KR100918807B1 - Antibacterial polymer composition and method of forming an antibacterial polymer film - Google Patents

Abstract

PURPOSE: An antibacterial polymer composition is provided to ensure strong sterilizing power or antibacterial activity by reducing copper contained in a polymer. CONSTITUTION: An antibacterial polymer composition includes a copper-containing polymer and organic solvent. The antibacterial polymer composition has antibacterial activity for microorganism through reduction processing. The copper-containing polymer has a repeating unit represented by formula 1. A method for forming an antibacterial polymer film comprises the steps of: forming a copper-containing polymer film on a substance by applying the polymer composition; and imparting an antibacterial property for microorganism to the copper-containing polymer film by reducing the copper-containing polymer film using a reducing agent through chemical reduction, thermal reduction, and photo reduction.

Description

Antimicrobial polymer composition and method for forming antimicrobial polymer film using same {Antibacterial polymer composition and Method of forming an antibacterial polymer film}

The present invention relates to an antimicrobial polymer composition and a method of forming the antimicrobial polymer membrane using the same. More specifically, the present invention relates to an antimicrobial polymer composition having improved antimicrobial activity and a method of forming an antimicrobial polymer membrane using the same.

Recently, new antimicrobial materials have been reported continuously as the demand for materials having antimicrobial functions increases with the development of functional materials. Antimicrobial materials can be broadly classified into organic and inorganic antimicrobials. Practical organic antimicrobials combine functional groups such as ammonium salts, phosphonium salts, pyridine compounds, organic halogen compounds, chiazoline compounds, and phenols.They have excellent antibacterial properties, but they are deteriorated over time and used for a long time. Is not suitable.

In order to solve the problem of the low molecular weight organic antimicrobial agent, a method of mixing the low molecular weight antimicrobial agent with a polymer has been proposed. However, if the antimicrobial agent is mixed with the polymer and used as described above, the antimicrobial persistence may be problematic. Therefore, research on a new polymer antimicrobial agent in which an antimicrobial agent is bound to a polymer is in progress. For example, Korean Patent Laid-Open Publication No. 2004-7003345 discloses an antimicrobial polymer made of polystyrene having N-halamine introduced with excellent antibacterial properties as a starting material of highly crosslinked polystyrene beads. However, the antimicrobial polymer should be used in a state where the polystyrene used as the base material is a hard solid bead and dispersed in a solvent. Therefore, the antimicrobial polymer has a disadvantage in that it can be used only in a range that does not impair dispersion stability for secondary processing such as spraying or solution coating.

Inorganic antimicrobial agents are advantageous in terms of durability compared to organic antimicrobial agents, and in many cases, inorganic antimicrobial agents of metals and nonmetals are used. As representative metals used in the inorganic antimicrobial agent, metals such as silver (Ag), copper (Cu), nickel (Ni) and oxides thereof are known to have excellent antibacterial properties. In particular, copper is chemically stable as an element belonging to Group 11 (IB group) of the periodic table. Copper can have both valences of +1 and +2, but is usually present in +2, and the higher the valence, the higher the stability. The copper is a metal having a distinctive red luster and is excellent in malleability, ductility, and workability, and also has a relatively good strength. When heated, it becomes dark cuprous oxide (CuO), and when heated to 1,000 degreeC or more, it becomes reddish-purple cuprous oxide (Cu ₂ O). It also directly combines with sulfur, chlorine and phosphorus, and does not oxidize in pure dry air, but rusts due to moisture in ordinary air, and is mainly made of basic copper carbonate CuCO ₃ ㅇ Cu (OH) ₂ Create

According to the related art related to an antimicrobial substance using copper having such characteristics, copper is coated on a surface of a substrate or mixed with a general polymer to be applied to an antimicrobial product. For example, Japanese Laid-Open Patent Publication No. 2002-521339 discloses a technique for forming a metal pyrithione as a shell with a metal oxide or a metal hydroxide as a core, and a composition containing the composite. In addition, Korean Patent Laid-Open Publication No. 10-2006-0126986 reports that a composition including a copper salt and a diluent of N-hydroxy-N-cyclohexyldiagenium oxide has antibacterial activity. Korean Patent Publication No. 10-2005-0089608 discloses a method for preparing an antimicrobial polymer by mixing copper oxide with a polymer such as acrylonitrile-butadiene-styrene copolymer (ABS), polypropylene (PP), polyethylene (PE), and the like. I'm reporting.

However, in the above-described method, since copper is dispersed in a polymer, only a small amount of copper should be used in the range of not impairing the physical properties of the polymer in order to manufacture a product through extrusion, molding, etc., and thus the antibacterial property is limited. In addition, in order to effectively exhibit the antimicrobial properties, the antimicrobial material should be present on the surface, but in the case of simple mixing, copper is not evenly dispersed in the polymer and is often accumulated in a specific part, and thus the antimicrobial activity against the dose may be very low.

Accordingly, an object of the present invention is to provide an antimicrobial polymer composition having improved antimicrobial activity.

Another object of the present invention to provide a method for forming an antimicrobial polymer membrane using the above-described antimicrobial polymer composition.

Antimicrobial polymer composition according to an embodiment for achieving the above object of the present invention comprises a copper-containing polymer and an organic solvent having a repeating unit represented by the following structural formula (1).

......(1)

......(One)

In formula 1, R ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group, R ₂ represents an electron donating group or an aliphatic or aromatic hydrocarbon chain having the electron donating functional group at the terminal, Z represents a ligand-binding functional group or ligand-binding compound coordinated with copper, and n is an integer of 1 to 10,000.

Copper-containing polymer according to an embodiment of the present invention may include a carbonyloxy group (-COO-), a carbonylamino group (-CONH-), a carbonylthio group (-COS-) as the electron donating functional group have.

Copper-containing polymer according to an embodiment of the present invention is a cyano group, thiocyanato group, alkoxy group, aryloxy group, alkyl cyano group, arylcyano group, alkylthio group, aryl as the ligand-binding functional group or ligand-binding compound It may be a thio group, an alkylamino group, a dialkylamino group, an arylamino group or a diarylamino group, or an aliphatic or aromatic hydrocarbon compound having at least one double bond or triple bond coordinated to copper, and the like.

According to one embodiment of the present invention, the copper-containing polymer may include a repeating unit represented by the following Structural Formula 2 or 3.

......(2)

......(3)

...... (3)

In the above formulas 2 and 3, R ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group, X represents a residue removed hydrogen from the hydroxyl group, a residue removed one hydrogen from the amino group or a residue removed from the thiol group, R ₃ represents a C ₁ -C ₁₀ aliphatic hydrocarbon chain or a C ₃ -C ₃₀ aromatic hydrocarbon chain, Z represents a cyano group, a thiocyanato group, an alkoxy group, an aryloxy group, an alkylcyano group, an arylcyano group, an alkylthio group , An arylthio group, an alkylamino group, a dialkylamino group, an arylamino group or a diarylamino group, or an aliphatic or aromatic hydrocarbon compound having at least one double bond or triple bond coordinated to copper, and n is an integer of 1 to 10,000. to be.

According to an embodiment of the present invention, the antimicrobial polymer composition may further include additives such as pigments, dyes, reinforcing agents, fillers, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents or mixtures thereof. .

In the method for forming an antimicrobial polymer membrane according to an embodiment for achieving the above object of the present invention, the object by applying a copper-containing polymer composition comprising a copper-containing polymer and an organic solvent having a repeating unit represented by the formula 1 A copper-containing polymer film is formed on the phase. The copper-containing polymer film is subjected to a reduction treatment to impart antimicrobial activity to microorganisms.

According to one embodiment of the invention, the step of reducing the copper-containing polymer film may be carried out by heat treatment of the copper-containing polymer at a temperature of 150 to 220 ℃. According to another embodiment of the present invention, the step of reducing the copper-containing polymer film may be performed by wet treating the copper-containing polymer with a reducing agent. According to another embodiment of the present invention, the step of reducing the copper-containing polymer film may be performed by irradiating light to the copper-containing polymer.

The antimicrobial polymer composition according to the embodiments of the present invention described above has a strong antibacterial or bactericidal activity against microorganisms by reducing copper contained in the polymer. The reduced copper has the property of sterilizing or removing microorganisms as it is oxidized in contact with microorganisms. Since the antimicrobial polymer composition is distributed evenly in a form in which the copper is not simply mixed with the polymer but bonded to the polymer, the antimicrobial polymer composition has excellent antimicrobial activity compared to the amount of copper input. In addition, the antimicrobial polymer composition is excellent in physical properties such as adhesion, heat resistance, coating properties, it can be usefully applied to various materials such as fibers, fabrics, plastic materials, inorganic materials, metal materials.

Hereinafter, an antimicrobial polymer composition and a method of forming an antimicrobial polymer membrane using the same according to preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

However, the present invention is not limited to the following embodiments, and a person of ordinary skill in the art may implement the present invention in various other forms without departing from the technical spirit of the present invention.

The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise, and the terms "comprises" or "consists of" include, but are not limited to, features, numbers, steps, operations, components, parts, or parts described in the specification. It is to be understood that the combination is intended to be present, but not to exclude in advance the possibility of the presence or addition of one or more other features or numbers, steps, operations, components, parts or combinations thereof. Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art, and are not construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.

In the present invention, "aliphatic hydrocarbon" and "alkyl" mean saturated straight, branched or cyclic hydrocarbon chains. In one embodiment of the invention the aliphatic hydrocarbon or alkyl may comprise 1 to 30 carbon atoms, and in another embodiment may comprise 1 to 10 carbon atoms. Aliphatic hydrocarbons or alkyls may or may not be substituted with chemically possible substituents. Examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, hexyl, cyclopropyl and the like. In the present invention, "aryl" means an aromatic hydrocarbon chain, the number of rings may be one, two or more, and may include 3 to 14 carbon atoms. Examples of aryl include phenyl group, naphthyl group, anprasenyl group and the like. The aryl group may or may not be substituted with a chemically possible substituent.

Antimicrobial Polymer Composition

The antimicrobial polymer composition includes a copper-containing polymer and an organic solvent having a repeating unit represented by Structural Formula 1 below, and has antimicrobial activity against microorganisms through a reduction treatment.

......(1)

......(One)

In formula 1, R ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group, R ₂ represents an electron donating group or an aliphatic or aromatic hydrocarbon chain having the electron donating functional group at the terminal, Z represents a ligand-binding functional group or ligand-binding compound coordinated with copper, and n is an integer of 1 to 10,000.

In Structural Formula 1, the electron donating functional group of R ₂ and the bond of copper (R ₂ -Cu), and the bond of copper and Z (Cu-Z) are ligand bonds in the form of ligand coordinated with copper. Each ligand bond may be coordinated with one ligand to copper, or two or more ligands may be coordinated multiplely.

In the above formula 1, the electron donating functional group of R ₂ can be any functional group capable of supplying electrons to copper. In addition, the electron donating functional group may include oxygen, nitrogen, or sulfur having an unshared electron pair. For example, a carbonyloxy group (-COO-), a carbonylamino group (-CONH-), a carbonylthio group (-COS-), etc. are mentioned as said electron donating functional group. Examples of the aliphatic or aromatic hydrocarbon chain of R ₂ include C ₁ -C ₃₀ substituted or unsubstituted alkylene, oxyalkylene, alkyleneoxy, arylene, oxyarylene, aryleneoxy, and the like. It is not limited.

In Structural Formula 1, Z can be any ligand that coordinates with copper to form a complex compound. Examples of the ligand binding functional group include cyano group, thiocyanato group, alkoxy group, aryloxy group, alkyl cyano group, arylcyano group, alkylthio group, arylthio group, alkylamino group, dialkylamino group, arylamino group or diaryl An amino group etc. are mentioned. More specific examples of Z include cyano, thiocyanato, methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, t-butyloxy, phenyloxy, methylcyano and ethyl cya Furnace group, propylcyano group, butylcyano group, phenylcyano group, methylthio group, ethylthio group, phenylthio group, methylamino group, ethylamino group, dimethylamino group, isopropylamino group, t-butylamino group, phenylamino group, diphenylamino group Although these etc. are mentioned, It is not limited to these.

In addition, Z may be a C ₂ -C ₃₀ aliphatic or aromatic hydrocarbon compound or the like having at least one double bond or triple bond coordinated to copper. Examples include, but are not limited to, cyclohexene, cyclooctadiene, cyclopentadiene, butadiene, pentadiene, hexadiene, octadiene, and the like.

In one embodiment of the present invention, the antimicrobial polymer composition may include a polymer having a repeating unit represented by the following Structural Formula 2 or 3.

......(2)

......(2)

......(3)

...... (3)

In formulas 2 and 3, R ₁ , Z and n are substantially the same as formula 1, X represents a residue removed hydrogen from the hydroxyl group, a residue removed one hydrogen from the amino group or a residue removed from the thiol group, R ₃ represents a C ₁ -C ₁₀ aliphatic hydrocarbon chain or a C ₃ -C ₃₀ aromatic hydrocarbon chain.

In the above formulas 2 and 3, when X is a residue obtained by removing hydrogen from the hydroxyl group, the functional group bonded to copper becomes a carbonyloxy group (-COO-). When X is a residue which removed one hydrogen from an amino group, the functional group which couple | bonds with copper turns into a carbonylamino group (-CONH-). In addition, when X is a residue which removed the hydrogen of a thiol group, the functional group couple | bonded with copper turns into a carbonylthio group (-COS-).

In one embodiment of the present invention, the polymer having a repeating unit represented by Structural Formula 1 may be prepared by preparing a copper-containing unsaturated monomer, and then polymerizing the unsaturated monomer. First, the copper-containing unsaturated monomer may be prepared by reacting an unsaturated monomer such as a vinyl monomer or an acrylic monomer with a copper complex compound. For example, butene acid, pentenoic acid, undecylene acid, (meth) acrylic acid, butene amide, pentene amide, undecylene amide, (meth) acrylamide, propentionic acid, butene ionic acid, pententionic acid, undecylenic acid Unsaturated monomers such as onic acid and 2-methylpropi-2-enthic acid may be substituted with copper cyanide, copper alkoxide, copper-cyclooctadiene, copper-cyclohexene, copper-cyclopentadiene, copper-butadiene, copper-pentadiene, and copper- By reacting with hexadiene, a copper-octadiene complex, and the like, an unsaturated monomer having a copper complex bonded to a side chain may be prepared. The unsaturated monomer may be prepared from a copper-containing polymer through a conventional polymer polymerization reaction such as radical polymerization. An initiator such as azobisisobutylnitrile (AIBN) may be used for the radical polymerization.

In another embodiment of the present invention, the polymer having a repeating unit represented by Structural Formula 1 may be prepared by replacing a copper complex compound in the side chain of the polymer in a polymerized state. For example, polymers, such as poly (meth) acrylic acid and poly (meth) acrylamide, may be substituted with copper cyanide, copper alkoxides, copper-cyclooctadiene complexes, copper-cyclohexene complexes, copper-cyclopentadiene complexes, and copper-butadiene complexes. The copper-containing polymer in which the copper complex is bonded to the side chain may be prepared by substitution reaction with a copper complex such as a copper hexadiene complex.

In one embodiment of the present invention, the copper-containing polymer included in the antimicrobial polymer composition may be a copolymer of a polymer having a repeating unit of Structural Formula 1 and a polymer not containing copper. The polymer forming the copolymer with the polymer of Formula 1 may be an olefin, styrene, (meth) acrylic acid ester, (meth) acrylamide, itaconic acid diester, maleic acid ester, fumaric acid diester, N-alkylmaleimide, male anhydride. It can be prepared using at least one of unsaturated monomers such as acid, acrylonitrile, vinyl ether, vinyl ester, vinyl ketone, vinyl heterocyclic compound, glycidyl ester, unsaturated nitrile, unsaturated carboxylic acid.

Examples of the olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, and the like. Examples of styrene include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chlormethyl styrene, methoxy styrene, acetoxy styrene, chlor styrene, dichlor styrene, bromine styrene, trifluoromethyl styrene, Vinyl benzoic acid methyl ester etc. are mentioned.

Examples of acrylic esters and methacrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, 2- Methoxyethyl acrylate, 2-butoxyethyl acrylate, 2-phenoxyethyl acrylate, chlorethyl acrylate, cyanoethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, Furfuryl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate Acrylate, octyl methacrylate, benzyl methacrylate, cyanoacetoxyethyl methacrylate, Lebenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-methoxyethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylamino Phenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate , Hydroxypropyl acrylate, hydroxypropyl methacrylate, 3-chloro '32 -hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2,2-dimethylhydroxypropyl acrylate , 5-hydroxypentyl acrylate, diethylene glycol monoacrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, 2,2-dimethyl-3-hydroxy Hydroxypropyl methacrylate may be mentioned, 5-hydroxy-propyl methacrylate, diethylene glycol monomethacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxy ethyl vinyl ether, chlorethyl vinyl ether, 1- Methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butyl aminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, vinyl phenyl ether And vinyl tolyl ether, vinyl chlorphenyl ether, vinyl-2,4-dichlorphenyl ether, vinyl naphthyl ether, vinyl anthranyl ether and the like.

Specific examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutylate, vinyl dimethyl propionate, vinyl ethyl butyrate, vinyl valerate, vinyl caproate, vinyl chlor acetate, and vinyl dichlorate. Acetates, vinylmethoxy acetate, vinylbutoxyacetoacetate, vinylphenylacetate, vinylacetoacetate, vinyllactate, vinyl-β-phenylbutylate, vinylcyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorbenzoate, Vinyl tetrachlorobenzoate, vinyl naphthoate, and the like.

Examples of acrylamide include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, t-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acryl Amide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide and the like. Examples of methacrylamide include methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, t-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, and hydride. Oxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2 -Acetoacetoxyethyl) methacrylamide, etc. are mentioned.

Acrylamides having a hydroxy group can also be used, for example N-hydroxymethyl-N- (1,1-dimethyl-3-oxo-butyl) acrylamide, N-methylolacrylamide, N-methylolmethacryl Amide, N-ethyl-N-methylol acrylamide, N, N-dimethylol acrylamide, N-ethanol acrylamide, N-propanol acrylamide, N-methylol acrylamide, etc. are mentioned.

As itaconic acid diester, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc. are mentioned, for example. Examples of maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumaric acid diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like.

Examples of the vinyl ketone include methyl vinyl ketone, phenyl vinyl ketone, methoxy ethyl vinyl ketone, and the like. Examples of the vinyl heterocyclic compound include vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone and the like. As an example of glycidyl ester, glycidyl acrylate, glycidyl methacrylate, etc. are mentioned. Examples of the unsaturated nitrile include acrylonitrile, methacrylonitrile and the like. As an example of N-alkyl maleimide, N-ethyl maleimide, N-butyl maleimide, etc. are mentioned. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like, and anhydrides such as fumaric acid, itaconic acid and maleic acid. These copolymerizable monomers can be used individually or in mixture of 2 or more types.

In the copolymer, the molar ratio (n / m) of the repeating unit (n) of the old breakfast 1 to the repeating unit (m) containing no copper may be appropriately adjusted in consideration of the copper content. For example, the molar ratio (n / m) may range from 0.00001 to 10,000.

In one embodiment of the present invention, the molecular weight of the copper-containing polymer included in the antimicrobial polymer composition may be appropriately adjusted in consideration of solubility in solvents, viscosity, coating properties of the thin film, and the like. For example, the copper-containing polymer may have a number average molecular weight in the range of 500 to 500,000. When the number average molecular weight of the copper-containing polymer is less than 500, the polymer may not exhibit the properties of the polymer or the thermal and mechanical properties may be reduced. In addition, when the number average molecular weight exceeds 500,000, solubility in organic solvents may be lowered, and thus it may be difficult to process the solution in a solution state.

In embodiments of the present invention, the content of the polymer included in the antimicrobial polymer composition may be appropriately adjusted in consideration of the viscosity of the composition, the solubility of the polymer, the coating property and the like. For example, the antimicrobial polymer composition may include the copper-containing polymer in a range of 0.1 to 50% by weight based on the total weight of the composition, but is not limited thereto.

In embodiments of the present invention, the antimicrobial polymer composition may include ether, ester, ketone, glycol, alcohol, and the like as an organic solvent. Specific examples of the organic solvent include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and mixtures thereof, but are not limited thereto. It doesn't happen.

In embodiments of the present invention, the content of the organic solvent included in the antimicrobial polymer composition is not particularly limited and may be appropriately adjusted in consideration of the molecular weight, solubility, viscosity, and the like of the polymer. In one embodiment the content of organic solvent may range from 40 to 99.89% by weight (when using an additive) relative to the total weight of the composition, and in another embodiment the content of organic solvent may be from 50 to 99.9% by weight. May be in the range (if no additives are used). However, it is not limited to the above content range.

In one embodiment of the present invention, the antimicrobial polymer composition may further include various additives in consideration of its use, application object, physical properties, and the like. Examples of the additives include pigments, dyes, reinforcing agents, fillers, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents, nucleating agents or mixtures thereof. More specific examples of the additive include, but are not limited to, carbon fiber, calcium carbonate, clay, silica, alumina, carbon black, magnesium hydroxide, and the like.

The content of the additive may be appropriately adjusted in consideration of the use and physical properties of the composition. For example, the antimicrobial polymer composition may include, but is not limited to, an additive in the range of about 0.01 to 10% by weight based on the total weight of the composition.

In embodiments of the present invention, the polymer included in the antimicrobial polymer composition does not have antimicrobial activity per se, and has antimicrobial activity through a reduction treatment for copper. The copper of the polymer can be reduced by thermal, optical or chemical reduction methods. The reduced copper is oxidized again by contact with the microorganisms to inactivate, sterilize or remove the microorganisms. In particular, since the antimicrobial polymer composition is evenly distributed in a form in which the copper is not simply mixed with the polymer but bonded to the main chain of the polymer, the antimicrobial polymer composition has excellent antimicrobial activity compared to the amount of copper input. In addition, the antimicrobial polymer composition is excellent in physical properties such as adhesion, heat resistance, coating properties, it can be usefully applied to various materials such as fibers, fabrics, plastic materials, inorganic materials, metal materials.

Manufacturing method of antimicrobial polymer membrane

1 is a flowchart illustrating a method of forming an antimicrobial polymer film according to embodiments of the present invention.

Referring to Figure 1, by mixing the above-described copper-containing polymer and an organic solvent to prepare a polymer composition containing copper (S10). The copper-containing polymer has a property of being easily dissolved in an organic solvent. By using these properties, the polymer composition may be prepared by dissolving a copper-containing polymer in an organic solvent.

The prepared copper-containing polymer composition is coated on the object to form a copper-containing polymer film (S20). The object may be made of various organic or inorganic materials, including fibers, fabrics, plastic materials, inorganic materials, metallic materials, or wood.

For example, the polymer composition may be used to mix or coat various kinds of fibers or fabrics such as cotton, hemp, wool, nylon, synthetic fibers, artificial leather, and the like. In addition, the polymer composition may be applied to various kinds of plastic materials such as polyurethane (PU), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), and ethylene vinyl acetate (EVA). In addition, the polymer composition may be applied to inorganic or metal materials requiring antimicrobial processing.

As a method of applying the polymer composition to the object, a general method of applying the composition may be appropriately selected. For example, methods such as spray coating, spin coating, wet coating and the like can be used. In addition, the polymer composition may be coated on an object and then dried under reduced pressure to prepare a copper-containing polymer film. The copper-containing polymer film formed on the object as described above may have an amorphous transparent property.

Thereafter, the copper-containing polymer membrane is reduced to reduce copper of the polymer to impart antimicrobial activity to the polymer membrane (S30). Copper of the copper-containing polymer film may be reduced by heat, light or chemical reduction. The reduced copper is oxidized again by contact with the microorganisms to inactivate, sterilize or remove the microorganisms.

According to one embodiment of the present invention, the reduction of copper may be performed by heat treatment of the polymer film. The copper bonded to the side chain of the polymer may be reduced by the supply of thermal energy. The heat treatment temperature is sufficient if the temperature is higher than enough to supply the energy required for the reduction of copper. For example, a heat treatment process for the reduction of copper may be performed at a temperature range of about 150 to 220 ° C. However, when the temperature of the heat treatment process is a high temperature such as 250 ° C, the polymer forming the main chain may be decomposed, which is not preferable.

According to another embodiment of the present invention, the reduction of copper may be performed by wet treating the polymer membrane with a chemical reducing agent. Reducing agents include hydrogen, relatively unstable hydrogen compounds such as hydrogen iodide, hydrogen sulfide, aluminum hydride, lower oxides such as carbon monoxide and sulfur dioxide, salts of lower oxygen acids such as sulfite, sodium sulfide, and electrically positive compounds such as magnesium and zinc. Metals that tend to be positive cations, organic compounds with low oxidation degree, such as sodium borohydride (NaBH ₄ ) and lithium aluminum hydride (LiAlH ₄ ), may be used, but are not limited thereto.

According to another embodiment of the present invention, the reduction of copper may be performed by irradiation with light. As the light source, any light having energy enough to reduce copper can be used. For example, ultraviolet rays, gamma rays, electron beams, or the like may be used as the light source.

In embodiments of the present invention, the antimicrobial polymer membrane prepared as described above has antimicrobial properties such as inhibiting or killing the growth of microorganisms. The antimicrobial polymer membrane has antimicrobial activity against various microorganisms such as viruses, specific microorganisms or specific organisms.

Examples of the microorganisms include the fungi Aspergillus niger and Chathamium globosum, Saccharomyces cerevisiae and Candida albicans, yeast. Organisms Pseudomonas fluorescens, Pseudomonas aeruginosa, Alcaligenes faecalis, and Staphylococcus aureus, Staphylococcus epidermis epidermis, Corynebacterium xerosis, Propionibacterium acnes, Pityrosporum ovale, Aspergillus niger, Alternaria alternata (Alternaria alternata), Aspergillus versicolor, Aureobasidium pullulans ), Cladosporium cladosporioides, Penicillium purpurogenum, Phoma violacea, Rhodotorula rubra, Sporobolomises rose Sporobolomyces roseus, Stachybotrys chartarum, Ulocladium atrum, Chlorella sp, Pleurococcus sp, Nostocmuscorum, Oscill Lattoria tenuis, Stichococcus bacillaris, Trentepohlia aurea, and the like.

In one embodiment of the present invention, the antimicrobial polymer membrane has excellent antimicrobial activity such as killing E. coli within a few hours in contact with E. coli.

Since the antimicrobial polymer membrane prepared by the above method is distributed evenly in a form in which the copper is not simply mixed with the polymer but bonded to the polymer, the antimicrobial activity is excellent and the antibacterial performance can be continuously exhibited compared to the amount of copper input. In addition, the antimicrobial polymer membrane is excellent in physical properties such as adhesion, heat resistance, coating properties, it can be usefully applied to various materials such as fibers, fabrics, plastic materials, inorganic materials, metal materials.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples are provided to illustrate the present invention, and the present invention is not limited to the following examples and may be variously modified and changed.

Synthesis of Copper-Containing Monomers

Synthesis Example 1

An acrylate monomer having a copper complex substituted in the side chain was prepared according to the above scheme.

Specifically, 4 g of copper chloride was dissolved in 200 mL of a 2-normal hydrochloric acid solution, and then 10 g of 1,5-cyclooctadiene (COD) was added and stirred for 10 minutes. The resulting solid was filtered off and washed with water and normal hexane. Drying under reduced pressure for 24 hours yielded about 5.7 g of cyclooctadiene and copper primary complex (ClCu (COD)). 10.4 g of the first complex was dispersed in 300 mL tetrahydrofuran (THF), and 10.8 g of sodium methacrylate was added thereto and stirred. The solution was filtered through a filter, the solvent was evaporated and recrystallized with acetone to obtain about 6.3 g of an acrylate monomer having a copper complex substituted in the side chain.

The structure of the obtained monomer was confirmed using infrared (IR) spectrum and elemental analysis. Infrared spectral results of the monomers are shown in FIG. 2. In the elemental analysis, the carbon (C) content was 56.59% and the hydrogen (H) content was determined to be 7.04%, and the theoretical value for C ₁₂ H ₁₇ O ₂ Cu was 56.25% and hydrogen (H) content. It is similar to 6.64%.

Preparation of Copper-Containing Polymers

Synthesis Example 2

1 g of monomer, 2 g of methacrylic acid, 7 g of methacrylate and 0.5 g of azobisisobutylnitrile (AIBN) prepared in Synthesis Example 1 were dissolved in 100 g of tetrahydrofuran and refluxed at 80 ° C. for 17 hours. The reacted solution was put in a large amount of ethyl acetate to precipitate a polymer, and then filtered and dried under reduced pressure to obtain about 5 g of a copolymer.

The number average molecular weight of the obtained polymer was about 3,700, the weight average molecular weight was about 6,400, and the polydispersity index (PDI) was about 1.7.

Synthesis Examples 3 to 5

Except for the monomer content and the content of methacrylate, a copolymer polymer was prepared in substantially the same manner as in Synthesis example 2. The content of the monomers used in the preparation of the polymer and the number average molecular weight (Mn), weight average molecular weight (Mw) and dispersion degree (PDI) of the obtained polymer are shown in Table 1 below. The unit of content of monomer in Table 1 is g.

Table 1

Synthesis Example 6

Dissolve about 8.8 g of polymethacrylic acid with a mass mean molecular weight of about 45,000 in about 100 mL tetrahydrofuran (THF), add about 0.21 g of cyclooctadiene and copper primary complex (ClCu (COD)), and stir thoroughly. It was. After filtering the solution through a filter, the solvent was evaporated to obtain about 10.8 g of the acrylate polymer with the copper complex substituted in the side chain and the substitution rate of the theoretical copper complex was about 1%.

Synthesis Example 7

Dissolve about 8.7 g of polyacrylamide having a mass average molecular weight of about 10,000 in about 100 mL tetrahydrofuran (THF), add about 0.21 g of cyclooctadiene and copper primary complex (ClCu (COD)), and stir sufficiently. It was. After filtering the solution through a filter, the solvent was evaporated to obtain about 10.7 g of acrylamide polymer having a copper complex substituted in the side chain, and the substitution rate of the theoretical copper complex was about 1%.

Formation of Antimicrobial Polymer Membrane

Example 1

An antimicrobial polymer membrane was formed using the polymer prepared in Synthesis Example 2. Specifically, about 1 g of the polymer prepared in Synthesis Example 2 was dissolved in about 19 g of cyclohexanone to prepare a copper-containing polymer composition. The copper-containing polymer composition was evenly applied to the silicon wafer having a length and width of 2 cm by spin coating, and then dried under reduced pressure to prepare a copper-containing polymer film.

The polymer film formed on the silicon wafer was reduced by using a chemical reducing agent. A 10% (w / w) sodium borohydride aqueous solution was used as a reducing agent, and the wafer on which the polymer film was formed was immersed in the solution for about 10 seconds for reduction.

Example 2

An antimicrobial polymer membrane was prepared in substantially the same manner as in Example 1 except that the reduction was performed by a photoreduction method using ultraviolet light instead of the chemical reduction method. Ultraviolet rays having a wavelength of 157 nm were irradiated to the copper-containing polymer film for about 1 minute and then reduced.

Example 3

An antimicrobial polymer membrane was prepared in substantially the same manner as in Example 1 except that the reduction was performed by heat reduction instead of chemical reduction. The wafer on which the copper-containing polymer film was formed was left in an oven at 200 ° C. for about 1 hour to reduce copper.

Comparative Example 1

Using the polymer prepared in Preparation Example 1, a copper-containing polymer film was prepared on a silicon wafer in substantially the same manner as in Example 1. The specimen was prepared without any surface treatment for the copper-containing polymer film.

Evaluation of Antimicrobial Activity of Polymer Membranes

The antimicrobial activity against the microorganisms was evaluated by contacting the polymer membranes prepared in Examples 1 to 3 and Comparative Example 1 with the microorganisms. As the microorganism, E. coli, an indicator microorganism, was used. E. coli culture is added dropwise onto the wafer on which the polymer film is formed, and then cultured for a predetermined time to propagate E. coli. After desorption, the number of microorganisms was measured using a dilution plate method. Table 2 shows the measurement results of the microbial bacterial count after the start time, 3 hours and 24 hours. The number of bacteria of the microorganism was 100% of the total number of bacteria at the start.

TABLE 2

Referring to Table 2, in the case of the non-reducing copper-containing polymer film of Comparative Example 1, the E. coli populations increased rapidly. In contrast, in the reduced-copper-containing polymer membranes of Examples 1 to 3, more than 99% of E. coli was killed after 3 hours, and all of E. coli were killed after 24 hours. Therefore, the copper-containing polymer film formed using the polymer of Preparation Example 1 did not have antimicrobial properties before the reduction treatment, but was confirmed to have a strong antimicrobial activity against the microorganisms after the reduction treatment. In addition, in the case of the polymers prepared in Synthesis Examples 3 to 7, it was confirmed that after the reduction treatment with heat, ultraviolet rays or reducing agents have an excellent antibacterial activity similar to the polymer of Synthesis Example 2.

The antimicrobial polymer composition according to the embodiments of the present invention described above has a strong antibacterial or bactericidal activity against microorganisms by reducing copper contained in the polymer. That is, the copper in the reduced state has the property of sterilizing or removing the microorganisms while being oxidized in contact with the microorganisms. Since the antimicrobial polymer composition is evenly distributed in a form in which the copper is not simply mixed with the polymer but bonded to the polymer, the antimicrobial activity can be excellent in antimicrobial activity and antibacterial performance compared to the dosage of copper. In addition, the antimicrobial polymer composition is excellent in physical properties such as adhesion, heat resistance, coating properties, can be applied to a variety of materials, such as textiles, textiles, plastic materials, inorganic materials, metal materials, as an antimicrobial agent in various industries, such as automobiles It can be useful.

As described above with reference to preferred embodiments of the present invention, those of ordinary skill in the art can be variously modified and modified within the scope of the present invention without departing from the spirit and scope of the present invention described in the claims below. It will be appreciated that it can be changed.

1 is a flowchart illustrating a method of forming an antimicrobial polymer film according to embodiments of the present invention.

2 is a graph showing an infrared spectrum analysis result of the copper-containing monomer prepared in Synthesis Example 1.

Claims (13)

An antimicrobial polymer composition comprising a copper-containing polymer and an organic solvent having a repeating unit represented by the following Structural Formula 1 and having antimicrobial activity against microorganisms through a reduction treatment.

......(One) (In Formula 1, R ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group, R ₂ represents an electron donating group or an aliphatic or aromatic hydrocarbon chain having the electron donating functional group at the end. , Z represents a ligand-binding functional group or ligand-binding compound coordinated to copper, n is an integer from 1 to 10,000) The antimicrobial agent according to claim 1, wherein the electron donating functional group is selected from the group consisting of a carbonyloxy group (-COO-), a carbonylamino group (-CONH-), and a carbonylthio group (-COS-). Polymer composition. According to claim 1, Z in the structural formula 1 is a cyano group, thiocyanato group, alkoxy group, aryloxy group, alkylcyano group, arylcyano group, alkylthio group, arylthio group, alkylamino group, dialkylamino group, An arylamino group or a diarylamino group, or an aliphatic or aromatic hydrocarbon compound having at least one double bond or triple bond coordinated to copper. The antimicrobial polymer composition of claim 1, wherein the copper-containing polymer comprises a repeating unit represented by the following Structural Formula 2 or 3.

......(2)

...... (3) (In the above formulas 2 and 3, R ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group, X represents a residue removed hydrogen from the hydroxyl group, a residue removed one hydrogen from the amino group, or a residue removed from the thiol group, R ₃ represents a C ₁ -C ₁₀ aliphatic hydrocarbon chain or a C ₃ -C ₃₀ aromatic hydrocarbon chain, Z is a cyano group, a thiocyanato group, an alkoxy group, an aryloxy group, an alkylcyano group, an arylcyano group, an alkyl thi Or an aliphatic or aromatic hydrocarbon compound having at least one double bond or triple bond coordinated to copper, or an arylthio group, an alkylamino group, a dialkylamino group, an arylamino group or a diarylamino group. Is an integer) The antimicrobial polymer composition of claim 4, wherein Z in Structural Formulas 2 and 3 is cyclohexene, cyclooctadiene, cyclopentadiene, butadiene, pentadiene, hexadiene or octadiene. The method of claim 1, wherein the copper-containing polymer is a repeating unit of the formula 1, olefin, styrene, (meth) acrylic acid ester, (meth) acrylamide, itaconic acid diester, maleic acid ester, fumaric acid diester, N- Repetition resulting from at least one monomer selected from the group consisting of alkylmaleimides, maleic anhydride, acrylonitrile, vinyl ethers, vinyl esters, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles and unsaturated carboxylic acids An antimicrobial polymer composition comprising a copolymer comprising a unit. The method of claim 1, wherein the antimicrobial polymer composition further comprises at least one additive selected from the group consisting of pigments, dyes, reinforcing agents, fillers, heat stabilizers, weather stabilizers, antistatic agents, lubricants, slip agents and nucleating agents. Antimicrobial polymer composition. Forming a copper-containing polymer film on an object by applying a polymer composition comprising a copper-containing polymer having an repeating unit represented by Structural Formula 1 and an organic solvent; And And reducing the copper-containing polymer film by chemical reduction, thermal reduction, or light reduction using a reducing agent to impart antimicrobial activity to the copper-containing polymer film.

......(One) (In Formula 1, R ₁ represents a hydrogen atom or a C ₁ -C ₁₀ alkyl group, R ₂ represents an electron donating group or an aliphatic or aromatic hydrocarbon chain having the electron donating functional group at the end. , Z represents a ligand-binding functional group or ligand-binding compound coordinated to copper, n is an integer from 1 to 10,000) The method of claim 8, wherein the reducing treatment of the copper-containing polymer film is performed by heat treating the copper-containing polymer at a temperature of 150 to 220 ° C. 10. The method of claim 8, wherein the reducing treatment of the copper-containing polymer film is performed by wet treating the copper-containing polymer with a reducing agent. The method of claim 8, wherein the reducing of the copper-containing polymer film is performed by irradiating the copper-containing polymer with light. The method of claim 8, wherein the antimicrobial polymer membrane has bactericidal activity against Escherichia coli. The method of claim 8, wherein the object comprises a fiber, a fabric, a plastic material, an inorganic material, a metallic material, or wood.

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