KR100351626B1 - Anti-discoloring antibacterial silver substances and their antibacterial-agent composition - Google Patents

Abstract

The present invention relates to an anti-chromic silver antimicrobial compound and an antimicrobial composition containing the same, and more particularly, exhibits low solubility in water and has a dissolution property in ammonia water or dimethyl sulfoxide (DMSO) and structurally a phenyl group or Because it contains naphthalene group, it is easily hydrolyzed and reacts with an object containing an atom having a lone pair electron, thereby forming a chelate, which has excellent antimicrobial persistence, less discoloration due to light, and especially due to low toxicity. The present invention relates to an antimicrobial composition containing an anti-chromic silver antimicrobial compound useful as an antimicrobial agent for life, and a specific high molecular weight material which plays a role of suppressing photo discoloration together with the silver antimicrobial compound.

Description

Anti-discoloring antibacterial silver substances and their antibacterial-agent composition

The present invention relates to an anti-chromic silver antimicrobial compound and an antimicrobial composition containing the same, and more particularly, exhibits low solubility in water and has a dissolution property in ammonia water or dimethyl sulfoxide (DMSO) and structurally a phenyl group or Because it contains naphthalene group, it is easily hydrolyzed and reacts with an object containing an atom having a lone pair electron to form a chelate, so it has excellent antimicrobial persistence, less discoloration by light, and especially due to low toxicity. The present invention relates to an anti-chromic silver antimicrobial compound useful as an antimicrobial agent for life, and to an antimicrobial composition containing a specific high molecular weight material that plays a role of suppressing photo discoloration together with the silver antimicrobial compound.

Metal ions such as silver, copper, zinc and the like exhibit antimicrobial activity to kill bacteria, and many antimicrobial agents using them have been developed. Among the metal ions, silver ions (Ag ⁺ ) are particularly excellent in antimicrobial activity. Therefore, studies on antimicrobial agents and antimicrobial treatment methods using the same have been made in various ways.

The antimicrobial treatment methods known at present are largely classified into 1) mixing method, 2) surface coating method, 3) surface adsorption method, and 4) surface reaction method. Characteristics and representative examples of each treatment method are as follows:

1) Mixing method

Silver compounds have excellent antibacterial properties but have the disadvantage of discoloration to brown to black color by light. Therefore, in order to prevent the color change of the product caused by the discoloration of the silver compound, many methods have been developed to introduce silver ions into the white inorganic powder so that the silver ions are not easily visible even if they are discolored. This antimicrobial powder is mainly used to prepare antimicrobial polymer products by mixing with high molecular materials. Representative examples of the antimicrobial treatment method using the mixing method are as follows: a method of introducing silver ions into the ion exchange position of the zeolite, which is a porous alumina, as an antimicrobial agent [US Pat. No. 4,911,898]; A method of using an anti-chromic material such as benzotriazole in order to prevent discoloration of silver zeolite (US Pat. No. 4,938,955); A method of preventing discoloration of silver by coating a water-soluble fluorine resin on silver zeolite [Japanese Patent Laid-Open No. 10-45410]; A method for preparing an antimicrobial powder in which silver ions are introduced into lime phosphate such as hydroxide apatite such that silver discoloration is less visible by white lime phosphate [US Patent No. 5,266,534]; Antimicrobial powder in which antimicrobial metal ions such as silver are introduced into calcium carbonate [Japanese Patent Laid-Open No. 7-17803]; A method of preventing discoloration by supporting silver thiosulfite on silica gel and then coating a hydrolyzed alkoxysilane (Japanese Patent Laid-Open No. 9-221599); Silver thiosulfatosilver is supported on silica gel, and then a styrene monomer is added to this silica gel dispersion aqueous solution to produce an antimicrobial powder having excellent dispersibility. [Japanese Patent Application Laid-Open No. 4-233727] and the like.

In addition, a method of imparting antimicrobial properties by mixing water-insoluble silver salts and colloids with high molecular materials is also used. For example, silver nitrate and sodium thiocyanide (NaSCN) were added to a polyvinyl alcohol aqueous solution and spun to produce an antimicrobial fiber (Japanese Patent Laid-Open No. 6-341013).

2) Surface coating method

A method for producing an antimicrobial product by coating an antimicrobial material on the surface of a polymer material and a coating antimicrobial agent have been developed. Representative examples are as follows: a method of treating a composition containing silver, a copper salt, carbon black and the like and an organic alkoxysilane which is a reactive organic compound to impart antimicrobial properties to the object to be treated [Japanese Patent Laid-Open No. 9-103972] ; A method for producing antimicrobial fibers by coating a surface of the fiber with a composition mixed with an antimicrobial powder such as titanium oxide, silver zeolite, or the like as a reactive polymer binder (Japanese Patent No. Hei 7-157595); Mixing silver and gold powders in a polymer solution and printing them on the fabric to impart antimicrobial properties (Japanese Patent No. Hei 9-20058); A viscous antimicrobial composition containing a metal oxide containing silver and a water-soluble polymer aqueous solution [WO 98/28983]; A method of chelating an antimicrobial metal such as silver on a protein such as ferritin and coating it on the surface of the biotransplant material to prevent bacterial infection [WO 98/31404]; And a method of imparting antimicrobial properties by plasma coating a metal salt containing silver on a base surface such as a fiber (US Patent No. 4728323, Japanese Patent No. Hei 9-112142).

3) Surface adsorption method

Methods of preparing an antimicrobial agent containing silver ions in fine powder form or colloidal form and adsorbing them on the surface of a polymer product have been developed. Representative examples are as follows: an antibacterial agent prepared by dispersing a silver salt such as silver acetate in an alcohol or an aqueous alcohol solution and containing benzotriazole which inhibits discoloration thereof (Japanese Patent Laid-Open No. 9-165775); A method of impregnating polyester or acrylic fibers in a colloidal solution in which metal oxides such as silver, copper, zinc, tin, aluminum, and iron having a particle size of 500 μm or less are dispersed, and treating them at a temperature above 60 ° C. Japanese Patent Application Laid-Open No. 9-13269; A method for preparing an antimicrobial substance by introducing silver ions into a colloidal titanium oxide (US Patent No. 5730995); And antimicrobial fibers (Japanese Patent Laid-Open No. 10-28027) prepared by placing a nylon fabric in a dyeing bath containing a silver / titanium oxide antimicrobial agent and a dye and treating it for 35 minutes at 80 ° C.

4) Surface reaction method

The surface reaction method refers to a method of imparting antimicrobial activity by forming a chelate by ion / coordination bond by reacting silver ions on the surface of the polymer material. Representative examples are as follows: protein glycol is reacted with thioglycolic acid to hydrolyze disulfide groups to form thiols, and metal functional groups containing copper, zinc, tin, etc. are reacted with these functional groups to introduce metal ions. Technology for antimicrobial processing of wool [ J. Antibact. Antifung. Agents , 20 (2) , 69-76, 1992; A technique for producing fibers using polyamides containing sulfone groups and providing antimicrobial properties by ion-bonding silver ions to sulfone groups [USSR 233835, 1968]; After reacting a monomer containing a carboxyl group with a fiber such as cotton, nylon, polyester, etc., zinc, iron, silver ions and the like are reacted with this carboxyl group to impart antimicrobial activity. -337966; Hydrolyzing the acrylic fiber with a sodium hydroxide solution to form a carboxyl group, and then ion-bonding silver ions to the functional group and reacting sodium carbonate to impart antimicrobial activity (Japanese Patent Laid-Open No. 3-199418); A method of imparting antimicrobial activity by reacting copper ions with an acrylic fiber having an amine group introduced therein (JP-A-5-132857); Dipping a polyurethane sponge in an aqueous tin chloride hydrochloric acid solution and then washing, adding 0.3 to 10 g / L of silver nitrate in an aqueous solution, reacting and washing to prepare an antimicrobial polyurethane sponge [Japanese Patent Laid-Open No. H6-6-684684]; Take one or more of SnCl ₂ , SnSO ₄ , SnCl ₄ , Sn (SO ₄ ) ₂ and dissolve it in an aqueous solution of hydrochloric acid or sulfuric acid to make a treatment solution. Put a polyurethane sponge on this solution to perform surface treatment and wash. A method for producing an antimicrobial sponge by resurfacing the solution in an aqueous solution; A method of producing a antimicrobial fabric by treating the cotton fabric with an aqueous solution of caustic soda, an aqueous solution of hydrochloric acid, an aqueous solution of tin chloride and an aqueous solution of silver nitrate in order to produce an antimicrobial fabric [Japanese Patent Laid-Open No. 7-215811]; Antibacterial fiber produced by reacting silver nitrate with an acrylonitrile-containing acrylic fiber at 95 ° C. for 30 minutes (Japanese Patent Laid-Open No. 3-136649); And antibacterial acrylic fibers (Japanese Patent Laid-Open No. 9-13221) treated with silver nitrate and then treated with sodium thiocyanide.

As described above, a number of methods have been developed to impart antimicrobial activity with silver. However, methods known to date have the following disadvantages.

In the case of the mixing method, the antimicrobial powder is mixed with plastic and molded. In the existing patents, silver nitrate (AgNO ₃ , LD ₅₀ = 50 mg / kg), which is highly toxic when preparing the antimicrobial powder, may be harmful to the human body. And there is a problem to lower the quality of the product by discoloration of silver nitrate. Nitric acid can also be converted to nitrite when ingested in the body, which can cause metaemoglobinemia and form nitrosamines, which are currently recognized to be carcinogenic [Scientia Horticulturae, 1996]. In addition, there is a risk of environmental pollution that hassle that needs to be sufficiently purified after supporting in inorganic powder to remove excess silver nitrate.

The surface coating method is a method of coating an antimicrobial substance on the surface of a product by using a binder. The use of powder type antimicrobial agent decreases the physical properties, feel and quality of the product, and the antimicrobial agent is easily lost due to friction. There is this.

The surface adsorption method is a method of physically adsorbing ultrafine antimicrobial particles on the surface of a polymer. This method applies a temperature during the antimicrobial treatment to increase the size of the porous material on the surface of the fiber by thermal expansion, and then insert the antimicrobial particles into the porous material. Way. Since this method requires a high treatment temperature, the treatment cost is relatively high and the washing resistance of the treated antimicrobial agent is not excellent.

In addition, the surface reaction method is a method of providing antimicrobial activity by ionizing or coordinating silver ions to functional groups such as amine groups, carboxyl groups, thiol groups, and sulfone groups on the surface of the polymer material. However, the patents published so far are performing two or more multi-step reactions in order to introduce these functional groups on the surface of the polymer, so that the antibacterial treatment cost is high and the antibacterial treatment time is long. Meanwhile, silver nitrate is generally used as the antimicrobial silver compound used in the surface reaction method. As described above, silver nitrate is highly toxic and serves as a strong oxidizing agent, which may cause skin irritation and age the product. In particular, there is a problem of discoloration easily by light. According to the experiments of the present inventors, when the concentration of silver nitrate with an aqueous solution of 1 mg / L or more antibacterial treatment has a problem that the product is severely discolored by light to have a brown to black.

A good antimicrobial agent must meet the following requirements: ① excellent antimicrobial activity, ② good antimicrobial persistence, which does not dissipate antibacterial activity by washing, ③ no discoloration by light, ④ low or no toxicity, ⑤ simple and economical antibacterial treatment.

The present invention has developed a new antimicrobial agent that satisfies the above requirements.

Silver (Ag) is absorbed into the bacteria to inhibit protein synthesis to kill the bacteria, as well as disrupt the electron transfer system in the cell membrane outside the bacteria to kill the bacteria. Therefore, silver (Ag) is ionized and dissolved in water and exhibits antimicrobial activity even if the bacteria are not absorbed into the body. That is, silver (Ag) exhibits sufficient antimicrobial activity even when attached to the surface of the material, so even if a small amount of silver (Ag) does not disappear from the surface, it exhibits antimicrobial activity. That is, when silver (Ag) is introduced to the surface of the material, it is not necessary to introduce a large amount if only silver is prevented from being lost. In addition, by minimizing the amount of the silver compound it is possible to economically antibacterial treatment and to prevent discoloration, which is the biggest problem of the silver-based antimicrobial agent.

Accordingly, the present inventors have completed the present invention by developing a new silver compound exhibiting excellent antimicrobial activity even in a small amount, paying attention to the properties of silver (Ag) as described above.

Accordingly, an object of the present invention is to provide a new silver-based antimicrobial compound having excellent antibacterial activity and antimicrobial persistence and low toxicity, and in particular, little color change by light. In addition, the present invention has another object to provide an antimicrobial composition containing the silver-based antimicrobial compound and a high molecular material that serves to inhibit photochromism.

1 is a virtual diagram of coordination bonds between cellulose and silver ions.

2 is a virtual diagram of coordination bonds between amide groups and silver ions contained in polyurethane or the like.

3 is a virtual diagram of coordination bonds between polyvinyl alcohol and silver ions.

Figure 4 is a virtual diagram of the coordination bond between the ester group and the silver ions contained in the polyester and the like.

The present invention is characterized by an anti-chromic silver antimicrobial compound which exhibits low solubility in water, has solubility in ammonia water or dimethyl sulfoxide (DMSO), and structurally contains a phenyl group or a naphthalene group.

In addition, the present invention is the silver-based antimicrobial compound; A polymer emulsion selected from acrylic emulsion, natural rubber latex, silicone emulsion, fluororesin emulsion, and polyurethane emulsion; A liquid silver antimicrobial composition containing a solvent or a dispersion medium selected from water, ammonia water and dimethyl sulfoxide is included.

In addition, the present invention includes a silver-based antimicrobial powder on which a silver-based antimicrobial compound and a polymer material are supported on a carrier selected from zeolite, calcium phosphate, ocher and charcoal powder.

Referring to the present invention in more detail as follows.

The new anti-chromic silver antimicrobial compound according to the present invention has low solubility in water and is hydrophobic so that it is not easily released by water during washing, but is easily dissolved by a small amount of ammonia water or dimethyl sulfoxide, thereby forming a chemical bond with an object to be treated. It has properties that make it possible and structurally contains a phenyl group or a naphthalene group and shows excellent antimicrobial activity even when a small amount is used. The solubility of the antimicrobial compound acts as an important factor in determining the reactivity with the object. Among some silver compounds known to have antimicrobial activity, they have excellent anti-coloring properties but poor solubility. Due to the sticking, the washing resistance is relatively low. On the contrary, the new antimicrobial compound according to the present invention forms a chelating bond with the functional group included in the antimicrobial object after the antimicrobial treatment and thus is not lost by washing. The naphthalene group absorbs ultraviolet rays and absorbs the light energy required when silver (Ag) discolors, thereby preventing silver discoloration.

Specific examples of the silver-based antibacterial compound according to the present invention include a phenyl group-containing compound such as silver benzoic acid, naphthalene acetic acid, naphthalene group-containing compound such as silver naphsoic acid, silver naphthalene sulfonic acid, and the like. The silver-based antimicrobial compound of the present invention is hydrophobic, and has excellent advantages in dispersibility and mixing when forming with general plastics, and its application range is very broad.

In the antimicrobial treatment process by general surface reaction, the process of artificially introducing functional groups such as amine groups, carboxyl groups, thiol groups, sulfone groups, etc. to the antimicrobial treated materials prior to treatment of the antimicrobial agent, washing process for removing reactants, etc. This must be preceded essentially, and the introduction of a highly reactive functional group introduces an excess of silver compound into the surface of the object to be treated, thereby causing a problem of discoloration by the excess silver compound.

On the contrary, the antimicrobial compound according to the present invention is directly subjected to antimicrobial treatment without undergoing a washing process for removing reactants, including the introduction of a functional group, which is a lone electron pair due to the silver ions included in the silver compound of the present invention. This is because antimicrobial treatment of a workpiece containing atoms with pair electrons forms chelating by coordination bonds. In addition, since the antimicrobial compound according to the present invention is hydrophobic and has low affinity with water, it is not well released in water after forming chelating, and thus has excellent washing resistance.

As an object to be applied to which the antimicrobial compound of the present invention is applied, it is preferable that the functional group itself contains a lone pair electron such as a hydroxyl group, an amide group, an ester group, an ether group, or the like. Specific examples thereof include high molecular materials such as polyurethane, polyamide, polyvinyl alcohol, cellulose, wool, and polyester. When the antimicrobial compound of the present invention contacts the surface of the polymer material at room temperature, the silver compound may be held on the surface of the polymer by coordination bonds, and thus, an introduction process of a separate functional group is not required.

In order to confirm the coordination bond between the silver-based antimicrobial compound and the antimicrobial treatment according to the present invention, silver benzoic acid was dissolved in water and reacted with the antimicrobial treatment, dried and analyzed by ATR-IR spectrum. As a result, we go to the ether peak is 1016.74 cm ^-1 at 1019.02 cm ^-1 of the surface, the peak of C = O groups of the nylon ester group was moved to 1631.81 cm ^-1 at 1631.99 cm ^-1, of a polyurethane ether group was moved to the peak at 1091.36 cm ^-1 1091.67 cm ^-1, the C = O group peak of the ester groups of the polyester was moved to 1712.29 cm ^-1 1711.96 cm ^-1. It can be seen that the coordination bond between the antimicrobial compound and the antimicrobial treatment was formed due to the shift of the active peak toward the lower wavelength.

1 to 4 show an imaginary diagram of the chelate formed between the antimicrobial compound and the antimicrobial object. Substances containing hydroxyl and ether groups, such as cellulose, form chelate bonds between the silver ions and the isolated electron pairs of oxygen atoms in the hydroxyl and ether groups (see FIG. 1). Materials having amide groups, such as polyurethane, polyamide, wool, silk, etc., form chelate bonds between lone pairs and silver ions in the nitrogen and oxygen of the amide group (see FIG. 2). The virtual diagram of chelate bonds of polyvinyl alcohol is shown in FIG. 3, and the virtual diagram of chelate bonds of polyester is shown in FIG. 4.

On the other hand, the present invention includes an antimicrobial composition containing the silver-based antimicrobial compound, the antimicrobial composition of the present invention can obtain sufficient anti-coloring effect and antimicrobial activity by itself containing only the silver-based antimicrobial compound have. The present invention aims to minimize the concentration of silver-based antimicrobial compounds contained in the antimicrobial composition to improve economics as well as to suppress discoloration. The silver-based antimicrobial compounds may be contained in a concentration range of 1 to 50 ppm in the antimicrobial composition. To do that.

In addition, in order to obtain an antimicrobial composition having a better discoloration inhibiting effect, it is preferable to contain a polymer emulsion that acts as a photochromic inhibitor in a certain content ratio range. Suitable polymer emulsions for this purpose include polymers that are dispersed or dissolved in water, such as acrylic emulsions including acrylic resins, natural rubber latexes, silicone emulsions, fluororesin emulsions, polyurethane emulsions, etc. The material is appropriate. The polymer material forms a thin polymer film during the drying process after the antimicrobial treatment to block light, thereby preventing the antimicrobial compound from being directly exposed to light. Among the antimicrobial compositions according to the present invention, it is preferable that the above-mentioned polymer emulsion is contained in a concentration range of less than 0.5%. If the content exceeds 0.5%, there is a problem of changing the feel, physical properties and the like of the treated object. The antimicrobial composition according to the present invention exhibits excellent anti-coloring properties even when a small amount of polymer material is used, compared to a method of coating a powder or colloidal antimicrobial agent on a to-be-processed object using a polymer binder as in the surface coating method. There is an advantage that hardly changes the physical properties of the treatment. In addition, the antimicrobial agent by the surface coating method has a disadvantage that the antimicrobial agent may be precipitated during storage and powdery, so that the antimicrobial agent is easily lost by friction after the antimicrobial treatment, whereas the antimicrobial composition according to the present invention is completely dissolved in a solvent. Since the state does not occur as described above, excellent dispersibility and has the advantage of uniform antibacterial treatment.

On the other hand, the antimicrobial composition of the present invention described above may be used in liquid form or supported by a powder such as zeolite, calcium phosphate, charcoal powder, ocher, etc. to be prepared in powder form. As the solvent or dispersion medium used in the preparation of the antimicrobial composition, water, ammonia water, and dimethyl sulfoxide may be selected and used. The antimicrobial compound and the polymer emulsion used in the present invention may be dissolved in the solvent or dispersion medium. The chelate formation of can be easily made. In particular, when a small amount of ammonia of 0.1% or less is used together as a solvent or a dispersion medium, an excellent dissolution effect can be obtained. The ammonia forms a complex with the silver-based antibacterial compound so that the silver compound can be easily dissolved in water. After the antibacterial treatment is volatilized in the drying step does not affect the product at all. In addition, ammonia also serves to prevent discoloration of the antimicrobial treatment liquid. When the antimicrobial composition in which silver compound is dissolved is diluted with industrial water or tap water, it reacts with chlorine ions and sulfate ions contained in these water to produce silver chloride, silver sulfide, etc., and these compounds discolor by light and precipitate. Form. However, in the case of the antimicrobial composition containing ammonia, ammonia serves to prevent the formation of precipitates by dissolving the product compound. When using an antimicrobial composition containing a silver-based antimicrobial compound of about 10 ppm or less, such a phenomenon does not occur, it is not necessary to use ammonia. In addition, ammonia hydrolyzes the surface of the workpiece to allow the antimicrobial agent to react more smoothly with the surface of the workpiece, and also relaxes the crystallinity so that the antimicrobial compound can be absorbed into the workpiece.

On the other hand, most antimicrobial agents are in direct contact with the human body or food, so low toxicity is required. As shown in the imaginary diagram of chelating bonds (Figs. 1 to 4), when silver ions bind to the polar functional groups of the polymer material, the silver ions do not bind alone, but because their counterions are bound together. Toxicity will vary depending on the type of counterion. According to the regulations of the Japan Textile Product Evaluation Council, LD ₅₀ must be at least 1 g / kg body weight for use as an antimicrobial agent. Silver nitrate (AgNO ₃ ), which is used as a general silver antibacterial substance, has a disadvantage in that LD ₅₀ obtained by oral administration of mice has a very high toxicity as 50 mg / kg-weight [The Sigma-Aldrich Library of Chemical Safety Data]. On the contrary, the silver naphthalene acetic acid and benzoic acid used in the present invention have an advantage that LD ₅₀ shows very low toxicity at 5,000 mg / kg-weight or more and does not harm the human body at all.

As described above, the antimicrobial compound of the present invention has a low toxicity and discoloration property compared to silver nitrate (AgNO ₃ ), which has been generally used, and has the advantage of minimizing toxicity and preventing discoloration when used as an antimicrobial composition. In particular, when the antimicrobial powder is manufactured and used, it does not cause toxicity or discoloration even though a separate purification process is performed, which has the advantage of simplifying the powder manufacturing step.

On the other hand, the novel antimicrobial agent according to the present invention can exhibit the same antimicrobial activity even if it is contained in the to-be-processed object which antimicrobial activity is required as well as a surface treatment agent by post-processing fixation. For example, an antimicrobial polyurethane foam is produced by preparing an antimicrobial coating agent or adhesive or by foaming the antimicrobial agent in a polyurethane foam composition.

In particular, the antimicrobial composition of the present invention can be usefully used in the production of antimicrobial polyurethane foam. Currently, antimicrobial polyurethane foams are mostly prepared by including powdery antimicrobial agents such as silver-zeolites in the foam composition. In this way, when the powdered antimicrobial agent is used, it needs to go through a long stirring process in order to evenly disperse the antimicrobial agent in the foam due to the mutual coagulation of particles. There is a risk of harm to the environment and the operator has to wear a mask. Meanwhile, when the aqueous solution of the antimicrobial composition of the present invention is foamed using water instead of the water contained in the general polyurethane foam composition, it does not require a long time stirring process for dispersing the antimicrobial agent, which may be a problem in the powdered antimicrobial agent, and does not cause air pollution in the workplace It has advantages

Such a present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1 Selection of Silver Compounds

Various silver compounds were prepared in order to find a silver compound that can react at room temperature with a high molecular material having an isolated electron pair, which is an object of the present invention, and antimicrobial and discoloration properties of each of them were measured.

Sodium sulfate, sodium chloride, sodium acetate, potassium iodide, sodium thiocyanate, sodium ascorbate, sodium lactate, sodium picric acid, sodium benzoate, sodium naphthalic acid, sodium naphthoic acid, Each of sodium naphthalene sulfonate salts prepared 0.2M aqueous solution, and 100 ml of the aqueous solution was stirred, and 0.1M silver nitrate aqueous solution was added to each solution for 1 hour, and then filtered through a glass filter and dried in a drying oven.

50 ppm of the produced sulfuric acid, silver chloride, silver acetate, silver iodide, silver thiocyanate, silver ascorbic acid, silver lactic acid, silver picric acid, silver benzoic acid, naphthaleneacetic acid, naphsoic acid silver, naphthalenesulfonic acid silver, silver nitrate, etc. Dissolved or suspended in water at a concentration of 30 minutes at room temperature to antibacterial to nylon fabrics. The discoloration of this antimicrobial fabric was investigated according to the KS K 0218 method, and the antibacterial activity of the samples washed according to the KS K 0465 method was investigated by the shaking flask method. At this time, washing was performed 30 times with a neutral detergent and E. coli KCTC 1682 was used for antibacterial activity. The results are shown in Table 1 below.

As shown in Table 1, it is understood that silver nitrate, silver sulfuric acid, silver chloride, silver acetate, ascorbic acid, lactic acid, silver picric acid and silver are discolored due to light, and thus are not suitable for achieving the object of the present invention. Silver iodide and silver thiocyanated are relatively less discolored, but are not soluble in water, so they are not easily reacted with the object in the antimicrobial treatment, so they are not suitable for the purpose of the present invention.

On the other hand, benzoic acid, naphthalene acetic acid, naphsoic acid silver, and naphthalene sulfonic acid were relatively less discolored, and the antibacterial activity was excellent after washing. It is believed to have excellent antimicrobial persistence. In addition, these silver compounds contain a hydrophobic chemical functional group, naphthalene group, phenyl group, etc., and thus have no high affinity for water. Therefore, these silver compounds bound to the treated materials have little or no water absorption at the molecular level during water washing, so that the glass phenomenon due to ionization does not occur or less occurs, and thus, the antimicrobial persistence of the treated materials is considered to be excellent. .

Example 2 Measurement of Daylight Fastness and Antimicrobial Activity of Antimicrobial Compositions

Next, an antimicrobial composition was prepared with the composition as shown in Table 2, and diluted with industrial water to prepare 1.5% antimicrobial treatment solution.

For each of the prepared antibacterial treatment solution, the light fastness and antimicrobial activity were measured by the following method, and the results are shown in Table 3 below.

Daylight fastness was expressed as the whiteness of the fabric after 5 hours irradiation using a weather-O-meter (Atras Electric Devices Co., USA; light source: Xenone arc lamp) [KS K 0218 method]. Whiteness was measured by computer color mathing (Data Color, Switzerland).

Washing experiment was carried out using a Launder-Ometer (ModifiedGyrowash, JH Heal & Co.) according to the KS K 0465 method, the detergent was used a concentration of 2 g / ℓ of a neutral detergent, washing 10 minutes Washing, 5 min rinse was repeated for 30 times. At this time, the washing temperature was maintained at 30 ~ 40 ℃.

The samples used for the antimicrobial evaluation test was 0.75 g each, the size of 10 × 10 × 1 ㎣. The antimicrobial evaluation test was carried out according to the shake flask method (Dow corning test method 0923) using E. coli and staphylococcus aureus , and the sample was placed in the flask for 1 hour.

As a control, untreated material (control 1) and silver-based antimicrobial agent (Atomy ball- (S), manufactured by Catalysts & Chemicals of Japan) in 4% diluted antibacterial treatment at room temperature (Control 2) was used.

According to Table 3, the reason why the whiteness of the sponge shows a negative value is that yellow sponge was used as a sample. In the whiteness of the sample before light irradiation, the whiteness of the antimicrobial treated samples was lower than that of the control group 1 which was not antimicrobial treated. This is a phenomenon caused by the gloss decreases because of contact with water during the antibacterial treatment. In the case of silicone emulsion, however, the whiteness tends to increase, which is a phenomenon caused by the light scattering of the silicone resin film.

Comparing the whiteness after light irradiation with each other, Sample 1 and Sample 6 showed a slight decrease in light fastness compared to Control 1 and Control 2. Therefore, this antimicrobial composition is not suitable for the white matter sensitive to photochromism. However, there is no big problem even when used for dyeings that are not sensitive to photochromism. On the other hand, when the polymer emulsions were used as in Samples 2 to 5, the whiteness after irradiation with light was almost similar to that of Control 2 treated with atomy ball ™ or slightly improved in light fastness. Therefore, in the case of Samples 2 to 5, it was investigated as an antimicrobial composition that can be used for both white and dyeing products. On the other hand, in all cases, the whiteness of the wool was greatly reduced after light irradiation, which is a characteristic of the wool, which is caused by the protein degradation of the wool, which is a protein fiber.

The antimicrobial activity of the control group 2 and the antimicrobial agent according to the present invention was shown to be at least 90%, and the antimicrobial activity was excellent. However, after 30 washes or more, the reduction rate was generally very low for the control group 2. On the other hand, all of the treated antimicrobial treatment using the antimicrobial agent of the present invention showed a reduction rate of more than 80%. Therefore, the antimicrobial agent of the present invention was found to be superior to the antimicrobial durability compared to the control 2.

Yarn Textile Testing Laboratories and Japan's New Product Evaluation Committee for Textile Products are recognized as antimicrobial fibers if they exhibit a reduction of more than 70% in 10 washes. Therefore, it can be seen that the antimicrobial polymer materials according to the present invention exhibit very good antimicrobial activity.

Example 3 Antibacterial Powder

0.1 M silver benzoic acid and 10 ml of ammonia water were added to 1 L distilled water to completely dissolve the silver benzoic acid, and 400 g of zeolite (A type, 1.6 µm) was added thereto, followed by stirring for 3 hours. Then, the zeolite was filtered, dried at 100 ° C., and pulverized with a grinder to prepare a silver zeolite powder.

In the manufacturing process of the silver zeolite, instead of the zeolite, calcium phosphate was treated (calcium triphosphate) to prepare an antibacterial calcium phosphate powder including silver.

As a control, 400 g of zeolite (A type, 1.6 μm) was added to an aqueous solution of 0.1 M silver nitrate, thereby preparing silver zeolite.

For the antimicrobial powder prepared above, silver (Ag) content was measured by atomic spectrometry, and whiteness was measured by the method of Example 2, and the results are shown in Table 4 below.

As shown in Table 4, the content of silver supported on the inorganic powder was approximately similar to 4.9 to 5.1. However, the whiteness is relatively good compared to the control (silver nitrate) of the antimicrobial powder of the present invention, the reason for the low whiteness in the control is considered to have a large effect of the silver nitrate adsorbed on the powder surface.

Example 4 Preparation of Antimicrobial Polyurethane Foam

The antimicrobial agent of the present invention can not only antibacterial polyurethane sponge by the post-processing method as in Example 2, but also can be blended into the sponge foaming process to produce an antimicrobial polyurethane sponge.

Next, as shown in Table 5, the antimicrobial agent of the present invention was put in a polyurethane foam composition instead of water to prepare a polyurethane sponge. The density of the sponge according to the present example was 40.3 kg / m ^3, which was almost similar to that of the control group (density: 42.7 kg / m ³ ), indicating that the antimicrobial agent had no effect on the foaming process of the sponge.

Meanwhile, as a result of evaluating the antimicrobial activity of the sponge of the present Example using E. coli according to the method of Example 2, the antimicrobial activity of the sample was initially 100%, and the antibacterial activity of the samples washed 30 times also showed an antimicrobial activity of 99% or more. Appeared to be.

Example 5 Preparation of Antimicrobial Coatings and Adhesives

The antimicrobial agent of the present invention has dissolution characteristics that are soluble in water, ammonia, as well as dimethyl sulfoxide (DMSO). Therefore, when mixed with a high molecular material it can be applied as an antimicrobial coating agent or adhesive of the organic phase.

Next, as shown in Table 6, the antimicrobial solution of the present invention was mixed with an antimicrobial solution dissolved in dimethyl sulfoxide and a polymer solution to prepare a polymer solution that can be used as an excellent antimicrobial coating agent or adhesive.

Example 6 Oral Administration Toxicity Test

To investigate the toxicity of the antimicrobial compounds, male rats of 5 weeks of age were treated with silver sulfate, silver chloride, silver acetate, ascorbic acid, lactic acid, picric acid, silver iodide, benzoic acid, naphthalene acetic acid, and naphsoic acid. , Benzotriazole acid was orally administered once with 312.5, 625, 1250, 2500, and 5000 mg / kg of soybean oil, respectively, and observed dead animals up to 7 days. At this time, the breeding environment was 22 ± 3 ° C., relative humidity 50 ± 10%, and roughness 150 to 300 Lux.

As a result, the LD ₅₀ values in male rats were around 2500 mg / kg for sulfuric acid, acetic acid, ascorbic acid, lactic acid, picric acid, etc., silver benzoic acid near 5000 mg / mg, silver iodide, silver chloride, silver The silver naphsoic acid, the silver benzotriazole acid, etc. were respectively 5000 mg / kg or more. All of these results showed lower acute toxicity compared to silver nitrate (LD ₅₀ = 50 mg / kg), and especially silver silver benzoic acid and silver naphthaleneacetic acid used in this patent were found to be very safe compounds.

As described above, the silver-based antimicrobial compound according to the present invention is a new antimicrobial substance that can replace silver nitrate (AgNO ₃ ), which is commonly used, and thus has low toxicity and anti-coloring as compared with silver nitrate (AgNO ₃ ). The range of application is very wide.

Claims (8)

delete delete Benzoic acid, naphthalene acetic acid, silver naphtheic acid silver and naphthalene sulfonic acid silver 1-50 ppm, 0.001 to 0.5% of a polymer emulsion selected from acrylic emulsion, natural rubber latex, silicone emulsion, fluororesin emulsion, polyurethane emulsion, and A liquid silver antimicrobial composition, characterized in that it contains a solvent or a dispersion medium selected from water, ammonia water and dimethyl sulfoxide (DMSO). delete On a carrier selected from zeolite, calcium phosphate, ocher and charcoal powder Benzoic acid, naphthalene acetic acid, naphsoic acid silver and naphthalene sulfonic acid silver-based antibacterial compound, Silver-based antimicrobial powder, characterized in that the polymer emulsion selected from acrylic emulsion, natural rubber latex, silicone emulsion, fluororesin emulsion, polyurethane emulsion. delete delete delete