KR20060117875A - Antimicrobial detergent compositions - Google Patents

Abstract

Provided is an antimicrobial detergent composition that exhibits an excellent antibacterial activity even at a very low concentration and effectively sterilizes harmful microorganisms including pathogenic bacteria. The antimicrobial detergent composition is prepared by irradiating a solution including silver salts, silicate, and a water-soluble polymer, and comprises nano-size silica silver particles that are obtained by binding nano-size silver to silica molecules and water-soluble polymer and have a size of 0.5-30nm. A concentration of nano-size silica silver particles is 0.1-100ppm. The antimicrobial detergent composition further comprises surfactant.

Description

Antimicrobial detergent compositions

FIG. 1A is a flowchart illustrating a manufacturing process of nano-silica silver, and FIG. 1B is a TEM photograph of nano-silica silver generated after gamma-radiation.

2 shows the colloidal stability of nano-silica silver in water.

Figure 3 shows the results of comparing the absorption spectrum (403 nm) of nano-silica silver with water and silver ions.

4 shows the difference in absorbance (403 nm) of nano-silica silver prepared by varying the concentration of sodium silicate (Na ₂ SiO ₃ ).

5 shows an absorption spectrum (403 nm) of nano-silica silver with varying polyvinylpyrrolidone (PVP) concentrations.

6A and 6B show an absorption spectrum (403 nm) of nano-silica silver prepared by changing the type of water-soluble polymer (high levan or corn starch).

7 shows an absorption spectrum (403 nm) of nano-silica silver according to the change in irradiation dose.

Fig. 8 shows the antimicrobial effect after Rhizoctonia solani was treated with silica, nano-silica silver, 20 nm silver and 100 nm silver.

Fig. 9 shows the antimicrobial effect after Botrytis cinerea was treated with silica, nano-silica silver, 20 nm silver and 100 nm silver.

10 is Escherichia coli ( Esherichia) coli ) , Bacillus subtilis , Pseudomonas syringae subsp. syringae ) shows antibacterial effect according to the concentration of nano-silica silver.

Figure 11 shows the antimicrobial effect of the concentration of nano-silica on the chaetomium globosum ( chaetomium globosum ).

The present invention provides an antimicrobial detergent composition comprising 0.5 to 30 nm size nano-silica silver particles prepared by irradiating a solution containing silver salts, silicates, and water-soluble polymers with silica molecules and water-soluble polymers, and formulations thereof. The present invention relates to an antimicrobial cleaning agent prepared by chemical purification.

Microorganisms exist all around us, and there are also beneficial microorganisms that help humans, but on the other hand, there are harmful microorganisms that cause problems such as disease, odor, and aesthetic disgust. In particular, microorganisms exist in the body such as hair, body, hands, feet, etc. by the external environment, and microorganisms are present in the hair of a pet in large quantities. In addition, microorganisms exist in foods such as vegetables, fruits, fish, cooking utensils, tableware or cooking places, and microorganisms exist in toilets and the like. Human life is threatened by these existing microorganisms, and there is a need for an antimicrobial cleaner for sterilization and cleaning of microorganisms for safe and hygienic life. Accordingly, various antimicrobial cleaners have been developed.

For example, Korean Patent Application No. 2001-0081622 includes a deodorant function for odor generated in the kitchen, including pine needle extract and two or more organic acids, and an antibacterial function for microorganisms that cause odor or harmful to human body. Detergent compositions are disclosed. However, the composition disclosed above has a problem that the effect is not sufficient because the antibacterial effect is not sufficient when used in a conventional dilution ratio.

On the other hand, silver (Ag) is known as a potent fungicide that kills bacteria by minimizing and incapacitating enzymes that act on the metabolic function of unicellular bacteria (TN Kim, QL Feng, et al. J. Mater. Sci. Mater. Med., 9, 129 (1998). In addition to silver, heavy metals such as copper and zinc may also perform the same action, but silver has the strongest antibacterial effect and is also known to have an excellent effect on algae. As a substitute for chlorine and other toxic microbicides, continuous research has been conducted. To date, various inorganic antimicrobial agents using silver have been developed. For example, Korean Patent Application No. 10-2002-0021398 discloses a detergent composition having a sterilizing function and a manufacturing method by adding a solution activated with silver ions by electrolysis of high purity silver to the detergent. However, the compositions and methods disclosed in the patent are not only expensive to electrolyze silver but also difficult to make sufficient expectation for stability and antibacterial effect because the detergent composition containing silver ions is not specifically presented. have.

In addition, silver present in the ionic state has a good antibacterial activity, but due to its high reactivity, the state is unstable, so it is easily oxidized or reduced to metal depending on the surrounding environment, discoloring itself or causing coloring phenomenon in other materials, which has the disadvantage of poor sustainability. On the other hand, silver in the form of metals or oxides is stable to the environment, but has a disadvantage of using a relatively large amount due to low antibacterial activity.

Silver having the advantages and disadvantages as described above is currently in the spotlight of the nano-particles, and the nano-particle manufacturing method used in the antimicrobial cleaning agent using nano-silver, mechanical grinding (grinding) method, coprecipitation method, spraying method, There are various types such as sol-gel method, electrolysis method, and reverse phase microemulsion method, but such a manufacturing method has a problem in that it is difficult to control the size of particles to be formed or a lot of expense is required in preparing fine metal particles. For example, coprecipitation can not control particle size, shape, and size distribution by preparing particles in aqueous solution. Electrolysis and sol-gel methods are expensive to manufacture and difficult to mass-produce. It is easy to control the shape and size distribution, but the manufacturing process is very complicated and it is not practical.

On the other hand, the method of producing nanometer-sized particles by irradiation is advantageous in that the size, shape and size distribution of the particles can be easily controlled, can be produced at room temperature, and the manufacturing process is simple and mass production is possible at low cost. .

Korean Patent Registration No. 0425976 discloses a method for producing a nanometer-sized silver colloid by radiation and a nanometer-sized silver colloid. In this patent, silver salt is dissolved in tertiary distilled water, and then, as a colloidal stabilizer, sodium dodecyl sulfate (SDS), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), etc. And a method of producing a silver colloid by irradiating with radiation after purging with nitrogen. However, since the silver colloid prepared by this method has a particle size of 100 nm or more, a high concentration is required for use as an antimicrobial agent against microorganisms, especially fungi.

In addition to the methods described above, various attempts have been made to provide nano-silver that can be applied to various applications such as antibacterial, purification, and deodorization, and there is still a need to produce cheaper and more stable nano-silver in a simpler process.

Silicon (Si) is the second most abundant substance on earth, and is known to be absorbed by plants to increase disease resistance and stress resistance (Role of Root hairs and Lateral Roots in Silicon Uptake by Rice.JF Ma et al. Ichii Plant Physiology (2001) 127: 1773-1780 et al.). In particular, when the silicate aqueous solution is treated to plants, it has been reported to have an excellent preventive effect against the main pathogens of plants such as powdery mildew and mildew disease, as well as to promote the physiological activity of plants to induce plant growth, disease resistance and stress resistance. Suppressive effect of potassium silicate on powdery mildew of strawberry in hydroponics. T. Kanto et al. J. GenPlant Pathol. (2004) 70: 207-211 et al.). However, silica does not have a bactericidal effect against direct plant pathogens, and thus does not have an effect when a disease occurs.

Under this background, the present inventors have prepared a nano-silica silver particle in which nano-silver is combined with silica molecules and a water-soluble polymer by mixing silver salts, silicates and water-soluble polymers, and irradiating the same, and thus preparing the nano-silica silver particles The present invention is completed by revealing that it is possible to effectively sterilize harmful microorganisms including pathogens by providing an antimicrobial cleaning composition comprising such particles because the size is uniform and stable and exhibits excellent antimicrobial activity at very low concentrations. It was.

It is an object of the present invention to provide an antimicrobial detergent composition comprising 0.5 to 30 nm size nano-silica silver particles in which nano-silver is combined with silica molecules and water-soluble polymers by mixing silver salts, silicates and water-soluble polymers, and irradiating them with radiation. .

Still another object of the present invention is to provide a detergent prepared by formulating the above antibacterial detergent composition.

In one embodiment, the present invention provides an antimicrobial agent comprising nano-silica silver particles having a size of 0.5 to 30 nm combined with silica molecules and water-soluble polymers, prepared by irradiating a solution containing silver salts, silicates and water-soluble polymers. A cleaning composition.

As used herein, the term "nano-silica silver" refers to a composite in which nano-sized silver particles and silica molecules are combined with a water-soluble polymer. According to one specific embodiment, it can be prepared by irradiating a solution containing silver salts, silicates and water-soluble polymers. As one form of the above composite, a structure in which the nano-sized silver particles formed from the silver ions and silica molecules formed from the silicates, respectively or together surrounded by the water-soluble polymer, can be exemplified. The prepared nano-silica may form nanospheres separated or loose spherical aggregates in the colloidal state (FIG. 1B). These aggregates separate into nanoparticles simply by increasing the temperature. Conventionally, there were nano-silver particles coated with nano silver on silica particles, but unlike the nano-silica silver particles included in the antimicrobial cleaner composition of the present invention, these particles do not contain a water-soluble polymer in the particle composition. In addition, although the water-soluble polymer was used to form nano-silver particles, in this case, the water-soluble polymer was not used as a component of the nano-silver particles but as a dispersant for forming a colloidal solution.

The nano-silica silver included in the composition of the present invention absorbs light having a wavelength of 403 nm unique to the nano-silver as shown in the absorption spectrum shown in FIG. 3, and has a uniform nano particle size as shown in FIG. 1B. The particle size of the nano-silica silver is preferably 0.5 to 30 nm, more preferably 1 to 20 nm and most preferably 1 to 5 nm. Nano-silica silver is prepared by preparing a solution containing silver salt, silicate and water-soluble polymer, and irradiating the solution. The method further includes a bubbling step of bubbling (or purging) with an inert gas before, after or before irradiation with radiation. Nitrogen, argon, etc. can be used as an inert gas, Nitrogen gas is used preferably. This bubbling step is preferably performed for 10 to 30 minutes. In the method, in the preparation of a solution comprising silver salts, silicates and water soluble polymers, a radical scavenger is further included to quench radicals generated by irradiation. Such radical scavengers include alcohol, glutathione, vitamin E, flavonoids, ascrobic acid and the like. Examples of the alcohol that can be used include methanol, ethanol, nor-propanol, isopropanol (IPA), butanol and the like. Double isopropanol can be preferably used. The alcohol may be added in an amount of 0.1 to 20%, preferably 3 to 10% relative to the total solution comprising silver salts, silicates and water soluble polymers.

Silver salts that may be used to prepare the nano-silica silver contained in the composition of the present invention are silver nitrate (AgNO ₃ ), silver perchlorate (AgClO ₄ ), silver chlorate (AgClO ₃ ), silver chloride (AgCl), silver iodide (AgI), silver fluorine (AgF) ), Silver acetate (CH ₃ COOAg), and the like, and silver salt (eg, silver nitrate) that is well soluble in water can be preferably used. The water-soluble polymers used to prepare the nano-silica silver include polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid and derivatives thereof, levan, pullulan, gellan, water-soluble cellulose, glucan, xanthan, water-soluble starch, levan , Corn starch and the like, and double PVP can be preferably used. The silicate used in the production of the nano-silica silver may exemplify sodium silicate, potassium silicate, calcium silicate, magnesium silicate, and the like, and double sodium silicate may be preferably used. Prior to the present invention, the use of silicates for the preparation of nano-silver has not been disclosed. For the first time, the inventors used silicates, which are not in the form of silica, in the reaction with silver salts to provide nano-silica silver in which silica molecules and water-soluble polymers having excellent antimicrobial effects were combined with nano-silver. In the preparation of the nano-silica silver, silver salts and silicates are reacted in the range of 1: 0.5 to 1.3 weight ratio of silver salts: silicates. Preferably, the reaction is carried out at a weight ratio of 1: 1. Depending on the amount of silicate, the particle size of the nano-silica silver can be adjusted. If the amount of silicate is small, the particles become large, and if the silicate is excessive for silver salt, no particles are formed. In the preparation of the nano-silica silver, the silver salt and the water-soluble polymer are reacted in the range of 1: 0.5 to 2.5 by weight of silver salt: water-soluble polymer. Preferably, the reaction is carried out at a weight ratio of 1: 1. For the production of nano-silica, radiation such as beta rays, gamma rays, X-rays, ultraviolet rays, electron beams can be used. Gamma rays of 10 to 30 kGy doses may be preferably used.

In general, nano-sized particles can pass through the plasma membrane, and pathogenic bacteria absorb silica well. Nano-silica silver is absorbed into cells of pathogenic bacteria to increase the bactericidal power by silver-nanoparticles and to form a physical barrier against pathogenic bacteria related to the properties of silica which induces dynamic resistance to disease and increases resistance. Even after sex bacteria are sterilized, the disease can be prevented from recurring for some time.

The antimicrobial detergent composition of the present invention is in the form of a colloidal solution or powder thereof in which nano-silica silver is dispersed / suspended in a known detergent composition, and the weight percentages referred to in the present invention refer to the weight of the entire composition including the solvent. It is a standard.

The nano-silica silver contained in the antimicrobial detergent composition of the present invention preferably has a particle size of 0.5 to 30 nm or less, preferably 1 to 20 nm, more preferably 1 to 5 nm.

Nano-silica silver contained in the antimicrobial cleaner composition of the present invention may contain 0.1 to 100ppm, preferably 0.1 to 50ppm, more preferably 1 to 15ppm.

The term "antibacterial" of the present invention includes not only inhibiting the growth of microorganisms such as bacteria, fungi, etc., but also inhibiting their sterilization by inhibiting their survival.

Nano included in the compositions of the invention - silrikaeun is Candida (Candida), Cryptococcal kusu (Cryptococcus), Aspergillus (Aspergillus), tricot python (Trichophyton), trichomonas (Trichomonas), keto hate (Chaetomium), article Rio Cloud Gliocladium , Aureobasidium , Penicillium , Rhizopus , Cladosporium , Mucor , Pullularia , Trichoderma Trichoderma), Fu saryum (Fusarium), mazes potassium (Myrothecium), fungi and S, such as membrane say Ella (Memnoniella) cherry Asia (Escherichia), Bacillus (Bacillus), pseudo Pseudomonas (Pseudomonas), Kane Tony Stadium (Chetonium), star indicates a pillow Rhodococcus (Staphylococcus), keulrep when Ella (Klebsiella), Legionella (Legionella), salmo Pasteurella (Salmonella), Vibrio (Vibrio), excellent antimicrobial activity against bacteria such as rikechiah (Rickettsia).

The term "cleaner" of the present invention refers to materials and articles capable of building up, removing or dispersing solid and liquid dirt from the surface being cleaned, and the term "cleaning" refers to removing unwanted substances or microorganisms from the surface.

Antimicrobial detergent composition comprising 0.5 to 30 nm size nano-silica silver particles prepared by irradiating a solution containing the silver salt, silicate and water-soluble polymer of the present invention with nano-silver silica particles and water-soluble polymer as an active ingredient Silver surfactants, stabilizers, preservatives, wetting agents, antioxidants, colorants, water and the like and admixtures of at least one of these can be included. These adjuvants may be present in amounts of 98.0 to 99.9 weight percent of the composition.

Surfactants included in the compositions of the present invention may include surfactants known to those skilled in the art, including nonionic, anionic, cationic and amphoteric surfactants, the amount of which is 30 weight of the total composition. At least%, preferably at least 70% by weight. Selecting and determining the type and amount of the surfactant can be easily made by a person skilled in the art, and considering the precipitation degree, turbidity, etc. of the composition of the present invention, it is possible to select a surfactant suitable for colorless or colored. .

Preferred stabilizers that may be included in the compositions of the present invention may include, but are not limited to, glycol stearate. If a stabilizer is used its amount is typically about 0.1-5% by weight of the composition.

Preferred preservatives which may be included in the compositions of the present invention include, but are not limited to, tetrasodium ethylenediamine tetraacetic acid (EDTA), 1- (3-chloroallyl) -3,5,7-traaza-1-adama Tan, paraben, methylparaben, mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, phenoxyethanol, benzyl alcohol, benzophenone -4, methylchloroisothiazolinone, methylisothiazolinone, and the like and mixtures thereof. If a preservative is used, its amount is typically about 0.01 to 6% by weight of the composition, the preferred amount is about 0.05 to 4% by weight, more preferably about 0.1 to 2% by weight.

Preferred wetting agents that may be included in the compositions of the present invention include wheat protein (e.g., laudimonium hydroxypropyl hydrolyzed wheat protein), hair keratin amino acids, sodium peroxylincarbolic acid, panthenol, tocopherol (vitamin E), Dimethicone and the like and mixtures thereof. In addition, sodium chloride may be present, especially when hair keratin amino acids are included as wetting agents. Wetting agents are typically used from about 0.01 to 10% by weight, preferably from about 0.05 to 1.5% by weight, more preferably from about 0.01 to 1% by weight of the composition.

Preferred colorants that may be included in the compositions of the present invention include FD & C Green No. 3, Ext. D & C Violet 2, FD & C Yellow 5, FD & C Red 40, and the like and mixtures thereof. When used as a colorant, it is typically about 0.001 to 0.1% by weight of the composition, preferably about 0.005 to 0.05% by weight.

Antioxidants that may be included in the compositions of the present invention may be used both enzymatic and non-enzymatic antioxidants. Examples of natural enzymatic antioxidants include peroxide dismutase (SOD), catalase and glutathione peroxidase. Suitable non-enzymatic antioxidants include vitamin E (e.g. tocopherol), vitamin C (ascorbic acid), carotenoids, echinacoside and caffeoyl derivatives, oligomeric proanthocyanidins or proantanol (e.g. grapes). Seed extract), silymarin (eg milk thistle extract, silyboom marianium), ginkgo biloba extract ( Ginkgo biloba extracts), green tea polyphenols, and mixtures thereof. Carotenoids are potent antioxidants and examples thereof include beta-carotene, canthaxanthin, zeaxanthin, lycopene, lutein, crocetin, capxanthine and the like. Preferred antioxidants are vitamin E, vitamin C or carotenoids. Typical amounts of antioxidants are from about 0.001 to 1% by weight of the composition, with a preferred amount of about 0.01 to 0.5% by weight.

The composition of the present invention may contain other adjuvants commonly used in the art. Examples of such adjuvants include perfumes, dyes, solvents, opacifiers or pearlescent agents (e.g., esters of fatty acids and polyols, magnesium salts and zinc salts of fatty acids), copolymer dispersions, thickening agents (e.g. sodium chloride, potassium chloride, Ammonium chloride and sodium sulfate), fatty acid alkylolamides, cellulose derivatives, natural gums, plant extracts, albumin derivatives (e.g. gelatin), collagen hydrolysis products, natural or synthetic polypeptides, egg yolk, lecithin, lanolin and lanolin derivatives, fats , Oils, fatty alcohols, silicones, diodorants, antimicrobial agents, anti seborrheic substances, keratinizers (e.g. sulfur, salicylic acid, benzoyl peroxide, selenium sulfide, PG, FA, enzymes) and keratant agents (e.g. tar, sulfur , Salicylic acid, selenium sulfide, antibacterial agent, benzoyl peroxide, chlorhexidine, iodine, triclosan, antifungal agent, enzyme).

As one specific aspect of the present invention, the present invention is to provide a detergent prepared by formulating the antimicrobial detergent composition.

The antimicrobial cleaning composition according to the present invention includes, for example, a cleaning agent for washing a human body, a cleaning agent for washing a living environment, and the like.

In one specific embodiment, cleaners for use in cleaning the human body include, but are not limited to, hair toiletry, hair dressing and skin toiletry. Examples of these preparations include hair soaps, hair creams, aqueous and aqueous-alcoholic hair lotions, wave-setting lotions (hair fixatives), hairdressing creams and gels, hair sprays, hair tonin, hair oils, hair pomades, hair brilliants, and the like. And especially hair rinses and shampoos. Examples of skin toys include solid, liquid or powdered soap and detergent compositions, liquid creams and skin gels, skin oils, face lotions, astringents and deodorants, and the like.

In another specific embodiment, a cleaner for use in washing a living environment includes, but is not limited to, a cleaner for washing contaminants and microorganisms remaining in food; Cleaners for washing contaminants and microorganisms native to dishes, cooking utensils, household goods, and the like; Detergents for effectively washing contaminants and microorganisms native to infant products such as baby bottles and nipples; It can be used as a cleaning agent for effectively cleaning contaminants and microorganisms native to the places used for living such as walls, floors and the like.

The invention will be explained in more detail through the following examples. These examples are presented by way of example only, so that the present invention may be more understood, these examples should not limit the scope of the invention.

Example  1: with silica molecules and water-soluble polymers Combined  Nano- Silica of  Produce

1 g of sodium silicate (Na ₂ SiO ₃ ), 1 g of silver nitrate (AgNO ₃ ), 1 g of polyvinylpyrrolidone (PVP), and 12 ml of isopropyl alcohol (IPA) were added to distilled water and dissolved to a total volume of 200 ml. Ni-gas was prepared by bubbling by injecting nitrogen gas into the solution for 20 minutes and irradiating with gamma rays of 25 kGy.

Figure 1a is a flow diagram showing an embodiment of a method for producing nano-silica combined with silica molecules and water-soluble polymers in accordance with the present invention. The solution formed after gamma irradiation showed yellow color indicated by nano-silver particles. This demonstrates that the silica molecules formed by the reaction, the water-soluble polymer, and the silver particles combine to form stable nano-sized particles.

In order to confirm whether the particles prepared by the reaction were nano-silver particles, test spheres as shown in Table 1 were prepared, and left at room temperature for 24 hours to check the color change.

Test Manufacture Liquid Distilled water tap water Irradiation TW 0 0 45 ml ○ A 90 μl 0 45 ml ○ B 90 μl 45 ml 0 ○ C 90 μl 0 45 ml × D 90 μl 45 ml 0 × DW 0 45 ml 0 ○

*: Refers to the dissolved solution prepared in the above example.

TW: Tab water

DW: Deionized water

Test spheres A and B are prepared solutions in which the prepared solution is irradiated with radiation, and test spheres C and D are prepared solutions in which Ag ⁺ ions not irradiated are present. Test zones TW and DW are controls without silver ions or silver particles.

Ionic silver is easily oxidized and, if Cl ⁻ ions are present, they are browned and immediately precipitated with AgCl. Therefore, tap water containing Cl ⁻ ions can be used to check the state of silver. Ag ⁺ When present in an ionic state, it forms a precipitate and appears yellow when present as stable nano-silver particles. The results are shown in Table 2.

Test Color change TW Colorless → Colorless A Yellow → yellow B Yellow → yellow C Colorless → Reddish Brown D Colorless → Colorless DW Colorless → Colorless

As shown in Table 2, TW spheres, D spheres, and DW spheres were colorless without change of color after the first 24 hours, which means that no silver ions, chlorine ions, or silver ions and chlorine ions are present. On the other hand, sphere C changed color from colorless to reddish brown because silver ions formed AgCl with chlorine ions in tap water. On the other hand, spheres A and B showed yellow color without any change in color, indicating that stable nano-silver particles combined with silica molecules and water-soluble polymers were formed by irradiation to prevent AgCl precipitation even in the presence of chlorine ions. Indicates. This color change is shown in FIG.

The absorption spectrum of the prepared nano-silica silver of the present invention is shown in FIG. 3. FIG. 3 shows the absorption spectra of the preparations of the test spheres DW, B, and D shown in Table 2, and only the test zone B absorbs light having a wavelength of 403 nm, which is unique to nano-silver, and the test zones DW and D have the same wavelength. Did not absorb light.

As can be seen from the above neglect and absorption spectra results, stable nano-silica silver particles in which silica molecules and water-soluble polymers were combined by radiation irradiation with a solution containing sodium silicate, silver nitrate and PVP.

1b is a photograph of the prepared nano-silica silver observed with a transmission electron microscope (TEM). As seen in FIG. 1B, the nano-silica silver particles have a uniform particle size distribution with particle sizes of 1 to 5 nm less than 20 nm. Nano-silica silver particles may be isolated independently or form loose spherical aggregates caused by intermolecular attraction.

Example  2: silica molecules and water-soluble polymers Combined  Nano- Silica of  Produce

Performed in the same manner as in Example 1, but was prepared while only changing the concentration of sodium silicate (Na ₂ SiO ₃ ) to 0.5 to 2g. The test plots with varying concentrations are shown in Table 3.

Test lunar caustic Sodium silicate Total volume A 1 g 0.5g 200 ml B 1 g 0.75 g 200 ml C 1 g 1.0 g 200 ml D 1 g 1.5 g 200 ml E 1 g 2.0 g 200 ml F No gamma irradiation

Absorbance difference and color difference for nano-silica silver according to the concentration change of sodium silicate shown in Table 3 are shown in FIG.

As shown in Figure 4, the sodium silicate has the highest absorbance when the ratio of silver nitrate and 1: 1, the absorbance is reduced when the sodium silicate is 1.5 times or more than the silver nitrate. In addition, when the sodium silicate is 0.5 times or less than silver nitrate, the size of the silver particles is increased, as confirmed by the orange gold color.

As can be seen from the above observation, the amount of silicate added is important in the preparation of the nano-silica and the particle size of the nano-silica may be controlled by adjusting the amount of the silicate.

Example  3: with silica molecules and water-soluble polymers Combined  Nano- Silica of  Produce

It was carried out in the same manner as in Example 1, but prepared while changing only the concentration of polyvinylpyrrolidone (PVP) to 0.5 to 2g.

Absorbance difference and color difference for nano-silica silver according to the concentration change of PVP are shown in Table 4 and FIG. 5.

Test lunar caustic Sodium silicate PVP Total volume Absorbance (403nm) One 1 g 1 g 0.5g 200 ml 0.267 2 1 g 1 g 1 g 200 ml 0.325 3 1 g 1 g 2 g 200 ml 0.284 DW 0 0 0 200 ml 0.016

As shown in Table 4 and FIG. 5, polyvinylpyrrolidone (PVP) may be used at a concentration of 0.5 to 2 times that of sodium silicate (or silver nitrate) when sodium silicate and silver nitrate are used at the same ratio.

Example  4: silica molecules and water-soluble polymers Combined  Nano- Silica of  Produce

Performed in the same manner as in Example 1, but prepared using high levan or corn starch instead of only polyvinylpyrrolidone (PVP). Absorbance and absorbance spectra for the prepared nano-silica silver are shown in Table 5 and FIGS. 6A and 6B.

Test Absorbance (403nm) High Levan 0.208 Corn starch 0.211

As shown in Table 5 and FIGS. 6A and 6B, nano-silica silver may be prepared from polysaccharides such as levane or corn starch, although the absorbance is lower than that of polyvinylpyrrolidone (PVP).

Example  5: silica molecules and water-soluble polymers Combined  Nano- Silica of  Produce

It was carried out in the same manner as in Example 1, but was performed only by varying the radiation dose. Absorbance and absorbance spectra for the prepared nano-silica silver are shown in Table 6 and FIG. 7.

Gamma Radiation Dose Absorbance (403nm) Gamma Radiation Dose Absorbance (403nm) 05 kGy 0.037 20 kGy 0.152 10 kGy 0.063 25 kGy 0.184 15 kGy 0.115 30 kGy 0.211

As shown in Table 6 and Figure 7, the absorption was also shown at 10kGy and the absorption increased as the radiation dose increased. Thus, nano-silica silver can be prepared using radiation above 10 kGy.

Experimental Example  1: nano- Silica of  Antifungal activity against fungi

1-1. Nano- Silica of Liqtonia  And To Botrytis  Antifungal effect

The microbial culture medium (Difco PDA medium) was autoclaved and dispensed in 25 ml of Petri dishes, and before solidification (around 40 DEG C), silica molecules were mixed in Test A and B in Test B. Nano-silica silver was prepared in the mixing, 20 nm size silver particles were mixed in the test zone C, 100 nm size silver particles were mixed in the experimental zone D, and cooled to prepare a medium. Rhizoctonia solani (Department of Agricultural Biology, Chungnam National University) and Botrytis Ceria ( Botrytis ) were prepared in the prepared medium. cinerea ; A solid medium cultured with Chungnam National University) was inoculated with a 5 mm diameter circle and inoculated, and cultured at room temperature for 2 days to confirm the growth of microorganisms. The concentration of the mixed material in each test sphere was 6 ppm and 0.3 ppm.

As shown in FIG. 8, the test group A containing only silica molecules showed the same results as the control regardless of the concentration, and the control group at the concentration of 0.3 ppm in the C and D test groups containing 20 nm silver and 100 nm silver. The same result as shown. However, in the B test sphere containing the nano-silica silver of the present invention, the growth inhibition effect of Rhizoctonia solani was remarkable even at a low concentration of 0.3 ppm.

In addition, as shown in FIG. 9, the test group A containing only silica molecules showed the same results as the control regardless of the concentration, and the concentration of 0.3 ppm in the test group B and D mixed with silver of 20 nm and silver of 100 nm Shows the same result as the control. However, the C test spheres mixed with nano-silica silver showed remarkably superior growth inhibition effect of Botrytis cinerea compared to 20 nm silver and 100 nm silver even at a low concentration of 3 ppm.

1-2. Nano- Silica of  Antimicrobial effect on pathogenic fungi

Candida rucitania lusitaniae), Candida Trophy Charis (Candida tropicalis), Candida albicans (Candida albicans), Candida krusei (Candida krusei), Candida Gras Braga other (Candida glabrata ), Candida parapsilosis , Cryptococcus neoforms ( Cryptococcus) neoformans ), Mucor Ramosis mousse ramosissmus), Aspergillus Fu Micah Charters (Aspergillus fumigatus), Aspergillus plastic booth (Aspergillus flavus ) and Minimal Inhibitory Concentration (MIC) concentrations were measured for Aspergillus terreus . Nano-silica silver, tolnaftate, amphotericin B, and itraconazole for the MIC concentrations of the strains were measured by AFST-EUCAST (Anitifungal Susceptibility Testing Subcommittee of the European Committee on Antibiotic Susceptibility Testing ; Rodriguez-Tudela et al., (2003) Method for the determination of minimum inhibitory concentration by broth dilution of fermentative yeasts.Clinical Microbiology and Infection, 9, I-VIII). This process is described in the National Committee for Clinical Laboratory Standards (2002) Reference Method for Broth Dilution Antifungal Susceptibility Testing of Yeast-Second Edition: Approved Standard M27-A2.NCCLS, Wayne, PA, USA. for Clinical Laboratory Standards) reference process.

Specifically, Candida among pathogenic fungi Ryu and Cryptococcus neoformans and Mucor ramosissmus are used for 24 hours using Dextrose agar medium (SDA), while Cryptococcus neoformans and Muco ramossis are 48 hours. Incubate at 35 ° C. for 5 hours, collect 5 colonies of 1 mm or less, suspend them in 5 ml of physiological saline (8.5 g / L NaCl; 0.85% saline), and use the RPMI 1640 medium. ^The cells were adjusted to ³ cells / ml and used as inoculum bacteria. In addition, Aspergillus was incubated for 7 days at 35 ° C. using potato dextrose agar medium (PDA), and 5 ml of sterilized distilled water and a drop of Tween 20 were added to the spores. Scrape and put in a test tube and allowed to stand for 3 to 5 minutes, then only the supernatant was taken to control the concentration of the bacteria solution to 2 × 10 ⁴ CFU / ㎖ was used as inoculum bacteria. Nano-silica silver of the antifungal activity was used as the nano-silica silver prepared in Example 1, which was again made a 2-fold dilution series using RPMI 1640 medium. In addition, tolnaftate, amphotericin B, and itraconazole, the control drugs, were dissolved in dimethyl sulfoxide (DMSO) and made a 2-fold dilution series using RPMI 1640 medium. Final concentration was 2.5%. 100 μl of the dilution medium prepared above and 100 μl of the inoculum solution were dispensed into a 96 well plate, and adjusted so that the final concentration of the 2-fold dilution series was 128 μg / ml to 0.0313 μg / ml. 96 well plates inoculated with Candida and Aspergillus fumigatus were incubated at 35 ° C. for 48 hours, while Cryptococcus neoformans and Mucor ramosissmus were 35 ° C. Incubated for 72 hours at. After cultivation, visual observation was performed to determine the concentration at which the growth of bacteria was inhibited as the minimum growth inhibition concentration (MIC) (1 ≧ µg / ml). The results are shown in Table 7.

Pathogenic fungi Nano-silica silver Tolnaftate Amphotericin B Itraconazole Aspergillus flavus ATCC 64025 2 > 128 4 0.25 Aspergillus fumigatus ATCC 16424 One 64 One 0.5 Aspergillus terreus ATCC 46941 One 0.25 16 0.0625 Candida albicans ATCC 10231 One > 128 0.5 0.0625 Candida albicans A207 (clinical isolate) 2 > 128 0.5 0.0625 Candida glabrata ATCC 48435 4 > 128 One One Candida krusei ATCC 6258 One > 128 One 0.25 Candida lusitaniae ATCC 42720 0.5 > 128 0.5 0.125 Candida parapsilosis ATCC 34136 One > 128 One 0.25 Candida tropicalis ATCC 13803 2 > 128 0.5 0.0625 Cryptococcus neoformans ATCC 36556 8 > 128 0.125 0.25 Mucor ramosissmus ATCC 90286 One > 128 0.25 One

Unit: μg / ml

As shown in Table 7, nano-silica silver showed antifungal activity against Candida, Cryptococcus, Muco and Aspergillus pathogenic fungi.

Experimental Example  2: nano- Silica of  Antibacterial Effect According to Concentration

In order to investigate the growth inhibition effect of bacteria according to the concentration of nano silver combined with silica molecules and water-soluble polymers, Escherichia coli ), Bacillus subtilis KCTC 1021, Pseudomonas syringae subsp . syringae KCTC 2440) was used. Placed in a conical flask 500㎖ 100㎖ LB medium, with shaking at 190rpm group rotary aerobic conditions, in the 37 ℃ S. Cherry cyano coli (Escherichia coli), and the other bacteria were cultured at 30 ℃ 15 to 16 hours. After incubation, 20 μl of the culture solution of each strain was inoculated in LB agar medium containing nanosilver combined with silica molecules and water-soluble polymers at concentrations of 0, 1, 10, 100, and 1000 ppm. Escherichia coli was then incubated at 37 ° C. and the rest of the bacteria at 30 ° C. for 6-7 days.

Escherichia coli (Esherichia coli), Bacillus subtilis (Bacillus subtilis 1021), Pseudomonas Syringe (Pseudomonas syringae subsp.syringae 2440 growth inhibition effect is shown in FIG.

In the Gram-positive bacillus Bacillus subtilis, growth was reduced at 10 ppm compared to the control (LB agar plate). The growth of each strain was similar in, and the growth of nano-silica was completely inhibited in 100ppm containing medium.

Experimental Example  3: nano- Silica of To living bacteria  Antibacterial effect

In order to examine the antimicrobial effect on living bacteria according to the concentration of nano-silica silver, the concentration of nano-silica silver was 0.32ppm, 3.2ppm, 6.4ppm, 10ppm, and the ketomoglobulium (living bacteria at each concentration) Chaetomium The growth inhibition effect of globosum KCTC 6988) was confirmed.

Specifically, inoculation of the bacterium of the bacterium Chaetomium globosum KCTC 6988 (6 mm in diameter) into the MSA (Mineral Salts agar) plate medium containing 0.3-ppm, 3.2 ppm, 6.4 ppm, and 10 ppm of nano-silica silver Sections were inoculated and incubated for 7 days at 25 ° C. incubator. On the 7th day, the anti-microbial effect was compared with that without the nano-silica. The results are shown in Table 8 and FIG.

Fungus Inhibition rate of mycelial growth (%) 0 ppm 0.32 ppm 3.2 ppm 6.4 ppm 10 ppm Chaetomium globosum 0 100 100 100 100

Even when the concentration of the nano-silica silver was 0.32 ppm, the growth of ketium globodium was not observed. As a result, it was found that the nano-silica silver had an excellent antibacterial effect.

Experimental Example  4: nano- Silica of Rat  Used Transdermal administration  Toxicity Test

For the acute toxicity test of nano-silica silver in rats, SPF rats (supplied by Orient Co., Ltd.) rats (219.1 to 231 g) and five males (257.9 to 285.2 g) were used. As a group, the first group was percutaneously administered with sterile distilled water (manufactured by foreign pharmaceuticals) at a dose of 2 ml / kg / day, and the second group was 2 ml / kg of the nano-silica silver prepared in Example 1 Percutaneously administered at a dose of / day.

As a site for administration and the method of administration, the hair of the animal's dorsal area is depilated 6 × 8 cm 2 on the day before administration, and sterile distilled water or nano-silica silver for injection is applied to two layers of 4 × 4 cm 2 gauze on the day of administration. After uniform application at a dose of 2 ml / kg / day, sterile distilled water or nano-silica silver for injection was attached to the epilation site, and the vinyl epithelium was adhered to the epilation site using a medical bandage. The residual material was removed and washed with physiological saline, and observed for the following side effects or lethal for 8 days after administration.

On the day of dosing, toxic symptoms and the presence of dead animals were observed at least once daily at 1, 3 and 6 hours until 6 hours after administration, and at least once daily from the next day to 8 days after administration. Body weights were measured on days 4 and 8, and on day 8 after administration, the abdominal aorta was cut and bleeded after being opened under CO ₂ anesthesia.

As a result, in the case of acute toxicity transdermal administration, the mortality rate, general lesion symptoms, weight change and autopsy findings were not observed for 8 days at the dose of 2ml / kg / day.

Experimental Example  5: nano- Silica of  Antifungal Effect of Surfactant Addition

The antifungal effect of the nano-silica silver solution of Example 1 with surfactant added was investigated. Among the surfactants, PEG-400 (polyethylene glycol, CELL CHEMICAL) and CELNON-80TW (Sorbitan monoolate, CELL CHEMICAL) were selected. Aspergillus niger KCTC 6960 diluted with 3.25 × 10 ⁴ spores / ml with 0.05% Tween 20 solution was inoculated with a surfactant ratio of 9: 1 incubator at 9: 1 and left to stand for 60 minutes. The antifungal effect of the nano-silica silver added with surfactant was confirmed by smearing and incubating on PDA and MEA plates. The results are shown in Table 9. The positive control group was an aqueous solution of pure nano-silica silver with no surfactant added, and the negative control group was an aqueous solution in which only the surfactant was added to distilled water without adding the aqueous nano-silica solution.

Sample Colony No. PEG-400 0 80 TW 0 (+) Control 0 (-) Control 76

As seen above, it was confirmed that the nano-silica silver solution added with the surfactant except the (-) control group had the same antibacterial effect as the nano-silica silver solution without the surfactant added.

Experimental Example  6: nano- according to the mixing ratio of the surfactant Silica  Color and transparency of the solution

In order to investigate the chromaticity and transparency of the nano-silica silver solution according to the mixing ratio of the surfactant, 100-mL solution was prepared by adding nano-silica silver, TW-80 as a surfactant and water at various ratios, and the control and color and transparency were investigated. It was. The results are shown in Table 10.

division Content (ml / 100ml) Sedimentation degree ^a Turbidity ^b Chromaticity ^c 80 TW NSS S-1 0.5 0.2 0 0 One S-2 0.6 0.2 0 0 One S-3 0.7 0.2 0 0 One S-4 0.8 0.2 0 0 0 S-5 0.9 0.2 0 0 0 S-6 One 0.2 0 0 0 S-7 One 0.4 0 0 2 S-8 1.5 0.4 0 0 One S-9 2 0.4 0 0 0 S-10 2.5 0.4 0 0 0 S-11 3 0.4 0 0 0 S-12 5 One 3 3 5 ^d S-13 10 One 3 2 5 ^d S-14 15 One 3 2 5 ^d S-15 20 0.2 3 One 5 ^d

 a: Degree of precipitation-(none) 0 →→→→→→ 3 (diameter 5 mm or more)

b: Turbidity-(none) 0 →→→→→→ 3 (complete)

C: Chromaticity-(white) 0 →→→→→→ 5 (no change; chromaticity when NSS is added to DW)

d: turns grayish brown after a certain time

As seen above, S-1 to S-11 did not have any precipitation and turbidity, but S-12 to S-15 disappeared after the initial preparation, and precipitation and turbidity and color change occurred after 3 days. It was. Inversely proportional to the 80TW content, the higher the 80TW content was, the less precipitation and color change were observed. The 80TW content was observed to be 2-5 times higher in color than the nano-silica silver content.

Experimental Example  7: nano- Silica  Investigation of the precipitation of shampoo formulations containing particles

In the case of preparing the shampoo formulation containing the nano-silica silver particles, various changes were made to the additives and the manufacturing process in order to investigate whether the nano-silica silver particles were precipitated. Table 11 below shows the content of ingredients added in shampoo formulation.

division SPB -One SPB -2 SPB -3 Content (100 ml total) 30% Sodium Lauryl Sulfate 20.0 20.0 20.0 30% Sodium Polyethylenelauryl Sulfate 30.0 30.0 30.0 Palm oil fatty acid diethanolamide 3.0 3.0 3.0 Propylene glycol 2.0 2.0 2.0 Purified water + paraoxybenzoic acid 44.7 + 0.2 44.7 + 0.2 44.9 + 0.0 Nano-silica silver 0.1 0.1 0.1

SPB-1 was mixed in order of 30% sodium lauryl sulfate, 30% sodium lauryl sulfate, palm oil fatty acid diethanolamide, and propylene glycol, followed by warming and stirring at 70 ° C. for 12 minutes. To this mixture was added a mixture of purified water mixed with paraoxybenzoate and stirred for 10 minutes. Prepared by adding the aqueous solution of nano-silica at 58 ° C. and stirring again for 10 minutes.

SPB-2 is mixed with 30% sodium lauryl sulfate, 30% sodium lauryl sulfate, palm oil fatty acid diethanolamide, and propylene glycol, followed by stirring and warming up to 75 ° C. The mixture was stirred for 10 minutes by mixing with each other and stirred for 10 minutes, then added to the liquid nano-silica silver at 70 ℃ and stirred for 10 minutes in a hot water was stopped.

SPB-3 was prepared in the same manner except that paraoxybenzoate was not added in the above SPB-2 preparation method. Paraoxybenzoate is used as a preservative in shampoo formulations, and nano-silica is also excluded because it has antibacterial and antifungal activity.

The results are shown in Table 12 below. Precipitation did not occur in SPB-1 and SPB-2, but in SPB-3 without the addition of paraoxybenzoate, precipitation was remarkably visible.

division SPB -One SPB -2 SPB -3 Sedimentation - - +

Experimental Example  8: nano- Silica  Antimicrobial activity of cleaning agents containing particles

In order to compare the antimicrobial and bactericidal power of the cleaning agent according to the concentration of nano-silica silver in the cleaning agent containing nano-silica silver, the solution type cleaner (manufactured by Sino-Japan Emulsification Co., Ltd.) and the powder type cleaner (manufactured by Sarom Oil) were diluted 3,000 times in distilled water. A sample solution was prepared by adding nano-silica silver solution at 3.2 ppm and 6.4 ppm concentrations. The control was treated in distilled water without addition of the detergent. 500 ml of these samples and the control and spore dilution (3 × 10 ⁴ spores / ml) of Aspergillus niger KCTC 6960 were separated by 20 cm in two or three times with a single spray of about 0.8 ml. After spraying onto a test cloth (Cotton cloth, 100 × 100mm), the test piece incubated for 48 hours in a humidity maintained at 95% or higher and 25 ° C. was put in a square tray, and stirred for 15 or 30 minutes at 120 rpm in a rotary shaker. . After the sample solution and the control solution were removed, sterile water was added and shaken vigorously to perform the washing twice, and the spore sac of Aspergillus sniger was examined by culturing in a wet state and incubation at 25 ° C. The results are shown in Table 13 below.

Sample Sporangium number 15 min. 30 min. One 2 3 One 2 3 Powder Cleaner Nano-silica is 0 ppm 14 2 One One 0 0 Nano-Silica 3.2 ppm 0 0 0 0 0 0 Nano-silica 6.4 ppm 0 0 0 0 ^a 0 ^a 0 ^a Solution Cleaner Nano-silica is 0 ppm 3,175 ^b 13,950 ^b 9,425 ^b 4,225 ^b 9,650 ^b 14,550 ^b Nano-Silica 3.2 ppm 0 0 0 0 0 0 Nano-silica 6.4 ppm 0 0 0 0 0 0 Control 10,675 10,625 11,800

^a : The yellow color of the nano-silica silver solution appears after 2 washes.

^b : Since the number of spore sacs was large, the number of spore sacs with an area of 2x2 cm was measured and multiplied by 25.

The results showed that 100% of sporangium formation was suppressed in all samples in which nano-silica silver was added to the existing product. In the sample without the addition of nano-silica silver, the powdered detergent had a relatively high bactericidal power, but the solution-type detergent had no bactericidal power and showed similar spore sac formation as the control. The sample mixed with 6.4 ppm of the powdered detergent and the nano-silica silver was colored yellow after the second washing, but was not colored in the same concentration of the solution detergent. The detergent addition amount of the nano-silica silver was the most uncolored and high bactericidal effect was obtained when the final dilution use concentration is 3.2ppm.

The present invention is an antimicrobial cleaning composition comprising a nano-silica silver particles of 0.5 to 30nm size combined with a silica molecule and a water-soluble polymer, nano-silver prepared by irradiating a solution containing silver salt, silicate and water-soluble polymer, the microorganism By cleaning the surface of the human body and objects contaminated with antibacterial effect, it is possible to maintain a clean environment free from contamination.

Claims (6)

An antimicrobial detergent composition comprising nano-silica silver particles having a size of 0.5 to 30 nm combined with silica molecules and water-soluble polymers, prepared by irradiating a solution containing silver salts, silicates and water-soluble polymers. The composition of claim 1, wherein the concentration of the nano-silica silver is 0.1 to 100 ppm. The composition of claim 1 further comprising a surfactant. An antimicrobial cleaner comprising the composition of claim 1. The detergent of claim 4, which is a shampoo or hairdressing. The cleaning agent according to claim 4, which is selected from a food cleaner, a dish cleaner, a laundry cleaner, a household cleaner, and a baby cleaner.

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