KR101899075B1 - Nanostructured composite having long-lasting antibacterial and antibiofouling property and manufacturing method thereof - Google Patents

Abstract

Disclosed is a nanostructure composite exhibiting long-lasting antimicrobial or anti-biofouling performance and a method for producing the same. The nanostructured composite has a hydrophilic or amphoteric (inner layer) / lipophilic (outer layer) double porous nanoshell structure surrounding the porous-satellite nanoparticle complex, thereby maximizing the amount of the satellite nanoparticles enclosed in the complex And can exhibit long-term, long-lasting antibacterial or anti-biofouling performance by uniformly controlling the distance from the satellite nanoparticles to the surface of the complex and preventing the satellite nanoparticles from escaping from the complex.

Description

TECHNICAL FIELD The present invention relates to a nanostructure composite exhibiting long-lasting antibacterial or antibiotic fouling performance, and a nanostructured composite having the nanostructured composite having a long-lasting antibacterial and antibiofouling property and manufacturing method thereof.

Long-lasting antimicrobial or antibiotic fouling performance, and a method for producing the same. Specifically, the present invention relates to a nanostructure composite exhibiting long-term sustainable antibacterial or antibiotic fouling performance, a composition containing the nanostructure composite, and an article such as a paint, a coating layer, a fiber, a ceramic, or a plastic, .

With the development of nanotechnology, antimicrobial compositions using silver nanoparticles and silver nanocomposites have been developed and antimicrobial products using them have been produced and consumed. Especially, as the interest in environment and hygiene has increased, the application range of medical devices and hospital products as well as everyday household appliances, household appliances, and building materials are increasing.

Silver nanoparticles can be classified as (1) particles themselves, (2) oxidizing and releasing silver ions, (3) releasing active oxygen species, exhibiting antibacterial properties, and being oxidized by oxygen in the air, And gradually releases silver ions and active oxygen species. Therefore, in the case of an air filter coating agent which is required to exhibit antibacterial properties by being exposed to the air in a solid state, the silver nanoparticles in the aqueous solution maximize the antibacterial effect when the coated silver nanoparticles are directly in contact with the filtered harmful microorganisms, And the silver ions and active oxygen species released from the silver nanoparticles have antimicrobial effect. Therefore, the influence of silver nanoparticles varies depending on the size and concentration of silver nanoparticles, the time, the structure of silver nanoparticles, and the like.

Efforts have been made to utilize the long-term antimicrobial effect by mixing the silver nanoparticles directly with the paint composition or coating composition using the characteristic that silver nanoparticles are oxidized and release silver ions. However, silver nanoparticles are difficult to produce a uniform composition due to their agglomeration characteristics in the paint composition or coating composition, and even when the coating is difficult, the swelling characteristics of organic and inorganic materials are different. Therefore, It is difficult to control the speed and it is difficult to secure a stable release rate of the silver ion since the silver nanoparticles can be separated using the gap of the swollen polymer.

Therefore, development of a metal nanocomposite structure capable of achieving long-term effective antimicrobial or anti-biofouling effect while maintaining dispersibility and physico-chemical stability is required.

An aspect of the present invention is to provide a nanostructured composite which can exhibit long-term effective antibacterial or antibiotic fouling performance.

Another aspect of the present invention provides an antimicrobial or antibiotic fouling composition comprising the nanostructure complex.

Yet another aspect of the present invention provides a method of making the nanostructure composite.

In one aspect of the invention,

A core porous body and satellite nanoparticles comprising satellite nanoparticles bonded to the surface of the central porous body;

A hydrophilic or ampholy porous nanoshell covering the surface of the porous body-satellite nanoparticle composite; And

A lipophilic porous nano shell covering the surface of the hydrophilic or amphiphilic porous shell;

≪ / RTI > is provided.

The porous body-satellite nano-

Center porosity;

A molecule having a first end covalently bonded to the surface of the central porous body and a functional group at a second end; And

And a satellite nanoparticle having a size of 5 nm to 50 nm bonded to the functional group while surrounding the functional group.

The outer diameter of the nanostructure composite may be 100 nm to 10 탆.

The thickness of the hydrophilic or ampholyte nanosphere may be 1 nm to 50 nm.

The thickness of the lipophilic porous nano-shell may be 1 nm to 30 nm.

The central porous body and the hydrophilic or ampholy porous nanoshell may each independently include at least one selected from silica, zeolite and alumina.

The lipophilic porous nano-shell may be selected from silica, zeolite and alumina bonded with aliphatic hydrocarbons having 4 to 20 carbon atoms, or at least selected from among silica, zeolite and alumina containing a poly (alkylene oxide) block copolymer or a surfactant One can be included.

The lipophilic porous nano-shell may have a silica nanoshell structure bonded with an octadecyl group.

The molecule includes 2 to 20 hydrocarbon chains, and the functional group at the second terminal may be at least one selected from the group consisting of an amine group, a thiol group and a carboxyl group.

The satellite nanoparticles may be metal nanoparticles, metal oxide nanoparticles, or a combination thereof.

Wherein the metal nanoparticles include at least one selected from the group consisting of Ag, Cu, Au, Pt, Pd, Fe, Ni, Co,

The metal oxide nanoparticles are _{FeO, Fe 2 O 3, Fe} 3 O 4, CoFe 2 O 4, NiFe 2 O 4, MnFe 2 O 4, TiO 2, ZrO 2, CeO 2, Al 2 O 3, MgO, ZnO , Cu ₂ O, and CuO.

For example, the satellite nanoparticles may include silver nanoparticles, copper nanoparticles, a combination of silver and copper, or dissimilar metal nanoparticles of silver and copper.

According to another aspect of the present invention, there is provided a composition comprising the above nanostructure complex.

According to another aspect of the present invention, there is provided an antimicrobial or antibiotic fouling article comprising the nanostructure complex described above. The antimicrobial or anti-biofouling article may be a coating, a coating layer, a fiber, a ceramic, or a plastic.

According to another aspect of the present invention, there is provided a method for preparing a nanostructure composite, which comprises: impregnating an ionized solution of a satellite nanoparticle into a hydrophilic or amphoteric porous nanoshell; subjecting the nanostructure complex to a salt or metal nanoparticle by natural drying; A method of observing the size of the pores is provided.

According to another aspect of the present invention,

Using water as a solvent to obtain a first solution in which a first composite containing a central porous body and satellite nanoparticles bonded to the surface of the central porous body is dispersed;

The first solution is added with at least one selected from the group consisting of a silica precursor, a zeolite precursor and an alumina precursor as an alcohol, an ammonia water catalyst, and a precursor material in an amount of 90 to 110 parts by volume based on 100 parts by volume of the water, 1 complex to form a hydrophilic or ampholy porous nanoshell; And

Adding a water catalyst and an ammonia water catalyst to a second solution in which the second composite is dispersed in alcohol, adding at least one selected from a silica precursor, a zeolite precursor and an alumina precursor as a precursor material, Obtaining a third complex having a lipophilic porous nanosphere formed on the surface of the composite;

The method comprising the steps of:

The alcohol may be ethanol.

In the step of obtaining the second composite, a silica precursor containing tetraethoxysilane, tetramethoxysilane, or a combination thereof may be used as the precursor material.

In the step of obtaining the third composite, a mixture of tetraethoxysilane and octadecyltrimethoxysilane may be used as the precursor material.

The preparation method can be carried out under an inert atmosphere in which light is blocked.

The nanostructured composite according to an embodiment has hydrophilic or amphoteric (inner layer) / lipophilic (outer layer) double porous nanoshell structure surrounding a porous-satellite nanoparticle composite, By maximizing the amount of particles, by uniformly controlling the distance from the satellite nanoparticles to the surface of the complex, and by preventing the satellite nanoparticles from escaping from the complex itself, long-term effective long-term antimicrobial or anti-biofouling performance .

FIG. 1A is a cross-sectional schematic view of a porous body-satellite nanoparticle composite (first composite) used as a starting material of a nanostructure composite according to an embodiment, FIG. 1B is a cross-sectional schematic view of a nanostructure composite 3 composite).
2 is a TEM image (left) of a SAgS N composite particle synthesized by changing the amount of TEOS and a reaction scale in Example 1, and a TEM image (right image) in which a part of the particle is enlarged.
3 is a TEM image of a SAgSS ^o composite particles prepared in Example 2, conditions for changing the thickness of the shell to change the oil in the reaction scale or the parent.
Figure 4 shows the Z-contrast HAADF-STEM image (a) obtained by slowly and naturally drying the third composite sample on the TEM grid in Example 3 and the element mapping (b) and (b) It is an image.
FIGS. 5A to 5C are TEM images of an aqueous solution of each complex according to time in Example 4, together with ion elution evaluation. FIG.
FIGS. 6A to 6D are graphs showing the relationship between the silver ion dissolution test setting (a), the silver ion dissolution evaluation result (b), and the paint image before and after the silver ion dissolution experiment c) and a cross-sectional partial SEM image (d) of each painting after the silver ion dissolution experiment.
Fig. 7 is a photograph of a biofouling evaluation experiment (a) and a picture (b) painted before and after the biofouling experiment in the surface water of the paint including the composite in Example 6.

Hereinafter, the present invention will be described in detail with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.

The nanostructured composite according to one aspect,

A core porous body and satellite nanoparticles comprising satellite nanoparticles bonded to the surface of the central porous body;

A hydrophilic or ampholy porous nanoshell covering the surface of the porous body-satellite nanoparticle composite; And

A lipophilic porous nano shell covering the surface of the hydrophilic or amphiphilic porous shell;

.

The nanostructured composite has a uniform distribution in a concentric circle near the surface and at the same time a metal nanoparticle as large as possible is used as compared with a case where metal nanoparticles are dispersed in a spherical porous particle, And the release rate of metal ions can be controlled.

The nanostructure composite is prepared by using the porous material-satellite nanoparticle composite shown in FIG. 1A as a starting material, and then forming a hydrophilic or ampholy porous nanoshell 40 on the surface of the porous material-satellite nanoparticle composite as shown in FIG. And the lipophilic porous nano-shell (50), thereby uniformly controlling the distance from the satellite nanoparticles to the surface of the nanostructured composite, and preventing the deviation of the satellite nanoparticles from the nanostructure complex . This can lead to long-lasting antimicrobial or anti-biofouling effects.

First, the porous body-satellite nanoparticle composite (hereinafter also referred to as "first composite") shown in FIG. 1A will be described. 1A is an enlarged view of the bonding relationship between the porous body 10 and the satellite nanoparticles 20 via molecules including functional groups.

According to one embodiment, the porous body-satellite nanoparticle composite (first complex) has a core porous body 10, a first end bonded to the surface of the porous body 10, And a satellite nanoparticle 20 having a size of 5 nm to 50 nm bonded to the functional unit 32 while surrounding the functional unit 32. The functional nanoparticle 20 may be a nanoparticle.

The porous body 10 may include at least one selected from the group consisting of silica, titania, zirconia, alumina, and zeolite. Molecules having a functional group can be easily bonded to the surface thereof, and the effect of improving the adsorption performance by the porosity can be expected.

As the molecule 30 containing a functional group to be bonded to the surface of the porous body 10, for example, a derivative of a trialkoxysilane can be used. The other end of the carbon chain having a functional group at the terminal and having 2 to 20 hydrocarbon atoms Is bonded to the trialkoxysilane. Therefore, it can be easily bonded to the surface of the porous body 10 by applying the sol-gel method. When alumina or zeolite is used instead of silica as the porous body 10, a functional group can be provided to the porous body 10 using a trialkoxy alumina derivative or a trialkoxy silane derivative. The functional group 32 at the second terminal may include at least one selected from the group consisting of an amine group, a thiol group, and a carboxyl group.

The satellite nanoparticle 20 first binds the satellite nanoparticle seed 21 to the functional group 32 at the second end of the molecule 30 bound to the porous body 10 and the satellite nanoparticle seed 21 ) To grow the structure (22) surrounding the functional group (32).

The satellite nanoparticle 20 is adhered to the surface of the porous body and then grown at a room temperature so that the satellite nanoparticle grows as it surrounds the organic molecules on the surface of the porous body, There is an advantage of easy process. Further, when the satellite nanoparticles 20 are further grown, networking between the nanoparticles occurs, resulting in a robust structure that can never fall off from the surface of the porous body. The satellite nanoparticles can be enclosed within the complex with a uniform distance from the surface of the nanostructure complex by the dual nanoshell.

The satellite nanoparticles 20 may be metal nanoparticles, metal oxide nanoparticles, or a combination thereof. The metal nanoparticles may include at least one selected from the group consisting of Ag, Cu, Au, Pt, Pd, Fe, Ni, Co and alloys thereof. The metal oxide nanoparticles may include, for example, _{FeO, Fe 2 O 3, Fe} 3 O 4, CoFe 2 O 4, NiFe 2 O 4, MnFe 2 O 4, TiO 2, ZrO 2, CeO 2, Al 2 O 3, MgO, ZnO, Cu 2 O and CuO And at least one selected from the group consisting of The satellite nanoparticles 20 may be nanoparticles of a core-shell structure composed of a combination of these.

For example, the satellite nanoparticles may include silver nanoparticles, copper nanoparticles, a combination of silver and copper, or dissimilar metal nanoparticles of silver and copper. These nanoparticles can exhibit excellent antibacterial and antibiotic fouling effects by being oxidized in the air as particles themselves and releasing silver or copper ions and active oxygen species.

The satellite nanoparticles 20 may range in size from 5 nm to 50 nm. In the above range, the content of the satellite nanoparticles encapsulated in the nanostructure complex can be maximized to include a large amount of the antibacterial component. However, if it exceeds 50 nm, there is a possibility that the satellite nanoparticles are adhered to each other and become a monolithic shell covering the entire porous body.

The porous body-satellite nanoparticle complex (first complex) can be produced by referring to the method disclosed in Korean Patent No. 10-1304474427, for example.

As shown in FIG. 1B, on the surface of the prepared porous body-satellite nanoparticle composite (first composite), a double nanoshell structure of a hydrophilic or ampholy porous nanoshell 40 and a lipophilic porous nanoshell 50 .

The hydrophilic or ampholy porous nano-shell 40 may be the same material as the internal porous body 10 and other materials, but in order to cover the satellite nanoparticles, . The hydrophilic or ampholy porous nanoshell 40 may be a material selected from, for example, silica, zeolite, and alumina. Materials such as silica and zeolite synthesized through sol-gel reaction are amorphous metal oxides (MO), which exhibit both amorphous and non-polar amorphous dispersions of MOM, M-OH or MO ^- type functional groups on the surface . The porous nano-shell 40 having hydrophilicity or amphibicity can easily coat the lipophilic porous nano-shell 50.

The thickness of the hydrophilic or ampholyte nanosphere may be 1 nm to 50 nm. Hydrophilic or ampholytic nanoshell thicknesses of at least 1 nm allow the lipophilic nanoshells to be readily produced, and if the thickness of the nanoshell is too thick, the oxidation reaction of the satellite nanoparticles and the metal ion and activity The diffusion rate of the aqueous solution containing the oxygen species is too slow, so that the antibacterial and antibiotic fouling effect can be weakened, so that it is preferably 50 nm or less.

On the surface of the hydrophilic or ampholy porous nano-shell 40, a lipophilic porous nano-shell 50 is formed.

Even if the metal ions are eluted from the satellite nanoparticles through the lipophilic porous nano-shell 50 by wrapping the lipophilic porous nano-shell 50 on the surface of the hydrophilic or ampholytic porous nano-shell 40, It is possible to provide a nanostructure complex which can maintain the structure without being broken down and ensures uniform dispersion of the oil-based coating material and coating agent, and can release metal ions stably for a long period of time.

The surface of the hydrophilic or ampholy porous nano-shell 40 is wrapped with the lipophilic porous nano-shell 50 so that an aqueous solution containing silver ions and active oxygen species oxidized and diffused by air is hydrophilic or both The silver ions impregnated in the pores of the hydrophilic or amphoteric porous nanoshell are reduced to silver nanoparticles by light and the size of hydrophilic or amphoteric pores is measured by TEM image Can provide a breakthrough analytical method that can be viewed as.

 The lipophilic porous nano-shell 50 may be, for example, a material selected from silica, zeolite and alumina bonded with aliphatic hydrocarbons having 4 to 20 carbon atoms. Alternatively, the oleophilic porous nano-shell 50 may be prepared by subjecting a Sol gel reaction to a solution containing a poly (alkylene oxide) block copolymer or a surfactant such as cetyltrimethylammonium bromide (CTAB) , Zeolite, and alumina. For example, the lipophilic porous nano-shell may have a silica nanoshell structure bonded with an octadecyl group.

The thickness of the lipophilic porous nano-shell 50 may be 1 nm to 30 nm. If the thickness of the lipophilic porous nanoshell is at least 1 nm or more, the satellite nanoparticles can be kept for a long time. If the lipophilic (hydrophobic) nanoshell is too thick, It can not be diffused, so that it is preferably 30 nm or less.

The outer diameter of the nanostructure composite may be 100 nm to 10 탆. When the outer diameter is in the above range, aggregation of the nanostructure composite can be prevented easily, and it can be mixed with other composition to ensure proper dispersibility.

According to another aspect of the present invention,

Using water as a solvent to obtain a first solution in which a first composite containing a central porous body and satellite nanoparticles bonded to the surface of the central porous body is dispersed;

The first solution is added with at least one selected from the group consisting of a silica precursor, a zeolite precursor and an alumina precursor as an alcohol, an ammonia water catalyst, and a precursor material in an amount of 90 to 110 parts by volume based on 100 parts by volume of the water, Obtaining a second composite having hydrophilic or ampholytic porous nanospheres formed on the surface of the first composite; And

Adding a water catalyst and an ammonia water catalyst to a second solution in which the second composite is dispersed in alcohol, adding at least one selected from a silica precursor, a zeolite precursor and an alumina precursor as a precursor material, And obtaining a third complex having a lipophilic porous nanoshell formed on the surface of the composite.

Generally, when gold or silver nanoparticles are dispersed in an alcohol solvent such as ethanol, they are easily agglomerated and intergranular fusion occurs, which results in failure. Since the first complex of the porous body-satellite nanoparticles is exposed to the surface of the satellite nanoparticles, the particles may agglomerate when dispersed in alcohol. So, if you try to wrap the first complex with a hydrophilic or ampholy porous nanoshell using alcohol as a solvent, as in a normal St? Ber process, the reactants can become clumped and fail.

In contrast, in the method of preparing a nanostructured composite according to an embodiment, water is first used as a solvent to maximize the dispersibility of the first complex of the porous body-satellite nanoparticles, and then the hydrophilic or amphoteric porous nano- In order to appropriately control the reaction rate of the sol-gel reaction using the precursor material of the shell, a second complex comprising a hydrophilic or ampholyporous nanoshell on the surface of the first complex may be prepared by adding a water-like alcohol.

After securing the dispersibility of the first complex of the porous material-satellite nanoparticles by using water as a solvent, a volume of alcohol such as water is added, and an ammonia water catalyst is added, and then rapidly selected from a silica precursor, a zeolite precursor and an alumina precursor , The second complex having a hydrophilic or ampholytic porous nanoshell having a uniform thickness on the surface of the first composite and having excellent dispersibility can be prepared.

In the step of obtaining the second complex, the alcohol may be ethanol, for example.

In the step of obtaining the second composite, the precursor material may be a silica precursor including tetraethoxysilane, tetramethoxysilane, or a combination thereof. The second composite thus produced exhibits hydrophilicity basically because its surface is composed of Si-O-Si, Si-OH, Si-O ^- and the like, but may exhibit a poor dispersibility even in a nonpolar material.

In order to prepare the oleophilic porous nanoclust on the surface of the second composite, the second composite is dispersed in alcohol, and after adding a water catalyst and an ammonia water catalyst, at least one precursor material selected from a silica precursor, a zeolite precursor and an alumina precursor is added The third complex can be prepared by proceeding with the Solzel reaction.

In the step of obtaining the third complex, the alcohol may be ethanol, for example.

In the step of obtaining the third composite, for example, a mixture of tetraethoxysilane (TEOS) and octadecyltrimethoxysilane (ODTMS) may be used as the precursor material. The thickness of the lipophilic silica nanoshell can be controlled by adjusting the amount of TEOS and ODTMS.

The third composite thus prepared has aliphatic hydrocarbons bound to the outermost lipophilic silica nanocosil, which can be uniformly and uniformly dispersed in the nonpolar solvent and can be uniformly mixed with the oil paint or coating agent. Therefore, the third complex can be applied or molded to an oily substance to provide a product exhibiting long-lasting antibacterial or anti-biofouling function.

The nanostructure composite may be prepared in air, but it may be performed in an inert atmosphere in which light is blocked.

The nanostructured composite thus prepared can be used to impart antimicrobial or anti-biofouling properties to oil-based paints, oil-based coatings, ceramics, fibers and plastics. The composition comprising the nanostructured composite can be uniformly mixed and dispersed with the oil-based coating or the oil-based coating, and the release rate of the metal ion after the coating is controlled for a long period of time. Thus, a stable antibacterial or anti- .

A coating layer, a fiber layer, a coating layer, a coating layer, or the like, which has been imparted with an antibacterial or antibiotic fouling function by mixing, spraying, or molding a composition comprising the nanostructured composite with one of a lubricant coating, a coating composition, a fiber composition, , Ceramics, plastic, and the like can be provided.

The composition comprising the nanostructure complex may be mixed with a conventional oily substance to form an antimicrobial or anti-biofouling function.

EXAMPLES The following examples and comparative examples illustrate exemplary embodiments in more detail. The following examples are provided to further clarify and easily understand the present invention, and thus the scope of the present invention is not limited by these examples.

The porous spherical nanoparticle composite (first composite) used in the following examples was prepared in accordance with Korean Patent No. 10-1304427. On the surface of a porous body having an average diameter of 250 nm, silver nanoparticles having a size of about 30 nm The first complex solution (5.2 x 10 ¹¹ particles / mL, 0.0152 g / mL) was prepared by uniformly growing the particles and dispersing them in distilled water.

Hereinafter, the first complex is referred to as " SAg ", the second complex as " SAgS ", and the third complex as " SAgSS ^o " in order to facilitate understanding of the structure from the name of the complex. In the abbreviation of the complex, the first letter S means hydrophilic or amphoteric silica (S) porosity in the center of the complex; The second character, Ag , refers to a satellite nanoparticle layer composed of silver (Ag) bonded to the surface of the porous body; The third letter S means a hydrophilic or amphoteric silica (S) porous nanocosilver which surrounds said porous-satellite nanoparticles; And the fourth letter S ^o refers to a lipophilic silica (S ^o ) porous nanoshell surrounding the hydrophilic or amphiphilic silica porous body nanocapsule.

Example  1: Both sex Porosity Nano shell  Wrapped Porosity - Preparation of satellite nanoparticle complex (second complex = SAgS)

1.7 mL of distilled water was added to 2.3 mL of the above-mentioned first complex solution, diluted with 4 mL of ethanol, and stirred for 5 minutes. 0.5 mL of ammonia water was added thereto, and the mixture was stirred for 5 minutes. Tetraethoxysilane (TEOS) was added in the required amount, and the mixture was stirred for 3 hours while blocking the light. The shells thicker than 20 nm were divided into two portions of TEOS, and the first portion was added and the second portion was added for 3 hours, followed by stirring for 5 hours. The reason for the reaction in two times is that when the two doses are added together in one batch, they are aggregated to form lumps. After completion of the reaction, the solid product was rinsed with ethanol using centrifugation, and then dispersed and stored in ethanol. A TEM image of the product (SAgS) according to the amount of reactants under each reaction condition is shown in FIG. 2 and the thickness of the amorphous porous nanoshell is measured from the TEM image, and is shown in Table 1 together with the reaction conditions. The sample name of the TEM image corresponds to the second composite sample name in Table 1 and the second complex is named SAgS N (N = 1-6) series. In Table 1, the standard reaction is the reaction using the above-mentioned amounts of reactants. In the case of the reaction in which the condition is scaled up, the standard reaction is represented by x m. It can be seen that as the concentration of the first complex in the reaction solution is the same, the thickness of the porous nano-shell increases as the amount of added TEOS increases.

Second complex name SAgS1 SAgS2 SAgS3 SAgS4 SAgS5 SAgS6 Reaction scale
(Standard × m) × 1 × 1 × 1 × 1 × 1 × 50 TEOS, mL
(Primary) 0.025 0.05 0.08 0.05 0.08 4.5 TEOS, mL
(Secondary) 0.08 0.08 4.5 Thickness of shell, nm 5 13 20 25 50 33

Example  2: Both sex / Lipophilic  Double Porosity Nano shell  Wrapped Porosity - satellite nanoparticle complex (third complex = SAgSS ^o )

2.8 mL (6.0 x 10 < ¹¹ > particles / mL) of the second complex solution synthesized in Example 1 was centrifuged and dispersed in 8 mL of ethanol. 0.24 mL of distilled water and 0.16 mL of ammonia water were added to the solution, and the mixture was stirred for 10 minutes. Then, 0.014 mL of TEOS and 0.006 mL of octadecyltrimethoxysilane (ODTMS) were added and stirred for 1 day. To make thicker lipophilic nano-shells, TEOS and ODTMS in a ratio of 7: 3 were added or added as shown in Table 2 and reacted for another day. After completion of the reaction, the reaction mixture was centrifuged and the solid was washed with a small amount of ethanol / ethanol / toluene mixed solvent, and dispersed in toluene. The TEM image of the product was shown in FIG. 3 and the thickness of the amphiphilic / oleophilic porous nano-shell was measured from the TEM image. The results are shown in Table 2 together with the reaction conditions. In the TEM image, the left part shows the composite particle and the right part shows the one composite particle image, and the lower part shows the image of the composite particle having a thicker lipophilic nanoshell thickness. It said sample of TEM images are consistent sample name and a third complex in Table 2, the third composite was named ^{SAgSS o n (n = 1,} 5, 10) series. In Table 2, the standard reaction is the reaction using the above-mentioned amounts of reactants. In the case of the scale-up reaction, x n is used. In the case of the scale-up reaction, the remaining substances except TEOS and ODTMS All proceeded × n times. The thickness of the hydrophobic nano-shell was the case thicker than synthetic SAgSS ^o 1 is named SAgSS ^o 1 ^o ₂ and 1 ₃ SAgSS. In the TEM image, the gray part is the silica shell and the black part is the silver nanoparticle. Looking closely at the gray area, it can be seen that the two layers are distinguished by the dark (31-45 nm) and the soft (8-46 nm) layers due to the different electron density of amphoteric silica and lipophilic silica.

Third complex SAgSS ^o 1 SAgSS ^o 5 SAgSS ^o 10 SAgSS ^o 1 ₂ SAgSS ^o 1 ₃ Reaction scale (standard × n) × 1 × 5 × 10 × 2 × 2 TEOS, mL 0.014 0.077 0.16 0.09 0.09 0.09 ODTMS, mL 0.006 0.033 0.07 0.038 0.038 0.038 Thickness of amphiphilic shell, nm 45 35 31 23 28 Thickness of lipophilic shell, nm 9 9 8 24 46

Example 3: Pore size analysis of silica shell by TEM image

One drop of the third complex solution synthesized in Example 2 was dropped on the TEM grid and naturally dried in a dark atmosphere for 12 hours or more to form silver nanoparticles of uniform size only in the pores of the amphibious shell as shown in FIG. Results of elemental mapping (c) for TEM images (a, b) and silver components were obtained. A silver ion solution formed by partially oxidizing and dissolving silver nanoparticles in the second composite in air is trapped in the pores of the amorphous silica shell and slowly dried to form uniform silver particles of about 1-2 nm in size It is believed to be reduced to nanoparticles. This phenomenon was not observed in the second complex without lipophilic shells on the surface, and only in the third complex with the hydrophobic shell on the surface. Since the hydrophobic shell is formed on the surface, only the solvent slowly evaporates for a long time and the silver ion is trapped in the pores of the amphibious shell and is interpreted as being reduced to silver by light. Until now, it has been known to measure the pore size indirectly by measuring the amount of gas adsorbed and desorbed by the BET surface analysis method. However, it is possible to observe the size of the pores directly from the TEM image of the present invention.

Example  4: 1st  Complex SAg ), Second  Complex SAgS ), Third  Complex SAgSS ^o ) In the water, the ion elution evaluation

In order to measure the amount of ion in the water of the pore - satellite nanoparticle complex wrapped with single and double porous nano - shells, the third distilled water was stirred in the air for one day and air saturated water was used. 120 mL of each solution having a particle concentration of 1 × 10 ¹⁰ cells / mL of the first complex and the second complex was prepared, and the mixture was slowly stirred while the light was blocked. 13 mL of the solution was centrifuged over time, and 10 mL of the supernatant was analyzed by a specialized institute (KIST Characterization Center, AAS analysis) to determine the concentration of eluted silver ions, and the results are shown in Table 3. Since the third complex is not dispersed in water and flocculates or floats, five 13 mL solutions each having a particle concentration of 1 × 10 ¹⁰ / mL are prepared, and one solution is centrifuged with time while light is blocked. After separating and filtering with filter paper, 10 mL of the filtered solution was submitted to the KIST Characterization Center for determination of the eluted silver ion concentration. The centrifuged solid was subjected to TEM image and shown in FIG. In the case of the first complex ( SAg ) (a), the Ostwald ripening phenomenon of silver nanoparticles proceeded for 24 hours, and the distribution of silver nanoparticles bound to the silica surface was slightly changed, but there was no significant change. The eluted silver ions were adsorbed on the surface of silver nanoparticles by the Ostwald ripening phenomenon and showed the lowest concentration among the three complexes. In the case of the second complex ( SAgS ) (b), the density of the silver nanoparticle layer gradually decreased over time and the thickness of the nanopore of the porous body became thinner. At 96 hours, Agglomerated particles of silver nanoparticles were observed. In the case of the third composite ( SAgSS ⁰ ) having about 30 nm thick amphiphilic shell and about 9 nm thick lipophilic shell (c), the dissolution of silver ions in the suspension state On average, we could observe progress. The density of the silver nanoparticle layer gradually decreased with time in the complex, and at 96 hours, in some composite particles, the inner amorphous porous nanoshells were dissolved together with the silver nanoparticles to form void spaces Part) was observed. From these observations, it was confirmed that the presence of ampholyte nanospheres hinders the Ostwald ripening phenomenon of the silver nanoparticle layer and accelerates the one-way change in oxidation of silver nanoparticles to ions. In other words, in the solutions of the second and third complexes, silver ions were eluted in the complex until the silver ion concentration was supersaturated, and silver nanoparticles were precipitated on the fourth day to rapidly decrease the silver ion concentration. On the other hand, it was confirmed that silver ions could be stably eluted for a long time without breaking the whole structure due to existence of double nanoparticles of amphoteric / lipophilic porous body. The sample having a thickness of 24 nm and the sample having a thickness of 46 nm was also subjected to the elution test in an aqueous solution for 2 days in the same manner as above. However, the elution from the sample having a thickness of 9 nm of the lipophilic porous shell Less than 10% of the concentration was eluted. Therefore, it was judged that the elution rate was too slow.

Concentration (ppm) of silver ions eluted from each complex into aqueous solution Elution time Of undiluted solution
Total Ag 0 h 6 h 1 d 2 d 4 d The first complex
SAg 103 0.72 1.21 3.60 1.47 0.25 The second complex
SAgS 72.3 1.95 9.05 8.98 8.46 3.08 Third complex
SAgSS ^o 40 0.65 3.12 10.3 13.4 2.84

Example  5: Second  Complex SAgS ) And Third  Complex SAgSS ^o ) ≪ / RTI > composition and the evaluation of ion elution in water in the paint film

First, two substrates of 90 mm x 90 mm area were prepared by attaching a Scotch tape to the edge of a square acrylic plate to a uniform thickness (0.226 mm). The second and third composites were centrifuged to a silver content of 0.2 wt% (11.27 mg) relative to the oil paint, respectively, and dispersed in 0.5 mL of a thinner, followed by mixing well with 5 mL (5.635 g) of an oil paint. Since the first complex was hydrophilic, it did not disperse in the hydrophilic thinner but aggregated into a large lump, so the experiment was not carried out anymore. The second composite was observed as a part of the heterogeneous colloid in the thinner liquid, but the dispersibility was not bad, and the third composite was uniformly dispersed very well. Each paint mixture was dropped on an acrylic substrate prepared beforehand, pushed to a uniform thickness, filled with a substrate having a size of 90 mm x 90 mm, and dried naturally for one week or more while blocking light. As shown in FIG. 6 (a), two beakers containing 1.5 L of distilled water were prepared, each acrylic plate was hung on a lid, immersed in a solution, and 10 mL of a solution was taken over time while slowly stirring with blocking light The concentration of eluted silver ions was analyzed (KIST Characterization Center ICP QMS analysis). The cumulative concentration of eluted silver ions is shown in Figure 6 (b), replacing the entire solution with fresh distilled water at appropriate times to prevent the solution from saturating with silver ions. The amount of silver contained in the wet paint of 90 mm x 90 mm x 0.226 mm volume on the acrylic plate was calculated to be 3.75 mg, and from the third composite containing paint for 90 days to 0.456 mg (12%) and from the second composite containing paint 0.253 mg (6.7%) of silver ions were eluted. Therefore, it is expected that the dissolution time of more than 2 years can be secured by simple estimation. FIG. 6 (c) shows the acrylic plate before and after the start of the silver ion dissolution experiment and there is no difference in appearance, and the paint is firmly bonded to the acrylic plate. In the cumulative concentration (b) data, it was found that the amount of silver eluted from the paint containing the third composite was much greater than the amount of silver eluted from the paint containing the second composite, although it contained the same amount of silver . It is considered that this is due to the fact that the dispersibility in the oil-based paint is much better than the dispersibility of the second complex because the lipophilicity of the third complex is excellent. That is, as shown in FIG. 6 (d), the third composite is observed in many groups of one, two or three, while the second composite is present in the paint in the form of several aggregates. The excellent dissolution of silver ions from the widely dispersed tertiary complex is more advantageous, so that excellent antimicrobial and antibiotic fouling effects are predicted. The paint containing the second composite is also expected to exhibit a mild but consistent antimicrobial and anti-biofouling effect.

Example  6: Second  Complex SAgS ) And Third  Complex SAgSS ^o Evaluation of antibiotic fouling performance of oil-based paint film with composition

The paint mixture prepared in Example 5 was coated on a slide glass in the same manner as in Example 5 and dried. Unlike when applied to an acrylic plate, the paint film including the second and third composites showed a light brown color when applied to a slide glass. The test water was floated on the Jungnung Stream, about 100 m upstream of the Jongam Bridge in Seongam-dong, Seongam-dong, Seoul, on July 4, two days after the heavy rains, and three beakers each containing 0.5 L were prepared. I put it on the glass wall as shown in a) so as to lock it, cover it with aluminum foil so that dust did not enter, and stir it slowly. Taken out after 36 days, dried naturally, and photographed, and the results are shown in Fig. 7 (b). There was much biofouling on the painted slide glass, and the biofouling (arrow part) was weakly progressed on the painted slide glass including the second composite, but the painted slide including the third composite There was no biofouling on the glass. Better yet, the paint film containing the second and third composites was firmly bonded to the slide glass, while the painted slide glass was squashed with a submerged paint film.

Example  7: Third  Complex SAgSS ^o ) Antimicrobial Performance Evaluation of Oil-Based Paint Film Containing Composition

The paint mixture solution (oil-based paint containing the third composite SAgSS ^o ) prepared in Example 5 was painted on an acrylic plate having a size of 50 mm x 50 mm by the same method as in Example 5 and dried to prepare eight paint. The FITI test institute (KOLAS No. 1 internationally accredited testing institute) commissioned an antibacterial test by the JIS method (film-sticking method), and the results are attached below and summarized in Table 4. It has been confirmed that the oil paint film containing SAgSS ^o exhibits more than 99.9% of antibacterial activity against Escherichia coli and Staphylococcus aureus.

Antibacterial effect of antimicrobial oil paint film (after 24h) blank Antibacterial oil paint film E. coli
Starting concentration = 1.3 × 10 ⁴
CFU / mL 1.3 × 10 ⁶ <0.63 Staphylococcus aureus
Starting concentration = 1.3 × 10 ⁴
CFU / mL 2.5 x 10 ⁴ <0.63

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. . Accordingly, the scope of protection of the present invention should be determined by the appended claims.

Claims (21)

A core porous body and satellite nanoparticles comprising satellite nanoparticles bonded to the surface of the central porous body;
A hydrophilic or ampholy porous nanoshell covering the surface of the porous body-satellite nanoparticle composite; And
A lipophilic porous nano shell covering the surface of the hydrophilic or amphiphilic porous shell;
&Lt; / RTI &gt; The method according to claim 1,
The porous body-satellite nano-
The central porous body;
A molecule bound to the surface of the central porous body at the first end and comprising a functional group at the second end; And
Satellite nanoparticles having a size of 5 nm to 50 nm bonded to the functional group while surrounding the functional group;
&Lt; / RTI &gt; The method according to claim 1,
Wherein the nanostructure composite has an outer diameter of 100 nm to 10 占 퐉. The method according to claim 1,
Wherein the hydrophilic or ampholy porous nanoshell has a thickness of 1 nm to 50 nm. The method according to claim 1,
Wherein the lipophilic porous nanoshell has a thickness of 1 nm to 30 nm. The method according to claim 1,
Wherein the central porous body and the hydrophilic or ampholy porous nanoshell each independently comprise at least one selected from silica, zeolite and alumina. The method according to claim 1,
The lipophilic porous nano-shell may be selected from silica, zeolite and alumina bonded with aliphatic hydrocarbons having 4 to 20 carbon atoms, or at least selected from among silica, zeolite and alumina containing a poly (alkylene oxide) block copolymer or a surfactant One containing a nanostructured complex. The method according to claim 1,
Wherein the lipophilic porous nano-shell has a silica nanoshell structure bonded with an octadecyl group. 3. The method of claim 2,
Wherein the molecule comprises 2 to 20 hydrocarbon chains, and the functional group at the second terminal is at least one selected from the group consisting of an amine group, a thiol group and a carboxyl group. The method according to claim 1,
Wherein the satellite nanoparticles comprise metal nanoparticles, metal oxides, or combinations thereof. 11. The method of claim 10,
Wherein the metal nanoparticles include at least one selected from the group consisting of Ag, Cu, Au, Pt, Pd, Fe, Ni, Co,
The metal oxide nanoparticles are _{FeO, Fe 2 O 3, Fe} 3 O 4, CoFe 2 O 4, NiFe 2 O 4, MnFe 2 O 4, TiO 2, ZrO 2, CeO 2, Al 2 O 3, MgO, ZnO , Cu ₂ O, and CuO. The method according to claim 1,
Wherein the satellite nanoparticles comprise silver nanoparticles, copper nanoparticles, silver or copper, or silver and copper dissimilar metal nanoparticles. 13. A composition comprising a nanostructured complex according to any one of claims 1 to 12. An antimicrobial or antibiotic fouling article comprising a nanostructure complex according to any one of claims 1 to 12. 15. The method of claim 14,
Wherein the article is a paint, a coating layer, a fiber, a ceramic, or a plastic. 12. A nanostructured composite according to any one of claims 1 to 12, wherein an ionized solution of satellite nanoparticles is confined in a hydrophilic or amphoteric nanoparticle and then reduced to salt or metal nanoparticles by natural drying to form a permeable A method of observing the size of pores with an electron microscope. Using water as a solvent to obtain a first solution in which a first composite containing a central porous body and satellite nanoparticles bonded to the surface of the central porous body is dispersed;
The first solution is added with at least one selected from the group consisting of a silica precursor, a zeolite precursor and an alumina precursor as an alcohol, an ammonia water catalyst, and a precursor material in an amount of 90 to 110 parts by volume based on 100 parts by volume of the water, Obtaining a second composite having hydrophilic or ampholytic porous nanospheres formed on the surface of the first composite; And
Adding a water catalyst and an ammonia water catalyst to a second solution in which the second composite is dispersed in alcohol, adding at least one selected from a silica precursor, a zeolite precursor and an alumina precursor as a precursor material, Obtaining a third complex having a lipophilic porous nanosphere formed on the surface of the composite;
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt; 18. The method of claim 17,
Wherein the alcohol is ethanol. 18. The method of claim 17,
Wherein in the step of obtaining the second composite, a silica precursor comprising tetraethoxysilane, tetramethoxysilane, or a combination thereof is used as the precursor material. 18. The method of claim 17,
Wherein in the step of obtaining the third composite, a mixture of tetraethoxysilane and octadecyltrimethoxysilane is used as the precursor material. 18. The method of claim 17,
Wherein the method is performed in an inert atmosphere in which light is blocked.

Images