KR20050077998A - Antibiotic silver-egg membrane protein complex, antibiotic material coated with silver-egg membrane protein complex and a method for preparing the same - Google Patents

Abstract

The present invention relates to a silver egg shell membrane protein complex and its powder obtained by mixing and heating a silver-containing compound selected from an egg shell membrane, silver nitrate (AgNO ₃ ) or silver sulfate (Ag ₂ SO ₄ ), a reducing agent, and an optional deodorant, and then adding an oxidizing agent. And an egg shell membrane, a silver-containing compound, a reducing agent, and a rosin resin were mixed and heated, and then an oxidizing agent solution containing an aqueous hydrogen peroxide solution (3 to 35% by weight) and a quaternary ammonium salt solution (10 to 50% by weight) was added thereto. A method for preparing an antimicrobial silver egg shell protein composition and an antimicrobial silver egg shell protein binding comprising mixing and heating an egg shell membrane, a silver containing compound, and a reducing agent, coating the mixture on a material, and immersing the material in an oxidant. It relates to a method for producing a material. The present invention provides an antimicrobial material excellent in human affinity and color fastness by imparting antimicrobial property to fibers, leather, wallpaper, super medium, paper, wood, paint and the like.

Description

Antibiotic Silver-Egg Membrane Protein Complex, Antibiotic Material Coated With Silver-Egg Membrane Protein Complex And A Method For Preparing The Same}

The present invention relates to an antimicrobial silver-vehicle membrane protein complex and its powder, an antimicrobial material coated with silver-veil membrane protein complex and a method for producing the same. More specifically, the present invention relates to an antimicrobial silver-ovary membrane protein complex in which silver is finely dispersed by binding ionic silver to the egg shell membrane protein, a powder of the complex, and an antimicrobial material coated with the silver-vehicle membrane protein complex and a method of preparing the same. will be.

Conventionally, egg shells obtained after using egg whites and egg yolks such as eggs are discarded, or in some cases, egg shell membranes are separated and removed, and egg shells, which are shells, have been used as calcium for food or livestock feed. In this case, the discarded eggshell membrane may be preferable in terms of recycling resources while preventing environmental pollution.

Techniques for separating egg shells and egg shells have already been developed (Korean Patent Registration Nos. 335476 and 406929), but little technology using egg shells has been developed. As a technique for using egg shell membranes, a technique of hydrolyzing egg shell membranes with alkali and using them as a colorant for aqueous paints (Korean Patent Application No. 2003-47562), and processing the egg shells and egg shells together to prepare a calsite compound, Only a very small number of technologies are used as raw materials (Korean Patent Application No. 2001-1951).

Silver is widely known as a non-toxic antibacterial metal. Silver-containing fibers and yarns are known to block electromagnetic waves, prevent static electricity, have heat insulation, thermal insulation, and antibacterial properties, and their use is increasing.

Silver-containing fibers are generally manufactured by melting silver yarns, and are used by mixing and weaving with common fiber yarns. However, the method of manufacturing the silver horn fiber is difficult to effectively exhibit the antimicrobial activity against microorganisms of several nm or less due to the high production cost of the silver and difficult to finely distribute the silver to several micrometers or less, and it is not uniform in the horn fiber weaving. There was a problem that it was difficult to show antibacterial properties.

In addition, there is a method of preparing fine powdered silver or neutralizing it by supporting silver nitrate on porous such as silica and drying to prepare powder and coating it on the fiber using synthetic resin as a binder to use it as antimicrobial silver fiber. Low washout rate was high, or the synthetic resin emulsion was used as a binder.

In the present invention, by dispersing by using a silver ion binding reaction having a size of 0.5nm or less to obtain an antimicrobial silver-warm membrane protein complex which enables ultrafine distribution of silver. Therefore, finely distributed silver shows excellent antimicrobial activity, and due to fine dispersion, the specific surface area is large, and the antimicrobial efficiency is high. In addition, after disassembling the disulfide chain in the egg shell membrane protein, the silver-vessel membrane protein penetrates into the fibrous tissue, and the fastness is excellent in the recombination reaction of the disulfide by the oxidizing agent. In addition, by using the eggshell protein, which is a natural material, as a binder, the human friendliness is excellent, and the resource recycling property is high by using the discarded eggshell membrane.

The present inventors have developed a silver-vessel membrane protein complex that improves the adhesion of silver and recycles resources by manufacturing a complex of egg shell membranes and silver in order to solve the problems of the prior art related to silver (Ag) -containing antimicrobial materials and to recycle the discarded resources. It was.

It is an object of the present invention to provide an antimicrobial silver-warm membrane protein complex and powder thereof which can be utilized to impart antimicrobial properties to various materials using antimicrobial egg shell membrane proteins as binders of silver ions.

Another object of the present invention is to develop an environment-friendly high value-added antimicrobial product using a egg shell membrane which is a natural substance instead of a chemical binder to disperse silver.

It is still another object of the present invention to provide an antimicrobial material and a method for producing the same, which enhance the antimicrobial efficiency by expanding the specific surface area of silver by ion-bonding the carboxyl group of the egg shell membrane and distributing the silver in ultrafine units.

Another object of the present invention is to reduce the manufacturing cost by shortening the process by dispersing the silver without using a separate bonding process using a chemical binder, it provides a human-friendly non-toxic material by using the egg shell of the egg as a food by-product as a binder will be.

The present invention is obtained by mixing and heating a egg-containing membrane, a silver-containing compound selected from silver nitrate (AgNO ₃ ) or silver sulfate (Ag ₂ SO ₄ ), and a reducing agent, followed by heating and then oxidizing agent, and obtaining and drying and pulverizing the silver egg shell membrane protein complex. It relates to a composite powder. In addition, the present invention provides various antimicrobial materials obtained by coating the composite and a method of manufacturing the same.

The first aspect of the present invention is a silver-containing compound (B), a reducing agent (C) and an optional rosin resin deodorant (E) selected from an egg shell membrane (A), silver nitrate (AgNO ₃ ) or silver sulfate (Ag ₂ SO ₄ ). The present invention relates to a silver egg shell protein complex obtained by mixing and heating at a temperature of 30 to 100 ° C. followed by administration of an oxidizing agent (D). Since the composite is finely dispersed in silver, when applied to a material for providing antimicrobial properties, the composite may exhibit high antimicrobial properties, and may be used to impart antimicrobial properties to various materials.

The second aspect of the present invention relates to a powder obtained by drying and pulverizing the silver egg shell protein complex as described above, the complex can be easily used in a variety of materials through powdering.

For example, the powder may be mixed with an organic solvent such as urethane or acrylic, and then applied to a surface of a non-absorbent product such as vinyl, plastic, or wood, or used as a raw material in melt extrusion of synthetic fibers or injection molding of plastic products. It can be mixed and used, and can also be mixed and used for raw materials of various paints or chemical products. Drying takes place at 40 to 90 ° C., and grinding is carried out using a general mill. Drying and grinding processes can be easily carried out by those skilled in the art.

The antimicrobial silver-warm membrane protein complex or powder thereof is mixed with a resin such as polyurethane, polyacrylic, saturated or unsaturated polyester, polyamide, polyvinyl chloride, silicone, natural fibers such as cotton, hemp, wool, natural yarn, Synthetic fibers, synthetic yarns, paper, leather, wallpaper, construction materials such as paper, floorboards and paints, mixed or coated with wood, or chemical products such as antibacterial sprays, soaps, shampoos, hair care products, fabric softeners and laundry detergents. It can be used as an additive. The manufactured materials are used in various fields such as feminine hygiene products, diapers, and clothes.

Hereinafter, each component of the present invention will be described in detail.

(A) Egg Membrane

The egg shell is the egg shell of eggs such as eggs, and is mainly produced as a by-product of egg white and egg yolk. At this time, the by-products are in the state that the outer shell (egg) and inner shell (egan eggshell or egg shell) are attached, but the outer shell is separated from calcium and used for food or feed. In this case, the separated cuticle, which occupies about 4 to 5% of the outer shell, is used as the egg shell membrane used in the present invention, and can be used as it is without discarding artificial treatment. In general, the egg shell membrane A separated from the egg contains a certain amount of water, and the pure solid content excluding water accounts for 5 to 30% by weight.

This egg shell membrane is composed of fibrous, spongy structure with a thickness of 0.01 to 0.02 mm, and its major amino acids are histidine (C ₆ H ₉ N ₃ O ₂ ) and cystine (Cystine / C ₆ H _12). N ₂ O ₄ S ₂ ), proline (Proline / Formula: C ₅ H ₉ NO ₂ ) keratin, collagen, and the like molecular weight of about 100,000 or more fibrous structural protein or light protein.

In the present invention, the silver ions in the silver-containing compound are combined with the carboxyl groups in the amino acids constituting the eggshell membrane protein to form an ultrafine distribution of molecular units, thereby tightly binding silver to the subject.

In addition, amino acids, such as cystine in eggshell membranes, have an oxidation-reversible reversible functional group, such as a disulfide group, which is an important component to allow silver to be firmly attached to the material.

That is, when the disulfide bond in the egg shell membrane protein is reduced to the mercapto group by a reducing agent, it becomes an aqueous solution which is well dissolved in water and finely distributed, and is easily applied or filled to a subject to be coated with silver such as fiber. After that, when the disulfide bond is restored by the oxidizing agent, excellent fastness can be given.

(B) silver-containing compound

Silver (Ag) in this invention is a raw material which gives antimicrobial property and heat retention to a material.

Silver ions of silver-containing compounds and carboxyl groups of egg shell membrane proteins ionically bind to form antimicrobial silver proteins.

The silver-containing compound may be any general compound capable of providing silver ions (Ag ⁺ ), but silver nitrate (AgNO ₃ ) or silver sulfate (Ag ₂ SO ₄ ) is particularly preferable.

(C) reducing agent

The reducing agent according to the present invention is for reducing disulfide bond (SS) in egg shell membrane protein to mercapto group (-SH HS-), and a general reducing agent such as an aqueous alkali solution may be used, but sodium hydroxide (NaOH) or potassium hydroxide (KOH) may be used. The aqueous solution containing alkali metal salts, such as), is the most preferable. These substances are strongly alkaline to break disulfide (S-S) bonds of eggshell membrane proteins and bind to hydrogen to substitute mercapto group (-SH HS-) structures. At this time, the initial egg shell membrane protein, which was flake-like by the reducing agent, dissolves in the disulfide skeleton and is dispersed in a particulate form.

Most preferably, it is used in the form of an aqueous alkali solution containing 10 to 50% by weight of sodium hydroxide or potassium hydroxide.

(D) oxidizing agent

The oxidizing agent according to the present invention oxidizes the mercapto group (-SH HS-) formed by the above reduction reaction to restore to disulfide (S-S) bond, and at the same time, silver protein is fixed to a material for providing antimicrobial activity, thereby improving fastness.

Citric acid, hydrogen peroxide, hydrochloric acid, acetic acid, formic acid, or sulfuric acid are used as the oxidizing agent. Of these, odorless citric acid, which is used for food and has excellent human friendliness, is most preferred. However, when the material is made of natural leather or wallpaper which cannot undergo washing or refining process, it is preferable to use hydrogen peroxide having self-extinction by exposure to air. desirable.

The oxidizing agent is preferably used in the form of an aqueous solution containing 3 to 20% by weight of each oxidizing agent.

In addition, 0.1 to 5 parts by weight of a quaternary ammonium salt solution (10 to 50% by weight) may be used in 100 parts by weight of an aqueous solution of hydrogen peroxide (3 to 35% by weight). Quaternary ammonium salts act as antimicrobial and oxidation aids, providing flexibility to the product and acting as a water stabilizer. The mixed oxidant is particularly useful in preparing one-part silver egg shell protein compositions.

(E) Deodorant

The present invention uses a deodorant such as rosin as a remover of the odor caused by the egg shell membrane.

Rosin base is a natural resin obtained by distilling rosin. It is pale yellow or brown, transparent and glassy gloss. Its main ingredients include abiete acid (C ₂₀ H ₃₀ O ₂ ), neo-abiate acid, and repopi. It contains resinous acids such as maric acid, hydroabietic acid, fimaric acid and dextonic acid, and also contains a small amount of ash.

When the rosin is heated, rosin penetrates deeply into the spongy body of the egg shell membrane protein and binds to release the odor and give a unique brush. In addition, after the combination of the silver and the protein is applied to the surface inhibits the separation of silver and protein, and also serves to enhance the adhesive strength when applied to the fiber and the like.

The third aspect of the present invention provides a method for producing an antimicrobial silver-vessel membrane protein binding material comprising mixing and heating an egg shell membrane, a silver-containing compound, and a reducing agent, coating the mixture on a material, and immersing the material in an oxidant. It is about. In order to remove the smell of the egg shell during the manufacturing process, the egg shell membrane and the silver-containing compound may be mixed, and then a deodorant such as rosin resin may be further added.

The manufacturing method will be described in detail as follows.

100 parts by weight of an aqueous solution containing 20 to 50% by weight of the eggshell membrane (A) and 0.5 to 30 parts by weight of an aqueous solution containing 1 to 30% by weight of silver-containing compound (B) (silver content of about 10,000 to 200,000 ppm) are mixed. At this time, the carboxyl ion (COO ⁻ ) in the egg shell membrane protein (COO ⁻ · P · NH ₃ ⁺ ) attracts the silver ions (Ag ⁺ ) of the silver-containing compound, resulting in electrostatic bonding and due to the strong binding capacity of COO ⁻ Silver ions enter the protein complex to form stable ionic bonds. Silver ions crosslink and bind to two or more polypeptides to form a silver-protein conjugate. This reaction is a silver transition process and the reaction conditions are preferably performed for 5 to 60 minutes at a temperature of 30 to 100 ℃. The reaction time may be changed by those skilled in the art according to the content of the raw material.

As the silver transition (silver-containing compound) of the present invention, silver nitrate or silver sulfate is used.

The deodorization process then optionally takes place. Since the eggshell membrane is used separately from eggs, a characteristic smell such as egg fishy smell may remain, and thus the deodorizing process (E) such as rosin paper is carried out.

Rosin paper can also be processed into liquid rosin paper as follows.

30 to 130 parts by weight of water is added to 100 parts by weight of rosin paper, and 30 to 230 parts by weight of sodium hydroxide or potassium hydroxide solution (solid content of 10 to 45%) is added thereto and mixed for 5 to 180 minutes at a heating temperature of 45 to 100 ° C. Hydrolysis to prepare a liquid rosin paper. 0.5 to 30 parts by weight of the pre-formed liquid rosin paper is added to the mixture of 100 parts by weight of the aqueous solution of the egg shell membrane and 0.5 to 35 parts by weight of the silver nitrate solution. In the present invention, the rosin paper is defined as including not only a general rosin paper, but also a liquid rosin paper prepared as described above.

Then, 0.5 to 30 parts by weight of an aqueous solution of sodium or potassium hydroxide (solid content of 10 to 50%) was added to the mixture as a reducing agent (C), followed by reduction for 30 to 360 minutes at a temperature of 60 to 110 ° C, followed by cooling to 35 ° C or less. Let's do it. In this process, the disulfide bond (-S-S-) of the egg shell membrane protein is cleaved and the mercapto group (-SH HS-) is formed by binding to hydrogen (H). This forms a water-soluble compound of hydrolyzed microparticles, thereby forming a water-soluble liquid that is capable of dipping or coating the material. At this time, some of the silver ions bonded to the carboxyl group are combined with the hydroxyl group of the reducing agent to change into a brown silver hydroxide (AgOH) state.

The resulting mixture can be ground using a grinder such as a mixer if necessary.

0.1 to 30 parts by weight of the aqueous solution containing the silver-warmed membrane protein complex prepared as described above is mixed with 100 parts by weight of water and diluted, and the diluent is coated with a material to be coated with silver, for example, cotton, nylon, polyester, acrylic, and the like. Materials such as fabrics, threads, natural leather, synthetic leather, wallpaper, paper, pulp and wood are immersed or coated with knives, sprays and rollers. After dipping, the material is sufficiently wetted with diluent to remove excess liquid and dried at 50 to 100 ° C. for 10 seconds to 3 hours.

Then use 1 to 30% aqueous solution of citric acid, hydrogen peroxide, hydrochloric acid, acetic acid, formic acid, or sulfuric acid as oxidizing agent (D), or quaternary ammonium salt aqueous solution (10 to 10 parts by weight) in 100 parts by weight of aqueous hydrogen peroxide solution (3 to 35%). 50%) The oxidation process is carried out using a mixture of 0.5 parts by weight. The amount of the oxidizing agent used is sufficient in an amount sufficient to sufficiently immerse the material, and is not particularly limited. The material is immersed in the oxidant solution and then dried or contacted with a knife, spray, roller, or the like, and the excess oxidant is removed by drying.

The disulfide bond chain is disconnected by the reduction reaction by the reducing agent, and the mercapto group, which was formed, loses hydrogen and is oxidized, thereby partially restoring the disulfide bond (-SH HS-+ O → -SS- + H ₂ O). As a result, the protein becomes more robust, so that the crystallinity of the protein and silver is relatively higher, and the fastness is further improved by combining with the microstructure of the material. At this time, the silver hydroxide produced during the reduction process is neutralized, the hydroxyl group is removed, the browning is also disappeared, and pure colored metal silver protein binding material is obtained.

Finally, by removing the oxidizing agent and the reaction product by using purified water in a normal washing process and drying, an antimicrobial silver protein binding material using the egg shell membrane of the present invention has excellent antibacterial and high human affinity.

In the present invention, the silver cation of silver nitrate or silver sulfate (B) and the carboxyl group anion of the amino acid of the egg shell membrane protein (A) are ion-bonded to form a silver-vessel membrane complex. The addition of rosin paper (E) removes the odor and successively adds sodium hydroxide or potassium hydroxide (C) as a reducing agent to cleave the disulfide bond of eggshell membrane protein and reduce it to the mercapto group structure so that the protein is water-soluble and pulverized. A silver hydroxide aqueous solution of microparticles | fine-particles is prepared. The material is immersed in this aqueous solution or the aqueous solution is applied to the material, dried, immersed in an oxidizing agent (D) such as citric acid aqueous solution, oxidized, and washed with water to obtain an antimicrobial silver protein binding material.

The fourth aspect of the present invention relates to a method for producing a one-component antimicrobial composition to which the oxidizing agent is added in advance by simplifying an oxidation process that is separately performed after immersion of a material by applying the above manufacturing process. An egg shell membrane, a silver containing compound, a rosin paper, and a reducing agent may be added, heated, and then pulverized, and then the oxidizing agent may be mixed to obtain a one-component silver-shell membrane protein-containing composition.

The one-component type is a solution of a silver egg shell protein solution and an oxidizing agent, to compensate for the shortcomings of the two-step process of immersing the subject in a silver protein solution, followed by drying and then immersing and drying the oxidant. The final product, one-component composition has the advantage that it can be easily applied to the subject in one process only.

Specific examples for carrying out the method are as follows.

100 parts by weight of the egg shell membrane aqueous solution containing 20 to 50% by weight of the egg shell and 0.5 to 30 parts by weight of the aqueous solution containing 1 to 30% by weight of the silver-containing compound were mixed and stirred while heating, followed by 0.5 to 30 parts by weight of the reducing agent and 0.5 rosin resin. To 30 parts by weight of the mixture is heated and then cooled to wet pulverization, 50 to 150 parts by weight of the oxidizing agent mixed 0.1 to 5 parts by weight of a quaternary ammonium salt aqueous solution to 100 parts by weight of hydrogen peroxide aqueous solution to prepare a silver egg shell membrane protein composition. The detailed conditions necessary for the implementation, such as the reaction temperature and time of each step for carrying out the process, are the same as in the two-component production method described above.

The silver-vessel membrane protein complex, powder thereof, and silver-vessel membrane protein-containing composition prepared according to the present invention are used according to the characteristics of the material to be treated. When applied to water-absorbing materials such as paper, wood, and fibers, it is formulated as an aqueous solution and used by dipping or coating the material. Water-absorbing materials such as vinyl or plastic are mixed with an organic solvent and coated. Or mixed with plastic resin and molded.

The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example 1

2000 g of water was mixed with 1000 g of eggshell membrane (22% solids), and 228 g of an aqueous solution of silver nitrate (17% silver nitrate) was added thereto, followed by stirring at 90 ° C. for 30 minutes. 100 g of rosin paper and 50 g of water were mixed, and 100 g of aqueous potassium hydroxide solution (30% of potassium hydroxide) was added thereto, followed by mixing at 70 ° C. for 1 hour. 62 g of the liquid rosin paper thus prepared was added to the mixture, and after 10 minutes, 50 g of a sodium hydroxide aqueous solution (40% solids), a reducing agent, was added thereto, reacted at 100 ° C. for 90 minutes, and then cooled to 35 ° C. or less. Then it was wet milled with a rotary blade mixer at 10000 rpm. 2 g of the wet mill was mixed with 98 g of water and immersed in a white piece of cotton (circle having a diameter of 4.8 cm). After soaking sufficiently, the resultant was sufficiently squeezed out and dried at 80 ° C. for 60 minutes.

After immersing the fiber pieces again in 100 g of 30 ° C. aqueous citric acid solution (15% solids) as an oxidizing agent, and drying them after 30 minutes, after drying 100 times in water at 50 ° C. two times, the quaternary ammonium salt 7% mixed fiber softener mixed 0.5% After immersion in water, it was dried and dried to obtain a specimen.

The antimicrobial test was performed on the silver protein binding fiber (sample) using the egg shell membrane thus prepared. Antimicrobial activity was measured according to the antimicrobial test method of KS K 0693-2001 fabrics.

Sample weight: 0.4 g

Standard Cannon: Cotton (KS K 0905-1996)

Nonionic surfactant: TWEEN 80 (0.05%)

-Strain used (public strain)

1) Staphylococcus aureus ATCC 6538

Inoculation concentration: 1.3 ± 0.3 × 10 ⁵ / ml

2) Klebsiella pneumoniae ATCC 4352

Inoculation concentration: 1.4 ± 0.3 × 10 ⁵ / ml

Inoculate the specimen 1 with the standard fabric (control group 1), the untreated cotton piece (Comparative test group 1), and the specimen of Example 1 (test group 1) to measure the number of viable cells after culture. Table 1 shows. In addition, inoculated with the test strain 2 to the standard fabric (control group 2), the white cotton pieces (Comparative test group 2), and the specimen of Example 1 (test group 2) that was not treated in Example 1 Was measured and shown in Table 2.

Initial bacterial count (bacterial number / ml) Number of bacteria after 18 hours (bacteria / ml) Bacteriostatic rate ^* (%) Control group 1 1.3 x 10 ⁵ 6.0 x 10 ⁶ - ^** Comparative test group 1 1.3 x 10 ⁵ 4.4 x 10 ⁶ 27.1 Test group 1 1.3 x 10 ⁵ <10 99.9

*% Reduction of bacteriostatic = (Mb-Mc) / Mb × 100

Here, Mb = viable cell count after 18 hours of incubation of the control group, Mc = viable cell number after 18 hours of culture of the test group.

** Control 1 increased bacterial count 46 times after 18 hours

Initial bacterial count (bacterial number / ml) Number of bacteria after 18 hours (bacteria / ml) Bacteriostatic reduction (%) Control 2 1.4 x 10 ⁵ 6.7 x 10 ⁶ - ^* Comparative test group 2 1.4 x 10 ⁵ 5.3 x 10 ⁶ 20.6 Test group 2 1.4 x 10 ⁵ <10 99.9

* Control 2 increased 48 times after 18 hours

As shown in Tables 1 and 2, the standard cells were increased by 46 and 48 times, respectively, after 18 hours of inoculation. In addition, Comparative Test Groups 1 and 2, which were not treated according to the present invention, showed low bacteriostatic reduction rates of 27.1% and 20.6%, respectively. The number of bacteria was reduced by 99.9%, indicating a perfect antimicrobial effect.

Example 2

2000 g of water was mixed with 1000 g of egg shell membrane (22% of solid content), 228 g of an aqueous solution of silver nitrate (17% of nitric acid) was added, and the mixture was stirred at 90 ° C for 30 minutes. 62 g of the liquid rosin paper prepared as in Example 1 was added to the mixture, and after 10 minutes, 50 g of an aqueous sodium hydroxide solution (40% solids) as a reducing agent was mixed and reacted at 100 ° C. for 90 minutes, and then cooled to 35 ° C. or less, and 10000 rpm Wet grinding with a rotary blade equipped mixer. Mix 2 g of the wet pulverized product with 98 g of water, dip a white piece of cotton (rounded with a diameter of 4.8 Cm), soak it sufficiently, and dry it to squeeze out the excess liquid at a fiber weight ratio of 1: 1 in fiber weight and 60 minutes in a warm air at 80 ° C. Dried.

After immersing the fiber fragments in an aqueous solution of hydrogen peroxide (3%) at 25 ° C. as an oxidizing agent and drying it for 60 minutes, after drying two times with 100 times of water washing in hot water at 50 ° C., the quaternary ammonium salt (5.5% solids) mixed fiber softener was 0.5%. After immersion in mixed water, it was dried by drying.

Example 3-Preparation of Leather

2000 g of water was mixed with 1000 g of eggshell membrane (22% of solid content), 228 g of an aqueous solution of silver nitrate (17% of nitric acid) was mixed, and stirred for 30 minutes at a temperature of 90 ° C. 62 g of the liquid rosin paper prepared as in Example 1 was mixed with the mixture, and after 10 minutes, 50 g of an aqueous sodium hydroxide solution (40% solids) as a reducing agent was mixed, reacted at 100 ° C. for 90 minutes, cooled to 35 ° C. or lower, and rotated at 10000 rpm. Wet grinding with a mounting blender. 2 g of the wet milled product was mixed with 98 g of water, and 100 g / 1 m 2 was applied to the surface of the natural leather by spraying.

100 g / 1m2 was applied to the treated natural leather by spraying an aqueous solution mixed with 100 parts by weight of hydrogen peroxide (3%) and 0.5 parts by weight of quaternary ammonium salt (30%) at 25 ° C. as an oxidizing agent. It dried for 120 minutes at 60 degreeC warm air.

The same process as in Example 3 is suitable for the production of natural leather, wallpaper, etc., which cannot be washed / purified by using hydrogen peroxide having self-extinguishing property when exposed to air as an oxidant.

Antimicrobiality test of the antimicrobial leather prepared as described above was carried out. Antimicrobial activity was measured according to the antimicrobial test method of KS K 0693-2001 fabrics.

Sample weight: 0.4 g

Standard Cannon: Cotton (KS K 0905-1996)

Nonionic surfactant: TWEEN 80 (0.05%)

-Strain used (public strain)

1) Staphylococcus aureus ATCC 6538

Inoculation concentration: 1.6 ± 0.3 × 10 ⁵ / ml

2) Klebsiella pneumoniae ATCC 4352

Inoculation concentration: 1.4 ± 0.3 × 10 ⁵ / ml

Inoculated with the test strains 1 and 2 in the standard fabric and the leather pieces of Example 3, respectively, and measured the number of viable cells after cultivation are shown in Tables 3 and 4 as the control group 3 and 4, test groups 3 and 4.

Initial bacterial count (bacterial number / ml) Number of bacteria after 18 hours (bacteria / ml) Bacteriostatic reduction (%) Control group 3 1.6 x 10 ⁵ 7.2 x 10 ⁶ - ^* Test group 3 1.6 x 10 ⁵ <10 99.9

Control 3 increased by 45 times

Initial bacterial count (bacterial number / ml) Number of bacteria after 18 hours (bacteria / ml) Bacteriostatic reduction (%) Control 4 1.4 x 10 ⁵ 6.7 x 10 ⁶ - ^* Test group 4 1.4 x 10 ⁵ <10 99.9

Control 4 increased by 48 times

As shown in Tables 3 and 4 it was confirmed that the antimicrobial treated specimens exhibited a perfect antimicrobial effect.

Example 4 Preparation of Antimicrobial Silver-Protein Complex Powders

2000 g of water was mixed with 1000 g of egg shell membrane (22% of solid content), 228 g of an aqueous solution of silver nitrate (17% of nitric acid) was added, and the mixture was stirred at 90 ° C for 30 minutes. 62 g of the liquid rosin paper prepared as in Example 1 was added to the mixture, and after 10 minutes, 50 g of an aqueous sodium hydroxide solution (40% solids) as a reducing agent was mixed and reacted at 100 ° C. for 90 minutes, and then cooled to 35 ° C. or lower, and as an oxidizing agent. 3% by weight of an aqueous citric acid solution (50% solids) was mixed to neutralize, condensed, dried at 50 to 90 ° C for 24 hours, and dry pulverized with a rotary blade equipped mixer at 10000 rpm to prepare a powdered antimicrobial silver-protein complex.

Example 5: Preparation of Oxidizer Composite Composition

2000 g of water was mixed with 1000 g of eggshell membrane (22% of solid content), 228 g of an aqueous solution of silver nitrate (17% of nitric acid) was mixed, and stirred for 30 minutes at a temperature of 90 ° C. 62 g of the liquid rosin paper prepared as in Example 1 was mixed with the mixture, and after 10 minutes, 50 g of a sodium hydroxide aqueous solution (40% solids) as a reducing agent was mixed, reacted at 100 ° C. for 90 minutes, cooled to 35 ° C. or lower, and rotated at 10000 rpm. The composition was mixed by wet grinding with a mounting mixer and 3000g of an aqueous solution mixed with 100 parts by weight of hydrogen peroxide (15%) and 0.5 parts by weight of quaternary ammonium salt (30%) as an oxidant, and the composition was mixed with 94g of water and 6g of the composition. Dipped sufficiently wet and dried to dry for 180 minutes in a warm air of 60 ℃.

The antimicrobial silver-protein complex using the eggshell membrane according to the present invention can be applied to textiles, and can be used for baby clothes, therapeutic socks, bed covers, patient clothes, gowns of nurses and doctors, and applied to leather shoes, sneakers, and car seats. It can be used as furniture. In addition, when applied to paper or pulp, it can be used as a diaper, feminine hygiene products, wet wipes, wallpaper, etc., and can also be used as an additive for household goods such as shampoo, soap, detergent, fabric softener, antibacterial spray, construction, paint, and the like. Can be.

The silver protein binding material according to the present invention is a high value-added resource saving material having non-toxic antibacterial properties and human affinity. Silver is known as non-toxic antibacterial metal for human body, but it is difficult to apply to fiber, and it is difficult to apply antibacterial effect because it is composed of powder. When used, it is difficult to effectively distribute the microorganisms to several micrometers or less, and thus, it is difficult to effectively exhibit the antimicrobial activity against microorganisms of several nanometers or less. In the present invention, the ultrafine distribution is possible due to the dispersion distribution by the silver ion reaction bond of 0.5 nm or less size, which is excellent in antimicrobial activity and has a large specific surface area, and thus high efficiency. It has excellent fastness by forming. In addition, by using the egg shell protein as a binder, it is excellent in nature and human friendliness, and has good advantages in terms of resource recycling by using food by-products.

Claims (19)

A silver-vessel membrane protein complex obtained by heating by mixing a egg shell membrane, a silver-containing compound selected from silver nitrate (AgNO ₃ ) or silver sulfate (Ag ₂ SO ₄ ), and a reducing agent, followed by administration of an oxidizing agent. According to claim 1, wherein the reducing agent is a silver egg shell membrane protein complex is an aqueous alkali solution containing 10 to 50% by weight of sodium hydroxide or potassium hydroxide. The acidic or hydrogen peroxide aqueous solution (3 to 35% by weight) containing 0.1 to 30% by weight of an acid selected from the group consisting of hydrogen peroxide, citric acid, hydrochloric acid, acetic acid, formic acid, and sulfuric acid. Silver-veil membrane protein complex, which is a mixture of quaternary ammonium salt aqueous solution (10-50 wt%). The silver-vessel membrane protein complex according to claim 1, wherein the rosin resin is further added to the egg shell membrane-containing mixture. The method according to any one of claims 1 to 4, which is used as an additive for imparting antimicrobial properties to hair cleaning and care agents, toiletries and bath products, clothing detergents and fabric softeners, feminine hygiene products, diapers, and paints. Silver-ovarian membrane protein complex. A silver-ovarian membrane protein complex powder obtained by drying and pulverizing the silver-warm membrane complex according to any one of claims 1 to 4. 100 parts by weight of an egg shell aqueous solution containing 20 to 50% by weight of the egg shell membrane; 0.5 to 30 parts by weight of an aqueous solution containing 1 to 30% by weight of a silver containing compound selected from silver nitrate (AgNO ₃ ) or silver sulfate (Ag ₂ SO ₄ ); 0.5 to 30 parts by weight of a reducing agent; And 50 to 150 parts by weight of an oxidizing agent mixed with 0.1 to 5 parts by weight of a quaternary ammonium salt solution (10 to 50% by weight) in 100 parts by weight of an aqueous solution of hydrogen peroxide (3 to 35% by weight). The composition of claim 7, wherein the reducing agent is an aqueous alkali solution containing 10 to 50% by weight of sodium hydroxide or potassium hydroxide. According to claim 7, Silver- egg shell membrane protein composition further comprises 0.5 to 30 parts by weight of the rosin resin. The egg shell membrane, the silver-containing compound, the reducing agent, and the rosin resin were mixed and heated, followed by the addition of an aqueous oxidizing agent solution containing an aqueous hydrogen peroxide solution (3 to 35% by weight) and an aqueous quaternary ammonium salt solution (10 to 50% by weight). A method of making the egg shell protein composition. A method of producing an antimicrobial silver-veil membrane protein binding material, comprising mixing and heating an egg shell membrane, a silver containing compound, and a reducing agent, coating the mixture on a material, and immersing the material in an oxidant. The method according to claim 10 or 11, wherein the silver-containing compound is silver nitrate (AgNO ₃ ) or silver sulfate (Ag ₂ SO ₄ ). The method according to claim 10 or 11, wherein the reducing agent is an aqueous alkali solution containing 10 to 50% by weight of sodium hydroxide or potassium hydroxide. The method of claim 11, wherein the oxidizing agent is an acidic aqueous solution containing 0.1 to 30% by weight of an acid selected from the group consisting of hydrogen peroxide, citric acid, hydrochloric acid, acetic acid, formic acid, and sulfuric acid. The method of claim 11, wherein the material is fiber, yarn, leather, wallpaper, chopping paper, paper, pulp or wood. The production method according to claim 10 or 11, wherein the rosin resin is further added to the egg shell membrane-containing mixture. The method according to claim 10 or 11, wherein the silver-containing compound is mixed in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the egg shell membrane. The method of claim 11, wherein the coating of material is made by impregnating the silver protein conjugate or applying the silver protein conjugate to the material. An antimicrobial silver protein binding material prepared according to claim 11.