KR20200025722A - Method for antimicrobial coating of wood - Google Patents

Abstract

The present invention relates to a method for manufacturing an antibacterial wood material and, more particularly, to a wood material coated with metal nanoparticles and a method for manufacturing the same. The present invention relates to the method for manufacturing the antibacterial wood material, comprising: a first step of exposing a first metal precursor to the wood material; a second step of converting the first metal precursor coated on the wood material into metal particles to manufacture a wood material coated with metal particles; a third step of atomic layer deposition of a second metal precursor on the wood material coated with the metal particles; and a fourth step of introducing a reaction gas into the wood material with the atomic layer-deposited second metal precursor.

Description

Method for antimicrobial coating of wood

The present invention relates to a method for producing an antimicrobial wood material and an antimicrobial wood material prepared therefrom, and more particularly, to a wood material coated with antimicrobial metal nanoparticles and a method for manufacturing the same.

Most commercially available humidifiers and electronic fragrances use ultrasonic waves to diffuse humidification or fragrance by vibration energy. This method can disperse liquids faster in a simpler way than in heated and evaporative methods, but it requires a sterilization step because water droplets contain pre-grown bacteria in the container and diffuse outward. However, due to the reports that most fungicides are toxic and may affect the organs as well as the lungs or respiratory organs, a safe sterilization method is required.

As hardware specifications of electric and electronic devices are gradually advanced, wood materials are preferred as high-quality textures and eco-friendly materials for enhancing the design and practical functions of humidifiers and electronic fragrances. The interior of the wood material has a number of pores of several μm in size, the moisture can be immediately discharged through this pore structure can implement excellent humidification and aroma function.

Wood is a natural material and contains many pores therein, and thus has excellent advantages as a natural humidification or fragrance material. However, wood may deteriorate physical properties in a high humidity environment. In addition, the components such as lignocellulosic, lignin, and cellulose constituting the wood can be easily rotted by various bacteria, there is a problem that the durability of the wood can be reduced.

Therefore, in order to apply wood materials to electronic devices such as humidifiers and electronic fragrances, antibacterial and waterproof coating treatments must be performed in the wood materials. However, when the general antimicrobial coating method is used, the pores in the wood of several μm diameter or less are not used to prevent the excellent properties of the wood and moisture is difficult to be discharged to the outside of the wood. Accordingly, there is a need for a technology capable of maintaining a pore structure of several μm in the size of wood and providing a uniform antimicrobial coating layer in the pores to impart antimicrobial properties.

Korean Patent Publication No. 2013-0106997

An object of the present invention is to provide an antimicrobial wood material coated with a metal on the surface of the wood material.

Another object of the present invention is to provide a wood material excellent in antibacterial activity by promoting the generation of free radicals by coating different metals on the surface of the wood material.

It is another object of the present invention to provide an antimicrobial wood material having superior waterproofing properties compared to untreated wood material.

Another object of the present invention is to provide a coating method of antimicrobial wood material for coating a metal oxide through an atomic layer deposition process.

Another object of the present invention is to provide an antimicrobial wood humidifier and electronic wood fragrance that can diffuse humidification and fragrance through wood materials.

The method for producing an antimicrobial wood material according to the present invention includes a first step of exposing a metal precursor to a wood material and a second step of converting the metal precursor coated on the wood material into metal particles.

In the method of manufacturing an antimicrobial wood material according to an embodiment of the present invention, the first step may include an immersion step of immersing wood in a metal precursor solution containing the metal precursor.

In the method of manufacturing an antimicrobial wood material according to an embodiment of the present invention, the second step may include introducing a reducing agent into the wood material coated with the metal precursor.

In the method for producing the antimicrobial wood material according to an embodiment of the present invention, the metal precursor may be a silver precursor.

In the antimicrobial wood material according to an embodiment of the present invention, the antimicrobial wood material may be a metal nanoparticle is coated on the surface of the wood pore.

In the method of manufacturing an antimicrobial wood material according to an embodiment of the present invention, the first step may include atomic layer deposition of the metal precursor.

In the method of manufacturing an antimicrobial wood material according to an embodiment of the present invention, the second step may include introducing a reaction gas after the atomic layer deposition step.

In the method for producing an antimicrobial wood material according to an embodiment of the present invention, the metal precursor may be a titanium precursor.

In the antimicrobial wood material according to an embodiment of the present invention, the antimicrobial wood material may be a metal oxide coated on the wood pore surface.

In the method for producing an antimicrobial wood material according to the present invention, a first step of exposing a first metal precursor to a wood material, converting the first metal precursor coated on the wood material to metal particles to produce a wood material coated with metal particles And a third step of atomically depositing a second metal precursor on the wood material coated with the metal particles, and a fourth step of introducing a reaction gas into the wood material on which the second metal precursor is atomically deposited. do.

In the method of manufacturing the antimicrobial wood material according to an embodiment of the present invention, the first metal precursor and the second metal precursor may be different from each other.

In the method of manufacturing an antimicrobial wood material according to an embodiment of the present invention, the first metal precursor may include a silver precursor, and the second metal precursor may include a titanium precursor.

In the antimicrobial wood material according to an embodiment of the present invention, the antimicrobial wood material may be the first metal and the second metal oxide is coated on the wood pore surface.

Antimicrobial wood material according to an embodiment of the present invention has the advantage that can be maximized antimicrobial coating by promoting the generation of free radicals by coating different metal precursors.

The antimicrobial wood material according to an embodiment of the present invention has an advantage that the pore structure in the wood material is well preserved even when the surface of the wood material is coated with metal.

Antimicrobial wood material according to an embodiment of the present invention has the advantage that at the same time has an excellent waterproof properties compared to the wood material that is not antibacterial coating.

Antimicrobial wood material according to an embodiment of the present invention is a wood material through an atomic layer deposition process

The advantage is that the metal oxide can be coated on the surface.

Antimicrobial wood material according to an embodiment of the present invention has the advantage that can be applied to the antimicrobial wood humidifier and electronic wood fragrance can be humidified and aroma spread through the wood material.

The method for producing an antimicrobial wood material according to an aspect of the present invention includes a first step of exposing a metal precursor to a wood material and a second step of converting the metal precursor coated on the wood material into metal particles.

More specifically, the present invention may be exemplified by the following first, second and third aspects according to the method of exposing the metal precursor to a wood material, but is not limited thereto.

The first aspect of the present invention may include immersing a wood material in a metal precursor solution containing a metal precursor and reducing the metal precursor coated on the wood material to metal particles using a reducing agent.

A second aspect of the present invention may include atomic layer deposition of a metal precursor on a wood material and converting the metal precursor into metal particles using a reaction gas.

According to a third aspect of the present invention, after the first aspect, the second aspect may be implemented. More specifically, immersing a wood material in a metal precursor solution containing a first metal precursor, reducing the metal precursor coated on the wood material to metal particles using a reducing agent, the wood material coated with the metal particles Atomic layer deposition of a second metal precursor on, and converting the second metal precursor into metal particles using a reaction gas.

First, the first aspect of the present invention will be described in more detail.

In the first aspect of the present invention, immersing the wood material in the metal precursor solution containing the metal precursor may mean to penetrate the metal precursor solution into the pores of the wood material.

In a first aspect of the invention, the metal precursor solution may comprise a metal precursor and a solvent. In addition, it may further include an additive commonly used as needed.

The metal precursor may be a metal salt of a metal selected from the group consisting of silver (Ag), palladium (Pd), platinum (Pt), gold (Au), and alloys thereof. More specifically, the metal precursor may be a silver (Ag) precursor.

The silver precursor is specifically, for example, silver nitrate, silver acetate, silver perchlorate, silver chloride, silver chlorate, silver iodide and silver fluoride (silver iodide) Silver fluoride) may be any one or a combination of two or more selected from the group consisting of, but is not limited thereto.

The palladium precursor is palladium acetate ((CH ₃ COO) ₂ Pd), palladium chloride (PdCl ₂ ), palladium bromide (PdBr ₂ ), palladium iodide (PdI ₂ ), palladium hydroxide (Pd (OH) ₂ ), palladium nitrate ( Pd (NO ₃ ) ₂ ), palladium oxide (PdO), palladium sulfate (PdSO ₄ ), potassium tetrachloropallarate (K2 (PdCl ₄ )), potassium tetrabromopallamate (K ₂ (PdBr ₄ )), tetra Amminepalladium chloride (Pd (NH ₃ ) ₄ Cl ₂ ), tetraamminepalladium bromide (Pd (NH ₃ ) ₄ Br ₂ ), tetraamminepalladium nitrate (Pd (NH ₃ ) ₄ (NO ₃ ) ₂ ), tetraammine Palladium tetrachloropalladic acid ((Pd (NH ₃ ) ₄ ) (PdCl ₄ )) and ammonium tetrachloropallamate ((NH ₄ ) ₂ PdCl ₄ ), etc. But not limited to this.

Wherein the platinum precursor is platinum chloride (PtCl _2, PtCl _4), bromine painter (PtBr _2, PtBr _4), iodide, platinum (PtI _2, PtI _4), platinum chloride and potassium _{(K 2 (PtCl 4))} , hexachloroplatinic acid ( H ₂ PtCl ₆ ), platinum sulfite (H ₃ Pt (SO ₃ ) ₂ OH), platinum oxide (PtO ₂ ), tetrachloride platinum (Pt (NH ₃ ) 4Cl ₂ ), hydrogen carbonate tetraamine platinum (C ₂ H1 ₄ N ₄ O ₆ Pt), tetraamine platinum hydrogen phosphate (Pt (NH ₃ ) ₄ HPO ₄ ), tetraamine platinum hydroxide (Pt (NH ₃ ) ₄ (OH) ₂ ), tetra nitrate platinum (Pt (NO ₃ ) ₂ (NH ₃ ) ₄ ) and tetraamine platinum tetrachloroplatinum ((Pt (NH ₃ ) ₄ ) (PtCl ₄ )) and the like, but may be one or two or more combinations selected from the group consisting of, but not limited thereto.

The gold precursors are gold chloride (AuCl), gold bromide (AuBr), gold iodide (AuI), gold hydroxide (Au (OH) ₂ ), tetrachlorosuccinate (HAuCl ₄ ), potassium tetrachlorosuccinate (KAuCl ₄ ), tetrabro It may be, but is not limited to, one or two or more combinations that may be selected from the group consisting of potassium succinate (KAuBr ₄ ) and gold oxide (Au ₂ O ₃ ).

The solvent may be used without limitation as long as the solvent can impregnate the wood material and dissolve the metal precursor, for example, water, alcohol, ether solvent, acetate solvent, carbonate solvent, aliphatic solvent, alicyclic It may be a group solvent and an aromatic solvent.

The metal precursor solution may include the metal precursor in a concentration of 0.1 to 100 mg / ml, specifically, may be included in a concentration of 1 to 10 mg / ml.

The immersion step may be performed in a standby state or a reduced pressure state. The atmospheric state may be to immerse the wood in the tank containing the metal precursor solution, the reduced pressure may be to immerse the wood in the tank containing the metal precursor solution installed in the decompression chamber. More specifically, by leaving some of the exposed parts of the wood material under reduced pressure and immersing the remaining part of the wood material in the metal precursor solution, the metal precursor solution is uniformly infiltrated throughout the pore structure of the wood material to impregnate and apply This is only an example but not limited thereto.

The metal precursor solution may be uniformly infiltrated into the pores of the wood by the capillary phenomenon as the metal precursor is contained in the solution phase, it may be uniformly impregnated the pore surface. The metal precursor uniformly applied to the pore surface may be converted to metal nanoparticles uniformly applied within the pore structure by a subsequent second step.

The immersion step may be to immerse the wood material in the metal precursor solution for 10 minutes to 10 hours, specifically 10 minutes to 5 hours, more specifically may be immersed for 10 minutes to 60 minutes It is not restricted. In this case, the immersion temperature may be performed under mild conditions, and may be, for example, 25 to 100 ° C. However, the immersion temperature is not limited thereto.

The immersion step may be repeatedly performed one or more times, and the number of repetitions is not particularly limited. For example, the metal precursor solution may be applied to the pore surface of wood and dried, and then the same process may be repeated.

Next, the subsequent step of the dipping step includes converting the metal precursor coated on the wood material into metal particles. Specifically, after the immersion step may include a reduction step to convert the metal precursor into metal particles, through the reduction step may reduce the metal precursor applied to the surface of the wood material to the metal particles.

In the reduction step, a liquid phase reduction method may be used. In the liquid reduction, the metal precursor applied to the surface of the wood material by introducing a reducing agent may react with the reducing agent to uniformly form metal nanoparticle nuclei. Metal nanoparticle nuclei uniformly formed on the surface of the pores of the wood material is grown into metal nanoparticles can be produced antimicrobial wood material in which the metal nanoparticles are uniformly applied in the pores of the wood material.

As a more specific example, when the metal nanoparticles are silver nanoparticles, the production method of the silver nanoparticles may be thermal decomposition method, gas-phase condensation method, alcohol reduction method, It may be selected from the group consisting of a hydrogen reduction method (hydrogen reduction method), a liquid-phase reduction method (liquid-phase reduction method), and the like, in detail, a liquid phase reduction method may be used.

The liquid phase reduction method is relatively simple in process, easy to control the size and shape uniformity of particles according to the concentration, temperature, pH, etc., and can be mass-produced, which is very advantageous in terms of economy, and uniform particle distribution using the liquid phase reduction method. Silver nanoparticles having a can be prepared.

The liquid phase reduction method may convert a metal precursor into metal particles by introducing a reducing agent into a surface reactor, and in detail, may deposit a silver (Ag) molecule to form a nucleus. It can be coated on the surface reactor present on the surface of the.

As an example of the reducing agent, ethylene glycol, ethylene glycol, diethylene glycol, glycerol, propylene glycol, polyethylene glycol, polyethyleneimine, poly (ethylenimine), PEI ), Formaldehyde, sodium borohydride, citric acid, formamide, dimethyloformamide, hydrazine and ethanol It may be one or a combination of two or more, but is not limited thereto.

The reducing agent may be included in a concentration of 0.01 to 10% (w / v), in detail may be included in 0.1 to 5% (w / v), but is not limited thereto. Solvents that may be used with the reducing agent may be, for example, water, alcohols, ether solvents, acetate solvents, carbonate solvents, aliphatic solvents, alicyclic solvents, aromatic solvents.

The metal precursor is made of metal nanoparticles through a reduction process and a surfactant may be added to prevent aggregation and closure of the pore structure. The surfactant may act to uniformly generate and uniformly disperse the metal nanoparticles, wherein the surfactant may be included in the metal precursor solution or mixed with the reducing agent.

As the surfactant, anionic surfactants, cationic surfactants, nonionic surfactants and polymeric surfactants can be used. As one specific example, one or two or more combinations that may be selected from the group consisting of sodium dodecyl sulfate (SDS), polyvinyl alcohol (PVA), and polyvinylpyrrolidone (PVP) May be used but is not limited thereto.

The step of introducing the reducing agent may be performed at a temperature range of 100 ° C. or less, more specifically 30 to 100 ° C., and specifically, may be performed at a temperature range of 30 to 80 ° C.

Reduction of the metal precursor using the reducing agent may be performed for 10 minutes to 10 hours, specifically 10 minutes to 5 hours, more specifically 10 minutes to 60 minutes may be performed, but is not limited thereto. .

After the reduction reaction, the wood material coated with the metal particles may further include a drying step, and may be dried at 20 to 80 ° C. for 1 to 6 hours.

The dipping step and the reducing step may be repeatedly performed to form the metal particle coating layer, but are not limited thereto.

The size of the metal particles may be formed in the size of 1 nm to 100 nm, in detail may be 20 nm to 50 nm, more specifically 30 nm to 40 nm size but not limited to the numerical range Do not.

The metal particles prepared from the metal precursor may be metal nanoparticles, preferably the metal nanoparticles may be silver nanoparticles.

The silver nanoparticles may be coated on the surface of the wood material and the surface of the wood material to coat the silver nanoparticles having a uniform distribution on the wood material through an immersion step and a low temperature process for introducing the reducing agent.

The silver nanoparticle-coated wood material can provide the antimicrobial properties while protecting the pore structure of the wood material at the same time, it is particularly useful in that it is an environmentally friendly antibacterial wood material that does not require chemical fungicides.

Next, the 2nd aspect of this invention is demonstrated more concretely.

In a second aspect of the present invention, atomic layer deposition of a metal precursor on a wood material may mean depositing the metal precursor on the pore surface of the wood material.

The metal precursor used in the atomic layer deposition step is V, Al, Zn, Ti, Hf, Mg, Cu, Zr, Ca, Li, Sr, Ba, Sc, Y, Nb, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Ag, Cd, B, Ga, In, Si, Ge, Sn, Sb and Bi, or any one or a combination of two or more selected from the group consisting of It may be a metal compound. In more detail, the metal precursor may be a compound represented by Formula 1 below.

[Formula 1]

M (A) _a (B) _b

In Formula 1, M is a metal element; A and B are independently from each other -R ₁ , -OR ₂ , -N (R ₃ ) (R ₄ ), a halogen element, wherein R ₁ , R ₂ , R ₃ and R ₄ are independently substituted or unsubstituted A linear or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or a substituted or unsubstituted halogenated allyl group having 6 to 15 carbon atoms; a + b is the ionic value of M, and a and b are the integers of 0-M each below.

More specifically, the metal precursor may be a titanium precursor, and the titanium precursor may be at least one selected from the group consisting of titanium alkoxide and titanium halide.

Specific examples of the titanium precursor, titanium tetraisopropoxdie, titanium tetrabutoxide, titanium ethoxide, titanium methoxide, titanium tetrachloride (titanium tetrachloride) and the like may be selected from the group consisting of one or two or more combinations, but is not limited thereto.

The atomic layer deposition method may include a first step of exposing the raw material gas containing the metal precursor to the surface of the wood material, a second step of exhausting the by-product and residual raw material gas generated in the first step, the reaction gas It is carried out in a deposition cycle comprising a third process for supplying a, a fourth process for exhausting the by-products generated in the third process and the residual reaction gas, the deposition cycle may be repeated at least one or more times.

The first process may supply a raw material gas including a metal precursor to the chamber to expose the metal precursor to the surface of the wood material mounted in the chamber so that the metal precursor is adsorbed onto the wood material surface. The metal precursor may be exposed at a pressure range of 100 to 300 mTorr, and in detail, may be exposed at a pressure of 150 to 250 mTorr, but is not limited thereto.

Supply of the source gas containing the metal precursor may be performed in a pulsed manner, for example, a pulse for supplying the source gas may be performed for 0.001 to 10 seconds, the flow rate of the metal precursor may be 10 to 200 sccm have. More preferably, the pulse for supplying the source gas may be performed for 0.01 to 4 seconds. After the input of the raw material gas as described above, the metal precursor included in the raw material gas may further include an exposure step of waiting to be penetrated into the wood material. Although the execution time of the exposure process is not particularly limited, it may be performed for 1 to 60 seconds, more specifically for 1 to 10 seconds, but the present invention is not limited thereto.

The second process is a process of injecting an inert gas into the chamber to remove metal precursors and by-products that are not adsorbed to the wood material, as helium (He, helium), neon (Ne, Neon), argon (Ar, Argon), krypton (Kr, Krypton), xenon (Xe, Xenon) and radon (Rn, Radon) may be any one gas selected from, but is not limited thereto.

The inert gas of the second process may be supplied at a flow rate in the range of 100 to 5000 sccm for 1 to 60 seconds, more specifically 1 to 10 seconds.

The third step is to introduce a reaction gas that can react with the metal precursor adsorbed on the surface of the wood material in the first step, the metal precursor and the reaction gas is chemically reacted to form a metal oxide or metal nitride thin film Can be formed. Preferably, the metal oxide thin film may be formed, and the metal oxide thin film may be formed to improve the bonding strength between the metal oxide thin film and the wood material, and may provide an antimicrobial function to the wood material.

The reaction gas may be one or a combination of two or more selected from the group consisting of oxygen (O ₂ ), ozone (O ₃ ), H ₂ O, and hydrogen peroxide (H ₂ O ₂ ) and nitrous oxide (N ₂ O). Can be.

The reaction gas may be performed in a pulse process as described above, the input of the raw material gas, the pulse may be performed for 0.001 to 10 seconds, specifically 0.01 to 4 seconds, the flow rate of the reaction gas is 10 to 200 sccm May be, but is not limited thereto.

The third process may generate reaction gas radicals or ions by activating the reaction gas into a plasma, and the plasma may be generated through a direct plasma and a remote plasma.

The plasma power and radiation dose PD may be performed at a power of plasma of 50 to 300 W in terms of which a metal oxide atomic layer may be formed at a high deposition rate, and may be performed at a plasma power of 100 to 200 W in detail. Can be.

 The irradiation amount of the plasma may satisfy the irradiation amount PD of 2 to 15 Wsec / cm 2 and is preferably performed in a range of 5 to 10 Wsec / cm 2.

The density of the metal oxide thin film deposited on the surface of the wood material may be controlled by controlling the plasma power and the irradiation amount to adjust the density of the reaction gas radicals and ions, and may reduce defects in the metal oxide thin film.

The plasma may be irradiated for 1 to 20 seconds, and may be performed after being irradiated for 5 to 15 seconds in detail.

The third step using the plasma is carried out at a low temperature of 30 to 100 ℃ by reacting the metal precursor and radicals or ions, it is possible to suppress the thermal shock applied to the surface of the wood material.

The fourth process is to inject an inert gas in the chamber to remove the by-products generated in the third process, helium (He, helium), Neon (Ne, Neon), Argon (Ar, Argon), It may be any one selected from krypton (Kr, Krypton), xenon (Xe, Xenon) and radon (Rn, Radon), but is not limited thereto.

The fourth process may be supplied at a flow rate of 100 to 5000 sccm for 0.1 to 1000 seconds, it is possible to remove the by-products generated in the third process.

The thickness of the metal oxide thin film deposited on the surface of the wood material may be adjusted by repeating the deposition cycle of the atomic layer deposition method. The number of deposition cycles may be 1 to 5000 cycles, and in detail, may be 10 to 1000 cycles, but is not limited thereto.

The metal oxide thin film according to an embodiment of the present invention may be formed with a thickness of 1 nm to 100 nm on the surface of the wood material, and may be formed with a thickness of 20 nm to 50 nm in detail, but is not limited to the numerical range. .

Next, the 3rd aspect of this invention is demonstrated more concretely.

According to a third aspect of the present invention, a method of immersing a wood material in a metal precursor solution including a first metal precursor, reducing the metal precursor coated on the wood material to metal particles using a reducing agent, and coating the metal particles Atomic layer depositing a second metal precursor on the wood material, and converting the second metal precursor into metal particles using a reaction gas, wherein the first metal precursor and the second metal precursor are mutually It may be different.

More specifically, the first metal precursor may be a metal salt of a metal selected from the group consisting of silver (Ag), palladium (Pd), platinum (Pt), gold (Au), and alloys thereof. More specifically, the metal precursor may be a silver (Ag) precursor.

The metal of the second metal precursor is V, Al, Zn, Ti, Hf, Mg, Cu, Zr, Ca, Li, Sr, Ba, Sc, Y, Nb, Cr, Mo, W, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Ag, Cd, B, Ga, In, Si, Ge, Sn, Sb and Bi may be any one or more selected from the group consisting of. More specifically, the second metal precursor may be a compound represented by Formula 1 below.

[Formula 1]

M (A) _a (B) _b

In Formula 1, M is a metal element; A and B are independently from each other -R ₁ , -OR ₂ , -N (R ₃ ) (R ₄ ), a halogen element, wherein R ₁ , R ₂ , R ₃ and R ₄ are independently substituted or unsubstituted A linear or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, or a substituted or unsubstituted halogenated allyl group having 6 to 15 carbon atoms; a + b is the ionic value of M, and a and b are the integers of 0-M each below.

More specifically, the second metal precursor may be a titanium precursor, and the titanium precursor may be at least one selected from the group consisting of titanium alkoxide and titanium halide.

The metal particles prepared from the first metal precursor may be metal nanoparticles, and the metal oxides prepared from the second metal precursor may be nano-level thin films.

The dipping step may refer to immersing the wood material in the metal precursor solution containing the first metal precursor to infiltrate the metal precursor solution into the pores of the wood material.

The first metal precursor may be mixed in a solvent in which the metal precursor may be dissolved and included in a solution phase. As the first metal precursor is included in the solution phase, the first metal precursor may be uniformly infiltrated into the pores of wood by capillary action, and the surface of the first metal precursor may be uniformly impregnated with the first metal precursor. .

 The reducing step includes converting the metal precursor coated on the wood material into metal particles, wherein the first metal precursor impregnated and uniformly applied to the surface of the wood material is reduced to the first metal particles in a reducing atmosphere. Can be.

Specifically, the reduction of the first metal precursor may be performed through a liquid phase reduction method. In the liquid reduction, the first metal precursor applied to the surface of the wood material by introducing a reducing agent may react with the reducing agent to uniformly form the first metal nanoparticle nucleus. The first metal nanoparticle nuclei uniformly formed on the surface of the pores of the wood material may be grown into the first metal nanoparticles to produce an antimicrobial wood material in which the metal nanoparticles are uniformly applied in the pores of the wood material.

The size of the first metal nanoparticles may be formed in the size of 1 nm to 100 nm, in detail may be 20 nm to 50 nm, more specifically 30 nm to 40 nm but the numerical range Not restricted to

Atomic layer deposition of the second metal precursor on the wood material coated with the first metal precursor means atomic layer deposition of the second metal precursor on the surface of the wood material coated with the first metal particles. The second metal precursor may be deposited on the interface of the first metal particles and the surface of the wood material that is not coated with the first metal particles. Through this, the catalytic action of the first metal particles may be improved, generation of active oxygen may be promoted, and antimicrobial activity of wood materials may be enhanced.

In particular, by depositing a second metal precursor on the surface of the wood material coated with the first metal particles, oxidation of the wood material is suppressed, and the life of the first metal particle coating layer may be longer than that of the wood material coated with only the first metal particles. have.

The atomic layer deposition may include a first step of exposing the raw material gas including the second metal precursor to the surface of the wood material, and optionally, a second step of exhausting the by-product and residual raw material gas generated in the first step. .

The first process may supply a raw material gas including a second metal precursor to the chamber so that the second metal precursor is adsorbed onto the wood material surface on the wood material surface mounted in the chamber.

The supplying of the reaction gas may include a first process, optionally, a second process of evacuating the by-products generated in the first process and the residual reaction gas.

The first step is a step of introducing a reaction gas capable of reacting with the metal precursor adsorbed on the surface of the wood material, the second metal precursor and the reaction gas may be chemically reacted to form a metal oxide or metal nitride thin film form have. More specifically, the metal oxide thin film may be formed, and the metal oxide thin film may be formed to improve the bonding strength between the metal oxide thin film and the wood material, and the catalytic action of each of the first metal particles and the second metal oxide may be significantly improved. Thus, the generation of high active oxygen and excellent antibacterial property of the wood material can be obtained.

The deposition cycle including the first process, the second process, the third process, and the fourth process may be repeated at least once or more, thereby controlling the thickness of the second metal oxide thin film deposited on the surface of the wood material. have. The number of deposition cycles may be 1 to 5000 cycles, and in detail, may be 10 to 1000 cycles, but is not limited thereto.

The second metal oxide thin film may be formed with a thickness of 1 nm to 100 nm on the surface of the wood material coated with the first metal precursor, in detail may be formed with a thickness of 10 nm to 50 nm but the numerical range Not restricted to

The first metal precursor and the second metal precursor may be included in a molar ratio of 1: 2 to 1: 8, and specifically, may be included in a molar ratio of 1: 2 to 1: 6.

The first metal and the second metal oxide may be included in a weight ratio of 1: 0.01 to 1:50, and specifically, may be included in a weight ratio of 1:10 to 1:30.

The present invention also provides an antimicrobial article such as a humidifier or electronic fragrance containing an antibacterial wood material.

The following is more clearly described using the embodiments of the present invention. Experiments show the superiority of the present invention through the embodiments of the present invention, but this is only an example provided to help a more general understanding of the present invention, and is not limited to the embodiments to which the present invention is presented, it is usually in the field to which the present invention belongs. Those skilled in the art can make various modifications and variations from this description.

Example 1

A silver precursor aqueous solution was prepared by preparing 100 mL of a 0.5 M silver nitrate solution and then adding 5 ml of 0.1 wt% polyvinylpolypyrrolidone aqueous solution. The upper end of the wood was connected to a vacuum pump to reduce the pressure, and the remainder of the wood was immersed in an aqueous silver precursor solution and kept at room temperature for 6 hours, followed by drying.

After preparing 100 mL of 5% by weight aqueous solution of ethylene glycol, the water impregnated with silver nitrate was impregnated with silver nitrate at 30 ° C. for 6 hours to reduce silver nitrate, thereby preparing a wood material coated with silver nanoparticles.

Example 2

A wood material coated with a titanium dioxide thin film was manufactured by using a plasma enhanced atomic layer deposition (PEALD) apparatus. Specifically, the wood material is charged into an atomic layer deposition machine, and titanium isopropoxide (titanium tetraisopropoxdie) is supplied at a flow rate of 30 sccm under a pressure of 200 mTorr at a flow rate of 30 sccm, exposed for 10 seconds, adsorbed onto the wood material, and then argon. The gas (Ar) was purged by feeding it at a flow rate of 2000 sccm for 10 seconds. Thereafter, oxygen (O ₂ ) was supplied as a reaction gas in a plasma state at a flow rate of 400 sccm for 10 seconds to form an atomic layer of titanium dioxide. Specifically, the plasma power was 120 W and the plasma dose was applied at 7 Wsec / cm 2. In the subsequent step, argon (Ar) gas was purged by supplying at a flow rate of 2000 sccm for 10 seconds. By performing the above method 200 times in one cycle, a wood material on which a titanium dioxide thin film was finally deposited was manufactured. The thickness of the titanium dioxide thin film was 50 nm.

Example 3

The reaction was carried out in the same manner as in Example 2, except that H ₂ O was used as the reaction gas.

Example 4

A silver nanoparticle-coated wood material prepared in Example 1 was prepared, and then a titanium dioxide thin film was deposited on the silver nanoparticle-coated wood material by the same material and method as in Example 2.

 Example 5

The reaction was carried out in the same manner as in Example 4 except that H ₂ O was used as the reaction gas.

 Experimental Example 1

The antimicrobial test of the silver nanoparticles / titanium dioxide thin film coating layer was carried out as follows.

E. coli was incubated for 24 hours on each sample such as a Petri dish, Si substrate, and a silver nanoparticle / titanium dioxide-coated Si substrate, and the antibacterial activity was evaluated by measuring the number of E. coli.

The silver nanoparticles / titanium dioxide coated Si substrate was coated in the following manner. First, 100 ml of a 0.5 M silver nitrate solution was prepared, and then 5 ml of 0.1 wt% polyvinylpolypyrrolidone aqueous solution was added thereto, and 100 ml of 5 wt% aqueous solution of ethylene glycol was added and mixed. Was applied to a Si substrate and dried at 50 ° C. to coat the silver nanoparticles. Thereafter, in order to deposit a titanium dioxide thin film on the Si substrate coated with silver nanoparticles, the substrate was deposited by applying the same method as in Example 2 except for using the Si substrate coated with silver nanoparticles.

Initially, the number of E. coli cultured in each sample was equal to 1.3 x 10 ^4, and in the case of Petri dishes, the number of E. coli increased to 1.3 x 10 ⁶ after 24 hours. In the case of the Si substrate, the number of Escherichia coli increased to 2.2 x 10 ⁵ after 24 hours, which was about 17 times higher.In the case of the silver nanoparticle / titanium dioxide coated Si substrate, the amount of E. coli decreased by about 99.995% after 24 hours. Confirmed.

Claims (13)

A first step of exposing the metal precursor to the wood material;
Converting the metal precursor coated on the wood material into metal particles;
Method for producing an antimicrobial wood material comprising a. The method of claim 1,
The first step is a method of producing an antimicrobial wood material comprising a immersion step of immersing wood in a metal precursor solution containing the metal precursor. The method of claim 2,
The second step is a step of introducing a reducing agent to the metal precursor-coated wood material. The method of claim 2,
The metal precursor is a method of producing an antimicrobial wood material comprising a silver precursor. An antimicrobial wood material prepared by the method of any one of claims 1 to 4, wherein the metal nanoparticles are coated on the surface of wood pores. The method of claim 1,
Wherein the first step is the step of atomic layer deposition of the metal precursor is a method of producing an antimicrobial wood material. The method of claim 6,
The second step is a step of introducing a reaction gas after the atomic layer deposition step, the method of producing an antimicrobial wood material. The method of claim 6,
The metal precursor is a method for producing an antimicrobial wood material comprising a titanium precursor. An antimicrobial wood material prepared by the method of any one of claims 6 to 8, wherein the metal oxide is coated on the surface of the wood pores. A first step of exposing the first metal precursor to the wood material;
Converting the first metal precursor coated on the wood material into metal particles to prepare a wood material coated with the metal particles;
A third step of atomically depositing a second metal precursor on a wood material coated with the metal particles; And
And a fourth step of introducing a reaction gas into the wood material on which the second metal precursor is atomic layer deposited. The method of claim 10,
The first metal precursor and the second metal precursor is a different method for producing an antimicrobial wood material. The method of claim 10,
The first metal precursor is a silver precursor, the second metal precursor is a titanium precursor manufacturing method of the material. An antimicrobial wood material prepared by the method of any one of claims 10 to 12, wherein the first metal and the second metal oxide are coated on a wooden pore surface.