KR20170041928A

KR20170041928A - Organic-inorganic composite particle material having water repellent and antibiotic, and preparation method thereof

Info

Publication number: KR20170041928A
Application number: KR1020150140744A
Authority: KR
Inventors: 신교직; 최경호; 이상국; 강주희; 박인
Original assignee: 한국생산기술연구원
Priority date: 2015-10-07
Filing date: 2015-10-07
Publication date: 2017-04-18
Also published as: KR101818650B1

Abstract

The present invention relates to an organic-inorganic particle material having both water-repellent and antibacterial functions, and more specifically, to an organic-inorganic particle material having both water-repellent and antibacterial functions and to a method of producing the same, wherein the organic-inorganic particle material comprises: a core layer which is made of a metal oxide; an inner shell layer which is formed around the core layer and made of a compound having antibacterial properties; and an outer shell layer which is formed around the inner shell layer and made of a compound having water-repellent properties. Accordingly, the present invention maximizes the water-repellent and antibacterial properties and at the same time, simplifies the production steps to improve process efficiency and reduce production cost.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic and inorganic particulate material having water repellency and antimicrobial function,

The present invention relates to an organic or inorganic particulate material having both water repellency and antimicrobial function and a method for producing the same, and more particularly, to a particulate inorganic material comprising a core layer and a shell layer composed of a compound having antibacterial properties and a compound having water- The present invention relates to an organic or inorganic particulate material having both water repellency and antimicrobial function, and a method for producing the same.

The antifouling coating generally refers to the function of preventing surface contamination of the surface of the coating layer by a surface coating technique that prevents contamination by human fingerprints and external foreign objects on the surface of the product. The antimicrobial function is to kill or inhibit various viruses, bacteria, fungi Which is a surface coating material composed of a material having resistance and which is applied to various products requiring a clean and harmless use environment.

Fingerprints on the surface of the product are mainly caused by residual organic matter on the surface of the product, which is a technique that significantly reduces surface adsorption to organic materials. The remaining organic components are degraded over time Or bacteria may occur. Therefore, the anti-pollution technology and the antibacterial technology are complementary to each other in function.

Recently, the use of various display products such as smart phones, PDAs, PMPs, and tablet PCs equipped with a touch function has been exploding and consumers are increasingly demanding an interface that provides a clean and harmless use environment. Accordingly, there has been a rapid increase in demand for contamination and antimicrobial function in housings of home appliances including housings for refrigerators, washing machines, air conditioners, housings for IT products and automobiles as well as electronic products having touch functions.

At present, materials having both contamination and antibacterial function in the prior art are manufactured by mixing an antifouling material and an antibacterial functional material. Korean Patent Laid-Open Publication No. 2014-0069801 (entitled " Multifunctional Coating Structure and Method for Forming the Same ", hereinafter referred to as Prior Art 1) discloses a method for producing a hydroxylated inorganic carrier- Metal composite, and an antibacterial layer formed on the antimicrobial layer, and a method for forming the complex coating structure having both the antistatic coating layer and the antimicrobial layer.

KR 10-2014-0069801

In the prior art 1, an antimicrobial layer is formed by a first coating solution containing a compound having an antibacterial property on a substrate and a second coating containing a compound having antifouling property on the antibacterial layer The composite material is manufactured by a method of forming a contaminant layer with a solution.

However, such a configuration has a first problem that it is difficult to maximize the water repellency, contamination property, and antibacterial property of the surface, and there is a second problem that it is an obstacle to reduction of manufacturing cost by a method of manufacturing a material having respective properties . In addition, the above-described configuration has a secondary problem that the product does not meet the trend of becoming slimmer.

Accordingly, it is an object of the present invention to provide a novel organic and inorganic particle material having water repellency and antimicrobial properties at the same time and a method for manufacturing the same, in order to solve the above problems. The present invention also provides a technique relating to a coating composition and a functional film comprising a novel organic or inorganic particle material.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided a method for fabricating a semiconductor device, comprising the steps of: forming a core layer made of a metal oxide, an inner shell layer formed on an outer layer of the core layer and having an antibacterial function, Shell layer having a water repellent function and an antibacterial function simultaneously.

Another embodiment of the present invention provides an inorganic or organic particle material having a water-repellent and antimicrobial function, which is formed on the outer layer of the core layer and the core layer and is composed of a single shell layer simultaneously having an antibacterial function and a water-repellent function.

In the present invention the core layer, including at least one metal oxide selected from the group consisting of _{SiO 2, TiO 2, Al 2} O 3, SnO 2, ZnO, ZrO 2, CuO 2, CeO 2, ITO, ATO And has an average particle diameter of 5 to 200 nm. In addition, in the present invention, the inner shell layer may be formed of a polymer having a tertiary amine group or a quaternary ammonium group having antibacterial properties, at least one compound selected from polyurushiol, polyphenol, and allicin, Or a copolymer thereof. In the present invention, the outer shell layer may include a fluorine-based compound having water repellency. The thickness of the inner shell layer may be 5 to 100 nm, and the thickness of the outer shell layer may be 5 to 200 nm. In addition, the organic or inorganic particle material according to the present invention may have an average particle diameter of 15 to 500 nm.

The present invention also provides a method for producing a metal oxide nanoparticle comprising the steps of: preparing metal oxide nanoparticles; modifying the surface of the metal oxide nanoparticles with a thiol group to form a core layer; adding a lactam compound to initiate a polymerization reaction; Forming an inner shell layer by polymerizing a first monomer having a water repellent property; and forming an outer shell layer by copolymerizing a second monomer having water repellent property on the surface of the inner shell layer to form an outer shell layer, A method for producing a particle material is provided.

The present invention also provides a coating composition comprising an organic or inorganic particle material having both water repellent and antimicrobial functions, a solvent, a binder and a dispersing agent in a predetermined ratio.

The present invention also provides a functional film having a water contact angle of 100 to 140 °, which is made of an organic / inorganic particle material having water repellency and antibacterial function at the same time.

The present invention provides an organic or inorganic particulate material having both water repellency and antibacterial function simultaneously, thereby providing a first effect of maximizing water repellency and antibacterial properties of a functional material having water repellent and antibacterial functions, The second effect that the process time can be shortened and the production yield can be improved by using the retained particles and the manufacturing cost can be reduced.

As for the first effect, as shown in FIG. 2, a coating composition is prepared by using an organic / inorganic particulate material composed of a core, an antibacterial layer and a water-repellent layer and coated on the substrate, The conventional functional films prepared by mixing the antimicrobial compound (225) and the water-repellent particles (221), respectively, can have characteristics of excellent antimicrobial and water repellency as compared with the technology. In addition, in the prior art, a method of forming an antimicrobial layer on one side of a substrate and forming a water-repellent layer on the upper side thereof has been used to impart antibacterial and water-repellent properties at the same time. However, such a structure is difficult to maximize water- The thickness of the coating layer is too thick to fit the slimming trend of the product. However, when a film is produced using the particles according to the present invention, a slimmer antibacterial and water-repellent film can be produced.

In relation to the second effect and the third effect, the present invention is compared with the prior art in which an antimicrobial composition is prepared, a water-repellent composition is prepared, and an antimicrobial composition is coated and dried on one side of the substrate and then the water- The coating composition is prepared by using particles having both of the two properties simultaneously, and the coating composition is applied and dried, thereby shortening the process procedure and increasing the production yield. With this effect, the manufacturing cost can be further reduced.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a schematic cross-sectional view of a film having water repellency and antimicrobial properties simultaneously according to the prior art.
2 is a cross-sectional schematic diagram of a film that simultaneously has water repellency and antibacterial properties according to an embodiment of the present invention.
3 is a cross-sectional schematic diagram of an organic / inorganic particle material having water repellency and antibacterial function according to an embodiment of the present invention.
4 is a cross-sectional schematic diagram of an organic / inorganic particulate material having water repellency and antibacterial properties according to another embodiment of the present invention.
5 is a graph showing XPS measurement results of the organic / inorganic particle material according to Example 1 of the present invention.
6 is a graph showing XPS measurement results of the organic / inorganic particle material according to Example 2 of the present invention.
7 is a graph showing XPS measurement results of the organic / inorganic particle material according to the third embodiment of the present invention.
8 is an SEM image of an organic / inorganic particulate material according to Example 1 of the present invention.
9 is an SEM image of an organic / inorganic particulate material according to Example 2 of the present invention.
10 is an SEM image of an organic / inorganic particulate material according to Example 3 of the present invention.
11 is a graph showing the EDX analysis results of the organic / inorganic particulate material according to Example 1 of the present invention.
12 is a graph showing an EDX analysis result of the organic / inorganic particle material according to the second embodiment of the present invention.
13 is a graph showing the EDX analysis results of the organic / inorganic particles according to the third embodiment of the present invention.
FIG. 14 is a photograph showing the results of measuring the water contact angle of a film made of an organic / inorganic particulate material having both water repellency and antibacterial function according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when a part is referred to as "comprising ", it means that it can include other components as well, without excluding other components unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

3 is a schematic view of an organic / inorganic particulate material having water repellency and antimicrobial functions according to an embodiment of the present invention. According to the present invention, there is provided an organic or inorganic particulate material having both water repellency and antibacterial function, comprising a core layer made of metal oxide nanoparticles, an inner shell layer formed on the outer layer of the core layer and comprising a compound having antibacterial properties, And an outer shell layer formed on the outer layer of the inner shell layer and including a compound having water repellency.

Hereinafter, the present invention will be described in detail in the above-described manner for each layer constituting the organic / inorganic particle material according to the present invention.

In the present invention, the core layer may comprise a metal oxide. Specifically, the core layer is _{SiO 2, TiO 2, Al 2} O 3, SnO 2, ZnO, ZrO 2, CuO 2, CeO 2, but can include at least one metal oxide selected from the group consisting of ITO, ATO, But not limited to, metal oxides, metal nanoparticles, or polymer nanoparticles other than those described above. In addition, the core layer of the present invention may have an average particle diameter of 5 to 200 nm, but is not limited thereto. However, if the particle size of the core layer is less than 5 nm, it may be difficult to form a shell layer that provides water repellency and antibacterial function by increasing the agglomeration of nanoparticles due to an increase in surface energy. To solve this problem, Time and cost may be increased. When the average particle diameter of the core layer exceeds 200 nm, it may be easy to disperse the core layer in the solution to prepare the shell layer, but when the inorganic particle material having a core-shell structure is produced with a reduced specific surface area, It may be restricted to maximize the antibacterial property.

Next, the inner shell layer provided around the core layer may include a compound having an antibacterial property. Examples of the compound having an antibacterial property include a polymer having a tertiary amine group or a quaternary ammonium group, a polyurushiol, a poly Polyphenol, and allicin, or two kinds of copolymers. The above-mentioned compounds have the property of killing microorganisms which are harmful to humans or inhibiting the propagation or growth of microorganisms. In one embodiment of the present invention, the polymer having a tertiary amine group may be represented by the following formula (1).

[Chemical Formula 1]

(In the above formula (1), a represents 5 to 1000, and b represents 1 to 20. It is to be noted that R 1, R 2 and R 3 are the same as or different from each other, Lt; RTI ID = 0.0 > 1-10 < / RTI >

In one embodiment of the present invention, the polymer having a quaternary ammonium group may be represented by the following general formula (2).

(2)

(In the above formula (2), a is 5 to 1000, and b may be 1 to 20. However, it is not limited thereto. R4, R5 and R6 are the same or different, and each independently hydrogen, may be selected from 1 to 10 alkyl group. may be selected from addition, X is Cl, F, Br, I, CN, NO 3, CH 3 COO, CF 3 COO, OH, ClO, ClO 2, ClO ₃ , SCN, ClO ₄ , HCO ₃ , H ₂ PO ₄ , BF ₄ , TFSI, CF ₃ SO ₃ or CH ₃ SO ₃ .

In general, the quaternary ammonium compound is known to have a strong antimicrobial effect because of stronger interaction with ionic sites on the cell wall surface or microorganisms due to intramolecular cations and anions. The compound having antibacterial activity in the present invention may be a copolymer of a compound containing a tertiary amine group or a quaternary ammonium group.

It should also be noted that the average thickness of the inner shell layer in the present invention may be 5 to 200 nm, but is not limited thereto. However, when the thickness of the inner shell layer is out of the range of 5 to 200 nm, introduction of the outer shell layer formed in the inner shell layer is difficult and it may be difficult to sufficiently secure water repellency.

Next, in the present invention, the outer shell layer may include a fluorine-based compound having water repellency. In one embodiment, the fluorine-based compound may be a compound represented by Formula (3).

(3)

(In the above formula (3), a is 5 to 1000, b is 1 to 20, and y may be 1 to 19. It is to be noted that R7, R8 and R9 are the same or different from each other , Each independently selected from hydrogen, an alkyl group having 1 to 10 carbon atoms, and the like)

In addition, in the present invention, the fluorine-based compound providing water repellency may be any compound containing fluorocarbon (- (CF ₂ ) nCF ₃ ) in addition to the compound represented by Formula 3, .

Also, the thickness of the outer shell layer may be, but is not limited to, 5 to 200 nm. However, when the thickness of the outer shell layer is less than 5 nm, it may be difficult to ensure the minimum water repellency of the outer shell layer made of the compound having water repellency. When the thickness exceeds 200 nm, The uniformity of the surface can not be ensured during production of the film, and therefore, it may be difficult to apply the film to an optical film. In addition, the antibacterial and water repellency effects provided to the external environment may be relatively insufficient due to the decrease of the surface area.

4 is a schematic view showing an organic / inorganic particle material having water repellency and antibacterial function according to another embodiment of the present invention. The particle material having both water repellency and antibacterial function according to an embodiment of the present invention includes a core layer made of a metal oxide, a compound having an antibacterial property and a compound having water repellency around the core layer, And a single shell layer that simultaneously provides a single layer. The compound constituting the core layer and the single shell layer are the same as those described above, and a description thereof will be omitted. The thickness of the single shell layer providing water repellency and antibacterial properties may be 10 to 300 nm, but is not limited thereto. However, when the thickness of the single shell layer is less than 10 nm, it may be difficult to ensure the minimum antibacterial and water repellent properties by including fewer compounds having antibacterial and water repellent properties. When the thickness exceeds 300 nm, the antibacterial and water- However, when a film containing particles of the core-shell structure is finally prepared, the water repellency and antimicrobial effect provided to the external environment may be relatively inferior due to a decrease in surface area.

For the same reason as described above, the present invention specifies that the size of the organic or inorganic particle material having water repellent and antibacterial functions is 15 to 500 nm, but not limited thereto.

Hereinafter, a method for producing an organic / inorganic particulate material having both a water repellent function and an antibacterial function will be described.

First, metal oxide nanoparticles are prepared. The metal oxide nanoparticles provide a basis for forming a shell layer to be described later. It may be preferable to mix the metal oxide nanoparticles in a solvent to uniformly disperse the organic nanoparticles by applying a predetermined agitating force to the organic nanoparticles.

Second, the surface of the metal oxide nanoparticles is modified to form a core layer. The surface modification is carried out in order to directly bind a compound having antimicrobial properties and a compound having water-repellent properties to the surface of the metal oxide. In one embodiment of the present invention, the surface of the metal oxide nanoparticles may be modified with a thiol (-SH) group to form a core layer. The nanoparticles modified with the thiol group provide stable dispersibility in the dispersion medium, and can form a stable chemical bond with a compound described later to enhance the reaction efficiency.

Third, an inner shell layer is formed by polymerizing the first monomer having antibacterial properties on the surface of the core layer. The first monomer may include a vinyl-based monomer having a tertiary amine group, and the other may include a vinyl-based monomer including a quaternary ammonium group, urushiol, and a phenol-based monomer. Further, the first monomer may be polymerized on the surface of the core layer through suspension polymerization, emulsion polymerization, bulk polymerization, ionic polymerization, living radical polymerization, and the like, but is not limited thereto. However, in the case of suspension polymerization, emulsion polymerization and bulk polymerization, side chain reactions such as coupling or chain transfer reaction between radicals during the polymerization reaction may be accompanied by inhibition of chain growth and control of molecular weight. Further, in the case of ionic polymerization, it is possible to control the molecular weight to be relatively easy and to enable the polymerization reaction having a narrow molecular weight distribution. However, since a highly reactive ion is used, a step of removing oxygen, moisture, hydrogen and the like is additionally required . Therefore, the present invention proposes to produce particles of uniform physical properties and to form core-shell particles through living radical polymerization with excellent process efficiency. The living radical polymerization is largely divided into atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), and reversible addition fragmentation chain transfer polymerization (RAFT). And in one embodiment of the present invention, the organic-inorganic particle material can be produced by atom transfer radical polymerization. In one embodiment of the present invention, in order to initiate the atom transfer radical polymerization, the lactam compound may be added before the addition of the first monomer, and the polymerization reaction may be started by stirring for a predetermined time. In addition, the lactam compound may be at least one compound selected from caprolactam, butyrolactam. The lactam compound reacts with the core layer on which the thiol group is formed to cause hydrogen migration from the thiol group to the lactam compound, and the surface of the core layer and the lactam compound each have radicals. The core layer having a radical is added to the first monomer to form a polymer. In addition, the lactam compound having a radical can control the molecular weight and the molecular weight distribution because it acts as a radical trapping agent which keeps the concentration of growth type radicals growing on the surface of the core layer constant and low, do.

In addition, the step of initiating the polymerization reaction may be carried out at 60 to 100 캜 for a predetermined time. The temperature range is a temperature range at which radicals can be formed to initiate polymerization. At a temperature lower than 60 ° C, energy for forming radicals may not be sufficiently supplied to lower the polymerization reaction efficiency. There is a problem that it is difficult to ensure the stability of the reactant by excessively supplying heat to the reactant. Also,

Fourth, an outer shell layer is formed by copolymerizing a second monomer having water-repellent properties on the outer layer of the inner shell layer formed in the previous step. The second monomer may be a fluorine-based monomer that is known to have excellent water-repellent properties. In one embodiment of the present invention, the fluorine-based monomer may be a vinyl-based monomer substituted by fluorocarbon.

Further, in another embodiment of the present invention, the first monomer and the second monomer may be polymerized together on the surface of the core layer. The particles thus produced have a core-shell structure including a core layer and a single shell layer simultaneously having antibacterial and water-repellent functions as shown in Fig.

In the present invention, the polymerization of the first monomer and the second monomer may be carried out at 60 to 100 ° C for 15 to 24 hours, but is not limited thereto. However, when the reaction temperature is lower than 60 ° C as in the step of initiating the polymerization reaction, there is a problem that the heat required for carrying out the reaction is not sufficiently supplied and the yield is lowered and the reaction time is increased. , It is difficult to control the reaction heat and it may be difficult to secure the stability of the reactant. When the reaction time is less than 15 hours, the thickness of the shell layer formed through the polymerization reaction is so thin that it may be difficult to realize minimum antibacterial and water repellency. If the reaction time exceeds 24 hours, the thickness of the shell layer becomes excessively thick and the surface area may be lowered. In the case of forming a shell layer containing a polymer having a quaternary ammonium group in the production of an organic / inorganic particulate material according to the present invention, a method of polymerizing a monomer having a quaternary ammonium group as a first monomer as described above And a monomer having a tertiary amine group as a first monomer may be selected to prepare an organic or inorganic particle material, and then a halogenated alkyl may be added to react with a tertiary amine group to form a quaternary ammonium salt. Hereinafter, this will be described in the following examples.

In addition, the method may further include a step of washing the core-shell particles having the antibacterial and water-repellent functions at the same time to remove unreacted materials and by-products, and then washing the dried core-shell particles several times and drying the particles for a predetermined time.

Further, the present invention provides a coating composition comprising an organic / inorganic particle material having water repellency and antibacterial function at the same time.

In one embodiment of the present invention, the coating composition may include organic and inorganic particles having both water repellent and antimicrobial functions and an organic vehicle at a predetermined ratio. Preferably, the coating composition may include, but is not limited to, 2.5 to 50 parts by weight of an organic or inorganic particle material having water repellency and antibacterial activity simultaneously with 100 parts by weight of the organic vehicle. However, when the organic / inorganic particulate material is mixed in an amount of less than 2.5 parts by weight, the content of the organic / inorganic particulate material is low and the minimum water repellency and antimicrobial function can not be ensured. When the content is more than 50 parts by weight, It may be difficult to coat the composition of the present invention on a substrate of the composition for use, and the transmittance of the composition may be lowered so that application to a product requiring transparency may be limited.

In an embodiment of the present invention, the organic vehicle may comprise a solvent and a binder resin in a predetermined ratio, and the binder resin may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylate, hexyl (meth) acrylate, ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (Meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Containing acrylate-based or methacrylate-based monomer, low-density polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polymethylpentene, etc. One may be a polymer compound, an epoxy binder, polyurethane binder, a silicone-based binder, but is not limited to the known binder resin is stated that it is possible to be any which is. In order to control the viscosity of the coating solution and to facilitate the dispersion of the organic and inorganic particulate material, a coating composition may be prepared by mixing a solvent. Examples of the solvent include an alcohol-based solvent, a polyol- Any solvent which is generally used in the production can be used.

In addition, the coating composition may further include at least one additive such as a dispersant, a photoinitiator, a thermal initiator, and a stabilizer. The dispersant may be added to minimize aggregation between the organic and inorganic particles, and the addition of the dispersant may ensure long-term dispersion stability of the composition. In addition, the curing initiator plays a role of initiating a reaction in which the binder resin forms a three-dimensional network structure by heat or light. As the curing initiator, UV initiators and thermal initiators known in the art can be used as compounds capable of initiating the reaction by dissociating heat or light when formed by non-uniform decomposition to form radicals. For example, commercially available Irgacure 184, Irgacure 819, Iragacure 907 and Vicure 30 can be used. In addition, the coating composition may further contain additives known in the art in a predetermined ratio.

The present invention also provides a technique relating to a functional film prepared using a coating composition comprising an organic / inorganic particle material having both water repellent and antimicrobial functions. FIG. 1 is a schematic view of a film having water repellency and antibacterial properties at the same time according to the prior art, and FIG. 2 is a schematic view of a film simultaneously having water repellency and antibacterial properties according to an embodiment of the present invention. Hereinafter, the functional film according to the present invention will be described with reference to the drawings.

2, in the prior art, the emulsifier 221 and the antimicrobial compound 225 are mixed with an organic vehicle containing a solvent, a binder resin and a dispersant to prepare a coating composition, ), And then cured to form a coating layer 220, thereby preparing a functional film 200. On the other hand, in the present invention, a coating composition is prepared by mixing an organic vehicle particle material (100) having water repellency and antibacterial function at the same time with an organic vehicle and then coated on one side of the substrate 210 and cured to form a functional film 200 ), There is an advantage that the manufacturing cost of the functional film can be reduced by a process shortened compared with the prior art. In order to maximize the water-repellent effect on the surface, the film having water repellency and antimicrobial function simultaneously is manufactured so that the water repellent particles protrude to the surface to form a predetermined roughness. The water repellent particles and the antimicrobial compound have different polarities, It has been difficult to effectively exhibit the function of the antibacterial compound which is hydrophilic on the surface of the branching material. In addition, in the prior art, the production of a film containing a substance having a different polarity at the same time has provided a possibility of warpage and defects of the film.

However, as shown in FIG. 2, the functional film according to the present invention includes the inorganic or organic particle material 100 having water repellency and antibacterial function simultaneously on one surface of the base material 210, Can be minimized.

In addition, the film comprising the organic and inorganic particles having both water repellency and antibacterial function according to the present invention may have a water contact angle of 100 to 140 °. The antibacterial and water repellency characteristics of the film according to the present invention Will be described in more detail with reference to the following examples.

In addition, the organic or inorganic particle material having water repellency and antibacterial function according to the present invention, coating composition and film including the same can be applied to a housing of a display, an electronic appliance, a household appliance, or an automobile to provide water- , Food packaging materials, medical supplies, architectural paints, and the like.

Hereinafter, examples and experimental examples of the present invention will be described. The mechanism of the method for producing an organic / inorganic particulate material according to the present invention refers to the following reaction formula.

[Example 1]

1 g of silica powder having an average particle size of 80 nm was mixed with 10 ml of anhydrous toluene as a solvent, and the resultant mixture was ultrasonicated to disperse the silica powder. 1 g of (3-mercaptopropyl) trimethoxysilane was added to the dispersion, and the mixture was stirred at 60 ° C for 24 hours while maintaining the atmosphere in an argon atmosphere. After completion of the reaction, the reaction mixture was washed with methanol to remove unreacted materials and byproducts, and vacuum dried at 40 ° C. for 24 hours to obtain thiol-modified silica nanoparticles of white powder (hereinafter referred to as SiO ₂ -SH). (The yield here was 81%). Referring to Scheme 1 in this regard.

[Reaction Scheme 1]

0.5 g of the SiO ₂ -SH nanoparticle powder was mixed with 0.8 ml of?,? - Trifluorotoluene, and dispersed by spraying with ultrasound. To the mixture, 0.5 g of butylolactam was added, After stirring for 1 hour, 0.5 g of 2- (dimethylamino) ethyl acrylate was added, and the mixture was reacted at 90 DEG C for 24 hours with stirring.

Next, 0.5 g of 1H, 1H, 2H, 2H-perfluorooctyl acrylate (TFOA) as a fluorine compound was added and stirred at 80 ° C for 24 hours. After completion of the reaction was purified using an ether / ethanol mixture solution, and dried in vacuo at 60 ℃ for 24 hours to a powdery core-(hereinafter referred to, SiO ₂ -S @ F13A) shell particles was obtained. The final product was obtained in a yield of 80%. In this regard, reference is made to Scheme 2 below.

[Reaction Scheme 2]

[Example 2]

0.5 g of the SiO ₂ -SH nanoparticle powder prepared under the same conditions as in Example 1 was added with 0.5 g of butylolactam and stirred at 80 ° C for 1 hour to initiate the polymerization reaction. Next, Example 1 was repeated except that 0.5 g of 2- (Dimethylamino) ethyl acrylate and 0.5 g of 1H, 1H, 2H, 2H-perfluorooctyl acrylate (TFOA) were simultaneously added and the mixture was reacted at 80 DEG C for 24 hours with stirring. And dried and washed under the same conditions to prepare core-shell particles (hereinafter referred to as SiO ₂ -S @ F13A-Random) composed of a core layer and a single shell layer. The final product was obtained in a yield of 88%. In this regard, reference is made to Scheme 3 below.

[Reaction Scheme 3]

[Example 3]

0.5 g of the SiO ₂ -S @ F13A particles prepared by the method according to Example 1 and 1 g of 1-chlorododecane are completely dissolved in 20 ml of N, N-Dimethylformamide (DMF). Next, these mixed solutions are reacted under stirring in a nitrogen atmosphere at 80 DEG C for 24 hours. After completion of the reaction, the solvent was removed using a rotary evaporator, diethyl ether was added, and the reaction mixture was separated and purified by a centrifuge. The separated precipitate was vacuum-dried at 60 DEG C for 24 hours to obtain core-shell particles (hereinafter referred to as SiO2-S @ F13AD) containing a quaternary ammonium salt and a fluorine compound at a yield of 78%. See Scheme 4 in this regard.

[Reaction Scheme 4]

[Experimental Example 1] Analysis of structure and composition of core-shell particles

XPS, SEM and EDX analyzes were performed to analyze the structure and composition of the core-shell particles prepared according to Examples 1 to 3.

5 to 7 show XPS result graphs. (1S) at 650 to 700 eV, N (1s) at 400 eV, S (2p) at 100 to 300 eV and C (2s) at 100 to 300 eV through XPS analysis of the core-shell particles according to Examples 1 to 3, (1s) can be confirmed.

SEM photographs are shown in Figs. 8 to 10. Referring to this, it is confirmed that the core-shell particles of Examples 1 to 3 have a size of 100 nm or less. However, as shown in Fig. 9, the core-shell particle according to Example 2, which is composed of a single shell layer simultaneously exhibiting the core layer and the antibacterial and water-repellent properties, is different from the core-shell particle according to Example 1 and Example 3 , It can be confirmed that the surface has a predetermined roughness. This can be regarded as a result of simultaneous polymerization of the first monomer (antibacterial property) and the second monomer (water repellent property) having different polymerization rates on the surface of the core layer.

11 to 13 show the results of EDX analysis. With reference to this, the presence of F, N, S, C, and Si elements can be confirmed by EDX analysis of the core-shell particles according to Examples 1 to 3.

[Example 4]

80 wt% of ethanol, 10 wt% of OSR-120A as a binder and 10 wt% of core-shell particles according to Embodiment 3 were mixed and stirred to prepare a coating composition. This was applied to a glass substrate by spin coating (800 rpm, 12 seconds) and dried in a drying oven at 120 ° for 1 minute. The dried substrate was irradiated with UV at an intensity of 400 mJ / cm < 2 > to produce a film.

[Experimental Example 2] Evaluation of water repellency of film

A static water contact angle (KSL 2110) measurement was performed to evaluate the water repellency characteristics of the film produced according to Example 4. FIG. 14 shows the static water contact angle measurement result. As a result of measurement, the contact angle of the film produced according to Example 4 was confirmed to be 128 °.

[Experimental Example 3] Evaluation of antibacterial property of film

Antibacterial assay (ISO 22196) was performed to evaluate the antimicrobial effect of the film prepared according to Example 4, and the results are shown in Table 1.

Strain

sample
Bacterial killed after 24h [%]
Log [CFU / ml] After 24h

S.Aureus

Example 4

99.99
5.03
Control

0
-

E. coli

Example 4

99.99
5.12
control

0
-

Referring to Table 1, when the culture broth of the strain was plated on the film of Example 4 and cultured for 24 hours, it was confirmed that there was almost no viable cell count. In addition, it has been confirmed that the antimicrobial activity against two strains can provide an industrially suitable antimicrobial property with a value of 5 or more.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

100: inorganic and organic particle material
110: core layer
120: Inner shell layer (antibacterial function)
130: outer shell layer (water repellent function)
150: Single shell layer (water repellent and antibacterial function)
200: Functional film (water repellent and antimicrobial function simultaneously)
210: substrate
220: Coating layer
221: Foot importer
225: Antimicrobial compound

Claims

In an organic or inorganic particulate material having two functions at the same time,
A core layer made of a metal oxide;
An inner shell layer formed on an outer layer of the core layer and having a first function;
An outer shell layer formed on an outer layer of the inner shell layer and having a second function; , &Lt; / RTI >
Wherein the first function is an antibacterial function and the second function is a water-repellent function.

The method according to claim 1,
The metal oxide is water-repellent, it characterized in that it comprises _{SiO 2, TiO 2, Al 2} O 3, SnO 2, ZnO, ZrO 2, CuO 2, CeO 2, ITO, ATO 1 or more selected from the group consisting of and Organic particle material with antibacterial function at the same time.

The method according to claim 1,
Wherein the core layer has an average particle diameter of 5 to 200 nm.

The method according to claim 1,
Wherein the inner shell layer has a thickness of 5 to 200 nm.

The method according to claim 1,
Wherein the inner shell layer comprises a compound having an antibacterial property.

The method of claim 5,
The compound having an antibacterial property may be a polymer having a tertiary amine group or a quaternary ammonium group, at least one compound selected from the group consisting of polyurushiol, polyphenol, and allicin, Wherein the water-repellent and antimicrobial functions of the organic and inorganic particles are substantially the same.

The method of claim 6,
Wherein the polymer having tertiary amine groups is represented by the following formula (1).
[Chemical Formula 1]

(Wherein a is an integer of 5 to 1000, b is an integer of 1 to 20, R1, R2 and R3 are the same or different and independently selected from hydrogen and an alkyl group of 1 to 10 carbons do.)

The method of claim 6,
Wherein the monomer having a quaternary ammonium group is represented by the following formula (2).
(2)

(Wherein a is an integer of 5 to 1000, b is an integer of 1 to 20, R4, R5 and R6 are the same or different, and each independently selected from hydrogen and an alkyl group having 1 to 10 carbons and, X is Cl, F, Br, I, CN, NO 3, CH 3 COO, CF 3 COO, OH, ClO, ClO 2, ClO 3, SCN, ClO 4, HCO 3, H 2 PO 4, BF 4 , TFSI, CF ₃ SO ₃ or CH ₃ SO ₃ .

The method according to claim 1,
Wherein the outer shell layer has a thickness of 5 to 200 nm.

The method according to claim 1,
Wherein the outer shell layer comprises a fluorine-based compound having water-repellent properties.

The method of claim 10,
Wherein the fluorine-based compound is represented by the following formula (3).
(3)

(Wherein a is an integer of 5 to 1000, b is an integer of 1 to 20, y is an integer of 1 to 19, R1, R2 and R3 are the same or different, And an alkyl group having from 1 to 10 carbon atoms.

The method according to claim 1,
The organic or inorganic particle material may be,
The core layer; And
And a single shell layer formed on an outer layer of the core layer and having the first function and the second function.

The method of claim 12,
Wherein the single shell layer has a thickness of 10 to 300 nm.

The method according to claim 1,
Wherein the organic or inorganic particle material has an average particle diameter of 15 to 500 nm.

A method for producing an organic / inorganic particulate material having both a water repellent function and an antibacterial function according to claim 1,
i) providing metal oxide nanoparticles;
ii) forming a core layer by modifying the surface of the metal oxide nanoparticles;
iii) polymerizing a first monomer having an antibacterial property on the surface of the core layer to form an inner shell layer;
iv) forming an outer shell layer by copolymerizing a second monomer having water repellency on the surface of the inner shell layer;
Wherein the water-repellent layer has a water-repellent function and an antibacterial function at the same time.

16. The method of claim 15,
In the step ii), the metal oxide nanoparticles are surface-modified with at least one functional group selected from the group consisting of a thiol group, a hydroxyl group, an epoxy group and an amine group. Way.

16. The method of claim 15,
And adding a lactam compound between the step ii) and the step iii) to initiate a polymerization reaction. The method for producing an organic / inorganic particle material according to claim 1,

18. The method of claim 17,
Wherein the step of initiating the polymerization reaction is carried out at a temperature of 60 to 100 캜 for a predetermined period of time.

16. The method of claim 15,
Wherein the steps iii) and iv) are carried out at 60 to 100 DEG C for 15 to 24 hours.

16. The method of claim 15,
Wherein the first monomer comprises a vinyl monomer having a tertiary amine group, wherein the first monomer has a water repellent function and an antibacterial function.

The method of claim 20,
A method for producing an organic / inorganic particle material having both water repellency and antibacterial function, characterized in that after step iv), a halogenated alkyl is added and reacted with a tertiary amine group provided in the inner shell layer to form a quaternary ammonium salt .

16. The method of claim 15,
Wherein the second monomer comprises a fluorine-based monomer, wherein the water-repellent and antimicrobial functions are simultaneously achieved.

16. The method of claim 15,
The method of claim 1, further comprising washing and drying after step iv).

The coating composition according to any one of claims 1 to 14, which comprises an inorganic or organic particle material having both water repellency and antibacterial function,
Wherein the inorganic or organic particle material and the organic vehicle are mixed at a weight ratio of 0.1: 9.9 to 3: 7.

27. The method of claim 24,
Wherein the organic vehicle comprises a solvent and a binder resin, wherein the organic vehicle has both water repellency and antibacterial function.

27. The method of claim 24,
Wherein the composition for coating comprises a particle material having water repellency and antibacterial function, which further comprises a dispersing agent.

A film produced by incorporating an organic or inorganic particle material having both water repellency and antibacterial function according to any one of claims 1 to 14.

28. The method of claim 27,
Wherein the film has a water contact angle of 100 to 140 °.