WO2020067799A1 - Substrate treated with antimicrobial coating agent and method for producing same - Google Patents

Abstract

The present invention relates to: a substrate having an antimicrobial coating agent comprising urushiol and an inorganic antimicrobial agent immobilized and coated on the surface thereof; and a method for applying an antimicrobial coating on the surface of a substrate.

Description

Antibacterial coating agent treated substrate and method for manufacturing the same

Cross-citation with relevant application (s)

This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0115319 dated September 27, 2018 and Korean Patent Application No. 10-2019-0119139 dated September 26, 2019, and documents related to Korean patent applications All content disclosed in is included as part of this specification.

The present invention relates to a substrate coated with an antimicrobial coating agent comprising urushiol and an inorganic antimicrobial agent immobilized on a surface and an antibacterial coating method of the substrate surface.

Recently, as interest in air quality increases, the demand for indoor air cleaning increases, and accordingly, an air purification filter for removing foreign substances in the air has been developed. The high-efficiency filter used for air purification can effectively collect almost all harmful microorganisms, and the microorganisms collected in the filter can survive for a long time and even multiply. Therefore, by providing the filter with antibacterial or antibacterial properties, an antibacterial filter has been developed that can not only remove bacteria present in the filter, but also sufficiently remove or sterilize microorganisms such as bacteria, viruses, and fungi suspended in the air.

However, when an inorganic antimicrobial agent is to be used in a substrate such as an antibacterial filter, the inorganic antimicrobial agent is difficult to introduce into the filter because it exists in a particle size of several micros.

Accordingly, there is a need to develop a coating technology capable of immobilizing an antimicrobial agent on a surface of a substrate as well as imparting antimicrobial properties to various microorganisms.

An antimicrobial coating agent having antimicrobial activity against various microorganisms, including Gram-positive bacteria and Gram-negative bacteria, is immobilized and coated on a surface and provides an antibacterial coating method on the substrate surface.

As an example, an antimicrobial coating agent including urushiol and an inorganic antibacterial agent is coated on a surface, wherein the inorganic antibacterial agent is immobilized on the surface of the substrate while urushiol is crosslinked.

As another example, the step of adding an inorganic antibacterial agent to the coating agent containing urushiol; High temperature polymerization by impregnating the coating agent with a substrate; And comprising the step of drying the substrate, it characterized in that the inorganic antimicrobial agent is immobilized on the surface of the substrate fiber while the urushiol is crosslinked, provides an antibacterial coating method of the substrate surface.

An antimicrobial coating agent is provided with a substrate immobilized on the surface, and as the antimicrobial coating agent, a natural polymer having antibacterial properties, not synthetic polymers, is eco-friendly, easy to control the concentration of the coating agent, polymerizable through a drying method, chemical and It is excellent in thermal stability, and it is possible to coat the fiber, so it does not block pores, and has an excellent antibacterial effect due to inorganic antibacterial agents due to its thin coating thickness.

1 shows a scanning electron microscope (SEM) photograph of a surface of a substrate prepared according to an example and a comparative example of the present application.

Figure 2 shows a scanning electron microscope (SEM) photograph of the surface of the substrate prepared according to an embodiment and a comparative example before and after washing with water.

3 shows a scanning electron microscope (SEM) photograph of the surface of a substrate prepared according to an example and a comparative example of the present application.

Figure 4 shows the results of FT-IR analysis of the urushiol monomer and the heat-crosslinked polyurushiol.

Figure 5 shows the results of FT-IR analysis of the coated substrate according to an embodiment of the present application.

Figure 6 shows the results of the antibacterial experiment to confirm the antibacterial activity of the surface of the substrate prepared according to one embodiment and a comparative example herein.

According to an aspect of the present invention, an antimicrobial coating agent including urushiol and an inorganic antibacterial agent is coated on a surface, wherein an inorganic antimicrobial agent is immobilized on a substrate surface while urushiol is crosslinked.

The term "substrate" of the present invention is a material having a certain shape, and may be a material capable of supporting the antibacterial coating agent according to the present invention to be immobilized on a surface. The material of the substrate can be used without limitation, such as fibers, silicon, glass, metal, magnetic material, semiconductor, ceramic, non-woven fabric as a specific example; Acrylic polymers, such as poly (methyl methacrylate) (PMMA); Polyethylene (PE), polypropylene (PP), polystyrene, polyethersulfone (PES), polycycloolefin (PCO), polyurethane (polyiourethane) or polycarbonate (PC) ), But is not limited thereto. Additionally, the substrate can be modified to have reactivity or introduce a new layer of material. The shape of the substrate is not limited thereto, and may have various shapes such as a spherical shape or a plate shape.

When the coating agent is treated on the surface of the substrate, the inorganic antibacterial agent may be immobilized on the surface of the substrate while urushiol is crosslinked, preferably thermally crosslinked. In addition, the coating agent may be uniformly coated on the surface of the substrate.

In accordance with another aspect of the present invention, the step of adding an inorganic antibacterial agent to the coating agent containing urushiol; High temperature polymerization by impregnating the coating agent with a substrate; And drying the substrate, wherein an inorganic antimicrobial agent is immobilized on the surface of the substrate while urushiol is crosslinked.

The urushiol may be diluted in alcohol solvents or oils.

According to another aspect of the present invention, an antibacterial filter comprising the substrate is provided.

According to another aspect of the present invention, an air purification apparatus including an antibacterial filter is provided.

Urushiol is a phenolic substance that is the main component of latex of lacquer species including Rhus verniciflua, and the urushiol monomer contains two -OH groups adjacent to the benzene ring (catechol structure) and has 15 carbons adjacent to it. Or a structure in which 17 long-chain hydrocarbons are combined. The side chain hydrocarbon is a saturated hydrocarbon or an unsaturated hydrocarbon containing 1 to 3 double bonds. Urushiol consists of a catechol structure that has a strong antioxidant activity site (active site) and an amphiphilic structure that has a fat-soluble long side chain in the same molecule, and thus has excellent biocompatibility, strong antioxidant activity, and antibacterial activity. Can be represented.

Urushiol can be obtained by purification from lacquer, and the purification method is generally an extraction method using an organic solvent such as n-hexane, methanol, ethanol, isopropanol or butanol, but is not limited to this method. For example, after mixing the lacquer solution and a hydrophilic organic solvent, centrifugation is performed to separate the urushiol layer dissolved in the hydrophilic organic solvent, and heating is performed to remove the organic solvent and moisture from the separated urushiol layer. The urushiol can be obtained through the urushiol extraction step of extracting urushiol.

Urushiol may also be obtained through a variety of synthetic methods known in the art, or may be commercially available.

In addition, a person with a specific constitution causes dermatitis called 'lacquer' on the whole body just by accessing the lacquer tree. This allergen is urushiol. Therefore, when used as a monomer form, urushiol can cause an allergic reaction and can be used by polymerization. In the case of an urushiol solution, it is cured by an enzymatic reaction by laccase, and in the case of an urushiol extract, it is cured by hydrogen peroxide or It is common to introduce light-crosslinkable molecules to crosslink them.

In one embodiment of the present application, it was confirmed that urushiol is cured through simple thermal crosslinking in air when the coating composition of the present application is treated on the surface of the substrate through FT-IR analysis (see FIG. 5). In addition, in one embodiment of the present application, it was confirmed that urushiol has a chemically stronger bond and stronger adhesion by forming a polymer. Specifically, when the coating composition of the present application is treated on the surface of the substrate, urushiol is thermally crosslinked and cured, and is tightly bound to the inorganic antibacterial agent on the surface, so it was confirmed that there is no difference between the surface of the substrate before and after water washing (FIG. 2). In addition, it was confirmed that the inorganic antimicrobial agent was coated by urushiol and bound to the fiber surface, the surface was relatively smooth, and the fiber surface and particles were stably fixed because they were coated together during the urushiol curing process (FIG. 3).

In addition, urushiol contains a saturated or unsaturated alkyl group in the molecule, thereby imparting hydrophobicity to the substrate.

The term "inorganic antibacterial agent" is a general term for inorganic compounds containing metals or metal ions having antibacterial properties, such as silver, zinc, copper, and the like. The inorganic antibacterial agent may be liquid or solid, and preferably solid. Examples of inorganic antibacterial agents include, but are not limited to, inorganic materials such as zeolite, synthetic zeolite, metal oxide, zirconium phosphate, calcium phosphate, calcium zinc phosphate, ceramic, soluble glass powder, silica alumina, titanium zeolite, apatite, calcium carbonate, etc. Can be As a specific example, the inorganic antimicrobial agent may be ion exchange or adsorption of metal ions having excellent antibacterial properties, such as silver, copper, manganese, and zinc, on an inorganic carrier such as zeolite or silica alumina. As a preferred example, the inorganic antibacterial agent may be copper oxide, zinc oxide, zinc pyrithione, zeolite, and specifically zeolite containing silver ions.

Zeolites are crystalline aluminosilicates with multiple pores. Zeolite is an inorganic polymer material formed by three-dimensionally connecting silicon (Si) and aluminum (Al) through an oxygen atom, and has a fine crystal size of usually 1 μm. They are characterized by having various shapes and 0.3nm to 10nm nanopores depending on the type.

The zeolite may be one or more selected from the group consisting of A-type zeolite, X-type zeolite, Y-type zeolite, high silica zeolite, soulite, mordenite, anannite, clinoptilolite, cavirite, and enoninitite. have.

The zeolite crystal structure is loosely bonded to each atom, so the nano pores inside are usually filled with water molecules, and even when this moisture is released with high heat, the skeleton is retained, so other fine particles can be adsorbed. Since zeolite has excellent role of cation exchanger and foreign substance adsorption function due to numerous nano-sized pores, it can exhibit the effect of adsorbing and removing heavy metals or bacteria.

In addition, a large number of silver ions (Ag ⁺ ) are adsorbed to the zeolite, and thus can have excellent sterilization and antibacterial activity. Is sterile, and antimicrobial action of silver ions (Ag ⁺⁾ are silver ions (Ag ⁺⁾ makin done while the elution, the elution of the silver ions (Ag ⁺⁾ are Na ^+, Ca ^2+, Mg ²⁺ cations and the like of Ag ⁺ ions It is done through the ion exchange reaction of the liver. In addition, the eluted Ag ⁺ ions adsorb and bind -SH and COO ^- or OH ^- ions in the microbial bacterial body protein to cause cell transformation, leading to condensation-dehydration reactions, thereby making it difficult to metabolize and energy metabolize the bacteria. , As a principle of killing bacteria, it can exhibit sterilization and antibacterial effects.

In the present application, silver ions (Ag ⁺ ) exist in an ion-bonded state in zeolite.

It is preferable that the particle size of the zeolite, that is, the particle size is 1 to 3 μm, but when the size is smaller than 1 μm, there is a problem in that washing and drying costs in the manufacturing process are increased. In addition, inhalation toxicity by nanoparticles may occur. The use of larger than 3 μm may cause dispersion difficulties and clogging of the nonwoven fabric. Also, the reaction with the silver nitrate solution may not work well.

Urushiol has antibacterial activity against Gram-positive bacteria, and inorganic antibacterial agents have antibacterial activity against Gram-negative bacteria. The coating composition provided herein may have antibacterial activity to both Gram-positive bacteria and Gram-negative bacteria because urinol is thermally crosslinked when treated on the substrate surface, and the inorganic antibacterial agent is firmly fixed to the substrate surface.

As an example, a bacterium in which the coating composition of the present application exhibits antibacterial activity may be Gram positive or Gram negative, or may be non-responsive to Gram tests. Bacteria can also be aerobic or anaerobic. Bacteria can be pathogenic or non-pathogenic. Examples of bacterial species or genus include Abiotrophia, Achromobacter, Acidaminococcus, Acidovorax, Acinetobacter, Actinobacillus ), Actinobaculum, Actinomadura, Actinomyces, Aerococcus, Aeromonas, Afipia, Agrobacterium, Alkali Alcaligenes, Alloiococcus, Alteromonas, Amycolata, Amycolatopsis, Anaerobospirillum, Anaerorhabdus , Arachnia, Arcanobacterium, Arcobacter, Arthrobacter, Atopobium, Aureobacterium, Bacteroides, Foot Balneatrix, Bar Bartonella, Bergeyella, Bifidobacterium, Bilophila, Branhamella, Borrelia, Bordetella, Brachyspira ), Brevibacillus, Brevibacterium, Brevundimonas, Brucella, Burkholderia, Butiauxella, Butyrivibrio, Kalimatobacterium, Campylobacter, Capnocytophaga, Cardiobacterium, Catonella, Cedecea, Cellulomonas, Centipeda, Chlamydia, Chlamydophila, Chromobacterium, Chyseobacterium, Chryseomonas, Citrobacter, Clottact Clostridium, cholinecell (Collinsella), Comamonas, Corynebacterium, Coroxiella, Cryptobacterium, Delftia, Dermabacter, Dermatophilus ), Desulfomonas, Desulfovibrio, Dialerister, Dichelobacter, Dolosicoccus, Dolosigranulum, Edwardsiella , Eggerthella, Ehrlichia, Eikenella, Empedobacter, Enterobacter, Enterococcus, Erwinia, Ericipello Tricks (Erysipelothrix), Escherichia, Eubacterium, Ewingella, Exiguobacterium, Facklamia, Filifactor, Flavimonas Flavimonas, Flavobacterium, Francisella (Francisella), Fusobacterium, Gardnerella, Globicatella, Gemella, Gordona, Haemophilus, Hafnia ), Helicobacter, Helococcus, Holdemania, Ignavigranum, Johnsonella, Kingella, Klebsiella, Kocuria ), Kocerella, Kurthia, Kytococcus, Lactobacillus, Lactococcus, Lautropia, Leclercia, Legionella , Reminorella, Leptospira, Leptorichia, Leuconostoc, Listeria, Listonella, Megasphaera, Methylobacterium (Methylobacterium), Microbacterium, Micrococcus, U.S. Mitsuokella, Mobiluncus, Moellerella, Moraxella, Morganella, Mycobacterium, Mycoplasma, Myloplasma Myroides, Neisseria, Nocardia, Nocardiopsis, Ochrobactrum, Oeskovia, Oligella, Orientia, Phenibacillus, Pantoia, Parachlamydia, Pasteurella, Pediococcus, Peptococcus, Peptococcus, Peptostreptococcus, Photobacterium Photobacterium, Photorhabdus, Plesiomonas, Porphyrimonas, Prevotella, Propionibacterium, Proteus, Providencia, Pseudomonas, Pseudomonas Pseudonocardia, Pseudoramibacter, Psychrobacter, Rahnella, Ralstonia, Rhodococcus, Rickettsia, Localimei Rochalimaea, Roseomonas, Rothia, Luminococcus, Salmonella, Selenomonas, Serpulina, Serpulia, Serratia Shewenella, Shigella, Simkania, Slackia, Sphingobacterium, Sphingomonas, Spirillum, Staphylococcus , Stenotrophomonas, Stomatococcus, Streptobacillus, Streptococcus, Streptomyces, Succinivibrio, Suterella, Sutterella, Suterella, Suttonella, Tatumella, T Sisellaella, Trabulsiella, Treponema, Tropheryma, Tsakamurella, Turicella, Ureaplasma, and Baragococcus ), Veillonella, Vibrio, Weeksella, Wolinella, Xanthomonas, Xenorhabdus, Yersinia and Yokenella ( Yokenella).

Gram-positive bacteria, such as Mycobacterium tuberculosis, Mycobacterium bovis, Mycobacterium avium, Mycobacterium intracellular, Mycobacterium africanum, Mycobacterium kansasii, Mycobacterium marinum, Mycobacterium ulcerans, Staphylococcus aureus (Staphylococcus aureus), Staphylococcus epidermidis, Staphylococcus equi, Streptococcus pyogenes, Streptococcus agalactiae, Streptococcus agalactiae, (steria monocytogenes), Listeria ivanovii, Bacillus anthracis, bar Examples of C. subtilis, Nocardia asteroides, Actinomyces israelii, Propionibacterium acnes and Enterococcus species You can. Gram-negative bacteria include, for example, Clostridium tetani, Clostridium perfringens, Clostridium botulinum, Pseudomonas aeruginosa, Vibrio cholerae , Actinobacillus pleuropneumoniae, Pasteurella haemolytica, Pasteurella multocida, Legionella pneumophila, Salmonella typhi (Salmonella typhi) , Brucella abortus, Chlamydi trachomatis, Chlamydia psittaci, Coxella burnetii, Escherichia coli, Escherichia coli, Nisseria meningitiers N meningitidis), Neiserria gonorrhea, Haemophilus influenzae, he Haemophilus ducreyi, Yersinia pestis, Ersinia enterolitica, Escherichia coli, E. hirae, Burkholdere Burakholderia cepacia, Burkholderia pseudomallei, Francisella tularensis, Bacteroides fragilis, Fusobacterium nucleatum ), Cowdria ruminantium (Cowdria ruminantium) may be exemplified, but is not limited thereto.

In the coating agent of the present application, urushiol may be included in 1 to 20% by weight. When the content is less than 1% by weight, it is difficult to express the properties of urushiol with a content that is too small, and when it exceeds 20% by weight, the content of urushiol is too high, so that complete heat curing does not occur and unreacted substances may remain on the coating surface. . In addition, due to the high viscosity, problems may occur in the manufacturing process and void clogging of the substrate may occur.

In addition, the content of the inorganic antibacterial agent in the coating agent may be 0.1 to 1% by weight. When the inorganic antimicrobial agent is less than the above range, a problem that the antibacterial power decreases may occur, and when it exceeds the above range, a dispersibility may occur due to agglomeration between antimicrobial agents.

In addition, in the description of the present application, the content of urushiol on the substrate may be 15 to 170% by weight, and the content of the inorganic antibacterial agent may be 4 to 10% by weight. If it is less than the above range, a problem of reducing antibacterial activity may occur, and if it exceeds the above range, a void clogging phenomenon of the substrate may occur.

In an embodiment, the substrate may be a non-woven material. Non-woven fabric is a fiber with a flat structure made by forming a sheet-shaped web that tangles various fibers such as natural fibers, chemical fibers, glass fibers, and metal fibers according to mutual characteristics, and combined them by mechanical or physical methods. It is a structure. As the raw fiber, one or more selected from the group consisting of natural fibers and synthetic fibers may be used. For example, it may be a nonwoven material containing at least one selected from viscose rayon fiber, polypropylene fiber, polyethylene fiber, polyethylene terephthalate fiber, polyester fiber, nylon fiber and cellulose fiber. There is no particular limitation on the material or manufacturing method of the nonwoven fabric herein. Non-woven fabric is applicable as long as it is commonly used, preferably chemical bonding, thermal bonding, thermal bonding, air-ray non-woven fabric (Air Ray), wet non-woven fabric (Wet Ray), needle punching non-woven fabric (Needle) Punching, spanless (water zet), spun bond, melt blown, stitch bond and electrospinning spinning Can be The nonwoven fabric may have an average thickness of 0.1 to 5 mm or 0.2 to 1 mm, and may be appropriately changed depending on the type of device to which the substrate is applied.

An example of the present invention, the step of adding an inorganic antibacterial agent to the coating agent containing urushiol; High temperature polymerization by impregnating the coating agent with a substrate; And comprising the step of drying the substrate, it characterized in that the inorganic antimicrobial agent is immobilized on the surface of the substrate fiber while the urushiol is crosslinked, provides an antibacterial coating method of the substrate surface.

Urushiol can be diluted in organic solvents. For example, methanol, ethanol, propanol, butanol, benzene, toluene, ethylbenzene, diethylbenzene, xylene, C1-C4 alkyl acetate, methyl ethyl ketone, acetone, tetrahydrofuran, 1,4-dioxane, tere Finyu may be illustrated, but is not limited thereto. In an embodiment, urushiol may be diluted in alcoholic solvents or oils. The dilution concentration of urushiol is not particularly limited, for example, it can be diluted to 0.1 to 50% by weight, 0.5 to 30% by weight or 0.1 to 20% by weight in an organic solvent, and used by those skilled in the art as appropriate.

As a method of impregnating the substrate with the urushiol coating solution, an immersion method, a dipping method, a roller method, an air knife method, a spray method, etc. may be exemplified, but is not limited thereto.

The substrate into which the coating agent is introduced may be subjected to high temperature treatment to induce thermal crosslinking and polymerization reaction of urushiol. Urushiol is cured by the high temperature treatment and is tightly combined with the inorganic antibacterial agent on the surface, so that the inorganic antibacterial agent can be firmly fixed to the surface of the substrate. The heating temperature for inducing the polymerization reaction of urushiol may be 70 to 200 ° C, or 100 to 150 ° C, and the heating time may be 1 to 100 hours, or 1 to 72 hours, or 1 to 6 hours. The reaction time within the above range may be shorter as the temperature increases and longer as the temperature decreases. However, when the temperature exceeds 200 ° C, the polymerization reaction proceeds rapidly and it may be difficult to control the reaction. The reaction time can be appropriately adjusted while seeing the degree of immobilization of the coating agent on the surface of the substrate, but the reaction can be terminated at a time when the fluidity of urushiol is significantly reduced.

The substrate of the present application may be used as an antibacterial filter, and the antibacterial filter may be useful as an antibacterial filter applied to a vacuum cleaner, an air cleaner, a car, a refrigerator, an air conditioner, a gas mask, a water purifier, and a clean room.

In one example, the antibacterial filter may be an air filter that can be used for air purification. The air filter may be a vacuum cleaner or an air purifier filter used in the home, but may be an air filter used in an air purification facility or a dust collection facility that can be used in a large capacity in a vehicle or an industry such as a factory or research institute. In addition, the filter can also be used for water treatment.

Hereinafter, the present invention will be described in more detail by the following examples. However, these are only for illustrating the present invention, and the scope of the present invention is not limited by these examples.

Example 1. Preparation of antibacterial coating agent for surface treatment of substrate and antibacterial substrate

A coating agent for surface treatment of a substrate was prepared by adding a zeolite inorganic antibacterial agent containing silver ions to a natural coating agent based on an urushiol solution. To this end, a coating solution in which urushiol (Korea National Co., Ltd.) was diluted 1/30 in ethanol was prepared, and a zeolite containing silver ions (a product manufactured by Sunkwang Polymer Co., Ltd.) was added and dispersed. Zeolite containing silver ions was added to the coating solution at a rate of 0.3% w / v. 30 minutes of substrate of miracloth non-woven fabric (Sigma-Aldrich) on the prepared coating agent After soaking, high temperature polymerization and drying were performed at 140 ° C to introduce a coating agent on the substrate surface.

Example 2. Preparation of antibacterial coating agent for surface treatment of substrate and antibacterial substrate

A coating agent was prepared in the same manner as in Example 1, but the coating agent was introduced on the surface of the substrate after preparing the coating agent using a dilution of urushiol 1/5.

Example 3. Preparation of antibacterial coating agent for surface treatment of substrate and antibacterial substrate

A coating agent was prepared in the same manner as in Example 1, but a coating agent was prepared using a 1/100 dilution of urushiol, and then the coating agent was introduced on the surface of the substrate.

Comparative Example 1. Preparation of urushiol coating agent and antibacterial substrate

Urushiol (Korea National Co., Ltd.) was prepared by diluting urushiol with 1/30 in ethanol. The substrate of the miracloth nonwoven fabric (Sigma-Aldrich) was immersed in the prepared coating agent for 30 minutes, followed by high temperature polymerization and drying at 140 ° C to introduce a coating agent on the surface of the substrate.

Comparative Example 2. Preparation of inorganic antibacterial agent-containing coating agent and antibacterial substrate

In ethanol, a zeolite containing silver ions (a product manufactured by Sunkwang Polymer Co., Ltd.) was added and dispersed. Zeolite containing silver ions was added at a rate of 0.3% w / v. The substrate of the miracloth nonwoven fabric (Sigma-Aldrich) was immersed in the prepared coating agent for 30 minutes, followed by high temperature polymerization and drying at 140 ° C to introduce a coating agent on the surface of the substrate.

Comparative Example 3. Preparation of antibacterial coating agent for surface treatment of substrate and antibacterial substrate

Urushiol (Korea National Co., Ltd.) was prepared by diluting a coating solution 1/30 in ethanol, and a zeolite containing silver ions (a product manufactured by Sunkwang Polymer Co., Ltd.) was added and dispersed. Zeolite containing silver ions was added to the coating solution at a rate of 0.3% w / v. The substrate of miracloth nonwoven fabric (Sigma-Aldrich) was immersed in the prepared coating agent for 30 minutes and then dried at 30 ° C. to introduce a coating agent on the surface of the substrate.

Experimental Example 1. Scanning electron microscope (SEM) observation

As a result of observing the antibacterial substrate according to Example 1 with a scanning electron microscope (SEM), the coating agent was uniformly coated on the surface of the nonwoven fabric, and an inorganic antibacterial agent was attached to the surface of the fiber (FIG. 1). In particular, since urushiol is thermally crosslinked and cured and is tightly bound to the inorganic antibacterial agent on the surface, it has been confirmed that there is no difference in the surface of the substrate before and after water washing (FIG. 2). In addition, in the case of Example 1, the inorganic antimicrobial agent was coated by urushiol and bound to the fiber surface, the surface was relatively smooth, and the fiber surface and particles were stably fixed because they were coated together during the urushiol curing process (Fig. 3). ).

In Comparative Example 1, only urushiol was used as a coating agent without an inorganic antibacterial agent, and it was confirmed that the white non-woven fabric turned brown as the coating was cured, and it was confirmed through SEM pictures that the coating agent was uniformly coated on the surface of the non-woven fabric ( Figure 1).

In Comparative Example 2, only the inorganic antibacterial agent (silver ion-containing zeolite) was used as the coating agent without urushiol, and it was observed that a large amount of the inorganic antibacterial agent falls off after washing the coated substrate. In addition, in the absence of urushiol, it was observed that the inorganic antimicrobial agent was introduced into the nonwoven fabric in a bundled form (FIG. 2). In addition, the inorganic antibacterial agent (silver ion-containing zeolite) was in the form of a cube, had a rough surface, and was fixed to the fiber surface by simple physical adsorption (FIG. 3).

In the case of Comparative Example 3, a coating agent containing both urushiol and an inorganic antimicrobial agent was used, but the urushiol was not cured at a high temperature, and it could be observed that the inorganic antibacterial agent fell off after washing the coated substrate (FIG. 2).

Experimental Example 2. Infrared spectroscopy (FT-IR)

Through FT-IR analysis, it was confirmed that urushiol was cured through simple thermal crosslinking in air. To this end, each sample was cut to a size of 2 x 2 cm, and then measured in reflection mode (ATR).

Figure 4 shows the results of FT-IR analysis of the urushiol monomer and the heat-crosslinked polyurushiol. In FIG. 4, 3012 cm ^-1 is a = CH stretching vibration part, and this part is reduced as it is thermally crosslinked (-CH = CH- + -CH = CR1-> -CH-CH-CH-CR1) . 3600 ~ 3200 cm ^-1 is a -OH vibration part, which is sharp in the case of urushiol monomer, but the peak was broadened by hydrogen bonding as it was thermally crosslinked. It can be seen that 948 and 985 cm ^-1 decrease or disappear as the conjugated double bond of the urushiol monomer is thermally crosslinked. Therefore, it can be confirmed that the urushiol monomer is crosslinked through thermal crosslinking, and as a result, it becomes a cured polyurushiol form.

Based on this, FT-IR analysis of the antibacterial substrate coated according to Example 1 was performed, and the results are shown in FIG. 5. In FIG. 5, the FT-IR peak of the inorganic antibacterial agent (silver ion-containing zeolite) is 3600-3200 cm ^-1 -OH peak and 900-850 cm ^-1 Si-OH, 1100-1000 cm ^-1 Si-O. -Si peak. The -OH vibration portion of 3600 ~ 3200 cm ^-1 overlapped the peak of the urushiol monomer. The 1100 to 850 cm ^-1 portions were Si-OH and Si-O-Si peaks, and were classified as inorganic antimicrobial peaks. Through the fact that the peak intensity of the 1100 to 850 cm ^-1 portion was very large compared to other specific peaks, it was found that a number of inorganic antibacterial agents were present on the surface.

Experimental Example 3. Confirmation of antibacterial activity

Antibacterial experiments were performed on substrates except for Comparative Example 2 in which desorption of particles occurs in the washing process and Comparative Example 3 in which urushiol crosslinking is not formed. For the antibacterial test, KS K 0693, an antibacterial test standard, was suitably modified and used. Specifically, 0.4 g, 10 ⁴ CFU concentration of 4 ml of bacteria (1X PBS 4 ml, OD 600 nm = 1 value of 40 μl of bacteria) was added to an antibacterial fabric sample cut into 50 ml conical tubes. The control test piece was prepared by adding 0.4 g of untreated fabric instead of an antibacterial fabric sample. Staphylococcus aureus was used as a Gram-positive bacterium, and Escherichia coli was used as a Gram-negative bacterium. The strains were supplied by the Korea Microbial Conservation Center. The prepared sample was incubated for 24 hours at (37 ± 1) ° C using a shaking incubator. After the culture was completed, 16 ml of 1X PBS was added and diluted 5 times, followed by vortexing for 30 minutes to 1 hour depending on the type of fabric. This step is the process of removing the bacteria attached to the fabric or attached to the surface in a liquid state, and the miracloth fabric should be vortexed for at least 30 minutes and the spinning fabric for at least 1 hour. When the vortexing was completed, 100 μl of each was inoculated into agar solid medium, and then spread until it was absorbed into the medium using a spreader or glass beads. The solid medium was incubated at (37 ± 1) ° C. for 24 hours. Colonies of each Petri dish were counted and recorded. Then, the percentage of CFU in the antimicrobial sample compared to the control specimen was calculated to determine the percentage of bacteriostatic reduction.

As a result, in the case of the fibers coated with urushiol and the inorganic antimicrobial agent according to Example 1, Example 2, and Example 3, Staphylococcus aureus and Escherichia coli showed 99.9% antibacterial activity. However, in the case of the fiber coated with urushiol according to Comparative Example 1, there was no antibacterial activity in E. coli, and only 99.9% of the antibacterial activity in Staphylococcus aureus, a Gram-positive bacteria (FIG. 6).

From the above description, those skilled in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing its technical spirit or essential features. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. The scope of the present invention should be construed as including all changes or modifications derived from the meaning and scope of the following claims rather than the detailed description and equivalent concepts thereof.

Claims (13)

1. An antibacterial coating agent including urushiol and an inorganic antibacterial agent is coated on the surface,

   The substrate, characterized in that the inorganic antimicrobial agent is immobilized on the surface of the substrate while urushiol is crosslinked.
2. The substrate according to claim 1, wherein the inorganic antibacterial agent is an inorganic antibacterial agent including silver ion and zeolite, copper oxide, zinc oxide, or zinc pyrithione.
3. The substrate according to claim 1 or 2, wherein the content of urushiol in the coating agent is 1 to 20% by weight, and the content of the inorganic antibacterial agent is 0.1 to 1% by weight.
4. The substrate according to any one of claims 1 to 3, wherein the content of urushiol on the substrate is 15 to 170% by weight, and the content of the inorganic antibacterial agent is 4 to 10% by weight.
5. The substrate according to any one of claims 1 to 4, wherein the coating agent has antibacterial activity against Gram-positive bacteria and Gram-negative bacteria.
6. The substrate according to any one of claims 1 to 5, wherein the coating agent is uniformly coated on the surface.
7. The substrate according to any one of claims 1 to 6, wherein the substrate is a fiber.
8. Adding an inorganic antibacterial agent to the coating agent containing urushiol;

   High temperature polymerization by impregnating the coating agent with a substrate; And

   And drying the substrate.

   Characterized in that the inorganic antimicrobial agent is immobilized on the surface of the substrate while the urushiol is crosslinked,

   Method for antibacterial coating of substrate surface.
9. The method according to claim 8, wherein the urushiol is diluted in an alcoholic solvent or oils.
10. The method according to claim 8 or 9, wherein the inorganic antibacterial agent is an inorganic antibacterial agent including silver ion and zeolite, copper oxide, zinc oxide, or zinc pyrithione.
11. The method according to any one of claims 8 to 10, wherein the content of urushiol in the coating agent is 1 to 20% by weight, and the content of the inorganic antibacterial agent is 0.1 to 1% by weight.
12. The method according to any one of claims 8 to 11, wherein the content of urushiol on the substrate is 15 to 170% by weight, and the content of the inorganic antibacterial agent is 4 to 10% by weight.
13. The method according to any one of claims 8 to 12, wherein the coating agent has antibacterial activity against Gram-positive bacteria and Gram-negative bacteria.

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