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WO2024005466A1 - Composition de revêtement dur et procédé pour sa production - Google Patents

Composition de revêtement dur et procédé pour sa production Download PDF

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Publication number
WO2024005466A1
WO2024005466A1 PCT/KR2023/008793 KR2023008793W WO2024005466A1 WO 2024005466 A1 WO2024005466 A1 WO 2024005466A1 KR 2023008793 W KR2023008793 W KR 2023008793W WO 2024005466 A1 WO2024005466 A1 WO 2024005466A1
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Prior art keywords
hard coating
coating composition
silver nanoparticles
silver
weight
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Ceased
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PCT/KR2023/008793
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English (en)
Korean (ko)
Inventor
이창훈
편민욱
맹일호
장현지
이찬규
장진탁
오희봉
이태현
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Duksan Hi Metal Co Ltd
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Duksan Hi Metal Co Ltd
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Priority to CN202380049849.5A priority Critical patent/CN119452048A/zh
Publication of WO2024005466A1 publication Critical patent/WO2024005466A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver

Definitions

  • the present invention relates to a hard coating composition, and more specifically, to a hard coating composition with excellent antibacterial properties and a method for producing the same.
  • Hard coating is a technology widely applied to protect the surfaces of various plastic products such as building materials, automobile exterior parts, furniture, and display panels.
  • silver nanoparticles are known to have antibacterial and sterilizing properties, and have recently been applied in various fields such as paints, electronic devices, catalysts, and biomaterials, and are included in various products that come in contact with the human body. Methods for use are being developed.
  • the purpose of the present invention is to provide a hard coating composition that contains silver nanoparticles having antibacterial and sterilizing properties and has excellent dispersibility and antibacterial properties because the silver nanoparticles do not agglomerate within the hard coating composition.
  • Silver nanoparticles included in an amount of 0.02 to 0.2% by weight of the antibacterial hard composition and having a capping layer formed of a polymer on the surface;
  • An organic solvent that dissolves the binder resin and includes a ketone solvent includes a ketone solvent
  • It is characterized in that it contains a basic dispersant that disperses the silver nanoparticles.
  • the hard coating composition preferably has an antibacterial performance against staphylococci and E. coli of 99.9% or more after curing.
  • the basic dispersant is at least one selected from the group consisting of sodium hydroxide, diethanolamine, triethanolamine, and phosphine ligand-substituted substances.
  • the basic dispersant is preferably included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the silver nanoparticles.
  • the average particle diameter of the silver nanoparticles is preferably 5 to 50 nm.
  • the silver nanoparticles are preferably spherical.
  • the molecular weight of the capping agent is preferably 10,000 to 360,000.
  • the capping layer is preferably 0.5 nm to 10 nm.
  • the ketone solvent is preferably methyl ethyl ketone.
  • Another aspect of the present invention is,
  • the hard coating composition according to the present invention can be used for various purposes such as elevators, handles, and desks through coating. It is a coating material mainly applicable to transparent displays, and is characterized by excellent antibacterial and sterilizing properties as it contains silver nanoparticles.
  • the silver nanoparticles contains a basic dispersant so that the silver nanoparticles can be well dispersed without agglomerating. Even after the hard coating composition is applied to the plastic substrate and coated, the silver nanoparticles do not agglomerate and maintain a high surface area per unit area, resulting in excellent anti-fouling ability. has
  • Figure 1 is a schematic diagram showing the phenomenon in which silver nanoparticles applied to a hard coating solution fail to combine with methyl ethyl ketone (MEK), the main solvent of the hard coating solution, and the distance between silver nanoparticles shortens and agglomerates.
  • MEK methyl ethyl ketone
  • Figure 2 is a schematic diagram to explain the phenomenon in which silver nanoparticles applied to a hard coating solution do not disperse well and agglomerate in a hard coating solution in an acidic atmosphere.
  • Figure 3 is a schematic diagram to explain the phenomenon in which silver nanoparticles applied to the hard coating solution according to the present invention are well dispersed without agglomerating in the hard coating solution in a basic atmosphere.
  • Figure 4 is a schematic diagram showing a method of manufacturing a hard coating composition, which is an aspect of the present invention.
  • the terms comprise, comprises, and comprise mean to include the mentioned article, step, or group of articles, and steps, and any other article. , it is not used in the sense of excluding a step, a group of objects, or a group of steps.
  • a hard coating composition containing silver nanoparticles includes silver nanoparticles, a basic dispersant, a binder resin, and an organic solvent.
  • Silver nanoparticles are a material that plays a role in improving the anti-contamination ability of the hard coating composition.
  • silver particles coated with a capping agent are used.
  • the particle size increases due to agglomeration between silver particles due to steric hindrance along with electrostatic repulsion. It serves to prevent dispersion and increase dispersion safety.
  • the silver nanoparticles of the present invention are characterized by having a capping layer by binding a capping agent to the surface of Ag+ ions.
  • a capping agent refers to a polymer material that is attached to the surface of a silver nanostructure so that the surface of the silver nanoparticle can be crystallized.
  • the capping agent may be a surface-adhering polymer such as polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA), polyacrylamide (PAM), or polyacrylicacid (PAA), and is preferred. It is better to use PVP.
  • PVP polyvinylpyrrolidone
  • PVA polyvinylalcohol
  • PAM polyacrylamide
  • PAA polyacrylicacid
  • the molecular weight of the capping agent is preferably 10,000 to 360,000. If the molecular weight of the capping agent is less than 10,000, there may be a problem in that the polymer film formed is too thin to effectively prevent silver nanoparticles from agglomerating together. If the molecular weight of the capping agent is greater than 360,000, steric hindrance may occur due to the long polymer chain. Due to this, there is a problem in that it is difficult to attach to the surface of the silver precursor and silver nanoparticles cannot be formed well.
  • silver nanoparticles are used having an average particle diameter of 5 nm to 50 nm, preferably 20 to 40 nm. If the average particle diameter of the silver nanoparticles is less than the above range, there is a problem that the loss rate is large during the purification step after synthesizing the silver nanoparticles, and if it exceeds the above range, the surface area of the silver nanoparticles exposed per unit area compared to the same solid content There was a problem in that it was small and did not show good antibacterial performance.
  • the capping agent is mixed in an amount of 1,000 to 10,000 parts by weight, preferably 3,000 to 5,000 parts by weight, based on 100 parts by weight of the silver precursor.
  • the capping layer formed of PVP of silver nanoparticles has a thickness of 0.5 nm to 10 nm, and preferably has a thickness of 1 nm to 6 nm.
  • Silver nanoparticles are preferably included in 0.02 to 0.2% by weight of the weight of the hard coating composition. More preferably, it is contained in 0.09 to 0.12 wt%. If the content of silver nanoparticles is less than the above range, the surface area of the silver nanoparticles exposed per unit area becomes small and there may be a problem of poor antibacterial performance, and if it exceeds the above range, the viscosity of the entire composition increases, reducing workability. There may be a problem in that the adhesive strength with the substrate decreases after coating.
  • a typical solution synthesis method polyol synthesis method
  • Polyol refers to alcohols containing two or more hydroxy groups (-OH) in the molecule.
  • Polyol synthesis is a method of synthesizing silver nanostructures using polyols, i.e. polyhydric alcohols, as a solvent and reducing agent. .
  • a reduction reaction can be induced by adding a polymer material that acts as a growth control and protective film to preheated polyol along with silver ions.
  • the polymer material acts as a capping agent attached to the surface of the silver nanostructure, forming a capping layer surrounding the surface of the particle along with the redox reaction in the solution, and the synthesized silver nanoparticles remain for a long time. It keeps it stable.
  • Polyvinylpyrrolidone is a polymer material commonly used in the synthesis of silver nanoparticles.
  • PVP is a reducing agent that reduces silver ions to silver nanoparticles and a stabilizer that ensures stable dispersion of the synthesized silver nanoparticles. Can perform roles simultaneously.
  • silver nanoparticles can be produced by mixing and heating an ethylene glycol (EG) solution in which silver nitrate (AgNO3) is dissolved and an EG solution in which polyvinylpyrrolidone (PVP) is dissolved.
  • EG ethylene glycol
  • PVP polyvinylpyrrolidone
  • the basic dispersant is included to disperse well without agglomerating in the hard coating composition in order to exhibit antibacterial properties when applied to the hard coating composition.
  • Sodium hydroxide, diethanolamine, triethanolamine, substances with substituted phosphine ligands, etc. can be used as basic dispersants, and are contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent. It is desirable.
  • the dispersibility of silver nanoparticles varies depending on the applied solvent. For example, when silver nanoparticles with a PVP coating layer are dispersed in water or ethanol as shown in Figure 1, the oxygen atoms in the PVP molecule and the ethanol or water molecules Dispersibility may occur due to the electrostatic attraction between hydrogen atoms.
  • PVP which forms the capping layer of silver nanoparticles
  • MEK methyl ethyl ketone
  • typical hard coating solutions are acidic with a low pH, and as shown in Figure 2, electrons around the silver nanoparticles induce bonding with hydrogen cations (H+), causing the silver nanoparticles to agglomerate.
  • H+ hydrogen cations
  • Figure 3 is a schematic diagram to explain the phenomenon in which silver nanoparticles applied to a hard coating solution are well dispersed without agglomerating in a hard coating solution in a basic atmosphere.
  • the binder resin may include an acrylic-based, urethane-based, or silicone-based resin (or monomer).
  • Binder resins specifically include poly(methyl) acrylic acid and its salts, poly(methyl) acrylate, butyl ester, polyacrylamide, polyacrylonitrile, polyurethane, polyester, melamine, vinyl acetate, polyethylene, polypropylene, and polyester. It may include vinyl alcohol, polyethylene glycol, epoxy, siloxane, polydimethylsiloxane, or copolymers thereof.
  • the binder resin is preferably contained in an amount of 50 to 100 parts by weight, preferably 60 to 80 parts by weight, based on 100 parts by weight of the organic solvent.
  • the hard coating composition may further include a curing agent as a material for curing the binder resin.
  • a curing agent as a material for curing the binder resin.
  • the material of the hardener is not limited, but specifically, aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and azomethylphenol, and phenol.
  • Polyhydric hydroxy compounds such as novolak resin, orthocresol novolak resin, naphthol novolak resin, and phenol aralkyl resin, and their modified products, such as phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride.
  • Acid anhydride-based curing agents, dicyandiamide, imidazole, BF3-amine complexes, guanidine derivatives, etc. can be used, and it is preferable to use one or a mixture of two or more of the above-mentioned curing agents.
  • the curing agent is preferably contained in an amount of 5 to 10 parts by weight, preferably 5 to 8 parts by weight, based on 100 parts by weight of the organic solvent.
  • the organic solvent serves to control the flowability of the hard coating composition by dissolving the binder resin.
  • the organic solvent is alcohol such as methanol or isopropanol, ketone such as acetone, methyl ethyl ketone, methyl butyl ketone or methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, Ethers such as diethyl ether, dimethyl ether, or propylene glycol ether may be used, and it is most preferable to use methyl ethyl ketone to improve the adhesion of the hard coating film.
  • the organic solvent includes an organic solvent included in the Ag nanoparticle dispersion when producing Ag nanoparticles.
  • Additives may include non-basic dispersants, plasticizers, anti-settling agents, anti-foaming agents, thickeners, and anti-filming agents.
  • Non-basic dispersants include block copolymers, sodium naphthalenesulfonate, sodium alkylnaphthalenesulfonate, sodium phenolsulfonate, alkyl diphenyl ether, polyoxyethylene alkyl ether, nonionic surfactant, sodium polyacrylate, sodium olefin-maleate, condensed phosphate, Carboxymethylcellulose, amine derivatives, etc. can be used, and block copolymer-based dispersants can be used to improve the dispersibility of hard coating compositions.
  • the non-basic dispersant is preferably contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent.
  • the hard coating composition of the present invention has an antibacterial performance of 99.9% or more against staphylococci and Escherichia coli after curing.
  • a method for producing a hard coating composition is provided.
  • Figure 4 is a schematic diagram showing a method of manufacturing a hard coating composition, which is an aspect of the present invention.
  • the method for preparing a hard coating composition includes a silver nanoparticle preparation step, a silver nanoparticle dispersion preparation step, and a hard coating solution preparation step.
  • the silver nanoparticle manufacturing step includes a first solution manufacturing process for preparing a capping agent solution, a second solution manufacturing process for preparing a silver precursor solution, a synthesis process for synthesizing silver nanoparticles by mixing the first solution and the second solution, and It includes a purification process to purify silver nanoparticles.
  • the first solution preparation process is a step of preparing a capping agent solution by dissolving and heating the capping agent in a reducing solvent.
  • a capping agent refers to a polymer material that is attached to the surface of a silver nanostructure so that the surface of the silver nanoparticle can be crystallized.
  • the capping agent may be a surface-adhering polymer such as polyvinylpyrrolidone (PVP), polyvinylalcohol (PVA), polyacrylamide (PAM), or polyacrylicacid (PAA), and is preferred. It is better to use PVP.
  • PVP polyvinylpyrrolidone
  • PVA polyvinylalcohol
  • PAM polyacrylamide
  • PAA polyacrylicacid
  • the molecular weight of the capping agent is preferably 10,000 to 360,000. If the molecular weight of the capping agent is less than 10,000, there may be a problem in that the polymer film formed is too thin to effectively prevent silver nanoparticles from agglomerating together. If the molecular weight of the capping agent is greater than 360,000, steric hindrance may occur due to the long polymer chain. Due to this, there is a problem in that it is difficult to attach to the surface of the silver precursor and silver nanoparticles cannot be formed well.
  • the reducing solvent is a polar solvent in which the silver precursor and the capping agent are dissolved, and a solvent having at least two hydroxy groups in the molecule, such as diol, polyol, or glycol, may be used.
  • the reducing solvent includes ethylene glycol (EG), propylene glycol (PG), or glycerol, and more specifically, ethylene glycol, polyethylene glycol, 1, 2-propylene glycol, It may contain at least one of 1, 3-propylene glycol, glycerin, glycerol and diethyl glycol, preferably at least one of ethylene glycol, polyethylene glycol or propylene glycol, more preferably ethylene glycol. It is good to include .
  • EG ethylene glycol
  • PG propylene glycol
  • glycerol ethylene glycol
  • ethylene glycol polyethylene glycol
  • 1, 2-propylene glycol It may contain at least one of 1, 3-propylene glycol, glycerin, glycerol and diethyl glycol, preferably at least one of ethylene glycol, polyethylene glycol or propylene glycol, more preferably ethylene glycol. It is good to include .
  • the reducing solvent in an amount of 0.5 to 5 times the weight of the capping agent.
  • the first solution is prepared by adding a reducing solvent and a capping agent to the reactor, mixing and stirring using an impeller, and heating the reactor so that the internal temperature of the reactor is 140 to 170 degrees Celsius.
  • the second solution preparation step is a step of preparing a silver precursor solution by dissolving the silver precursor in a reducing solvent.
  • the silver precursor is a compound consisting of a silver cation (Ag+) and an organic or inorganic anion.
  • the silver precursor may be specifically selected from AgBF 4 , AgCF 3 SO 3 , AgClO 4 , AgNO 3 , Ag(CH 3 COO), AgPF 6 or Ag(CF 3 COO), or a mixture thereof.
  • the reducing solvent used in the second solution preparation step may be any of the reducing solvents listed in the above-mentioned first solution preparation step, and preferably includes one or more of the reducing solvents used in the first solution preparation step.
  • the reducing solvent acts as a reducing agent and reduces the silver precursor to form silver ions.
  • the reducing solvent it is preferable to mix the reducing solvent using 1 to 20 times the weight of the silver precursor.
  • the silver precursor solution formed by mixing the silver precursor and the reducing solvent is stirred and maintained at a temperature of 10°C to 30°C for 3 hours or more.
  • the synthesis step is a step of mixing the capping agent solution and the silver precursor solution prepared in the first solution preparation step and the second solution preparation step to form a mixed solution and synthesize silver nanoparticles.
  • a capping agent surrounds and binds to the surface of Ag+ ions reduced by a reducing solvent in the mixed solution to form a film or capping layer.
  • the formed silver nanoparticles preferably have a particle diameter of 5 nm to 50 nm, and the capping layer preferably has a thickness of 1 nm to 6 nm.
  • the thickness of the capping layer can be determined by removing the solvent and polymer, calculating the volume and mass of the Ag particles under the assumption that the silver nanoparticles are perfectly spherical, and then calculating the mass and volume of the polymer accordingly. In other words, assuming that PVP caps Ag in a spherical shape, the diameter of the capping portion is calculated backwards and calculated as expected.
  • the silver precursor may be mixed at a concentration of 0.01 mol/l to 1.0 mol/l with respect to the entire mixed solution, and may be mixed at a concentration of 5 g/kg to 100 g/kg by weight.
  • the concentration is less than 0.01 mol/l or 5 g/kg, the amount of nanoparticles produced decreases rapidly, and if the concentration is more than 1.0 mol/l or 100 g/kg, there is a problem of nanoparticles agglomerating due to overproduction. More preferably, it is mixed at 0.05 mol/l to 0.5 mol/l or 10 g/kg to 30 g/kg.
  • the capping agent is mixed in an amount of 1,000 to 10,000 parts by weight, preferably 3,000 to 5,000 parts by weight, based on 100 parts by weight of the silver precursor. If the capping agent is less than the above range, a problem occurs in which the diameter of the generated nanoparticles increases, and if it exceeds the above range, the thickness of the capping layer increases, making it difficult to exhibit antibacterial properties.
  • the purification step is a step in which the reacted nanoparticles are cooled to room temperature, washed and purified using acetone, ethanol, etc. to obtain synthesized silver nanoparticles.
  • the solvent and unreacted polymer are removed from the silver nanoparticles, the volume and mass of the obtained silver nanoparticles are calculated, and then the mass and volume of the polymer are calculated accordingly.
  • the thickness of the capping layer can be calculated by recalculating the diameter of the part capping the silver particles.
  • the silver nanoparticle dispersion preparation step is a step of preparing a dispersion by mixing the silver nanoparticles obtained in the silver nanoparticle preparation step with a dispersion solvent.
  • the dispersion solvent can be a solvent such as distilled water, ethanol, or isopropanol, and it is preferable to use the same solvent as the solvent used in the next step, the hard coating solution preparation step.
  • the silver nanoparticle dispersion preferably contains 5 to 25 parts by weight of silver nanoparticles, and more preferably 12 to 16 parts by weight, based on a total of 100 parts by weight.
  • the hard coating solution preparation step is a step of preparing a hard coating composition by mixing a binder resin, a silver nanoparticle dispersion, and a basic dispersant.
  • a hard coating composition is prepared by mixing a binder resin with a silver nanoparticle dispersion, adding a basic dispersant, and dispersing through a shaker.
  • the binder resin may include acrylic, urethane, or silicone resin (or monomer).
  • the binder resin includes poly(methyl) acrylic acid and its salts, poly(methyl) acrylate, butyl ester, polyacrylamide, polyacrylonitrile, polyurethane, polyester, melamine, vinyl acetate, polyethylene, polypropylene, and polyester. It may include vinyl alcohol, polyethylene glycol, epoxy, siloxane, polydimethylsiloxane, or copolymers thereof.
  • the hard coating composition may further include a curing agent as a material for curing the binder resin.
  • a curing agent as a material for curing the binder resin.
  • the material of the hardener is not limited, but specifically, aliphatic amines such as diethylenetriamine and triethylenetetramine, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and azomethylphenol, and phenol.
  • Polyhydric hydroxy compounds such as novolak resin, orthocresol novolak resin, naphthol novolak resin, and phenol aralkyl resin, and their modified products, such as phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride.
  • Acid anhydride-based curing agents, dicyandiamide, imidazole, BF3-amine complexes, guanidine derivatives, etc. can be used, and it is preferable to use one or a mixture of two or more of the above-mentioned curing agents.
  • the curing agent is preferably contained in an amount of 5 to 10 parts by weight, preferably 5 to 8 parts by weight, based on 100 parts by weight of the organic solvent.
  • the organic solvent serves to control the flowability of the hard coating composition by dissolving the binder resin.
  • the organic solvent includes alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monobutyl.
  • Ethers such as ether, diethyl ether, dimethyl ether, and propylene glycol ether can be used, and it is most preferable to use methyl ethyl ketone to improve the adhesion of the hard coating film.
  • the basic dispersant is a substance added to ensure that the PVP-coated silver nanoparticles are well dispersed in the organic solvent of the hard coating composition, and is composed of at least one type of sodium hydroxide, diethanolamine, triethanolamine, or a substance substituted with a phosphine ligand. You can use it.
  • the basic dispersant is preferably contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent.
  • the additive serves to control the overall dispersibility of the silver nanoparticles and hard coating composition.
  • additives may include non-basic dispersants, plasticizers, anti-settling agents, anti-foaming agents, thickeners, anti-filming agents, etc., and non-basic dispersants were used to improve the dispersibility of hard coating compositions.
  • Non-basic dispersants include block copolymers, sodium naphthalenesulfonate, sodium alkylnaphthalenesulfonate, sodium phenolsulfonate, alkyl diphenyl ether, polyoxyethylene alkyl ether, nonionic surfactant, sodium polyacrylate, sodium olefin-maleate, condensed phosphate, Carboxymethylcellulose, amine derivatives, etc. can be used, and a block copolymer-based dispersant is used to improve the dispersibility of hard coating compositions.
  • the non-basic dispersant is preferably contained in an amount of 0.005 to 0.05 parts by weight, preferably 0.01 to 0.03 parts by weight, based on 100 parts by weight of the organic solvent.
  • a non-basic dispersant it is preferable to use the basic dispersant and the non-basic dispersant in a ratio of 1:0.8 to 1:1.
  • the hard coating composition prepared according to the hard coating solution preparation step of the present invention is characterized by a pH of 2 to 6, preferably 2.5 to 5.5 at 25°C, and when the pH is less than 2, silver nanoparticles are well dispersed in the hard coating composition. There is a problem in that the distance between silver nanoparticles is shortened and they clump together, which causes the particle size of the silver nanoparticles to increase.
  • the second solution was added to the first solution to prepare a mixed solution, and stirred for 5 minutes to synthesize silver nanoparticles coated with PVP on the surface of the Ag particles.
  • the mixed solution was cooled to room temperature and purified to obtain silver nanoparticles.
  • the purification process involves adding acetone equivalent to more than 3 times the volume of the mixed solution to the silver nanoparticles, precipitating them using centrifugation, removing the supernatant containing unreacted polymers and synthetic residues, and then purifying PVP as a precipitate. Coated silver nanoparticles were obtained.
  • the purification process was performed three times to match the target polymer content, and 7.0 g of silver nanoparticles with an average particle diameter of 35 nm and an average thickness of the polymer capping layer of 5 nm were obtained.
  • a 15% dispersion was prepared using ethanol to prepare a dispersion of silver nanoparticles in the hard coating composition.
  • the hard coating compositions of Examples 2 to 4 were prepared using the same manufacturing method as Example 1 using the ingredients and mixing ratios shown in Tables 1 and 2 below.
  • the coating agent imparted with antibacterial properties of Examples 5 to 8 and Comparative Examples 3 to 4 was applied to the PET substrate, heated to 100°C, and then cured. A hard coating film was prepared.
  • the hard coating composition according to the present invention can be used for various purposes such as elevators, handles, and desks through coating, and can be mainly applied as a coating material applicable to transparent displays.

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Abstract

L'invention concerne une composition de revêtement dur antibactérien comprenant : des nanoparticules d'argent, qui sont contenues en une quantité de 0,02 à 0,2 % en poids de la composition de revêtement dur antibactérien et qui présentent une couche de recouvrement formée d'un polymère sur sa surface ; une résine liante ; un agent de durcissement qui durcit la résine liante ; un solvant organique qui dissout la résine liante et qui comprend un solvant de type cétone ; et un dispersant basique qui disperse les nanoparticules d'argent.
PCT/KR2023/008793 2022-06-27 2023-06-23 Composition de revêtement dur et procédé pour sa production Ceased WO2024005466A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119264757A (zh) * 2024-10-18 2025-01-07 江苏集萃表面工程技术研究所有限公司 一种海洋环境下IPNs防腐蚀抗菌涂层及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119566299B (zh) * 2024-12-04 2025-10-31 西北有色金属研究院 一种用于电子3d打印导电墨水的纳米银颗粒及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012506771A (ja) * 2008-10-31 2012-03-22 ディーエスエム アイピー アセッツ ビー．ブイ． 官能化ナノ粒子を含む付着防止コーティング組成物
JP2014139343A (ja) * 2006-08-07 2014-07-31 Inktec Co Ltd 銀ナノ粒子の製造方法及びこれにより製造される銀ナノ粒子を含む銀インク組成物
JP2017071562A (ja) * 2015-10-05 2017-04-13 住友ベークライト株式会社 抗菌性組成物
US20180055975A1 (en) * 2009-12-22 2018-03-01 Aap Implantate Ag Method for Producing a Dispersion Containing Silver Nanoparticles and Use of a Mixture Containing Silver Nanoparticles as a Coating Agent
KR20200001927A (ko) * 2018-06-28 2020-01-07 덕영산업주식회사 은나노 도료 제조방법

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102332025B1 (ko) 2021-06-24 2021-12-01 (주)쉐어켐 항균 코팅 조성 및 항균 나노입자를 포함하는 광학 필름 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014139343A (ja) * 2006-08-07 2014-07-31 Inktec Co Ltd 銀ナノ粒子の製造方法及びこれにより製造される銀ナノ粒子を含む銀インク組成物
JP2012506771A (ja) * 2008-10-31 2012-03-22 ディーエスエム アイピー アセッツ ビー．ブイ． 官能化ナノ粒子を含む付着防止コーティング組成物
US20180055975A1 (en) * 2009-12-22 2018-03-01 Aap Implantate Ag Method for Producing a Dispersion Containing Silver Nanoparticles and Use of a Mixture Containing Silver Nanoparticles as a Coating Agent
JP2017071562A (ja) * 2015-10-05 2017-04-13 住友ベークライト株式会社 抗菌性組成物
KR20200001927A (ko) * 2018-06-28 2020-01-07 덕영산업주식회사 은나노 도료 제조방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119264757A (zh) * 2024-10-18 2025-01-07 江苏集萃表面工程技术研究所有限公司 一种海洋环境下IPNs防腐蚀抗菌涂层及其制备方法和应用

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