용했다.Meanwhile, the specimens in FIGS. 7 and 8 used an electro-galvanized steel sheet (EGI) substrate.
도 9는, 방오 코팅 기재를, 10℃ 및 습도 80%인 환경에서 오염시킨 후의 모습을 3D 현미경으로 이미지화한 사진이고, 도 10은, 10℃ 및 습도 80%인 환경에서 오염된 방오 코팅 기재를, 면포로 청소한 후의 모습을 3D 현미경으로 이미지화한 사진이다. Figure 9 is a photograph imaged with a 3D microscope of an antifouling coating substrate after it was contaminated in an environment of 10°C and 80% humidity, and Figure 10 is a photograph of an antifouling coating substrate contaminated in an environment of 10°C and 80% humidity. , This is a photo imaged with a 3D microscope of the appearance after cleaning with a cotton cloth.
한편, 도 9 및 도 10의 시편은, 전기이연도금강판(EGI) 기재, 폴리비닐알코올 (polyvinylalcohol, PVA)을 물에 용해시킨 친수성 용액 및 불소실리콘을 하이드로플루오로에테르 (HFE)에 용해시킨 소수성 용액을 사용하여 제조했다. 에멀젼 혼합 코팅액은, 친수성 용액 90 중량%, 나머지 소수성 용액 및 기타 불순물을 포함하도록 제조했다. 도포 방식은 Dry on Dry 방식으로 수행했고, 건조 단계는 150℃에서 20분간 수행했다.Meanwhile, the specimens in Figures 9 and 10 are electroplated steel sheet (EGI) substrate, a hydrophilic solution obtained by dissolving polyvinyl alcohol (PVA) in water, and a hydrophobic solution obtained by dissolving fluorinated silicon in hydrofluoroether (HFE). Prepared using a solution. The emulsion mixed coating solution was prepared to contain 90% by weight of the hydrophilic solution, the remaining hydrophobic solution, and other impurities. The application method was Dry on Dry, and the drying step was performed at 150°C for 20 minutes.
도 7 및 도 8을 참고하면, 미코팅 기재의 경우에는, 10℃ 및 습도 80%인 환경에서 오염시킨 후의 오염도가 94.8%로 나타났고, 면포로 청소한 후의 오염도가 71.9%로 나타났다. 즉, 미코팅 기재는, 오염 방지가 거의 되지 않았을 뿐만 아니라, 청소성도 열위했다.Referring to Figures 7 and 8, in the case of the uncoated substrate, the degree of contamination after contamination in an environment of 10°C and 80% humidity was found to be 94.8%, and the degree of contamination after cleaning with a cotton cloth was found to be 71.9%. In other words, the uncoated substrate not only did little to prevent contamination, but also had poor cleaning properties.
도 9 및 도 10을 참고하면, 방오 코팅 기재의 경우에는, 10℃ 및 습도 80%인 환경에서 오염시킨 후의 오염도가 13.5%로 나타났고, 면포로 청소한 후의 오염도가 0.1%로 나타났다. 즉, 방오 코팅 기재는, 오염 방지 효과가 매우 우수했을 뿐만 아니라, 청소성도 월등히 향상되었다.Referring to Figures 9 and 10, in the case of the antifouling coating substrate, the contamination level after contamination in an environment of 10°C and 80% humidity was found to be 13.5%, and the contamination level after cleaning with a cotton cloth was 0.1%. In other words, the anti-fouling coating substrate not only had an excellent anti-fouling effect, but also significantly improved cleaning properties.
본 발명의 일 예에 의하면, 사용 환경에 따라 친수 및 소수 영역을 제어하여 청소성을 극대화시킨 방오 코팅막을 제공할 수 있다. 또한, 본 발명의 일 예에 의하면, 용액 기반으로 단순하고 경제적인, 방오 코팅막의 제조방법을 제공할 수 있다.According to an example of the present invention, it is possible to provide an antifouling coating film that maximizes cleaning properties by controlling the hydrophilic and hydrophobic areas depending on the usage environment. In addition, according to an example of the present invention, a simple and economical method of manufacturing an antifouling coating film based on a solution can be provided.

Claims (15)

  1. 친수성 용액이 소수성 용액에 분산된, 에멀젼 혼합 코팅액을 제조하는 단계;Preparing an emulsion mixed coating solution in which a hydrophilic solution is dispersed in a hydrophobic solution;
    기재 표면에 상기 에멀젼 혼합 코팅액을 도포하는, 코팅액 도포 단계;A coating solution application step of applying the emulsion mixed coating solution to the surface of the substrate;
    자연 증발에 의하여, 상 변화를 유도하는 단계; 및Inducing a phase change by natural evaporation; and
    건조 단계를 포함하는, 방오 코팅막의 제조방법.A method for producing an antifouling coating film, comprising a drying step.
  2. 청구항 1에 있어서,In claim 1,
    상기 코팅액 도포 단계 이전에, 기재 표면에 프라이머를 도포하는, 프라이머 도포 단계를 더 포함하는, 방오 코팅막의 제조방법.A method for producing an antifouling coating film, further comprising a primer application step of applying a primer to the surface of the substrate before the step of applying the coating solution.
  3. 청구항1에 있어서,In claim 1,
    상기 친수성 용액은, 친수성 고분자를 포함하고,The hydrophilic solution includes a hydrophilic polymer,
    상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함하는, 방오 코팅막의 제조방법.The hydrophilic polymers include polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, polyallylamine, and polyethyleneimine. ), a method for producing an antifouling coating film comprising at least one of polyalkyloxazoline and polyalkylamine.
  4. 청구항 1에 있어서,In claim 1,
    상기 친수성 용액은, 친수성 용매를 포함하고,The hydrophilic solution includes a hydrophilic solvent,
    상기 친수성 용매는, 물, 알코올, 아세톤 및 메탄올 중 적어도 하나를 포함하는, 방오 코팅막의 제조방법.The hydrophilic solvent includes at least one of water, alcohol, acetone, and methanol.
  5. 청구항 1에 있어서,In claim 1,
    상기 소수성 용액은, 소수성 고분자를 포함하고,The hydrophobic solution includes a hydrophobic polymer,
    상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함하는, 방오 코팅막의 제조방법.The hydrophobic polymer includes at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
  6. 청구항 1에 있어서,In claim 1,
    상기 소수성 용액은, 소수성 용매를 포함하고,The hydrophobic solution includes a hydrophobic solvent,
    상기 소수성 용매는, 하이드로플루오로에테르 (HFE), 플루오로에틸렌비닐에테르 (FEVE), 헥세인, 벤젠 및 톨루엔 중 적어도 하나를 포함하는, 방오 코팅막의 제조방법.The hydrophobic solvent includes at least one of hydrofluoroether (HFE), fluoroethylene vinyl ether (FEVE), hexane, benzene, and toluene.
  7. 청구항 1에 있어서,In claim 1,
    상기 에멀젼 혼합 코팅액은, 중량%로, 친수성 용액: 90 내지 99%, 나머지 소수성 용액 및 기타 불가피한 불순물을 포함하는, 방오 코팅막의 제조방법.The emulsion mixed coating solution includes, in weight percent, a hydrophilic solution: 90 to 99%, the remaining hydrophobic solution, and other unavoidable impurities.
  8. 청구항 7에 있어서,In claim 7,
    상기 에멀젼 혼합 코팅액은, SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함하는, 방오 코팅막의 제조방법.The emulsion mixed coating solution is a method of producing an antifouling coating film, further comprising at least one of SiO 2 nanoparticles and an antistatic agent.
  9. 청구항 1에 있어서,In claim 1,
    상기 기재는, 전기아연도금강판 (EGI), 폴리 프로필렌 (PP) 및 스티렌-아크릴로니트릴(SAN) 중 적어도 하나를 포함하는, 방오 코팅막의 제조방법.The substrate includes at least one of electrogalvanized steel sheet (EGI), polypropylene (PP), and styrene-acrylonitrile (SAN).
  10. 청구항 2에 있어서,In claim 2,
    상기 코팅액 도포 단계는, Wet-on-Wet 또는 Dry-on-Dry 방식으로 수행되는, 방오 코팅막의 제조방법.A method of manufacturing an antifouling coating film, wherein the coating liquid application step is performed by Wet-on-Wet or Dry-on-Dry method.
  11. 청구항 1에 있어서,In claim 1,
    상기 건조 단계는, 60 내지 150℃에서, 10 내지 30분간 수행되는, 방오 코팅막의 제조방법.The drying step is performed at 60 to 150°C for 10 to 30 minutes.
  12. 친수성 고분자와 소수성 고분자를 모두 포함하고,Contains both hydrophilic and hydrophobic polymers,
    면적분율로, 친수 영역 3.3 내지 31% 및 나머지 소수 영역을 포함하는, 방오 코팅막.An antifouling coating film comprising, by area fraction, 3.3 to 31% of the hydrophilic region and the remaining minor region.
  13. 청구항 12에 있어서,In claim 12,
    상기 친수성 고분자는, 폴리비닐알코올 (polyvinylalcohol, PVA), 폴리비닐피리딘 (polyvinylpyridine, PVP), 폴리아크릴산 (polyacrylic acid, PAA), 폴리아크릴아미드 (polyacrylamide), 폴리알릴아민 (polyallylamine), 폴리에틸렌이민 (polyethyleneimine), 폴리알킬옥사졸린 (polyalkyloxazoline) 및 폴리알킬아민(polyalkylamine) 중 적어도 하나를 포함하는, 방오 코팅막.The hydrophilic polymers include polyvinyl alcohol (PVA), polyvinylpyridine (PVP), polyacrylic acid (PAA), polyacrylamide, polyallylamine, and polyethyleneimine. ), an antifouling coating film containing at least one of polyalkyloxazoline and polyalkylamine.
  14. 청구항 12에 있어서,In claim 12,
    상기 소수성 고분자는, 불소실리콘, 아크릴, 에폭시, 폴리에틸렌, 폴리스티렌, 폴리염화비닐, 폴리테트라플루오르에틸렌, 폴리디메틸실록산, 폴리에스테르 및 폴리우레탄 중 적어도 하나를 포함하는, 방오 코팅막.The hydrophobic polymer includes at least one of fluorosilicone, acrylic, epoxy, polyethylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polydimethylsiloxane, polyester, and polyurethane.
  15. 청구항 12에 있어서,In claim 12,
    SiO2 나노입자 및 대전방지제 중 적어도 하나를 더 포함하는, 방오 코팅막.An antifouling coating film further comprising at least one of SiO 2 nanoparticles and an antistatic agent.
PCT/KR2023/002104 2022-04-07 2023-02-14 Antifouling coating film and manufacturing method therefor WO2023195625A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020220043567A KR20230144377A (en) 2022-04-07 2022-04-07 Antifouling coating film and its manufacturing method
KR10-2022-0043567 2022-04-07

Publications (1)

Publication Number Publication Date
WO2023195625A1 true WO2023195625A1 (en) 2023-10-12

Family

ID=88243064

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2023/002104 WO2023195625A1 (en) 2022-04-07 2023-02-14 Antifouling coating film and manufacturing method therefor

Country Status (2)

Country Link
KR (1) KR20230144377A (en)
WO (1) WO2023195625A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008308560A (en) * 2007-06-13 2008-12-25 Tohcello Co Ltd Method for producing surface stain resistant composite film
WO2009062518A1 (en) * 2007-11-12 2009-05-22 Biolocus A/S Anti-fouling composition comprising an aerogel
KR20130132524A (en) * 2010-12-21 2013-12-04 아크조노벨코팅스인터내셔널비.브이. Antifouling coating composition
KR20140089074A (en) * 2013-01-04 2014-07-14 세기하이테크건설 주식회사 A composite of eco-friendly organic·inorganic composite coating materials for stain protection of surface and construction method thereof
KR102275156B1 (en) * 2021-02-10 2021-07-08 주식회사 세기엔지니어링 A Composition of Environment-Friendly Anti-Dust Coating Agent and Coating Method of Thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008308560A (en) * 2007-06-13 2008-12-25 Tohcello Co Ltd Method for producing surface stain resistant composite film
WO2009062518A1 (en) * 2007-11-12 2009-05-22 Biolocus A/S Anti-fouling composition comprising an aerogel
KR20130132524A (en) * 2010-12-21 2013-12-04 아크조노벨코팅스인터내셔널비.브이. Antifouling coating composition
KR20140089074A (en) * 2013-01-04 2014-07-14 세기하이테크건설 주식회사 A composite of eco-friendly organic·inorganic composite coating materials for stain protection of surface and construction method thereof
KR102275156B1 (en) * 2021-02-10 2021-07-08 주식회사 세기엔지니어링 A Composition of Environment-Friendly Anti-Dust Coating Agent and Coating Method of Thereof

Also Published As

Publication number Publication date
KR20230144377A (en) 2023-10-16

Similar Documents

Publication Publication Date Title
WO2015050387A1 (en) Surface-modified separation membrane and method for modifying surface of separation membrane
WO2014123376A1 (en) Water and oil ultra-repellent structure and manufacturing method therefor
WO2017115921A1 (en) Graphene dispersion, method for preparing graphene-polymer composite, and method for manufacturing barrier film using same
WO2015183008A1 (en) Coating method using particle alignment
WO2017131400A1 (en) Water-repellent agent of silicone-based emulsion and fabric water-repellent processing method using same
WO2023195625A1 (en) Antifouling coating film and manufacturing method therefor
WO2024005345A1 (en) Core-shell-type fluorine-based resin particles having improved flowability and flocculation, and preparation method
CN115850861B (en) Polypropylene hydrophobic material and preparation method and application thereof
JP5526886B2 (en) Biaxially oriented polyarylene sulfide film for mold release
WO2016133301A1 (en) Method for wet etching of block copolymer self-assembly pattern
CN1810910A (en) Anti-fouling single-component room temperature sealing silicone sulfide glue and its production process
WO2018194366A1 (en) Electrostatic chuck sealed with sealant and method for manufacturing same
WO2014084590A1 (en) Coating method using particle alignment and particle coated substrate manufactured thereby
WO2009157693A2 (en) Water treating membrane and hydrophilizing method therefor
WO2021095990A1 (en) Ultralight release film
WO2024128530A1 (en) Method for manufacturing polymer membrane using gas pressure
WO2015167235A1 (en) Polyester film and method for manufacturing same
WO2020013578A1 (en) Porous fluoropolymer composite membrane and manufacturing method therefor
WO2012087076A2 (en) Synthesis of superhydrophobic copolymer using carbon dioxide solvent and application thereof
WO2013075638A1 (en) Conductive aqueous coating for outer protection of hard rubber charging roll
WO2019245154A1 (en) Cation exchange membrane comprising polymer support and manufacturing method therefor
WO2015026093A1 (en) Method for selecting solvent for solution process using solvent group index and system using same
WO2019039909A1 (en) Silica membrane production method
WO2020027612A1 (en) Spacer for optical device lens and method for manufacturing same
WO2020256394A1 (en) Method for manufacturing composite material, and composite material

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23784853

Country of ref document: EP

Kind code of ref document: A1