KR100992889B1 - Antibiotic composite substrate and a method of preparing the same - Google Patents

Abstract

The present invention relates to an antimicrobial composite substrate and a method for preparing the same, and specifically, (a) an organosilicon-based fourth compound in which 0.01 to 5.00 parts by weight of an organosilicon quaternary ammonium compound of formula 3 is dissolved in water based on 100 parts by weight of water. (B) preparing an organosilicon-based quaternary ammonium alginate complex reacting at 20 to 100 ° C. by adding 0.01 to 0.1 parts by weight of an alginate compound with respect to 100 parts by weight of water to the prepared aqueous solution; ; (c) adding 1 to 5.5 parts by weight of an ionic compound based on 100 parts by weight of the prepared composite to prepare antimicrobial bionanoparticles having a size of 1 to 200 nm; And (d) immersing the substrate in a solution containing the prepared antimicrobial bionanoparticles to support the nanoparticles on the substrate. By treatment, excellent antibacterial and deodorizing effect as well as excellent antimicrobial persistence, and relates to an environmentally friendly antimicrobial composite substrate and a method for producing the same.

(3)

_{Si (OR 1) a (CH} 2 -R 2 -N + R 3 R 4 R 5 X -) b

Wherein a + b = 4, a is an integer of 2 or more, b is an integer of 1 or more, R ₁ is an alkyl group of C ₁ -C ₃ , R ₂ is a C1-C25 linear or branched alkyl group, R ₂ , R ₄ , and R ₅ are each independently C 1 -C 12 aliphatic or aromatic hydrocarbons, and X is Br or Cl.

Antimicrobial, Bio, Nanoparticle, Alginate, Quaternary Ammonium, Composite Substrate, Fiber

Description

Antimicrobial composite substrate and method for preparing the same {Antibiotic composite substrate and a method of preparing the same}

The present invention relates to an antimicrobial composite substrate and a method for manufacturing the same. Specifically, the biodegradable natural polymer is chemically modified to be nano-noparticleized and treated to a product, thereby exhibiting excellent antibacterial and deodorizing effect as well as excellent antimicrobial persistence. It relates to an environmentally friendly antimicrobial composite substrate and a preparation method thereof.

With the development of science and technology, the demand for happiness through healthy living is increasing day by day. In recent years, the creation of a hygienic environment is very important due to the increase in the onset of various pathogens due to the occurrence of frequent yellow dust, the occurrence of risky environmental problems and the increase of interest in well-being. From this point of view, research and development for increasing the antimicrobial / deodorization of textile products to increase the hygiene environment to protect the human body with clothing directly surrounding the human body is increasing.

In the late 20th century, as synthetic chemistry developed remarkably, fibers having excellent physical and chemical properties were developed, but the problem of biodeterioration of fibers by microorganisms remains a big problem to be solved. In particular, organic natural fibers such as cotton, hemp, silk and wool, which are mainly composed of cellulose, collagen, keratin and fibroin, are very vulnerable to microorganisms. In addition, when the surface of the fiber is contaminated by organic matter, various microorganisms easily grow on the fiber using contaminants as a nutrient source, thereby causing damage to the product and various health problems.

When wearing textile products, body secretions such as sweat, sebum, and dirt adhere to the fiber surface with organic pollutants and become unsanitary. In the textile products with contaminants, odors are generated, and heat retention and breathability are lowered, resulting in poor fit. In addition, bacteria existing on the skin or microorganisms introduced from the outside generate odorous substances including volatile fatty acids by using organic compounds such as body secretions and pollutants attached to fibers as nutrients. Antibacterial / deodorant processing is a process that prevents the occurrence of odor by killing microorganisms or inhibiting proliferation on textile products.

Early antibacterial agents were used to pursue only antimicrobial effects rather than stability. However, at present, it has a high stability that does not chemically change into toxic substances by reacting with a bleach or detergent that greatly increases the stability, and does not impair the function or condition of the textile product and does not promote embrittlement such as discoloration or yellowing. The situation is moving to antibacterial agents. In addition, the durability and antimicrobial effect of the laundry for home washing and dry cleaning rather than a temporary antimicrobial effect is required.

Furthermore, in the future, antibacterial and deodorizing agents with higher stability are expected to be required. In this regard, high stability means not only laundry durability and antimicrobial durability but also biocompatibility and eco-friendliness. Even if the antibacterial deodorized processed fiber is discarded, discharged, or incinerated, it means that the processing agent has no effect on the ecosystem and living organisms.

In general, antimicrobial agents are required for washing resistance because they are mainly used in products that are in frequent contact with water such as fibers, shoes, scrubbers, medical supplies and the like. In general, when the product is treated with antimicrobial agents, the initial antimicrobial activity is almost 100%, but the antimicrobial activity is significantly reduced by contact with water such as washing.

There are many kinds of antibacterial agents for textile products developed to date. Antimicrobials contain mostly cations, which can disrupt or destroy the cell membranes of anionic bacteria, or diffuse into cells, disrupting metabolism.

On the other hand, antibacterial agents are largely classified into a release type and a fixed type. Release-type antimicrobial agent refers to an antimicrobial agent having a mechanism of slowly releasing an antimicrobial agent and killing bacteria around it. Examples of the antimicrobial agent include inorganic, organometallic, amide, and amphoteric surfactants. In contrast, fixed antimicrobial agents are sometimes referred to as non-release or defensive types, which have a mechanism of killing when bacteria come into contact with the antimicrobial agent while the antimicrobial agent is fixed by adsorption or chemical bonding to a substrate such as fiber. As a representative example thereof, there is an organosilicon quaternary ammonium system.

As described above, the release type antimicrobial has a disadvantage in that the release concentration gradually decreases due to the continuous release of the antimicrobial agent, and thus the antimicrobial activity gradually decreases, thereby reducing durability by repeated washing. On the other hand, since the fixed antimicrobial agent exhibits antimicrobial activity in a fixed state to the fiber, the antimicrobial effect may be relatively longer than that of the release type.

The organosilicon quaternary ammonium salt, a typical example of the fixed antimicrobial agent, has a structure in which a quaternary ammonium salt, which is a cationic surfactant, and silane are combined. Therefore, the silane portion of the antimicrobial agent chemically bonds with a bonding functional group (for example, a hydroxyl group) in the fiber or polymerizes itself to form a thin film on the surface of the fiber to fix the antimicrobial agent to the fiber. There is an advantage that can maintain the antimicrobial power by this property, but is fixed to the fiber by a chemical reaction occurring during the antimicrobial treatment to the fiber, there are the following problems.

1) The antimicrobial activity of the antimicrobial agent may be reduced due to the difficulty of sufficient chemical reaction between the silane group of the antimicrobial agent and the bonding function of the solid fiber. That is, chemical reactions generally have better reaction yields when reactants collide with each other in a freely movable state, but in this case, they are less reactive than liquid-liquid reactions. Will decrease.

2) It is not possible to form a uniform coating film on the fiber and the molecular weight of the resulting compound is not sufficient, so it is likely to detach easily.

3) When the fiber does not have a functional group to bind with the antimicrobial agent, only the antimicrobial agent reacts with each other to form a coating film. Therefore, the formed antimicrobial coating film forms a coating film on the fiber only by physical adsorption on the surface of the fiber. Will be.

4) The feel of fibers due to the coating film formation is reduced.

The above problems are not limited to organosilicon quaternary ammonium salts, but also other fixed antimicrobial agents.

Therefore, in recent years, studies have been conducted to nanofiberize inorganic metals having excellent antimicrobial activity to fibers. In other words, when the nanoparticles with the maximum surface area are treated to the fiber, even if there is no functional group capable of bonding between the nanoparticles and the fibers, they do not easily fall off when washed by simple physical adsorption. It also has the advantage that it does not affect the feel of the fiber, drape or the like. A representative example of such a function is silver nanoparticles. However, these inorganic metal nano particles are superior to organic antimicrobial agents in laundry durability and antimicrobial activity, but have various problems in terms of price and color. In addition, since the precious metal is expensive, there is a disadvantage in that color control is impossible due to the plasma effect of returning to the unique color of the metal.

Therefore, there is an urgent need for a new antimicrobial agent that improves washing resistance regardless of the chemical properties of the fiber, does not impair the inherent properties of the fiber, and retains antimicrobial properties for a long time and does not harm the human body at all.

At present, many studies have been made on the development of antibacterial agents that are harmless to the human body at home and abroad. In particular, researches on the antimicrobial properties of chitosan, titanium dioxide (TiO ₂ ), and silver (Ag) have been reported on the textile fabrics. .

Thus, in Korean Patent Invention No. 253161, an alginate fiber has been proposed, which is prepared by dissolving alginate in water to obtain a solution and spinning it in a water coagulant solution containing chitosan. However, the antibacterial activity of the chitosan is known to exhibit a cationic property due to the amino group of the molecular structure to exhibit an antimicrobial effect. Not all chitosans have a constant antimicrobial activity, but only chitooligosaccharides having a specific range of molecular weight can exhibit antimicrobial activity. However, there are many problems in treating chitosan on textile fabrics, such as low solubility above pH 6.5, low adhesion to textile fabrics, and changes in the texture and texture of the fibers. In addition, in order to firmly attach the chitosan to the textile fabric, the use of a resin or a crosslinking agent stiffens the touch, and the effect of the crosslinking agent of the resin or vinyl compound used on the human body should be confirmed.

Thus, in recent years, researches have been conducted to treat TiO ₂ , a photocatalyst, on fabrics to produce antibacterial fibers that are not toxic to humans. Photocatalyst has antibacterial effect by oxidation and reduction reaction by photoactivity when irradiated with ultraviolet rays. However, the photocatalyst also has an antimicrobial effect only when the concentration on the surface of the fiber is more than 10%, and when the applied concentration is low or the number of cells is high, the antimicrobial effect is inferior. In addition, when TiO ₂ is treated to cotton fabric, a covalent bond is formed between the hydroxyl group of the cotton and the hydroxyl groups of TiO ₂ , so that the initial fiber adhesion rate is large, but the adhesion rate is greatly reduced after 20 times washing.

On the other hand, research has been made to give antimicrobial properties by applying nanoparticles of silver (Ag) with excellent antibacterial power without harming the human body to nanoparticles. However, when the silver colloidal solution is treated to the textile fabric, the initial antimicrobial activity is excellent while the antimicrobial activity is reduced by repeated washing, and the silver particles are reported to be discolored by ozone or sulfur compounds in the air.

In addition, Korean Patent Laid-Open Publication No. 2004-106404 has proposed a fiber and fabric fabric: characterized in that it is finished with a mixture of (a) microencapsulated active ingredient and (b) a binder. However, the microencapsulation is also formed only by physical adsorption, there is a limit in improving the laundry resistance.

In order to solve the above problems, an object of the present invention is to apply the antimicrobial bio-nanoparticles to the substrate without damaging the intrinsic properties of the substrate, can retain the antimicrobial for a long time, to provide an environmentally friendly antimicrobial composite substrate and a method of manufacturing the same It is.

In order to achieve the above object, the present invention provides a step of preparing an aqueous solution of an organosilicon quaternary ammonium compound in which 0.01 to 5.00 parts by weight of an organosilicon quaternary ammonium compound of Formula 3 is dissolved in water; b) preparing the organosilicon-based quaternary ammonium-alginate alginate composite reacting at 20 to 100 ° C. by adding 0.01 to 0.1 parts by weight of an alginate compound based on 100 parts by weight of water to the prepared aqueous solution; (c) adding 1 to 5.5 parts by weight of an ionic compound based on 100 parts by weight of the prepared composite to prepare antimicrobial bionanoparticles having a size of 1 to 200 nm; And (d) immersing the substrate in a solution containing the prepared antimicrobial bionanoparticles to support the nanoparticles on the substrate.

(3)

_{Si (OR 1) a (CH} 2 -R 2 -N + R 3 R 4 R 5 X -) b

Wherein a + b = 4, a is an integer of 2 or more, b is an integer of 1 or more, R ₁ is an alkyl group of C ₁ -C ₃ , R ₂ is a C1-C25 linear or branched alkyl group, R ₂ , R ₄ , and R ₅ are each independently C 1 -C 12 aliphatic or aromatic hydrocarbons, and X is Br or Cl.

The present invention also provides an antimicrobial composite substrate prepared by the above method.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. First of all, it should be noted that in the drawings, the same components or parts denote the same reference numerals as much as possible. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

The terms "about "," substantially ", etc. used to the extent that they are used herein are intended to be taken to mean an approximation of, or approximation to, the numerical values of manufacturing and material tolerances inherent in the meanings mentioned, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.

Sodium alginate (SA), also known as Algin used in the present invention, is a kind of polysaccharides (Polysacaride) extracted from seaweeds such as seaweed, seaweed, kelp, etc., with no toxicity and excellent gel formation ability. It is known, and is represented by the formula (1).

[Formula 1]

The sodium alginate is biodegradable, has excellent biocompatibility, and has been studied as a polymer material for human insertion, and has a characteristic of forming a gel by divalent ions such as calcium or barium. And immobilization of enzymes. As described above, alginate is a material suitable as an environment-friendly antibacterial material that is harmless to the human body and harmless to the human body because it is decomposed in nature.

Thus, the SA is a beta-di-mannuronate (β-D-mannuronate) and alpha-L-guluronate units (α-L-guluronate) unit is bonded by 1-4 glycosidic linkage (glycosidic linkage) a natural high polymer ^{acid, Ca 2+, Mg 2+, Sr} 2+, 2 ions and exhibits a strong affinity for divalent ions of the aqueous solution containing a divalent ion in the alkaline earth metal such as Ba ²⁺ are Na ⁺ While being substituted with ions, it can be rapidly crosslinked to form a gel to form a gel as shown in the following formula (2).

[Formula 2]

On the other hand, although the alginate has biocompatibility and biodegradability, since there is no functional group capable of exhibiting antimicrobial activity by itself, the present invention uses a chemical modification of quaternary ammonium to make these biomaterials exhibit antimicrobial properties. To give antimicrobial properties.

Therefore, in the present invention, a biomaterial having excellent biocompatibility or biodegradability, that is, chemically modified to have antimicrobial deodorization by using alginate, which is a natural polymer extracted from seaweeds such as seaweed and kelp, is nanoparticles The antimicrobial bionanoparticles having excellent performance are to be prepared by the treatment.

1 is a manufacturing process of the antimicrobial composite substrate according to an embodiment of the present invention. Referring to Figure 1, the organosilicon-based quaternary ammonium compound aqueous solution manufacturing step S100, complex manufacturing step S200, antimicrobial bio nanoparticles manufacturing step S300 and may be carried out to the supporting step S400.

First, in step S100 of preparing an aqueous solution of an organosilicon-based quaternary ammonium compound, (a) 0.01 to 5.00 parts by weight of the organosilicon-based quaternary ammonium compound of Formula 3 with respect to 100 parts by weight of water is dissolved in water to organosilicon-based quaternary ammonium Compound aqueous solutions can be prepared.

(3)

_{Si (OR 1) a (CH} 2 -R 2 -N + R 3 R 4 R 5 X -) b

Wherein a + b = 4, a is an integer of 2 or more, b is an integer of 1 or more, R ₁ is an alkyl group of C ₁ -C ₃ , R ₂ is a C1-C25 linear or branched alkyl group, R ₂ , R ₄ , and R ₅ are each independently C 1 -C 12 aliphatic or aromatic hydrocarbons, and X is Br or Cl.

Examples of the organosilicon quaternary ammonium compound of Formula 3 include 3-trimethoxy silyl octadecyl dimethyl ammonium chloride of Formula 4.

[Formula 4]

When the organosilicon-based quaternary ammonium compound is added in less than 0.01 parts by weight, it is difficult to form a complex with the alginate compound to be added later, if it exceeds 5.00 parts by weight, when the antimicrobial bio-nanoparticles production step to be described later, Due to the excess ammonium compound, agglomeration occurs during the reaction between the complex and the ionic compound, so that the size of the particles is too large to form a complex lump of micrometer size or larger than the nano-size may further reduce the effect expression.

Composite preparation step S200 in the aqueous solution is prepared by the (b) the organosilicon-based quaternary ammonium alginate complex reacting at 20 to 100 ℃ by adding 0.01 to 0.1 parts by weight of the alginate compound with respect to 100 parts by weight of water in the prepared aqueous solution Steps may proceed.

When the alginate compound is added in less than 0.01 parts by weight, the addition amount of SA is too low, the antimicrobial expression is insignificant, when it exceeds 0.1 parts by weight, in the step of producing antimicrobial bio-nanoparticles to be described later, the alginate compound is more than 0.1 parts by weight Aggregation occurs during the reaction between the prepared TSA-SA complex and the ionic compound, the particle size is not a nano size of a complex size of more than μm size may be further reduced the effect expression.

The alginate compound may be selected from ammonium alginate, sodium alginate, potassium alginate, calcium alginate, propylene glycol alginate, alginic acid and mixtures thereof, with sodium alginate being preferred.

The organosilicon quaternary ammonium alginate complex of the present invention may be any reactant of the organosilicon quaternary ammonium compound and the alginate compound.

Thus, the organosilicon quaternary ammonium alginate complex of the present invention is a 3-trimethoxy silyl octadecyl dimethyl ammonium chloride-sodium alginate complex represented by Formula 5 prepared according to Scheme 1 below ([{3- (Trimethoxysilyl ) propyl} octadecyl dimethylammonium chloride] -Sodium alginate Complex (hereinafter, TSA-SA complex) is preferred.

Scheme 1

In Scheme 1, trimethoxy silyl octadecyl dimethyl ammonium chloride [{3- (Trimethoxysilyl) propyl} octadecyl dimethylammonium chloride; TSA] is added to an aqueous solution prepared by adding 0.01 to 5.00 parts by weight based on 100 parts by weight of water (pure). Sodium alginate (SA) is added in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of water, dissolved, and reacted at a temperature of 40 to 100 ° C. to prepare a TSA-SA composite.

In the reaction, SA having a hydroxyl group (-OH) capable of forming a crosslink with TSA is dissolved in water to cause a liquid phase reaction, thereby causing a mutual covalent reaction. Accordingly, TSA is a hydroxyl group (-OH) is formed by dissociation of methoxy group (-OCH ₃ ) by water, the hydroxyl groups of the formed TSA reacts with the hydroxyl group of SA to form a covalent bond such as CO-Si, TSA- SA complexes may be formed.

Then, the antimicrobial bionanoparticles manufacturing step S300 to the prepared TSA-SA complex (c) 1 to 5.5 parts by weight of the ionic compound is added to 100 parts by weight of the prepared complex to prepare antimicrobial bionanoparticles of 1 to 200nm size. The step may proceed.

Using the property of the ion such as the alginates of the prepared TSA-SA complex calcium ions (Ca ^{2 +),} or barium ion (Ba ^{2 +)} Compound 2 is rapidly combined with the ion to form a gel, the above-prepared The antimicrobial bionanoparticles of the present invention can be prepared by dropwise addition of calcium chloride (CaCl ₂ ) solution to the TSA-SA complex. The ionic compound is preferably added in 1 to 5.5 parts by weight based on 100 parts by weight of the TSA-SA composite. If the ionic compound is added in less than 1 part by weight, the antimicrobial expression is insignificant, and if it exceeds 5.5 parts by weight, it is difficult to form nano-sized particles due to the association of the excess amount of the ionic compound.

The ionic compound is a compound containing an element selected from the group consisting of Be, Mg, Ca, Sr, Ba, Ra, Ag, Cu, Zn, Sn, Pt, Ti, Ge and mixtures thereof, CaCl ₂ or BaCl ₂ And the like are more preferred.

In addition, in the production of the antimicrobial bionanoparticles of the present invention, it is preferable to form the ionic compound by dropwise addition to the aqueous TSA-SA composite solution. This is because when the aqueous solution of the complex is added dropwise to the ionic compound, the complex is aggregated to the ions of the ionic compound to form nanoscale formation.

The prepared antimicrobial bionanoparticles preferably have a size of 10 to 200 nm, more preferably 50 to 150 nm. When the size of the bio-nanoparticles is less than 50 nm, it is difficult to form the particles. When the size of the bio-nanoparticles exceeds 200 nm, nanoparticles are aggregated as a result of containing a large amount of the organosilicon-based quaternary ammonium-alginated alginate polymer composite. This might happen.

Finally, in step S400 of supporting the antimicrobial bionanoparticles on which the prepared antimicrobial bionanoparticles are supported, the substrate is immersed in a solution containing the prepared antimicrobial bionanoparticles and the antimicrobial bionanoparticles on the substrate. After carrying out the supporting step, the antimicrobial composite substrate carrying the antimicrobial bionanoparticles of the present invention may be prepared.

Applying the prepared antimicrobial bionanoparticles to the substrate, the substrate may be a fiber, wallpaper, antifouling paint, and the like, but is not limited thereto.

Accordingly, the present invention provides an antimicrobial composite substrate prepared by the above method. The present invention also provides an antimicrobial composite substrate for fibers, wallpaper, or paint as the antimicrobial composite substrate.

As a preferred embodiment of the present invention as a substrate, it will be described an application example to a textile product, but is not limited thereto.

In general, when the nanoparticles of the polymer is treated to the fiber, not only does it have a property of not being easily dropped by washing due to the large surface area regardless of the property of the fiber material, but also does not harm the inherent properties of the fiber. Have.

Therefore, the alginate modified to exhibit the antimicrobial properties of the present invention can be nano-processed to the fiber.

Generally, antibacterial and deodorizing fibers are processed by treating antimicrobial agents to fabrics, and there are yarn improvement methods in which antimicrobial agents are incorporated in the polymerization and spinning stages of the fibers, and post-treatment processing methods in which the antimicrobial agents are treated to the fabric in the final stage of dyeing. Since the antimicrobial bionanoparticles prepared in the present invention are in the form of organic polymers, they are more suitable for post-treatment processing than for yarn improvement.

The post-treatment processing method has a variety of methods, such as spray method, dipping method, padding method, coating method, lamination method, the most commonly used dipping method and padding method.

Among the fibers treated with the antimicrobial bionanoparticles of the present invention, in particular, natural fibers have a functional group capable of bonding with other substances such as hydroxyl groups, and the antimicrobial bionanoparticles of the present invention also have a hydroxyl group, so that besides physical adsorption, Covalent bonds are formed between the fibers and the nanoparticles, so that the washing resistance can be exerted.

As described above, the antimicrobial bionanoparticles of the present invention exhibit excellent antimicrobial activity against a wide range of microorganisms and have low toxicity and are harmless to humans and the environment.

In addition, the composite substrate treated with the antimicrobial bionanoparticles of the present invention retains antimicrobial activity for a long time even after repeated use or washing, and does not discolor the object due to no discoloration by light (light).

In addition, when manufacturing the antimicrobial composite substrate of the present invention, by applying a pre-designed ratio there is an effect that is easily produced by mixing without a special device.

In addition, the antimicrobial composite substrate of the present invention can be applied to any place where antimicrobial properties such as wallpaper, antifouling paint as well as fibers are required.

Through the following examples will be described in more detail.

Example  One

0.05 g of sodium alginate (SA) was dissolved in TSA aqueous solution in which 0.05 g of {3- (Trimethoxysilyl) propyl} octadecyl dimethylammonium chloride (TSA) was dissolved in 100 ml of deionized water (DIWater). Liquid phase reaction at to prepare a TSA-SA complex.

1 is an infrared spectroscopy (FT-IR) result of an organosilicon quaternary ammonium ammonium alginate according to a preferred embodiment. Referring to FIG. 1, (a) shows the results of infrared spectroscopy of sodium alginate (SA), and the characteristic peak of the hydroxyl group (-OH) of SA was found at 3,400 cm ⁻¹ , and (b) As a result of infrared spectroscopy of {3- (Trimethoxysilyl) propyl} octadecyl dimethylammonium chloride (TSA), it can be seen that the characteristic peak of TSA's long alkyl chain (C ₁₈ H ₃₇ ) is large at 2,800-2,900 cm-1. . In addition, (c) is an infrared analysis of the TSA-SA conjugate produced by the above reaction, when viewed as a group of TSA may appear at the same time in 3,400 cm ^-1 from a hydroxyl group (-OH) and the SA ^-1 2,800-2,900cm It can be seen that the TSA-SA complex was prepared.

10 ml of calcium chloride (CaCl ₂ ; 20 mM) was added dropwise to the prepared TSA-SA complex to prepare the antimicrobial bionanoparticles of the present invention.

2 is a SEM photograph of the antimicrobial bionanoparticles according to Example 1 of the present invention. Referring to Figure 2, it can be seen that the fine nanoparticles of 1㎛ or less formed in the shape of a sphere.

Example 2

It was prepared in the same manner as in Example 1 except adding 0.25 g of TSA.

Example 3

Prepared in the same manner as in Example 1, except adding 0.50 g of TSA.

Example  4

It was prepared in the same manner as in Example 1 except adding 1.00 g of TSA.

Example  5

Prepared in the same manner as in Example 1, except adding 2.50 g of TSA.

The prepared antimicrobial bionanoparticles are shown in Table 1 below.

TABLE 1

division D.I.Water SA TSA 20 mM CaCl ₂ Particle size unit ml g g ml nm Example 1 100 0.05 0.05 10 99.4 ± 19.5 Example 2 100 0.05 0.25 10 117.1 ± 13.6 Example 3 100 0.05 0.50 10 159.2 ± 49.3 Example 4 100 0.05 1.00 10 166.8 ± 74.6 Example 5 100 0.05 2.50 10 169.6 ± 61.2

In the results of Table 1, it can be seen that nanoparticles having a size of 100 to 200 nm were prepared. As the concentration of the TSA increases, the size of the particles increases.

Example  6

The cotton fabric was immersed in the antimicrobial bionanoparticle colloid solution prepared in Example 1 for about 1 minute and dried at 120 ° C. to prepare a cotton fabric treated with the antimicrobial bionanoparticles.

Example  7

The cotton fabric was immersed for 1 minute in a colloidal solution in which the amount of the antimicrobial bionanoparticles prepared in Example 1 was increased to 40 ppm, and then dried at 120 ° C. to prepare 40 ppm of the antimicrobial bionanoparticles.

Example 8

The antimicrobial bionanoparticles prepared in Example 1 was prepared in the same manner as in Example 7, except that the amount was increased to 60 ppm.

Example 9

The antimicrobial bionanoparticles prepared in Example 1 was prepared in the same manner as in Example 7, except that the amount was increased to 80 ppm.

Comparative example  One

Regular cotton fabrics were prepared.

3A is a SEM photograph of a cotton fabric according to Comparative Example 1. FIG.

Figure 3b is a SEM picture of a cotton fabric treated with antimicrobial bio nanoparticles according to Example 6 of the present invention. Referring to Figure 3b, it can be seen that the antimicrobial bio nanoparticles of the present invention are evenly distributed on the cotton fabric.

* Test Methods

1. Antibacterial activity

In order to investigate the antimicrobial activity of the cotton fabric treated with the antimicrobial bionanoparticles prepared in Example 6 of the present invention, Escherichia coli (E. coli) ATCC25922, Staphylococcus aureus ATCC 6538P, which is considered as a representative pathogenic microorganism, was investigated.

Evaluation of the antimicrobial activity was put into 1.5 g of cotton fabric treated with the antimicrobial bionanoparticles of the present invention in a test cell suspension of bacteria number 10 ⁷ CFU / ml through the pre-culture, 6 to 8 hours at a speed of 150 rpm / 37 at 37 ℃ After vibrating incubation, the number of viable cells before and after incubation was measured by continuous dilution plate using the following equation.

Percentage reduction = (B-A) / B × 100

A: Number of bacteria per ml in the flask after shaking

B: Number of bacteria per ml in flask before shaking

At this time, only the microbial solution was tested as a control group without adding a sample, and the microbial reduction rate was less than 10%, and only the microbial reduction rate for an untreated sample was 30% or less.

1) E. coli

Juicy medium consisting of 10 g of Bacto-peptone, 5 g of Beef extract, 5 g of NaCl, and 1000 ml of distilled water was used as E. coli ATCC 25922 as a culture strain, and cultured for 24 hours at 37 ° C., which was used as an E. coli culture. 1.5 g of the bio-nanoparticle treated cotton fabric was chopped and placed in 100 ml of distilled water, inoculated with 1 ml of a previously prepared pathogenic microbial culture, and shaken at 37 ° C. and 250 rpm for 1 hour. After shaking for 1 hour, 1 ml of shake was collected and cultured for 24 hours using a Nutrient agar plate. The number of viable cells was counted by continuous dilution plate culture method. The results are shown in Table 2.

2) Staphylococcus aureus

Culture medium using S. aureus ATCC 6538P consisted of Digest of casein 13.6 g, Papaic digest of soybea meal 2.4 g, Dextrose 2 g, Dipottasium phosphate 2 g, NaCl 4 g, distilled water 1000 ml. Culture conditions were incubated at 37 ℃ for 24 hours, and then a certain amount (1 ml) was taken and contacted with the bio-nanoparticle treated cotton fabric and shaken at 37 ℃, 250 rpm. After shaking for 1 hour, 1 ml of shaking solution was collected, and the number of viable cells was counted by continuous dilution plate culture. The results are shown in Table 2.

TABLE 2

bacteria Viable Count (CFU / ml) Initial number of inoculated bacteria Comparative Example 1 Example 6 E. coli 1.7 × 10 ⁷ 1.5 × 10 ⁷ 0 S. aureus 2.2 × 10 ⁷ 1.9 × 10 ⁷ 0

2. Laundry resistance investigation

After washing the textile fabric in a washing machine in a water at 40 ° C. containing a certain amount of detergent (10, 20, 30 times) (washing method: KS K 0432), the remaining antibacterial activity was investigated and shown in Table 3 below.

[Table 3]

Washing count (times) bacteria Viable Count (CFU / ml) Initial number of inoculated bacteria Comparative Example 1 Example 6 10 E. coli 1.2 × 10 ⁷ 1.9 × 10 ⁷ 0 S. aureus 1.7 × 10 ⁷ 2.1 × 10 ⁷ 0 20 E. coli 1.8 × 10 ⁷ 1.5 × 10 ⁷ 1.2 × 10 ² S. aureus 2.1 × 10 ⁷ 1.6 × 10 ⁷ 0 30 E. coli 1.1 × 10 ⁷ 1.3 × 10 ⁷ 1.3 × 10 ³ S. aureus 1.5 × 10 ⁷ 2.0 × 10 ⁷ 0

In the results of Table 3, in the case of E. coli , the antimicrobial bionanoparticles of the present invention were treated with cotton fabric, that is, no detection until 10 washes in Example 6, but bacteria were detected in 20 and 30 washes. , Bactericidal rate is still more than 99.9%, it can be confirmed that the antimicrobial activity was not lowered even after dozens of washings, in the case of S. aureus bacteria are not detected at all even after 30 washes, the antimicrobial bio nanoparticles of the present invention is treated It was confirmed that the washing durability of the cotton fabric was excellent.

Figure 4a is a SEM photograph of the cotton fabric treated with antimicrobial bio nanoparticles after washing 10 times in accordance with Example 6 of the present invention.

Figure 4b is a SEM photograph of the cotton fabric treated with antimicrobial bio nanoparticles after washing 20 times in accordance with Example 6 of the present invention.

Figure 4c is a SEM photograph of the cotton fabric treated with antimicrobial bio nanoparticles after washing 30 times in accordance with Example 6 of the present invention.

4a to 4c, it can be seen that as the number of washing increases, the amount of antimicrobial bio-nanoparticles detached from the cotton fabric is not high, and still attached to the cotton fabric after 30 washings.

3. Investigation of washing resistance according to throughput of antimicrobial bionanoparticles

The textile fabric was washed 40 times in a washing machine at 40 ° C. containing a certain amount of detergent (washing method: KS K 0432) and the remaining antibacterial activity was investigated.

1) Candida albicans

C. albicans ATCC 11651 is a type of yeast that causes pathogens such as dermatitis, oralitis, athlete's foot, and esophagitis in humans. The culture medium of this strain was 10 g of Yeast extract, 20 g of Bacto peptone, 20 g of Glucose, and 1000 ml of distilled water. The culture conditions were used at 37 ° C. for 24 hours. The culture conditions were incubated for 24 hours at 37 ℃ and take a certain amount (1 ml) and contacted each cotton fabric as a sample and shaken at 37 ℃, 250 rpm. After shaking for 1 hour, 1 ml of shaking solution was collected, and the number of viable cells was counted by continuous dilution plate culture. The results are shown in Table 4.

[Table 4]

division Initial vaccination
Bacteria Comparative Example 1 Example 6 Example 7 Example 8 Example 9 Candia albicans
Viable Count (CFU / ml) 1.2 × 10 ⁷ 2.5 × 10 ⁶ 9.2 × 10 ⁵ 3.3 × 10 ³ 2.1 × 10 ³ 1.8 × 10 ³

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the inventions. It will be clear to those who have knowledge of.

1 is a manufacturing process of the antimicrobial composite substrate according to an embodiment of the present invention.

2 is an infrared spectroscopy (FT-IR) result of an organosilicon quaternary ammonium ammonium alginate according to a preferred embodiment.

Figure 3 is a SEM photograph of the antimicrobial bio nanoparticles according to Example 1 of the present invention.

4A is a SEM photograph of a cotton fabric according to Comparative Example 1. FIG.

Figure 4b is a SEM photograph of a cotton fabric treated with antimicrobial bio nanoparticles according to Example 6 of the present invention.

Figure 5a is a SEM photograph of the cotton fabric treated with antimicrobial bio nanoparticles after washing 10 times in accordance with Example 6 of the present invention.

Figure 5b is a SEM photograph of the cotton fabric treated with antimicrobial bio nanoparticles after washing 20 times in accordance with Example 6 of the present invention.

Figure 5c is a SEM photograph of the cotton fabric treated with antimicrobial bio nanoparticles after washing 30 times in accordance with Example 6 of the present invention.

Claims (8)

(a) preparing an aqueous solution of an organosilicon quaternary ammonium compound in which 0.01 to 5.00 parts by weight of an organosilicon quaternary ammonium compound of Formula 3 is dissolved in water; (b) preparing an organosilicon-based quaternary ammonium alginate complex reacting at 20 to 100 ° C. by adding 0.01 to 0.1 parts by weight of an alginate compound to the aqueous solution of the organosilicon-based quaternary ammonium compound prepared above ; (c) preparing an antimicrobial bionanoparticle having a size of 1 to 200 nm by dropwise adding 1 to 5.5 parts by weight of an ionic compound to 100 parts by weight of the organosilicon-based quaternary ammonium alginate composite; And (d) immersing the substrate in a solution containing the prepared antimicrobial bionanoparticles to support the nanoparticles on the substrate; Method for producing an antimicrobial composite substrate comprising a. (3) _{Si (OR 1) a (CH} 2 -R 2 -N + R 3 R 4 R 5 X -) b Wherein a + b = 4, a is an integer of 2 or more, b is an integer of 1 or more, R ₁ is an alkyl group of C ₁ -C ₃ , R ₂ is a C1-C25 linear or branched alkyl group, R ₂ , R ₄ , and R ₅ are each independently C 1 -C 12 aliphatic or aromatic hydrocarbons, and X is Br or Cl. The method of claim 1, The alginate compound is a method for producing an antimicrobial composite substrate selected from ammonium alginate, sodium alginate, potassium alginate, calcium alginate, propylene glycol alginate, alginic acid and mixtures thereof. The method of claim 1, The alginate compound is sodium alginate of Formula 1, The organosilicon quaternary ammonium compound is organosilicon quaternary ammonium compound of formula (4) prepared by the reaction of 3-trimethoxysilylpropyloctadecyl dimethylammonium chloride] {3- (Trimethoxysilyl) propyl} octadecyl dimethylammonium chloride] A method for producing an antimicrobial composite substrate, wherein the compound is an alginate complex. [Formula 1]

[Formula 4]

[Chemical Formula 5]

The method of claim 1, The ionic compound is a compound containing an element selected from the group consisting of Be, Mg, Ca, Sr, Ba, Ra, Ag, Cu, Zn, Sn, Pt, Ti, Ge and mixtures thereof. The method of claim 1, The ionic compound is CaCl ₂ or BaCl ₂ method for producing an antimicrobial composite substrate. The method of claim 1, wherein the substrate is a fiber, wallpaper, or paint. An antimicrobial composite substrate prepared by the method of any one of claims 1 to 6. The antimicrobial composite substrate of claim 7 is an antimicrobial composite substrate for fibers, wallpaper, or paint.

Images