KR102176226B1 - Antibacterial protective sheet and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an antibacterial protective film and a method for manufacturing the same. The antibacterial protective film includes: a protective sheet adhered to the surface of a substrate; a release sheet disposed at the bottom of the protective sheet; and an adhesive layer interposed between the protective sheet and the release sheet, wherein the protective sheet includes a sheet base layer, a coating layer disposed on the top of the sheet base layer, and a primer layer disposed at the bottom of the sheet base layer. The antibacterial protective film according to the present invention includes copper nanoparticles, and thus is not harmful to the human bodies, realizes an excellent antibacterial activity, is prevented from being contaminated with dust or foreign materials attached to the surface, and has flexibility to be adhered easily and simply even to a curved portion or stepped portion.

Description

Antimicrobial protective film and its manufacturing method {ANTIBACTERIAL PROTECTIVE SHEET AND MANUFACTURING METHOD THEREOF}

The present invention relates to an antibacterial protective film and a method for manufacturing the same, and more particularly, by manufacturing a protective film including copper nanoparticles, it is harmless to the human body and provides excellent antibacterial activity, and prevents contamination by attaching dust or foreign substances to the surface. The present invention relates to an antimicrobial protective film that can be easily and simply adhered to curved or stepped portions due to its elasticity and prevention, and a manufacturing method thereof.

In recent years, with the development of nanotechnology, it has become easier to manufacture inorganic particles or metal particles having a nano size. It is reported that inorganic or metal nanoparticles not only excellently implement the physical and chemical properties exhibited in the bulk state with a small amount due to their maximized surface area and quantum effects, but also exhibit properties different from those in the bulk state. .

As such, nanoparticles exhibit almost equal or superior effects to materials used in bulk even when used in a very small amount, and because nanoparticles are used in very small amounts, there is little toxicity to the human body and the environment. Recognized as a beneficial material, many studies are being conducted in the spotlight as a new material.

On the other hand, in recent years, as the public's health and health awareness has increased, the demand for synthetic resin films having antibacterial properties that can be used for various purposes is increasing. Particularly, in the case of small electronic devices such as common items that can be used by the public or frequently in contact with the hands of users, it is a recent trend that they are made using materials having antibacterial properties.

In addition, personal hygiene awareness is being further strengthened due to the fear of diseases without proper preventive measures such as Corona-19 and swine flu, and the demand for antimicrobial materials that can meet this is increasing rapidly.

In other words, with the development of industry, the demand for films using synthetic resins is rapidly increasing, and they are used in many parts of daily life. In addition, there is a growing demand for a film with functionality, not a general film, and recently, as interest in health increases, products with antibacterial properties with resistance to bacteria and bacteria have been developed and released.

Recently, products using various antibacterial agents have been released, and organic antibacterial agents are widely used as antibacterial agents, but there is a movement to refrain from using organic antibacterial agents due to increased resistance and harmfulness to the human body due to their basic characteristics.

In order to replace these organic antimicrobial agents, inorganic antibacterial agents and natural antimicrobial agents are used, but natural antibacterial agents have a high unit cost and a large amount of addition, so that antibacterial activity is expressed and the antibacterial persistence is low. In addition, in the case of inorganic antibacterial agents, antibacterial persistence is good, but there is a problem of harm to the human body.

For example, due to the discovery of the antibacterial properties of silver nanoparticles, antibacterial synthetic resin products containing silver nanoparticles have been released in various fields. Recently, due to the problem of the harm to the human body of silver nanoparticles, the silver nano fever blew and suddenly disappeared in home appliances. As a result, regulations on hazardous substances are becoming stricter in each country.

Therefore, by fusion of nanotechnology with an inorganic antibacterial agent with good antibacterial persistence, the amount of added antibacterial agent is good at least, and development of an antibacterial agent that is harmless to the human body is underway, and development of an antibacterial protective film using the same is a situation in which there is a lot of demand.

Domestic registered patent No. 10-1968198 (registered on April 5, 2019) Domestic registered patent No. 10-1160190 (registered on June 20, 2012) Korean Patent Publication No. 10-2020-0045601 (published on May 06, 2020)

The present invention provides a protective film including copper nanoparticles, which is harmless to the human body and realizes excellent antibacterial activity, prevents contamination by attaching dust or foreign substances to the surface, and has elasticity to easily and simply adhere to curved or stepped parts. It is to provide an antibacterial protective film that can be used and a method of manufacturing the same.

In addition, the present invention is an antimicrobial protective film that can provide flame retardancy to inhibit the spread of fire and the generation of toxic gases, block heat conduction, and have characteristics such as eco-friendly and excellent physical properties such as hardness, surface smoothness, and scratch resistance. And it is to provide a manufacturing method.

Various problems to be solved by the present invention are not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

Antimicrobial protective film according to the present invention is a protective sheet adhered to the surface of the substrate; A release paper located under the protective sheet; And an adhesive layer positioned between the protective sheet and the release paper, wherein the protective sheet includes a sheet paper layer, a coating layer positioned above the sheet paper layer, and a primer layer positioned below the sheet paper layer.

The sheet paper layer is formed by mixing and drying the sheet paper composition, and the sheet paper composition includes 5 to 10 parts by weight of copper nanoparticles, 1 to 3 parts by weight of expanded graphite powder, 2 to 4 parts by weight of gelite, and 0.1 to 1.5 parts by weight of peppermint extract. It may be included in a weight ratio of 200 to 400 parts by weight of a polyurethane resin, and 1 to 3 parts by weight of a dispersant.

The coating layer is formed by applying a coating composition to the top of the sheet layer and then drying, the coating composition is a self-emulsifying epoxy resin 50 to 70 parts by weight, acrylic modified polyester resin 10 to 20 parts by weight, graphene 0.5 to 1.5 It may be included in a weight ratio of 0.1 to 1 parts by weight of a conductive polymer, 1 to 3 parts by weight of a filler, and 0.5 to 1.5 parts by weight of a curing agent.

The primer layer is formed by applying a primer composition to the lower part of the sheet layer and then drying, the primer composition is 40 to 60 parts by weight of a polyurethane acrylate oligomer, 20 to 40 parts by weight of an acrylic monomer, 1 to 3 parts by weight of photocuring agent, 100 to 200 parts by weight of solvent, 3 to 7 parts by weight of polyvinyl alcohol, 0.1 to 1 parts by weight of natural rubber, 0.1 to 1.5 parts by weight of Thiourea compounds, poly It may be included in a weight ratio of 5 to 10 parts by weight of acrylic acid, 1 to 5 parts by weight of a phosphorus monomer, 0.1 to 1.5 parts by weight of an antioxidant, and 0.1 to 0.5 parts by weight of an antifoaming agent.

In addition, the method of manufacturing an antimicrobial protective film according to the present invention is to form a sheet layer by using a sheet composition, apply a coating liquid composition on the top of the sheet layer, and then dry to form a coating layer, and a primer composition is applied under the sheet layer. After coating and drying to form a primer layer, a protective sheet consisting of a coating layer, a sheet paper layer, and a primer layer is formed, and a hot melt adhesive is applied under the primer layer constituting the protective sheet to form an adhesive layer, and under the adhesive layer Release paper can be formed.

The sheet composition includes 5 to 10 parts by weight of copper nanoparticles, 1 to 3 parts by weight of expanded graphite powder, 2 to 4 parts by weight of gelite, 0.1 to 1.5 parts by weight of peppermint extract, 200 to 400 parts by weight of polyurethane resin, and 1 to It may be included in a weight ratio of 3 parts by weight.

The coating liquid composition includes 50 to 70 parts by weight of a self-emulsifying epoxy resin, 10 to 20 parts by weight of an acrylic modified polyester resin, 0.5 to 1.5 parts by weight of graphene, 0.1 to 1 parts by weight of a conductive polymer, 1 to 3 parts by weight of a filler, and a curing agent. It may be included in a weight ratio of 0.5 to 1.5 parts by weight.

The primer composition includes 40 to 60 parts by weight of a polyurethane acrylate oligomer, 20 to 40 parts by weight of an acrylic monomer, 1 to 3 parts by weight of a photocuring agent, 100 to 200 parts by weight of a solvent, polyvinyl alcohol (polyvinyl alcohol). alcohol) 3 to 7 parts by weight, natural rubber 0.1 to 1 parts by weight, Thiourea compounds 0.1 to 1.5 parts by weight, polyacrylic acid 5 to 10 parts by weight, phosphorus monomer 1 to 5 parts by weight, antioxidant 0.1 to 1.5 It may be included in a weight ratio of 0.1 to 0.5 parts by weight and an antifoaming agent.

Details of other embodiments are included in the detailed description.

The antimicrobial protective film according to the present invention is harmless to the human body by including copper nanoparticles and provides excellent antibacterial activity, prevents contamination by attaching dust or foreign substances to the surface, and has elasticity to easily and simply adhere to curved or stepped parts. Can be.

In addition, the antimicrobial protective film according to the present invention provides flame retardancy to inhibit the spread of fire and the generation of toxic gases, and at the same time block heat conduction, and has characteristics such as environmentally friendly and excellent physical properties such as hardness, surface smoothness, and scratch resistance. I can.

It will be fully understood that the embodiments of the technical idea of the present invention can provide various effects not specifically mentioned.

1 is a cross-sectional view schematically showing a cross section of an antimicrobial protective film according to the present invention.
Figure 2 is a photograph showing the antibacterial protective film prepared according to the present invention.

Advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

Unless otherwise defined, all terms including technical or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

Hereinafter, a preferred embodiment will be described in detail with respect to the antimicrobial protective film according to the present invention with reference to the accompanying drawings.

1 is a cross-sectional view schematically showing a cross section of an antimicrobial protective film according to the present invention, and FIG. 2 is a photograph showing an antimicrobial protective film prepared according to the present invention.

1 and 2, the antimicrobial protective film 10 according to the present invention is a protective sheet 100 that is adhered to the surface of a substrate to protect the surface of the substrate, and a release paper located under the protective sheet 100 (300) and an adhesive layer 200 positioned between the protective sheet 100 and the release paper 300.

In addition, in the antimicrobial protective film 10 according to the present invention, the protective sheet 100 includes a sheet supporting layer 140, a coating layer 120 positioned on the sheet supporting layer 140, and the sheet supporting layer ( 140) It includes a primer layer 160 located below.

The sheet paper layer 140 may be formed in the form of a film manufactured using a polyurethane resin, and the sheet paper layer 140 may be formed by mixing and drying the sheet paper composition.

The sheet composition includes 5 to 10 parts by weight of copper nanoparticles, 1 to 3 parts by weight of expanded graphite powder, 2 to 4 parts by weight of gelite, 0.1 to 1.5 parts by weight of peppermint extract, 200 to 400 parts by weight of polyurethane resin, and 1 to It may be included in a weight ratio of 3 parts by weight.

The copper nanoparticles may be included to impart antibacterial and deodorant properties, and the copper nanoparticles self-inhibit the propagation of bacteria and interfere with the metabolism of various microorganisms to eliminate the cause of unpleasant odors. Can be given.

For example, the copper nanoparticles may be copper oxide nanoparticles, and the copper oxide nanoparticles are surface-modified by stirring 0.1 to 2 parts by weight of silane based on 100 parts by weight of copper oxide powder having a particle size of 1 to 200 nm. The prepared copper oxide nanoparticles may be used.

That is, since the surface of the copper oxide powder is generally hydrophilic, it cannot be dispersed in the resin by OH groups and may be aggregated with each other, but in the present invention, the SIOH group and oxidation of the silane are modified by modifying the surface of the copper oxide powder with silane as described above. By causing hydrolysis between the OH groups on the surface of the copper powder and bonding, the hydrophobic OR group among the silanes is located on the surface of the copper oxide powder, so that the repulsive force between the OR groups, that is, the repulsive force between the copper oxide powders, can improve dispersibility.

In addition, the silane is vinyltriethoxysilane, vinyltrimethoxysilane, or vinyltri(2-methoxyethoxy)silane in order to improve dispersibility as described above. Silane) may be used, but is not necessarily limited thereto, and various silanes already known may be used.

The expanded graphite powder is a powdered expanded graphite. In general, graphite is a mineral in which a planar macromolecule in which 6-atomic rings of carbon atoms are infinitely connected in a plane form a layer, and its properties are good conductors of electricity, and polycene Due to its layered structure, it is flexible and active, and it is easy to split, but it is a macromolecule and has low reactivity.

However, since graphite is only connected by Van der Waals force between the carbon planes of the polycene structure, it is 35.5 nm wider than 14.2 nm, which is the spacing between carbon atoms, so that another atom is inserted into the gap between the layers to create an interlayer compound. I can. In other words, the interlayer compound is made by inserting many atoms, molecules, or ions into the gaps between the planes while maintaining the network plane of the graphite crystal.

That is, when an interlayer compound or residual compound coated with an acid such as sulfuric acid between the layers of graphite is rapidly heated to a temperature close to 1000°C, the acid vaporizes to generate a gas, and the graphite layer is formed by the expansion pressure of the gas. It expands by the fold, which is called expanded graphite.

In the present invention, the expanded graphite expands 30 to 50 times in the process of raising the temperature to 180° C. or more when a fire occurs and forms char, so it can play a role of imparting thermal insulation performance with non-combustibility. .

The gelite (Ge-lite) is called pozzolan, contains about 2.0ppm germanium and contains a large amount of far-infrared rays and anions, such as volcanic ash, silicate clay, silicate and the like. That is, the gellite emits far-infrared rays equivalent to about 180 times that of loess, promotes plant growth, has a humidity control function, releases negative ions and human body active energy, has a function of blocking harmful electromagnetic waves, and has a deodorizing and sterilizing effect. It also provides heavy metal neutralization effect.

The peppermint extract may be prepared using leaves and stems of mint, for example, the peppermint extract prepared by the following method may be used.

In order to prepare the mint extract, first, the same amount of mint leaves and stems were collected, and sodium hydrogen carbonate (NaHCO ₃ ) having a concentration range of 1 to 3 (w/w)% and a temperature of 33 to 37 °C was dissolved By washing with purified water for 1 to 5 minutes, foreign substances adhering to the leaves and stems of mint can be removed.

The peppermint (Mentha arvensis var piperascens) is a perennial perennial herb of the Lamiaceae family of a dicotyledonous plant, and is branched from the top by having a directionality in the plant itself and standing upright. The main ingredients of peppermint are alphapinene (+, -)), anisaldehyde, Daucosterol, Eugenol, Linalool, Menthone, (+ )-Neomenthol ((+)-Neomenthol).

These mints emit a refreshing and refreshing scent, and have bactericidal and antimicrobial action against microorganisms such as pathogenic fungi, E. coli, staphylococcus, etc. that cause eczema and scabies present in the skin or scalp.

In addition, peppermint has the effect of constricting the mucous membranes and blood vessels of the skin, paralyzing nerve peripherals, stopping pain, stopping itching, and so on, giving the skin a unique refreshing sensation, improving skin diseases, It is known to have an antioxidant effect, and menthol, which is the main component of mint, is medicated as a coating agent, pain reliever, stimulant, or drying agent, and is used as a flavoring or refreshing agent in toothpaste, candy, jam, cosmetics, and tobacco.

Next, the washed mint leaves and stems may be steamed with steam.

In the above step, the steaming may be performed by heating the washed leaves and stems of mint with water vapor at a temperature of 120 to 130°C at a pressure of 3 to 4kgf/cm ² for 30 to 40 minutes.

Next, the leaves and stems of the steamed mint can be dried.

In the above step, in order to prevent volatilization of chlorophyll or useful components of the leaves and stems of the mint leaves and stems during sunlight drying, the drying of the leaves and stems of the peppermint is 20 at a temperature of 15 to 20°C and a humidity of 55 to 60%. It can be dried for up to 30 hours.

Subsequently, the dried leaves and stems of mint may be heated to astringent and then cooled.

In the above step, the dried mint leaves and stems are first roasted at a temperature of 70 to 75°C for 3 to 5 minutes after putting the dried mint leaves and stems into a heating container, and the first roasted mint leaves and stems are 120 The second roasting for 10 to 40 seconds at a temperature of 130° C. may be performed by cooling the leaves and stems of the second roasted mint at a temperature of 20 to 30° C. for 30 to 60 minutes.

Next, the leaves and stems of peppermint cooled after the roasting may be extracted to prepare a peppermint extract.

In the above step, the leaves and stems of peppermint cooled after the roasting may be extracted using various extraction methods such as hot water extraction, organic solvent extraction, ultrasonic extraction, and supercritical extraction.

For example, the ultrasonic extraction method is an extraction solvent of distilled water, ethanol, methanol, butanol, acetone, ethyl acetate, hexane, propanol, hydrous butylene glycol, hydrous propylene glycol, 10 times more than one solvent selected from the group consisting of It refers to an extraction method performed using an ultrasonic extraction method of 1 hour to 10 hours, preferably 1 hour to 4 hours, after adding to 20 times the volume.

In addition, the supercritical extraction method refers to a dried and crushed sample and 500-700 mL of ethanol (99.5%) as a co-solvent, placed in a supercritical fluid extraction reactor (Natex, Autstria), and the temperature in the reactor is 65° C., the pressure is 450 bar, S It refers to a method of extracting under the conditions of 35 /F ratio (supercritical fluid kg/Feed kg).

The polyurethane resin may be, for example, an acrylic-modified polyurethane resin, and the acrylic-modified polyurethane resin may serve as a binder or an adhesive bonding the composition constituting the sheet paper composition.

As the acrylic-modified polyurethane, an acrylic-modified polyurethane prepared by the following manufacturing method may be used.

First, diisocyanate (Diisocyanate), polyol (Polyol) and organic solvent (Organic Solvent) can be prepared and mixed to prepare a mixed solution, the mixed solution is diisocyanate 1 mol (mol) and polyol 0.5 to 1.5 mol (mol) It is prepared in a ratio of, and the organic solvent may be included in an amount of 60 to 70% by weight (wt%) of the total content of the mixed solution.

The diisocyanate is toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (4,4'-Diphenylmethane diisocyanate (MDI)), hexamethylene diisocyanate (HDI)), Any one or more selected from the group consisting of isophorone diisocyanate (IPDI) and 4,4'-methylenebis (cyclohexyl isocyanate) (4,4'-Methylenebis (cyclohexyl isocyanate) (HMDI)) may be used. .

The polyol may be any one or more selected from polyether polyol or polyester polyol.

The organic solvent may be any one or more selected from the group consisting of toluene, methyl ethyl ketone, ethyl acetate, acetone, and dimethylformamide.

Next, it is possible to prepare a polyurethane (Isocyanate terminated Polyurethane) having an isocyanate terminal group by reacting the mixture consisting of the diisocyanate, a polyol and an organic solvent, the reaction at a temperature of 83 to 88 ℃ for 3 to 5 hours Can be done.

Next, a temperature of 83 to 87°C while adding 0.1 to 0.5 mol (mol) of a monomer (containing hydroxy group) to the isocyanate terminated polyurethane (Isocyanate terminated Polyurethane) By reacting for 2 to 4 hours in the polyurethane (Vinyl terminated Polyurethane) having a vinyl end group can be prepared.

The hydroxy group-containing monomer (Monomer (containing hydroxy group)) is 2-hydroxyethyl methacrylate (2-Hydroxyethyl methacrylate), 2-hydroxypropyl methacrylate (2-Hydroxypropyl methacrylate), 2-ha Any one or more selected from the group consisting of hydroxyethyl acrylate (2-Hydroxyethyl acrylate) and allyl alcohol may be used.

Subsequently, an acrylic-modified polyurethane may be prepared by reacting while adding a monomer to the polyurethane having a vinyl end group (Vinyl terminated Polyurethane). The polyurethane and the monomer each have a vinyl end group. It may be included in a weight ratio of 70 to 90% by weight of urethane and 10 to 30% by weight of monomer.

In addition, the acrylic-modified polyurethane adhesive may be prepared by reacting for 1 to 3 hours at a temperature of 75 to 80°C while adding a monomer to the polyurethane having a vinyl end group.

The monomer may be any one or more selected from the group consisting of styrene, methyl methacrylate, acrylonitrile, acrylic acid, and acrylic monomer.

The dispersant may be used to prevent precipitation of the sheet paper composition and to have dispersing properties.For example, the dispersant may include polyester-polydimethylsiloxane copolymer, dimethylol butanoic acid (DMBA), Any one or more selected from the group consisting of dimethylol propionic acid (DMPA) and methylenediethanolamine may be used.

The coating layer 120 is formed on the sheet support layer 140 and is provided to improve the surface strength of the antibacterial protective film 10, and the coating layer 120 is coated with a coating solution composition on the top of the sheet support layer 140 After drying it may be formed by drying, the coating liquid composition may be prepared including a self-emulsifying epoxy resin, an acrylic modified polyester resin, a conductive polymer, a filler and a curing agent.

That is, the coating liquid composition is 50 to 70 parts by weight of a self-emulsifying epoxy resin, 10 to 20 parts by weight of an acrylic modified polyester resin, 0.5 to 1.5 parts by weight of graphene, 0.1 to 1 parts by weight of a conductive polymer, 1 to 3 parts by weight of a filler And 0.5 to 1.5 parts by weight of the curing agent may be mixed and prepared.

The self-emulsifying epoxy resin is an epoxy resin having an active group that can be emulsified in itself, and the self-emulsifying epoxy resin is a self-emulsifying modified epoxy resin having an epoxy equivalent of 200 to 230 g/eq. , Weather resistance, water resistance, and other physical properties can be remarkably improved.

The acrylic-modified polyester resin is condensed and polymerized with a polybasic acid containing 40 to 50% by weight of anhydrous acid and 50 to 60% by weight of an aliphatic acid by condensation polymerization of a polyhydric alcohol containing 80 to 90% by weight of a diol and 10 to 20% by weight of a triol. To prepare a polyester resin having a value of 45 to 65 mgKOH/g, an acid value of 3 mgKOH/g or less, a glass transition temperature of 5 to 20°C, and a weight average molecular weight (Mw) of 2,500 to 3,500, and the polyester resin 50 to 60 weight % And 40-50% by weight of acrylic monomer are grafted to have a weight average molecular weight (Mw) of 5,000 to 7,000, a hydroxyl value of 50 to 60 mgKOH/g, an acid value of 3 mgKOH/g or less, and a glass transition temperature of 10 to 20°C An acrylic modified polyester resin in the range can be prepared.

The graphene is a material obtained by separating one layer of graphite and forming a two-dimensional planar structure in which carbon atoms are connected in a honeycomb-shaped hexagonal shape. Such graphene is a material applicable to flexible displays, electronic papers, and solar cells because it has very high electrical conductivity and does not lose its electrical properties when stretched or bent. In particular, graphene is expected to replace ITO (Indium Tin Oxide), which is currently used as a transparent electrode for touch screens, semiconductors, and displays, due to its very high light transmittance.

In other words, graphene is a carbon molecule formed by arranging carbon atoms in a hexagonal shape and being connected to each other, and has a very stable structure and is currently the thinnest and hardest nanomaterial in the world. Such graphene is almost transparent and absorbs only 2.3% of light.The graphene has a thermal conductivity coefficient of 5000W/m·K and a higher thermal conductivity coefficient than that of a nano carbon pipe or diamond, and its electron transfer rate is 15000cm at room temperature. ² /V·s or more shows a higher electron transfer rate than nano carbon pipes or silicon crystals.

In addition, the electrical resistivity of graphene is 10 ^-6 Ω·cm, which is lower than that of copper or silver, and thus, graphene has characteristics such as high conductivity, high thermal conductivity, high tensile strength, high strength, and high specific surface area. Due to the characteristics of graphene, it can be widely used in various fields such as electronics, aerospace and military industries, new energy, and new materials.

The conductive polymer may be any one or more selected from polyaniline, polypyrrol, polythiophene, polyethylene dioxythiophene, epoxidized amine, or fatty acid ester.

The conductive polymer may be included in a weight ratio of 0.1 to 1 part by weight in the coating liquid composition.If the conductive polymer is included in an amount less than 0.1 part by weight, the antistatic effect may be insignificant, and if it is contained in more than 1 part by weight, the coating layer The physical properties of (120) may be weakened.

The filler may play a role of controlling hardness, film formation, and gloss. For example, the filler includes calcium carbonate, clay, talc, magnesium silicate, kaolin, mica, silica, aluminum silicate, aluminum hydroxide. , By using any one or more selected from the group consisting of barium sulfate and barium sulfate, hardness, impact resistance, rust resistance, and the like can be improved.

The curing agent is included in the coating liquid composition and performs a function of reacting and curing on the sheet paper layer 140, and the curing agent may be used by mixing a curing agent resin and a curing accelerator.

Modified aliphatic polyamine may be used as the curing agent resin, and 2,4,6-tridimethylaminomethylphenol may be used as the curing accelerator, and the curing agent resin and the curing accelerator are 4 to 8 parts by weight of the curing agent resin, respectively And 1 to 2 parts by weight of the curing accelerator may be mixed and used.

The primer layer 160 is positioned under the sheet paper layer 140 to increase adhesion to the adhesive layer 200, and the primer layer 160 is formed by applying a primer composition to the lower portion of the sheet paper layer 140. After drying can be formed, the primer composition is a polyurethane acrylate oligomer, acrylic monomer, photocuring agent, solvent, polyvinyl alcohol, natural rubber, Thiourea It can be prepared including a compound, polyacrylic acid, a phosphorus monomer, an antioxidant and a defoaming agent.

That is, the primer composition is 40 to 60 parts by weight of a polyurethane acrylate oligomer, 20 to 40 parts by weight of an acrylic monomer, 1 to 3 parts by weight of a photocuring agent, 100 to 200 parts by weight of a solvent, polyvinyl alcohol (polyvinyl alcohol) 3 to 7 parts by weight, natural rubber 0.1 to 1 parts by weight, Thiourea compound 0.1 to 1.5 parts by weight, polyacrylic acid 5 to 10 parts by weight, phosphorus monomer 1 to 5 parts by weight, antioxidant 0.1 To 1.5 parts by weight and 0.1 to 0.5 parts by weight of the antifoaming agent may be mixed in a weight ratio.

The polyurethane acrylate oligomer is a UV-curable compound having a weight average molecular weight (Mw) of 3,000 to 30,000, and may be formed by reacting polycarbonate and polyester diol with isocyanate and acrylate.

The polyurethane acrylate oligomer contains a urethane bond as a repeating unit, and generally exhibits flexible physical properties.The polyurethane acrylate oligomer is of various types, aliphatic urethane acrylate and aromatic urethane acryl depending on the type of isocyanate used. It is divided by rate.

The aliphatic urethane acrylate oligomer is a non-yellowing type, and usually has 2 to 20 functional groups, and an aromatic urethane acrylate oligomer is a yellowing type, and has fast reactivity.

In addition, the polyurethane acrylate oligomer may have 3 to 15 functional groups, and the number of functional groups may impart surface hardness and strong adhesion to the adhesive layer 200 by interaction with a solvent and a photocuring agent. have.

Examples of the functional group include urethane acrylate, epoxy acrylate, carboxylic acid, carboxylic anhydride, an acrylate-based functional group having a C=C double bond (eg, methacrylate, acrylate, etc.), SH Groups, alcohols, esters, ethers, triethylene glycolate, chelating agents (e.g., aminotriethanolate, amino diethanolate, acetylacetonate, ethylacetoacetate, lactate, etc.), amine groups, amides , Oxazoline and carbamate may be used alone or in combination of two or more.

The acrylic monomer may serve as a diluent for increasing the strength of the primer layer 160 formed of the primer composition and lowering the viscosity of the primer composition.

For example, the acrylic monomer is isobornyl acrylate (IBXA), phenoxyethyl acrylate (PEA), 1,6-hexanediol diacrylate (1,6-Hexanediol diacrylate; 1 ,6-HDDA) and pentaerythritol triacrylate (Pentaerythritol triacrylate; PETA) may be used.

When the primer composition is applied to the lower part of the sheet paper layer 140 and then photocured using ultraviolet rays (UV), the photocuring agent absorbs ultraviolet rays to generate free radicals, thereby initiating a reaction and applied under the sheet paper layer 140. It can be used to polymerize and cure the primer composition.

The photocuring agent may be a known material, for example, the photocuring agent is a hydroxy ketone series such as 1-hydroxy cyclrohexyl phenyl ketone (Irgacure 184), alpha-amino Amino ketone series such as acetophenone (α-Amino Acetophenone, Irgacure 907), benzyl dimethyl ketal series such as Benzyl Dimethyl Ketal (Irgacure-651), phenyl bis(2,4,6,-trimethyl benzoyl) ( Bis-acyl phosphine series such as phenyl bis (2,4,6-trimethyl benzoyl), Irgacure 819), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) Mono-acyl phosphine (mono-acyl phosphine) type photocuring agent can be used alone or in combination of two or more.

The solvent may be used to improve workability and adhesion by controlling viscosity and fluidity when applying the primer composition, and the solvents include ether solvents, aromatic solvents, acetate solvents, ketone solvents, alcohol solvents Or, a solvent in which these are mixed may be used.

For example, as the ether solvent, propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethyl glycol monopropyl ether, diethyl glycol monobutyl ether, diethylene glycol-2-ethylhexyl ether, and the like may be used alone or in combination.

Toluene and xylene may be used alone or in combination as the aromatic solvent, and butyl acetate and ethyl acetate may be used alone or in combination as the acetate-based solvent. The ketone solvent may be used alone or in combination with acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.

As the alcohol-based solvent, diacetone alcohol (DAA), n-butanol, methanol, ethanol, isopropyl alcohol, and the like may be used alone or in combination.

The polyvinyl alcohol has characteristics such as excellent linearity, flat zig-zag conformation, high crystallinity, excellent alkali resistance to withstand pH 13.5 or higher, and excellent adhesion. Due to these characteristics, polyvinyl alcohol can be applied to polyvinyl alcohol fibers having high strength and high modulus of elasticity.

The application of the polyvinyl alcohol is expanding due to the excellent physical properties and various application ranges as described above. In particular, many studies have been conducted on the production of high-strength and high-elasticity gels and high-performance polyvinyl alcohol fibers using polyvinyl alcohol.

As an example, polyvinyl alcohol is applicable to a membrane separation technique using a polymer film. Polymer films are used in a very wide range of fields including chemical industry, biotechnology, resources, energy, and the environment. In particular, the pervaporation method capable of separating a liquid organic mixture or an organic aqueous solution has many advantages over traditional distillation methods, such as energy saving and device miniaturization, and is widely used in the production of anhydrous alcohol and separation of organic mixtures. Therefore, it can be said that polyvinyl alcohol has high utility in the field of polymer films.

In addition, polyvinyl alcohol can be applied to a technology for manufacturing microfibers by electrospinning technology. The method of producing microfibers by electrospinning technology is to induce the formation of a liquid jet in the solution discharged from the spinneret by applying a high voltage to the polymer resin solution, and at this time, the volatilization of the solvent is caused by an electrical repulsion force. It is characterized in that a fine fiber of a thickness is obtained by continuous stretching.

In particular, when using electrospinning technology, fiber yarns are accumulated in the collector in the form of a three-dimensional network of webs. These microfibers have high specific surface area and tension, as well as mechanical properties, chemical properties, and cell biomaterial recognition characteristics. do. Therefore, polyvinyl alcohol can be applied in a wide range of fields such as microfibers, industrial materials including filters, photochemical sensor materials, biomedical materials, and beauty materials.

The natural rubber (NR) is a rubber using raw materials produced from plants, and mainly uses raw materials produced from rubber trees. The natural rubber may be a general natural rubber or a modified natural rubber.

Any general natural rubber may be used as long as it is known as natural rubber, and the country of origin is not limited. In addition, the general natural rubber contains cis-1,4-polyisoprene as the main chain, but may contain trans-1,4-polyisoprene depending on the required properties.

Therefore, the natural rubber includes, as a main chain, trans-1,4-polyisoprene, such as, for example, Valata, which is a type of rubber of the Sapota family, in addition to the natural rubber containing cis-1,4-polyisoprene as the main chain. It may also contain natural rubber.

The modified natural rubber means that the general natural rubber is modified or purified. For example, examples of the modified natural rubber include epoxidized natural rubber, deprotein natural rubber, and hydrogenated natural rubber.

The thiourea compounds may be included in order to stably maintain the primer composition, and the thiourea compounds are thiourea (NH ₂ ) ₂ CS or the general formula (R1R2N)(R3R4N)C=S (here, R1, R2, R3, and R4 may each independently include a thiourea derivative represented by any one selected from a hydrogen atom, an ethyl group, or a methyl group).

The polyacrylic acid may be used as a water reducing agent to impart fluidity. In the present invention, the polyacrylic acid may be a conventional material known in the art, for example, WRM50 (LG Chemical Co., Ltd.) may be used as the polyacrylic acid.

The phosphorus monomer may be used to improve adhesion to the sheet paper layer 140. For example, the phosphorus monomer is bis[2-(methacyloyloxy)ethyl] phosphate (Bis[2-(methacyloyloxy) )ethyl] phosphate, DMEP), 2-(methacryloyloxy) ethyl phosphate (2-(methacryloyloxy) ethyl phosphate, MMEP) and Tris (2-methacryloyloxy) ethyl phosphate, TMEP ) Any one or more selected from the group consisting of may be used.

As the antioxidant, tetrakis[methylene-3-(dodecylthio)propionate]methane may be used, and the antioxidant is included in the primer composition to be used, thereby blocking UV rays and inhibiting radical decomposition of the cured coating film. have.

The antifoaming agent may be a conventional material known in the art. For example, Agitan 295 (Munzing, Germany) may be used as the antifoaming agent.

The adhesive layer 200 may be manufactured using a hot melt adhesive including a thermoplastic polymer material, and the hot melt adhesive including the thermoplastic polymer material is liquefied by heat to be adhered (ie, the lower surface of the primer layer 160). The adhesion can be expressed by being applied to. In general, solvent-type adhesives use organic solvents as a base material for liquefaction, so there is always a risk of fire and environmental pollution due to volatilization of organic solvents during use. On the other hand, hot melt adhesives do not contain organic solvents, so they are environmentally friendly and not harmful to the human body, and their use is increasing.

Typical hot melt adhesives contain tackifying resins, waxes, and other additives as constituents with ethylene vinyl acetate, styrene, or olefin as their main resins, and the tackifying resins include rosin and its derivatives, C5, C9 petroleum resins. , Terpene resin, etc. are used, and paraffin wax, microcrystalline wax, polyethylene wax, etc. may be used as the wax.

For example, as a hot melt adhesive for forming the adhesive layer 200, a known hot melt adhesive (SBS copolymer mixture) of Sunwoo Chemical may be used, and the hot melt adhesive of Sunwoo Chemical is SIS COPOLYMER ((Polystyrene-Polyisoprene -Polystyrene) (CAS NO. 25038-32-8) 15% by weight, hydrocarbon resin (HYDROCARBON RESIN) (CAS NO. 69430-35-9) 25% by weight, ROSIN ESTER (CAS NO. 68038-41) -5) 45% by weight, paraffin oil (PARAFFINE OIL) (CAS NO. 64742-54-7) 10% by weight and antioxidant (ANTIOXIDANT, hardener) (CAS NO. 6683-19-8) 5% by weight containing The composition may be made of a composition, and since the configuration of the hot melt adhesive is a known technology, a detailed description thereof will be omitted for convenience of description and clarity of the technical idea of the present invention.

The release paper 300 is attached to the lower portion of the adhesive layer 200 and may be provided to protect the adhesive layer 200, and the configuration of the release paper 300 is a well-known technology. For clarity of the technical idea, a detailed description thereof will be omitted.

Hereinafter, a preferred embodiment will be described in more detail with respect to the method of manufacturing an antimicrobial protective film according to the present invention with reference to the accompanying drawings.

First, the sheet paper layer 140 may be formed by using the sheet paper composition.

At this time, the sheet composition comprises 5 to 10 parts by weight of copper nanoparticles, 1 to 3 parts by weight of expanded graphite powder, 2 to 4 parts by weight of gelite, 0.1 to 1.5 parts by weight of peppermint extract, 200 to 400 parts by weight of polyurethane resin, and a dispersant It may be prepared by being included in a weight ratio of 1 to 3 parts by weight.

Next, the coating layer 120 may be formed by applying a coating solution composition on the top of the sheet paper layer 140 and drying it.

At this time, the coating composition is a self-emulsifying epoxy resin 50 to 70 parts by weight, acrylic modified polyester resin 10 to 20 parts by weight, graphene 0.5 to 1.5 parts by weight, conductive polymer 0.1 to 1 parts by weight, filler 1 to 3 parts by weight And 0.5 to 1.5 parts by weight of a curing agent.

Next, by applying a primer composition to the lower part of the sheet paper layer 140 and drying to form the primer layer 160, a protective sheet made of the coating layer 120, the sheet paper layer 140, and the primer layer 160 ( 100) can be formed.

At this time, the primer composition is a polyurethane acrylate oligomer (Oligomer) 40 to 60 parts by weight, acrylic monomer (monomer) 20 to 40 parts by weight, photocuring agent 1 to 3 parts by weight, solvent 100 to 200 parts by weight, polyvinyl alcohol (polyvinyl alcohol) 3 to 7 parts by weight, natural rubber 0.1 to 1 parts by weight, Thiourea compound 0.1 to 1.5 parts by weight, polyacrylic acid 5 to 10 parts by weight, phosphorus monomer 1 to 5 parts by weight, antioxidant 0.1 To 1.5 parts by weight and 0.1 to 0.5 parts by weight of the antifoaming agent.

Subsequently, by applying a hot melt adhesive under the primer layer 160 constituting the protective sheet 100 to form an adhesive layer 200, and forming a release paper 300 under the adhesive layer 200, according to the present invention An antibacterial protective film 10 can be prepared.

Hereinafter, a preferred embodiment will be described in more detail with respect to the antimicrobial protective film according to the present invention with reference to the accompanying drawings.

<Example>

First, a sheet paper layer was formed using a sheet paper composition, and a coating solution composition was applied on the top of the sheet paper layer, followed by drying to form a coating layer.

Next, a primer composition was applied to the lower portion of the sheet layer and dried to form a primer layer, thereby forming a protective sheet consisting of a coating layer, a sheet layer, and a primer layer.

Next, an adhesive layer was formed by applying a hot melt adhesive under the primer layer constituting the protective sheet, and a release paper was formed under the adhesive layer to prepare an antibacterial protective film.

Here, the sheet composition was prepared by mixing in a weight ratio of 8 parts by weight of copper nanoparticles, 2 parts by weight of expanded graphite powder, 3 parts by weight of gelite, 1 part by weight of peppermint extract, 300 parts by weight of polyurethane resin, and 2 parts by weight of a dispersant. .

In addition, the coating liquid composition is mixed in a weight ratio of 60 parts by weight of a self-emulsifying epoxy resin, 15 parts by weight of an acrylic modified polyester resin, 1 part by weight of graphene, 0.5 parts by weight of a conductive polymer, 2 parts by weight of a filler, and 1 part by weight of a curing agent. Was manufactured.

In addition, the primer composition is a polyurethane acrylate oligomer (Oligomer) 50 parts by weight, acrylic monomer (monomer) 30 parts by weight, photocuring agent 2 parts by weight, solvent 150 parts by weight, polyvinyl alcohol (polyvinyl alcohol) 5 parts by weight, It was prepared by containing 0.5 parts by weight of natural rubber, 1 part by weight of Thiourea compounds, 7 parts by weight of polyacrylic acid, 3 parts by weight of phosphorus monomer, 1 part by weight of antioxidant and 0.3 parts by weight of antifoaming agent.

<Comparative Example>

A protective film was prepared using the same composition as the Example, but in Comparative Example, unlike the Example, a coating layer was not formed, and the sheet paper composition did not contain copper nanoparticles and peppermint extract, and after forming a sheet paper layer, a protective film Was prepared.

1. Wear resistance test

The wear resistance of the protective film prepared as in the above example was measured, and the results are shown in Table 1 below.

Test method: KS F 3126 standard, (initial wear degree + final wear degree)/2 = pass if more than 350 times

Sample size: Test by making a 100mm diameter test disk

Quality standard: Test by replacing the wear wheel with a new wear wheel every 200 revolutions with S-42

Test Items Wear wheel Test result result Remark Initial wear point Final wear point Wear resistance S-42 Episode 380 Episode 460 Episode 420 pass

Referring to [Table 1], in the abrasion resistance test of the protective film prepared according to the Example, the initial wear point was 380 times and the final wear point was 460 times, and it was confirmed that excellent wear resistance properties were shown.

2. Measurement of physical properties

The physical properties of the protective film prepared as in the above example were measured and shown in Table 2 below.

division Example Test Methods Wrinkle resistance (mm) 88 Driver fall no problem Plastic chair Caster resistance (caster, chair wheel) no problem 55kg, 1000 round trips Scratch resistance (N) 1.3 Diamond chips Coin scratch no problem 11kg x 500mm/sec Coin stampability no problem 1,000mm/sec

Referring to [Table 2], it was confirmed that the protective film manufactured according to the Example has excellent durability.

3. Smokeability measurement

The fuming properties of the protective film prepared through the above examples were measured, and the measurement criteria for this were shown in the following [Table 3], and the measurement results are shown in the following [Table 4].

rank Test Items Exam conditions Conformity criteria Incombustible material
(1st grade) nonflammable
(Electric furnace combustion) Temperature difference between the maximum temperature and the final equilibrium temperature (℃) 750℃,
20 minutes burning 20℃ or less Mass reduction rate Less than 30% Gas Hazard Average stoppage time mouse 9 minutes or more Semi-incombustible material
(Level 2) Cone calorimeter Total heat release (MJ/m ² ) About 800℃,
10 minutes burning 8 MJ/m ² or less Time (sec) for heat release rate to exceed 20kW/m ² 10 seconds or less Full melting of the core material, changes in cracks and holes, etc. Visually No cracks, holes and melting of the core material Gas Hazard Average stoppage time mouse 9 minutes or more Flame retardant material
(Level 3) Cone calorimeter Total heat release (MJ/m ² ) About 800℃,
5 minutes burning 8 MJ/m ² or less Time (sec) for heat release rate to exceed 20kW/m ² 10 seconds or less Full melting of the core material, changes in cracks and holes, etc. Visually No cracks, holes and melting of the core material Gas Hazard Average stoppage time mouse 9 minutes or more

Example standard Cone calorimeter Total release rate (MJ/m ² ) 4.01 8 MJ/m ² or less Time (sec) for heat release rate to exceed 20kW/m ² 0 10 seconds or less Full melting of the core material, cracks and holes, etc. none No cracks, holes and melting of the core material emitting smoking none - Judgment Flame retardant grade 2 equivalent

As shown in [Table 4], it was confirmed that the protective film prepared according to the Example had excellent flame retardancy and exhibited physical properties corresponding to flame retardant grade 2.

4. Measurement of physical properties such as adhesion

Physical properties such as adhesive strength of the protective film prepared through the Examples and Comparative Examples were measured, and the results are shown in Table 5 below.

division Example Comparative example Adhesion (gf/mm) 7 6 Static electricity generation 10 ¹¹ or less 10 ¹¹ or less Film stiffness 4 One Number of foreign substances (ea/mm ³ ) 1 or less 1 or less Tensile strength (kg/cm ³ ) 384 245 Elongation(%) 820 625

Referring to the above [Table 5], it was confirmed that physical properties such as adhesion, static electricity generation characteristics, number of foreign substances, tensile strength, and elongation of the protective film prepared according to the Example were superior to those of the protective film prepared according to the Comparative Example. .

5. Surface smoothness

The surface of the protective film according to Examples and Comparative Examples was observed from the direction of a tilt of 20 to 30 degrees in light of a light fixture, and the uniformity of the surface layer (microscopic), the presence or absence of agglomeration and the surface properties of the coating layer, or The presence or absence of wrinkles was checked, and the grade was evaluated as follows, and the results are shown in Table 6 below.

A: It is uniform without microscopic aggregation on the surface layer, and irregularities or wrinkles are not observed in the coating layer.

B: Although microscopic aggregation is seen on the surface layer, it is very slight, and irregularities or wrinkles are not observed in the coating layer.

C: Microscopic aggregation is seen in the surface layer, but irregularities or wrinkles are not observed in the coating layer.

D: Microscopic aggregation is remarkably seen on the surface layer, and irregularities and wrinkles are also seen on the coating layer.

6. Scratch resistance

Scratch resistance was tested by reciprocating 10 times under 1kg/(2cm x 2cm) using a steel wool tester (WT-LCM100, manufactured by Korea Protec). Steel wool used #0000, the grade was evaluated as follows, and the results are shown in Table 6 below.

A: 0 scratches

A': 1 to 10 scratches

B: 11~20 scratches

C: 21~30 scratches

D: 31 or more scratches

Measurement result of the physical properties of the protective film division Surface smoothness Scratch resistance Example A A Comparative example A C

Referring to [Table 6], it can be seen that the protective film according to the embodiment has excellent surface smoothness and scratch resistance.

7. Antibacterial test

To prepare a protective film specimen (5 × 5 mm) prepared as in the above example, Bacillus subtilis, Escherichiaocli, and Salmonella typhimurium culture medium using a paper disk method The antimicrobial properties were investigated, and the results are presented in Table 7 below.

division Antibacterial activity (antibacterial ring of paper disk, diameter mm) Bacillus E. coli Salmonella Example 12.5 13.4 12.5

Referring to [Table 7], it was confirmed that the protective film according to the example had excellent antibacterial activity against all of Bacillus, E.

In the above, a preferred embodiment of the present invention has been described, but those of ordinary skill in the art to which the present invention pertains will understand that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. I will be able to. Therefore, it should be understood that the exemplary embodiment described above is illustrative in all respects and is not limiting.

10; Antibacterial protective film
100; Protective sheet 120; Coating layer
140; Sheet layer 160; Primer layer
200; Adhesive layer 300; Hyungji Lee

Claims (4)

A protective sheet adhered to the surface of the substrate;
A release paper located under the protective sheet; And
Including an adhesive layer positioned between the protective sheet and the release paper,
The protective sheet in the antimicrobial protective film comprising a sheet support layer, a coating layer positioned above the sheet support layer, and a primer layer positioned below the sheet support layer,
The sheet paper layer is formed by drying after mixing the sheet paper composition,
The sheet composition includes 5 to 10 parts by weight of copper nanoparticles, 1 to 3 parts by weight of expanded graphite powder, 2 to 4 parts by weight of gelite, 0.1 to 1.5 parts by weight of peppermint extract, 200 to 400 parts by weight of polyurethane resin, and 1 to It is included in a weight ratio of 3 parts by weight,
The coating layer is formed by applying a coating liquid composition on the top of the sheet and then drying,
The coating liquid composition includes 50 to 70 parts by weight of a self-emulsifying epoxy resin, 10 to 20 parts by weight of an acrylic modified polyester resin, 0.5 to 1.5 parts by weight of graphene, 0.1 to 1 parts by weight of a conductive polymer, 1 to 3 parts by weight of a filler, and a curing agent. Antimicrobial protective film, characterized in that included in a weight ratio of 0.5 to 1.5 parts by weight.
delete The method of claim 1,
The primer layer is formed by drying after applying a primer composition to the lower portion of the sheet paper layer,
The primer composition includes 40 to 60 parts by weight of a polyurethane acrylate oligomer, 20 to 40 parts by weight of an acrylic monomer, 1 to 3 parts by weight of a photocuring agent, 100 to 200 parts by weight of a solvent, polyvinyl alcohol (polyvinyl alcohol). alcohol) 3 to 7 parts by weight, natural rubber 0.1 to 1 parts by weight, Thiourea compounds 0.1 to 1.5 parts by weight, polyacrylic acid 5 to 10 parts by weight, phosphorus monomer 1 to 5 parts by weight, antioxidant 0.1 to 1.5 Antimicrobial protective film, characterized in that included in a weight ratio of 0.1 to 0.5 parts by weight and antifoaming agent.
To form a sheet paper layer using a sheet paper composition,
After applying the coating liquid composition on the top of the sheet layer and drying to form a coating layer,
The primer composition is applied to the lower part of the sheet layer and then dried to form a primer layer, thereby forming a protective sheet consisting of a coating layer, a sheet layer, and a primer layer,
Applying a hot melt adhesive under the primer layer constituting the protective sheet to form an adhesive layer,
Forming a release paper under the adhesive layer,
The sheet composition includes 5 to 10 parts by weight of copper nanoparticles, 1 to 3 parts by weight of expanded graphite powder, 2 to 4 parts by weight of gelite, 0.1 to 1.5 parts by weight of peppermint extract, 200 to 400 parts by weight of polyurethane resin, and 1 to It is included in a weight ratio of 3 parts by weight,
The coating liquid composition includes 50 to 70 parts by weight of a self-emulsifying epoxy resin, 10 to 20 parts by weight of an acrylic modified polyester resin, 0.5 to 1.5 parts by weight of graphene, 0.1 to 1 parts by weight of a conductive polymer, 1 to 3 parts by weight of a filler, and a curing agent. It is included in a weight ratio of 0.5 to 1.5 parts by weight,
The primer composition includes 40 to 60 parts by weight of a polyurethane acrylate oligomer, 20 to 40 parts by weight of an acrylic monomer, 1 to 3 parts by weight of a photocuring agent, 100 to 200 parts by weight of a solvent, polyvinyl alcohol (polyvinyl alcohol). alcohol) 3 to 7 parts by weight, natural rubber 0.1 to 1 parts by weight, Thiourea compounds 0.1 to 1.5 parts by weight, polyacrylic acid 5 to 10 parts by weight, phosphorus monomer 1 to 5 parts by weight, antioxidant 0.1 to 1.5 A method of manufacturing an antimicrobial protective film, characterized in that it is included in a weight ratio of 0.1 to 0.5 parts by weight and an antifoaming agent.

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