KR102160897B1 - Room temperature curing coating composition for peelable film coating having antibacterial property and coating method using it - Google Patents

Abstract

The present invention relates to a room temperature curing organic/inorganic hybrid antibacterial film-type coating composition which maintains an excellent antibacterial effect while being attached to a product and can be peeled off when necessary after forming an eco-friendly antibacterial coating film on a surface of the product, and to an antibacterial coating film construction method using the same. The antibacterial film-type coating composition comprises: an inorganic resin composition; an organic resin composition; and an antibacterial agent.

Description

Room temperature curing coating composition for peelable film coating having antibacterial property and coating method using it}

The present invention is curable at room temperature and relates to an antimicrobial film-type coating composition capable of forming a peelable antimicrobial coating film, and a construction method of an antimicrobial coating film using the same.

In the wake of the new coronavirus infection (Corona 19), along with new infectious diseases such as H1N1 flu, MERS, Zika virus, and super bacteria, concerns about infection are growing, and interest in hygiene and cleanliness is constantly increasing. The daily life of the people is also changing greatly, and sales of disinfection, sterilization, and antibacterial products for quarantine as well as voluntary social distancing are increasing rapidly.

Antibacterial products are widely used in the spray-type form, and are used in homes where there is a high risk of cross-infection such as toilets, cell phones, dining tables, remote controls, door handles, elevator buttons, handles, and desks in public facilities or multi-use facilities. These spray-type antibacterial products have the advantage of being easy to use, but there is a problem that the antibacterial effect is not continuous and is temporary. In addition, poor ventilation after spraying may adversely affect the human respiratory system.

In addition, a spray type and a method of minimizing indirect contact by attaching an antibacterial film to a portion of the human hand are used together.

The antibacterial film is constructed by laminating a film having antibacterial properties on a base film, forming an adhesive layer under the base film, and then pasting it in a sheet form, and it can be said that it has a more sustained antibacterial effect than spray. However, since it is applied in the form of a film, its application field is limited to a flat plate shape, so it cannot be applied to various products. In addition, when the antibacterial film is removed for removal after use, there is a problem that the antibacterial film is not removed cleanly by the adhesive layer or sticky residues exist on the surface of some products. In addition, the durability and solvent resistance are low, so when the antibacterial film is wiped with a cleaning solution, the antibacterial effect is greatly reduced.

Antibacterial spray can be used regardless of the shape of the product, but it cannot be applied to some materials such as electronic products due to its liquid form. In addition, in the case of antibacterial films, they are commercially available and applied mainly to electronic products, etc., and they cannot be attached to materials such as wood or stone, and their shape is also very limited.

Therefore, it is urgent to develop a new product that can be applied regardless of the material and shape of the product, and not only maintains excellent antibacterial effect during application, but is also easy to remove after use.

Republic of Korea Patent Publication No. 10-2014-0146428 (published on December 26, 2014) Republic of Korea Patent Registration No. 10-1615550 (2016.04.20 announcement) Korean Patent Registration No. 10-1632918 (2016.06.17 announcement)

Therefore, the applicant of the present invention conducts research to develop a composition that can be coated with spray, etc., regardless of the shape or material of the product, maintains the antibacterial effect while forming the coating film, and can be peeled off when necessary after use. As a result, an organic/inorganic hybrid antibacterial film-type coating composition including inorganic and organic resins was developed, and the antimicrobial coating composition is easy to use because it can be cured at room temperature after coating, and has functions as various protective films including antibacterial effects. In addition to having it, it was confirmed that it can be removed cleanly if necessary.

Accordingly, it is an object of the present invention to provide a peelable room temperature curable organic/inorganic hybrid antibacterial film-type coating composition.

In addition, the present invention provides an eco-friendly antibacterial coating film made of a peelable room temperature curable organic/inorganic hybrid antibacterial film-type coating composition.

The present invention provides a room temperature curing organic/inorganic hybrid antimicrobial film-type coating composition to protect the surface of a product through formation of a coating film and to enable peeling of the coating film.

At this time, the organic/inorganic hybrid antibacterial film-type coating composition includes an inorganic resin composition, an organic resin composition, and an antimicrobial agent, and the inorganic resin composition includes ceramic fine particles in a structure in which siloxane crosslinked, and the organic resin composition is dispersed in water. And acrylic resins and water-soluble polyurethane resins.

Further, the inorganic resin composition and the organic resin composition are cured to form a structure in which a linear polymer penetrates between a three-dimensional network structure.

In addition, the present invention provides a construction method using an antibacterial film-type coating agent for performing room temperature curing after applying a room temperature-curable organic/inorganic hybrid antimicrobial film-type coating composition to a product surface.

The antibacterial coating composition according to the present invention is capable of forming an eco-friendly antibacterial coating film, which maintains an excellent antibacterial effect while the product is attached, and is required with a function of continuous antibacterial effect after forming an antibacterial coating film on the surface of the product. There is an advantage that it can be removed because it can be peeled off.

In addition, by providing deodorization and decomposition of harmful substances, it is possible to inhibit the growth of bacteria harmful to the human body, block harmful gases, and block contamination of dangerous substances such as asbestos and radioactive substances. In addition, while having gas permeability, it has excellent performance as a protective film due to water resistance, abrasion resistance, contamination resistance, heat resistance, and chemical resistance.

In particular, since it can be cured at room temperature, it is possible to form a coating film without a separate heating device or UV irradiation, and it does not chemically and physically affect the product.

In addition, according to the use of a water-based solvent, it is possible to be free from the problem of harmfulness to the work environment during construction, and there is an advantage that a coating film can be formed regardless of the material, shape, and size of the product.

The present invention can be applied regardless of the material and shape of the product, and the room temperature curable organic/inorganic hybrid antibacterial film-type coating composition capable of producing an eco-friendly antibacterial coating film that can be removed when necessary as well as maintaining excellent antibacterial effect during application. Present.

Room temperature curing organic/inorganic hybrid antibacterial film-type coating composition is an organic/inorganic hybrid that has both the characteristics of the organic system and the characteristics of the inorganic system by mixing the inorganic resin composition and the organic resin composition, and a bonding reaction between them during the curing process To form an antibacterial coating film.

Each composition will be described in detail below.

Inorganic resin composition

The inorganic resin composition according to the present invention includes a composition in which ceramic fine particles, a silane coupling agent, a thickener, isopropyl alcohol, and water are mixed to modify the surface of the ceramic powder into a structure in which the silane coupling agent is crosslinked with siloxane by hydrolysis.

The hydrolysis reaction is shown in Scheme 1 below.

(Scheme 1)

-Si(OR)n + XH ₂ O → Si(OR) _nx + X ROH

The ceramic fine particle powder may be one selected from the group consisting of silicon dioxide, titanium dioxide, aluminosilicate, and combinations thereof. The ceramic powder may be solid or hollow spherical particles, and those having an average particle size of 2 to 20 μm are used.

The silicon dioxide and titanium dioxide have a quenching effect, and particles of 2 to 5 μm are used, and the aluminosilicate has an effect of increasing thermal insulation, and it is preferable to use hollow particles, the size of which is 5 to 20 μm. Use what is. These can be appropriately selected and used according to the type of product and the purpose of the protective film.

The silane coupling agent forms a siloxane crosslinked structure through a hydrolysis reaction, and this structure is combined with a hydroxyl group on the surface of the ceramic powder so that dispersion of the ceramic powder is easy and chemically stable. As such a silane coupling agent, at least one selected from the group consisting of methyltrimethoxysilane, decyltrimethoxysilane, epoxysilane, aminosilane, phenylsilane, tetraethoxysilane, and glycidyloxytrimethoxysilane. It is desirable. More preferably, an alkoxysilane-based silane coupling agent is used. The alkoxysilane material has both alkoxy and silane groups, which are reactive groups in the molecular structure, and can be easily converted into a three-dimensional network structure by hydrogen bonding. Since the bonding of the three-dimensional network structure is firmly bonded, it has a very high hardness, and this bonding structure has the advantage of being able to achieve a strong bond.

The thickener may be methyl cellulose or hydroxyethyl cellulose. The viscosity of the composition can be controlled by the use of such a thickener.

The solvent may be a mixed solvent of isopropyl alcohol (IPA) and water as a solvent for dispersing or hydrolyzing the inorganic resin composition, but is not limited thereto, and the use of such a solvent may impart fluidity to the coating film. have.

Looking at the optimum content ratio of the constituents constituting the inorganic resin composition and each component in the present invention, based on 100% by weight of the inorganic resin composition, ceramic powder 3 to 8% by weight, silane coupling agent 5 to 15% by weight, thickener 1 It is most preferred to include the balance of 5% by weight to 5% by weight, 40 to 60% by weight of isopropyl alcohol, and water.

If the content of the ceramic powder is less than the above range, it is difficult to exert a quenching effect and durability when forming an organic/inorganic hybrid antibacterial coating film. On the contrary, if the content of the ceramic powder exceeds the above range, the viscosity increases rapidly or a gel phenomenon such as porridge occurs. There is a problem that the inorganic hybrid antibacterial coating film is not formed and is broken. Therefore, with respect to 100% by weight of the inorganic resin composition, the content of the mixed powder of silicon dioxide and titanium dioxide is preferably 3 to 8% by weight.

In addition, if the silane coupling agent is less than the above range, the bonding with the organic resin composition is insufficient, and the adhesion to the product surface decreases, and if the silane coupling agent exceeds the above range, bubbles or peeling may occur. have. Therefore, it is preferable that the silane coupling agent is 5 to 15% by weight based on 100% by weight of the inorganic resin composition.

In addition, if the thickener is less than the above range, it is difficult to expect a viscosity increase effect due to the use of the thickener. Conversely, if the thickener is used beyond the above range, the fluidity may be greatly reduced due to high viscosity. Therefore, with respect to 100% by weight of the inorganic resin composition, the thickener is preferably 1% by weight to 5% by weight.

In addition, if the isopropyl alcohol is less than the above range, the reaction of the coating composition may be non-uniform, resulting in poor reproducibility, and if it exceeds 60% by weight, the coating composition may have insufficient ability to form a coating film. Therefore, with respect to 100% by weight of the inorganic resin composition, isopropyl alcohol is preferably 40 to 60% by weight.

Water is used as the balance, and it is preferable to mix and use nitric acid in an amount of 1 to 5% by weight so that the pH is adjusted to 1 to 2 to perform the hydrolysis reaction.

Optionally, the inorganic resin composition of the present invention may contain various pigments in the range of 5 to 20% by weight. A transparent protective layer or a protective layer having a color may be formed with or without the addition of the pigment.

Organic resin composition

The organic resin composition of the present invention comprises an alkyl methacrylate, an alkyl acrylate, an unsaturated carboxylic acid monomer, and a water-dispersible acrylic resin obtained by emulsion polymerization of a crosslinkable monomer, a water-soluble polyurethane resin, a thickener, a defoaming agent, an adhesive, and a residual amount of a solvent. do.

In addition to the flexibility, peelability, and water resistance of the organic/inorganic hybrid antibacterial coating film according to the mixed use of the water-dispersible acrylic resin and water-soluble polyurethane resin of the present invention, unlike the resin in the conventional patent, room temperature even without applying separate heat or UV Not only can curing be achieved, but also gas permeability can be increased.

The water-dispersible acrylic resin means that the acrylic resin is present in the form of an emulsion, and the water-soluble polyurethane resin means that the polyurethane is present in a state in which water is dissolved.

<Water-dispersion acrylic resin>

The water-dispersible acrylic resin according to the present invention is in the form of an emulsion, and a free emulsion is prepared using (i) an alkyl methacrylate, (ii) an alkyl acrylate, (iii) an unsaturated carboxylic acid monomer, and (iv) a crosslinkable monomer. After that, it is prepared by putting it in two steps.

Alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2- Ethylhexyl acrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, preferably one or more selected from the group consisting of isobornyl methacrylate, but is not limited thereto. Preferably, methyl methacrylate is used. The alkyl methacrylate is used in an amount of 30 to 60% by weight in the total composition.

Alkyl acrylate is methyl acrylate, ethyl acrylate propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, heptyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate and isodecyl acrylate. It is preferably one or more selected from the group consisting of, but is not limited thereto. Preferably, butyl acrylate is used. The alkyl acrylate is used in an amount of 35 to 70% by weight in the total composition.

The unsaturated carboxylic acid monomer is used for the purpose of improving adhesion and cohesion to the substrate. The unsaturated carboxylic acid monomer is preferably at least one selected from the group consisting of acrylic acid, itaconic acid, maleic acid, fumaric acid, methacrylic acid, and ethyl methacrylic acid, but is not limited thereto. Among these, it is preferable to use acrylic acid or methacrylic acid which is an unsaturated carboxylic acid. The unsaturated carboxylic acid is used in an amount of 1 to 10% by weight in the total composition.

The crosslinkable monomer is used to assist the crosslinking effect upon drying, and has crosslinking reactivity and high thermal stability. The crosslinkable monomers are glycidyl methacrylate, 3-butanediol diacrylate, 1,3-butanediol dimethagrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylic Rate, allyl methacrylate, trimethylolpropane triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, and preferably one or more selected from the group consisting of divinylbenzene, but limited thereto no. Among these, it is preferable to use glycidyl methacrylate. The crosslinkable monomer is used in an amount of 3 to 15% by weight in the total composition.

The polymerization reaction of the acrylic emulsion may be performed using a conventional emulsion polymerization method, but after preparing a pre-emulsion in order to facilitate the control of the reaction heat and polymerization degree, the pre-emulsion is added stepwise to polymerize, and then aging is performed.

<Manufacturing method>

(Pre-emulsion preparation step)

First, after adding water to the reactor, the above-described monomers are added. Here, 3 to 20 parts by weight of a surfactant, 0.1 to 5 parts by weight of an initiator, and 0.1 to 5 parts by weight of a buffer solution are added to 100 parts by weight of a total monomer to prepare a pre-emulsion.

The emulsion is prepared by mixing a mixture of monomers, water, and surfactant.

The surfactant is used for initial particle generation during the polymerization reaction, control of the size of the generated particles, and stability of the particles, and is composed of a hydrophilic group and a lipophilic group, and is divided into anionic, cationic and nonionic surfactants. Mainly, anionic and nonionic surfactants are often used, and they are often mixed with each other to complement mechanical stability and chemical stability.

More preferably, an anionic surfactant having an HLB value of 20.0 or higher and a nonionic surfactant having an HLB value of 6.0 to 10.0 are mixed at a predetermined ratio and used.

Anionic surfactants with an HLB value of 20.0 or higher include Sodium Lauryl Sulfate, Sodium Lauryl Ether Sulfate, Ammonium Lauryl Sulfate, and Ammonium Lauryl Ether Sulfate. Ether Sulfate), etc. are used, and as sodium lauryl sulfate, SUNFOM-S from Sunjin Chemical, SUNFOM-E from Sunjin Chemical as sodium lauryl ether sulfate, and SUNFOM-EA from Sunjin Chemical as ammonium lauryl sulfate are mentioned above. Examples do not limit the scope of the invention.

Nonionic surfactants having an HLB value of 6.0 to 10.0 are polyethylene oxide (PEO)-based surfactants, for example, MONOPOL NFE8 from Dongnam Synthetic, Brij30, Brij52, Brij72 from ICI, Tergitol.rtm from Union Carbide. 15-S-3, Tergitol.rtm. 15-S-5, Henkel's Dehydol LS-2, Japanese surfactant Koyo's BB-5, BC-5.5, OP-3, INEOS Oxide's Laureth-2, Laureth-3, Laureth-4, Dow Chemical's LA -2, LA-3, LA-4, etc., but the above examples do not limit the scope of the present invention.

By using more nonionic surfactants in the range of 2.5 to 5 parts by weight of nonionic surfactants compared to 1 part by weight of anionic surfactants, the two types of surfactants can reduce the particle size of the emulsion and form a stable emulsion. To be.

Surfactants in which these two types are mixed are used in an amount of 3 to 20 parts by weight based on 100 parts by weight of the total monomer, and if the content is less than the above range, it is difficult to emulsify. Conversely, if the amount exceeds the above range, emulsification is easy but adhesion And water resistance is poor.

The initiator of the polymerization reaction is preferably a water-soluble initiator, and specific examples include ammonium or alkali metal persulfate, hydrogen peroxide, peroxide, hydroperoxide, etc. In order to carry out the emulsion polymerization reaction at low temperature, one or more reducing agents Can also be used with

The reducing agent may be sodium bisulfite, sodium metabisulfite, sodium hydrosulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, and the like.

The buffer used in the polymerization reaction adjusts the pH and imparts stability to the acrylic resin (or latex) to be polymerized. Specifically, it is composed of sodium acetate, sodium bicarbonate, sodium carbonate, sodium phosphate, sodium sulfate and sodium chloride. It may be one or more selected from the group, preferably sodium acetate. The buffer is used in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the total monomer.

(1st polymerization step)

After 30 to 45% by weight of the pre-emulsion prepared in the above step is added to the reactor, a first polymerization reaction is performed.

The temperature of the polymerization reaction is performed at 0 to 100°C, preferably 40 to 85°C for 30 minutes to 2 hours.

(Second polymerization step)

Subsequently, the remaining pre-emulsion is added to perform a secondary polymerization reaction.

The secondary polymerization reaction is carried out at the same temperature as the primary, and is carried out for 2.5 to 5 hours for a conversion rate of 95% or more.

(Maturation stage)

The water-dispersible acrylic resin emulsion obtained through the secondary polymerization is aged for 1 to 3 hours at the same temperature to have a conversion rate of 99% or more.

The acidity (pH) of the water-dispersible acrylic resin emulsion prepared through these steps is preferably 4 to 9, more preferably 7 to 8.

In addition, the water-dispersible acrylic resin requires an appropriate glass transition temperature (Tg) in order to realize considerable heat resistance and adhesive strength, and an appropriate gel content is required to implement a considerable cohesive force.

The glass transition temperature (Tg) of the water-dispersible acrylic resin may be -30 to 20°C, preferably -15 to 15°C, and more preferably 0 to 15°C. If the glass transition temperature is less than the above range, heat resistance is deteriorated, and when the coating film is peeled off, residues remain to contaminate the product surface, and if it exceeds the above range, the adhesion is poor and easily lifted by moisture and gas.

At this time, it is preferable that the water-dispersible acrylic resin has a low molecular weight of 1000 to 50,000 g/mol of a weight average molecular weight (Mw), but when the weight average molecular weight is less than 1000, coating film formation is lowered, which is not preferable, and the weight average molecular weight is 50,000. If it exceeds, the separability after curing tends to decrease. In addition, gas permeability, durability, and chemical resistance can be secured under the weight average molecular weight condition.

It is advantageous in terms of securing physical properties to use the water-dispersible acrylic resin in the range of 60 to 80% by weight within 100% by weight of the total organic resin composition. If the content is less than or exceeds the above range, room temperature curing, gas permeability, film flexibility, ease of separation, and water resistance are lowered.

<Water-soluble polyurethane resin>

Water-soluble polyurethane resin is used to increase adhesion to the product and further increase the elasticity, tensile strength and flexibility of the coating film. The water-soluble polyurethane resin can be used by purchasing commercially available ones or directly manufactured and used.

According to one embodiment, the water-soluble polyurethane resin is prepared by condensation reaction of an isocyanate, a polyol, and an anionic chain extender to prepare a polyurethane prepolymer having an anionic group covalently bonded in the main chain; And converting an anionic group covalently bonded in the main chain of the polyurethane resin into a salt by adding sodium hydroxide to the polyurethane prepolymer.

The anionic group covalently bonded in the main chain of the polyurethane prepolymer becomes water-soluble or water-dispersible by sodium hydroxide. These water-soluble polyurethane resins have a solid content of 10 to 50% by weight in water dispersion.

The isocyanate may be selected from the group consisting of aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate, and specifically tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, hexamethylene- 1,6-diisocyanate, cyclohexylene-1,4-diisocyanate, methylenebis (4-cyclohexyl isocyanate), isophorone diisocyanate, and 4,4-methylenebis (cyclohexyl isocyanate) selected from the group consisting of There may be more than one type.

Polyols are at least one type from the group consisting of polyester polyols and polyether polyols, and those having a weight average molecular weight of 400 to 10,000 g/mol are used.

It is advantageous in terms of securing physical properties of elasticity, tensile strength, and flexibility of the coating film to use the water-soluble polyurethane resin in an amount of 10 to 30% by weight within 100% by weight of the total organic resin composition.

In addition to the above composition, the organic resin composition may further include a thickener, a defoaming agent, an adhesive, and an additional solvent.

For proper viscosity control, 1 to 2% by weight of a thickener such as methyl cellulose may be included, and 1 to 3% by weight of a silicone antifoaming agent, and polyvinyl alcohol (PVA) as an adhesive for adjusting the coating film thickness and improving adhesion It may contain 2 to 5% by weight.

In addition, water may be used as the solvent of the organic resin composition, and may be included in an amount of 100% by weight in combination with other components constituting the organic resin composition.

The room temperature curable coating composition comprising the above-described composition adds an organic resin composition to the inorganic resin composition to induce crosslinking so that the organic/inorganic hybrid antibacterial coating film has a structure in which a linear polymer penetrates between the three-dimensional network structure. do. Through this structure, the surface of the coating film is hardened, has durability, and at the same time, it has water resistance by securing hydrophobicity.

In this case, the inorganic resin composition is used in an amount of 3 to 20% by weight and an organic resin composition in an amount of 75 to 95% by weight, and an antimicrobial agent is included in an amount of 2 to 5% by weight.

The antimicrobial agent is at least one inorganic type selected from silver nano, zinc and silica; Alternatively, an organic antibacterial agent of vegetable oil may be used.

In addition, in the room temperature curing coating composition of the present invention, if necessary, additives such as various antifouling agents, anti-settling agents, leveling agents, additives, flame retardants, defoaming agents, wetting agents, dispersants, ultraviolet stabilizers, antioxidants, fillers, surfactants, etc. You can use additionally.

This room temperature curing coating composition is used as it is or diluted with water (within 5%) if necessary. Store in a cool and dark place above 0℃ considering freezing.

Organic/Inorganic Hybrid Antibacterial Coating Film

The present invention can provide a product with an eco-friendly antibacterial coating film formed by coating the organic/inorganic hybrid room temperature curing coating composition on the product surface and then forming an organic/inorganic hybrid antibacterial coating film on the surface through room temperature curing.

The organic/inorganic hybrid antimicrobial film-type coating composition according to the present invention includes desks or lockers of public facilities such as schools or religious facilities, or interior materials; Ceiling materials to block cell phones, computer peripherals, OA devices and asbestos dust; The interior of buildings such as bathrooms, kitchens, toilets, windows, and wallpaper; It can be applied as a protective film during metal painting or metal processing.

At this time, the construction method for the antibacterial coating is not particularly limited in the present invention, and known methods such as printing (screen, curved surface), spray coating (air, airless, etc.), dipping, roller, brush, etc. Can be used. At this time, the antibacterial coating composition may be diluted with water or a water-miscible solvent depending on the type of coating device and the coating conditions. Other coating-related conditions, such as coating temperature, are appropriately determined by the knowledge of those skilled in the art.

Before the antibacterial coating, pretreatment such as degreasing treatment to remove contaminants such as dirt and oil from the application site is performed, and the coating composition is used after filtering once with 100 mesh. For example, in the air spray process, a spray gun nozzle of 1.5 mm pie or more is applied, and transferred at a pressure of 1.0 to 1.5 kgf/cm ² .

Room temperature curing means that curing takes place at ambient temperature (5-35°C±5°C), preferably approximately 25±5°C, without separate heat treatment or UV irradiation. At this time, in order to accelerate the evaporation of the solvent (ie, water) during curing at room temperature, a method for removing water such as ventilation and/or heating may be appropriately used. At this time, the time required to form the coating film can be easily adjusted. However, the heating method is used only to evaporate water, and the heating conventionally used for curing the coating film is not required.

In this way, when forming an organic/inorganic hybrid antibacterial coating film, it can be cured at room temperature and can be applied regardless of the season, and other polymers (e.g., polyester) are excluded by using water as a solvent for the composition. , Polyurethane, etc.), since most of them are organic solvents, it is possible to solve problems that affect the health of workers or cause environmental pollution due to volatile substances during construction.

The thickness of the organic/inorganic hybrid antibacterial coating film may vary depending on the product, and has a thickness range of 20 to 200 μm. Subsequently, the organic/inorganic hybrid antibacterial coating film finally obtained through room temperature curing has a hydrophobic surface characteristic by bonding siloxane to the surface, and an organic polymer resin is distributed on the opposite side to facilitate adhesion to the interface.

The organic/inorganic hybrid antibacterial coating film according to the present invention cured at room temperature maintains high antibacterial properties while maintaining the coating film, reduces deodorization by adsorbing harmful gases such as CO, NOx, and SOx, and reduces asbestos and radioactive substances. It can block the same dangerous substances. In addition, it performs a protective function of the product surface through various physical properties along with gas permeability, and has the property of being peeled off if necessary.

In particular, when the gas permeability is high, the coating film is deformed or lifted by moisture, external air, or harmful gases (CO, NOx, SOx, etc.), and the reconstruction of the coating film is required. Accordingly, the organic/inorganic hybrid antibacterial coating film of the present invention has adequate gas permeability to extend the reconstruction period of the coating film, and the antibacterial effect can be maintained while the coating film is present. In the case of existing patents (Korean Registered Patent No. 10-1615550 and Registered Patent No. 10-1632918), it is impossible to cure at room temperature due to the use of various types of resins and organic solvents. In particular, it is not possible to form a dense coating film due to volatilization of an organic solvent or the like, so there is no consideration of gas permeability.

In addition, the existing peelable coating composition requires heating to form a cured film, and thus coating may not be possible depending on the type or material of the object to be coated. However, the antimicrobial coating composition of the present invention is capable of forming an organic/inorganic hybrid antibacterial coating film through room temperature curing without heating, and thus can be used in devices having electronic components or plastic products that are easily deformed by heating.

In addition to the above physical properties, the organic/inorganic hybrid antibacterial coating film according to the present invention has properties such as water resistance, abrasion resistance, stain resistance, heat resistance, and chemical resistance, and thus there is an effect of reducing time and cost loss due to reconstruction.

In addition, by freely using various additives such as pigments or sunscreens, it is possible to realize various colors, and to secure an energy saving effect by blocking UV rays and insulation.

The product to which such an organic/inorganic hybrid antibacterial coating film can be formed is not particularly limited in the present invention, and examples of the product include ferrous and non-ferrous metal products such as vehicles, other vehicles, machine parts, and home appliances; Wood products; glassware; Plastic products; Rubber products; Ceramic products; Building materials (ferrous and non-ferrous such as aluminum); Household electronics such as washing machines and refrigerators; Kitchen products such as frying pans, pots and bowls; furniture; Factory automation (FA) products; Office products such as cabinets and whiteboards; And their painted products. The peelable coating composition of the present invention is applied to an object to protect the object indoors and outdoors. At this time, the material of the product is also non-limiting, and may be one or more selected from concrete, metal (coating layer, plating layer), ceramics, plastic, glass, stone, wood, and paper, but is not limited thereto.

Organic/inorganic hybrid antibacterial coating films can be used to temporarily protect objects until peeling. Specifically, the antimicrobial coating film provides protection from stains on painted exterior panels or resin parts of automobiles; Protection of ventilators and kitchen utensils from dirt caused by oil and handling; Prevention of stains and scratches on walls and interior floors made of aluminum; Protection of the walls and floors of the painting booth from paint splatter; And it can be used for maintaining the appearance of the ski board made of FRP (fiber reinforced plastic) and preventing damage.

[Example]

Hereinafter, preferred examples are presented to aid in understanding the present invention, but the following examples are only illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

(1) Preparation of inorganic resin composition

A hollow body powder with an average particle size of 5 µm alumino silicate 7 wt%, isopropyl alcohol (IPA) 57 wt%, hydropropyl cellulose 5 wt%, methyltrimethoxysilane (TSL8113) 10 wt%, water (pH) A liquid mixed with nitric acid to be adjusted to 1 to 2)) was mixed (total 100% by weight) and hydrolyzed to prepare an inorganic resin composition including a hollow body powder subjected to surface modification treatment.

(2) Preparation of organic resin composition

(2-1) Preparation of water-dispersible acrylic resin

As a monomer, 42 g of MMA (methyl methacrylate), 46 g of BA (butyl acrylate), 4 g of MAA (methacrylic acid), and 8 g of GMA (glycidyl methacrylate) were used.

100 parts by weight of distilled water, 3 parts by weight of SLS as a surfactant, 3 parts by weight of Monopol NFE 8 (Dongnam Synthetic), 0.3 parts by weight of initiator KPS (potassium persulfate) and a monomer were added to the total 100 parts by weight of the monomers. Then, the mixture was stirred for 10 minutes to prepare a pre-emulsion.

After dissolving 0.33 parts by weight of SA (sodium acetate) in 2 parts by weight of distilled water in a separate reactor, 30% of the prepared pre-emulsion was added thereto, and the first emulsion polymerization was performed at 80° C. for 30 minutes under a nitrogen atmosphere. I did. Then, after the remaining pre-emulsion (70%) was added, the secondary emulsion polymerization was again performed at the same temperature for 3 hours and 30 minutes.

Next, the stirring was turned off and aging was performed at 80° C. for 2 hours, and then the temperature of the reactor was lowered to prepare an organic resin composition as an acrylic emulsion.

The prepared acrylic emulsion was measured as viscosity: 55 cps (25°C solid content: 49.8%, Tg: 10°C, MW: 20,000 g/mol.

(2-2) Organic resin composition

70% by weight of the water-dispersible acrylic resin prepared in (2-1) above, 10% by weight of a water-soluble polyurethane resin (Gangnam Hwaseong, KW-501), 2% by weight of methyl cellulose, 2% by weight of silicone antifoam, 5% by weight of polyvinyl alcohol %, and 11% by weight of water were added to prepare an organic resin composition.

(3) Room temperature curing organic/inorganic hybrid antibacterial coating film type coating composition manufacturing

A room temperature curing organic/inorganic hybrid antibacterial coating film-type coating composition was prepared by adding 5% by weight, 92% by weight, and 3% by weight of silver nanoparticles to the reactor, respectively, and then mixing the compositions of (1) and (2).

(4) Organic/inorganic hybrid antibacterial coating film manufacturing

The organic/inorganic hybrid antibacterial coating film-type coating composition prepared in (3) was blade-coated on a PET substrate and then cured at room temperature for 1 hour to prepare an organic/inorganic hybrid antibacterial coating film having a thickness of 100 μm.

Example 2

An acrylic emulsion was prepared in the same manner as in Example 1, except that 11.3g of SLS alone was used as a surfactant.

The prepared acrylic emulsion was measured to have viscosity: 54 cps (25°C solid content: 48.5%, Tg: -35°C, MW: 21,000 g/mol).

Example 3

When preparing the organic resin composition, an acrylic emulsion was prepared in the same manner as in Example 1, except that the polymerization was performed by adding 100% in step 1.

The prepared acrylic emulsion was measured to have viscosity: 57 cps (25°C solid content: 49.1%, Tg: 27°C, MW: 23,000 g/mol.

Comparative Example 1

As an organic resin composition, a coating composition was prepared using the organic resin composition disclosed in Example 1 of KR10-1615550.

Water-soluble acrylic resin with a weight average molecular weight of 20,000 g/mol ((meth)acrylic acid) 70% by weight, polyurethane resin 10% by weight, methyl cellulose 2% by weight, silicone antifoaming agent 2% by weight, polyvinyl alcohol 5% by weight, and water 11 An organic resin composition was prepared by adding% by weight.

In this case, in the preparation of a coating film using the coating composition, a 100 μm-thick organic/inorganic hybrid antibacterial coating film was prepared by curing at 60° C. for 1 hour after blade coating on the PET substrate.

Comparative Example 2

As an organic resin composition, a coating composition was prepared using the organic resin composition disclosed in Example 1 of KR10-1632918.

Based on 100 parts by weight of the organic composition in the reactor, 7 parts by weight of methyl ethyl ketone, 5 parts by weight of cyclo nucleic acid, 7 parts by weight of isopropyl alcohol, 5 parts by weight of methyl isobutyl ketone, 5 parts by weight of toluene, 3 parts by weight of butyl acetate, and xylene 3 parts by weight of a polyester resin (molecular weight 5000 to 8000 g/mol) 40 parts by weight and 20 parts by weight of polyurethane resin are mixed in the mixed solvent to prepare a mixed resin, and a pollution resistance improving agent (BYK3700) is included therein. After 5 parts by weight of the additive was added and mixed, the mixed solution was stirred at 300 rpm for 8 hours at room temperature to prepare an organic composition.

In this case, in the preparation of a coating film using the coating composition, a 100 μm-thick organic/inorganic hybrid antibacterial coating film was prepared by curing at 60° C. for 1 hour after blade coating on the PET substrate.

Comparative Example 3

The composition of Comparative Example 1 was allowed to stand at room temperature for 1 hour to perform curing, but it was impossible to form a cured coating film.

Comparative Example 4

The composition of Comparative Example 2 was allowed to stand at room temperature for 1 hour to perform curing, but formation of a cured coating film was not possible.

Test Example 1: Peeling properties

end. Adhesion

The organic/inorganic hybrid antibacterial coating film prepared in the above Examples and Comparative Examples was compressed at room temperature for 24 hours with a load of 20 g/cm ² , and then the physical properties were measured using a measuring device. At this time, the unit of adhesion was g/in and the measured value was measured 5 times to calculate the average value.

I. Peeling force

After preserving the organic/inorganic hybrid antibacterial coating film prepared in Examples and Comparative Examples at room temperature for 24 hours, a standard adhesive tape (TESA7475) was attached to the coated surface, and then the sample was applied at room temperature (25°C, 20 g/cm ² ). After 24 hours of compression, the physical properties were measured using a measuring device, at this time, the peel force unit was g/in and the measured value was measured 5 times to calculate the average value.

All. Remnant

The peeling site of the organic/inorganic hybrid antibacterial coating film prepared in the above Examples and Comparative Examples was peeled at 90° with a constant force (500 mm/min). After peeling, measure the number of residues of each specimen by area.

At this time, the presence or absence of residues was measured, and the diameter of the longest part was measured.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Adhesion (g/in) 8.3 8.1 8.0 7.4 7.3 Peel force (g/in) 9.8 9.4 9.4 12.4 15.5 Remnant none Less than 1mm Less than 1mm 5~7mm 6~8mm

Looking at the table above, the organic/inorganic hybrid antibacterial coating film prepared with the coating composition of Examples 1 to 3 has excellent adhesion compared to the coating films of Comparative Examples 1 and 2, and almost no residue is left even when peeling with low peeling force. It can be seen that it is very easy.

Test Example 2: Measurement of antibacterial activity

An antibacterial test was conducted using an organic/inorganic hybrid antibacterial coating film coated with the compositions of Examples and Comparative Examples. The experiment was carried out using the agar diffusion method (Paper disc method), and Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 8739, Enterococcus feacalis ATCC 29200), Salmonella typhimurium ( Salmonella typhimurium KCTC 1925) was inoculated on agar medium (LB agar). A paper disk was placed on the culture medium inoculated with bacteria, and the films of each Example and Comparative Example were loaded thereon, and 1 ml of physiological saline as a negative control was loaded onto the culture medium inoculated with bacteria, and cultured at 37°C for 48 to 96 hours. After that, the zone of inhibition was measured and the results are shown in the table below.

Strain Inhibition area (cm) Control Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Staphylococcus aureus - ++++ +++ +++ ++ ++ Coli - ++++ ++ ++ ++ ++ Enterococci - ++++ ++ ++ ++ + Salmonella typhimurium - ++++ +++ +++ + +

*Measured Value: Less than 0.5cm +, 0.5~1cm ++, 1~2cm +++, 2~3cm +++, 3cm or more ++++

In the above table, in the case of the control group, no inhibitory zone was observed for all four strains used, but the compositions of Examples 1 to 3 of the present invention showed a wide inhibitory zone for all four strains, thereby inhibiting the listing of bacteria and It can be seen that the removal activity is excellent. In addition, the antimicrobial activity was also shown in Comparative Examples 1 and 2, but showed lower activity compared to Examples 1 to 3.

Test Example 3: Chemical resistance evaluation

After forming the organic/inorganic hybrid antibacterial coating film obtained in the above Examples and Comparative Examples, after applying MEK (methyl ethyl ketone) to the gauze, rubbing with a certain force using gauze, the coating film peeled off to reveal the substrate. The number of rubbing until it was measured. At this time, the higher the number, the better the chemical resistance.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Count 45 times 35 times 33 times 30 times 30 times

Looking at the above table, it can be seen that the chemical resistance of the organic/inorganic hybrid antibacterial coating film prepared with the coating composition of Examples 1 to 3 is superior to the coating composition of Comparative Examples 1 and 2. These results mean that after installation of the antibacterial coating film, excellent antibacterial effects can be maintained continuously.

Test Example 4: Gas permeability evaluation (oxygen permeability measurement)

The organic/inorganic hybrid antibacterial coating film prepared with the coating composition of Examples and Comparative Examples was cut into 3.3 cm (width) x 21 cm (length), and oxygen permeability was measured under the conditions of a temperature of 23°C and a relative humidity (RH) of 0%. Each sample was measured 10 times, and the maximum and minimum values were discarded, and the average value of the remaining specimens was calculated.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Oxygen permeability (unit: cm3/㎡·day) 5.15 5.01 4.95 3.25 3.14

Looking at the above table, it can be seen that the gas permeability of the organic/inorganic hybrid antibacterial coating film made of the coating composition of Examples 1 to 3 is superior to that of the coating composition of Comparative Examples 1 and 2.

Test Example 5: Water resistance evaluation

After coating the coating composition of Examples and Comparative Examples on a PET wooden substrate to form a coating film, water was dropped on the surface, and then the contact angle was measured according to KS L 2110. At this time, the lower the contact angle is, the more hydrophobic it is, indicating excellent water resistance.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Contact angle (degree) 17.00 22.00 25.00 26.00 30.00

Looking at the above table, it can be seen that the water resistance of the organic/inorganic hybrid antibacterial coating film prepared with the coating composition of Examples 1 to 3 is superior to the coating composition of Comparative Examples 1 and 2.

Test Example 6: Hardness measurement

An organic/inorganic hybrid antibacterial coating film was prepared using the coating composition obtained in the above Examples and Comparative Examples, and the pencil hardness of the obtained coating film was measured according to KS D 6711.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Hardness 6H 5H 5H 5H 5H

Looking at the above table, it can be seen that the hardness of the organic/inorganic hybrid antibacterial coating film prepared with the coating composition of Example 1 was superior to that of the coating composition of Comparative Examples 1 and 2, and thus a high wear resistance.

Test Example 7: Pollution resistance evaluation

The organic/inorganic hybrid antibacterial coating films obtained in the above Examples and Comparative Examples were marked using oily magic and aqueous magic, respectively, and after 1 hour, the surface was washed with water and ethanol to check the marking marks with the naked eye.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Meteor magic No trace Some residual Some residual Some residual Some residual Mercury magic No trace No trace No trace Some residual Some residual

Looking at the above table, it can be seen that the stain resistance of the organic/inorganic hybrid antibacterial coating film prepared with the coating composition of Examples 1 to 3 is superior to the coating composition of Comparative Examples 1 and 2.

Test Example 8: Heat resistance evaluation

The organic/inorganic hybrid antibacterial coating films obtained in the above Examples and Comparative Examples were cut to a size of 4 Х20 cm, and then left at 90° C. for 30 minutes each using a high-temperature oven, and then it was confirmed whether cracks occurred on the surface.

<Evaluation criteria>

O: No cracks:

X: cracking

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 90℃/25% O O O O O 90℃/30% O O O O O 90℃/35% O O O X X

Looking at the above table, it can be seen that the heat resistance of the organic/inorganic hybrid antibacterial coating film prepared with the coating composition of Examples 1 to 3 is superior to the coating composition of Comparative Examples 1 and 2.

Claims (6)

To protect the surface of the product through formation of a coating film, and to enable peeling of the coating film,
It includes an inorganic resin composition, an organic resin composition, and an antibacterial agent,
The inorganic resin composition comprises ceramic fine particles in a crosslinked structure of siloxane,
The organic resin composition includes a water-dispersible acrylic resin and a water-soluble polyurethane resin, wherein the water-dispersion acrylic resin is 30 to 60% by weight of methyl methacrylate, 35 to 60% by weight of butyl acrylate, 1 to 10% by weight % Methacrylic acid and 3 to 15% by weight of glycidyl methacrylate are emulsion polymerized,
Wherein the inorganic resin composition and the organic resin composition form a three-dimensional network structure by curing,
Room temperature curing organic/inorganic hybrid antibacterial film-type coating composition.
The method of claim 1,
The inorganic resin composition is prepared through a hydrolysis reaction by mixing ceramic fine particles, a silane coupling agent, a thickener, isopropyl alcohol and water, and a room temperature curing organic/inorganic hybrid antibacterial film-type coating composition.
The method of claim 1,
The ceramic fine particles are one selected from the group consisting of silicon dioxide, titanium dioxide, aluminosilicate, and combinations thereof, room temperature curing organic/inorganic hybrid antimicrobial film-type coating composition.
delete The method of claim 1,
The antimicrobial agent is at least one inorganic type selected from silver, zinc and silica; Or organic-based antibacterial agent of vegetable oil, room temperature curing type organic / inorganic hybrid antibacterial film-type coating composition.
A construction method using an antibacterial film-type coating agent in which the composition according to any one of claims 1 to 3 and 5 is applied to the product surface and then cured at room temperature to form an antibacterial coating film on the product surface.