KR100587465B1 - Inorganic antibiotic agent with silver and thermal plastic resin master batch containing its - Google Patents

Abstract

The present invention is a masterbatch of a porous inorganic antimicrobial agent carrying silver and a thermoplastic resin containing the same, having antibacterial properties for long time use and excellent discoloration resistance to ultraviolet rays and discoloration resistance to heating when mixed with the resin. It relates to the manufacture of.

Inorganic antibacterial agent, silver (Ag), antibacterial, thermoplastic masterbatch

Description

Inorganic antibiotic agent with silver and thermal plastic resin master batch containing its

1 is a view showing an energy dispersive X-ray spectroscopic analysis of a representative silver-supported inorganic antimicrobial agent of the present invention, and

Figure 2 is a view showing the energy dispersion X-ray spectroscopic mapping analysis results of the representative silver-based inorganic antimicrobial agent of the present invention.

The present invention relates to a silver-supported inorganic antimicrobial agent capable of exhibiting excellent dispersibility in processing with a resin, extremely low discoloration and deterioration of the resin, and capable of exhibiting stable antibacterial activity over a long period of time, and more particularly, to a masterbatch of a thermoplastic resin including the same. For example, an antimicrobial thermoplastic resin prepared by blending, extruding, and molding an inorganic antimicrobial agent having silver supported on a carrier such as particulate precipitated silica, acid-treated kaolin, and layered clay minerals in thermoplastic resins such as polyethylene, polyamide, ABS, and polypropylene. It is about providing a masterbatch.

In general, it is known that metal ions such as silver ions, metal ions such as zinc ions have strong antibacterial properties. On the basis of this, in recent years, such antimicrobial metal ions are ion-exchangeable inorganic materials such as zeolite and zirconium phosphate which are aluminum silicate crystals (US Patent 4911898, 5900258, Japanese Patent Application Laid-Open No. 60-181002, Japanese Patent Application Laid-Open No. 3-83905). It is developed as an antimicrobial inorganic material that is safe by supporting on porous silica gel (Japanese Patent Laid-Open No. 8-183113) and can be used for a wide range of applications such as paint, synthetic fibers, and wallpaper.

Antimicrobial inorganic materials carrying silver ions are affected by sunlight, heat, pressure, chemicals, etc. during various processing or in the final use, and when they are affected by this, antibacterial action, appearance discoloration or mechanical Strength etc. may fall.

For example, when mixed with an antimicrobial inorganic resin carrying silver ions and used in an antimicrobial resin composition, it is known that the antimicrobial resin composition may be discolored over time due to ultraviolet rays such as sunlight, thereby lowering the merchandise value. This is caused by the discoloration in the process of converting the antimicrobial metal ions slowly released in the antimicrobial resin composition into metal particles by receiving ultraviolet rays.

In order to solve this problem, Japanese Patent Application Laid-Open No. 63-265809 proposes an antimicrobial zeolite in which ammonium ions are supported simultaneously with antimicrobial silver ions. This suggests that ammonium ions inhibit the dissolution of antimicrobial silver (Ag) ions to prevent discoloration.

However, when the antimicrobial silver ions are simultaneously supported with ammonium ions, they are still insufficient in thermal stability as in the case of using only silver ions as the antimicrobial metal, and discolor when heat-mixing the resin composition. By heat, this means that the free silver ions generated by the weak bonding force (adsorption force) between the inorganic carrier and the silver ions during the heat mixing with the resin are affected by the thermal energy by heating, and the silver ions are reduced by the heat to reduce the metal silver particles. It seems to be the result. In addition, Korean Patent Laid-Open Publication No. 1999-0055609 discloses antimicrobial resin residues of most active additives such as lubricants, lubricants, and mold release agents, which are added for the purpose of improving the active properties of the resin and the polymerization additives added during the resin synthesis and the resin properties. It is claimed that the resin discolors due to the reaction of silver ions with these additives.

For example, when the polypropylene resin is mixed, the color turns red at a heating temperature of 240 ° C.

In addition, Japanese Patent Laid-Open No. 62-7747 proposes to coat a silver-supported zeolite antimicrobial agent with silane to improve the moldability of the resin. This silane coating agent is effective in preventing discoloration by ultraviolet rays by preventing the release of silver ions by reducing the hygroscopicity of the zeolite. However, the silane coating agent is also not effective in preventing discoloration during heat mixing.

In the present invention, in the processing or end use of various kinds of silver-supported antimicrobial agents, inorganic silver is supported without deterioration of antimicrobial action by ultraviolet rays, heat, pressure, chemicals, etc., or physical properties such as appearance coloring or discoloration and mechanical strength. To provide a master batch of an inorganic antimicrobial agent and an antimicrobial thermoplastic resin containing the same.

Accordingly, in the present invention, as a result of intensive efforts to solve the above problems, it has been found that it is extremely useful to solve the above problems to support the silver colloid in a porous ceramic.

Hereinafter, the present invention will be described in detail.

The inorganic carrier used in the present invention may be at least one selected from porous silica, layered clay minerals, zeolites, layered phosphates, and the like.

Examples of the porous silica include synthetic and natural silica. For example, precipitated silica prepared by acid-alkali neutralization reaction by adding an acid solution to a sodium silicate solution, and fine precipitated silica and silica gel obtained by pulverizing the same. And spherical silica beads prepared by spray-drying a pulverized product thereof, sodium silicate or commercial silica sol solution, silica beads prepared by emulsion neutralization reaction in the presence of a surfactant, kaolinite (halloysite) or kaolinite ( activated silica powder obtained by eluting and removing acid-soluble components by acid treatment of kaloinite or serpentine.

Layered clay minerals include monmolite, virmiculite, kaolinite, kaolininlite, and sepiolite. Examples of the zeolite include synthetic zeolites and natural zeolites such as A-type zeolite, X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, mordenite and the like. Examples of the layered phosphate include zirconium phosphate and titanium phosphate.

In the present invention, the particle diameter of the inorganic carrier is in the range of 0.2 to 30 µm from the viewpoint of being easy to cope with various processing, and the average particle diameter is in the range of 0.4 to 15 µm, more preferably 0.4 to 6 µm. . In addition, the specific surface area of the inorganic carrier is preferably 50 m 2 / g or more of silver particles, and the upper limit thereof is not particularly limited but is usually 1000 m 2 / g or less.

In the present invention, the particle size of the metal silver fine particles supported on the inorganic carrier is preferably 5 nm or less, and in the case of more than the particle diameter, the color of the antimicrobial agent is pale gray depending on the size and loading of the silver after the inorganic carrier is supported. Or there is a problem of discoloration to dark gray. Metal silver fine particles with a particle diameter of 5 nm or less are 10 to 20 nm of metal silver colloid formed by reduction of a silver salt solution by a reducing agent under a W / O type emulsion with a surfactant, light (ultraviolet) reduction, and ultrasonic reduction. It can be prepared by adding.

In the invention, examples of the reducing agent used for the production of metal silver include hydrazine, ascorbic acid, sodium borohydride, sugars, aldehydes, iron salts and the like. And as a silver compound, a water-soluble silver compound is preferable, For example, silver nitrate, silver chloric acid, silver hexafluoroboric acid, silver sulfate, etc. are mentioned.

In the present invention, in order to evaluate the discoloration resistance of the silver-supported inorganic antimicrobial agent, the antimicrobial agent prepared below 10 cm, such as 40 W ultraviolet light, was allowed to stand and immersed for 200 hours in a 1.0 N sodium hydroxide solution at 25 ° C. for 48 hours and 800 ° C. in a nitrogen atmosphere. After 48 hours of treatment for discoloration was examined.

The thermoplastic resin used in the present invention is polyethylene resin, polypropylene resin, vinyl chloride resin, polyamide, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (SAN) resin, polycarbonate At least 1 sort (s) chosen from a thermoplastic resin group, such as resin, an acrylic resin, a fluororesin, etc. can be mentioned.

In the present invention, various known mixing methods may be used as the method for preparing the antimicrobial thermoplastic resin masterbatch. For example, a powder of polyamide or pellet and a silver-supported inorganic antimicrobial powder tumbler may be used as the base resin of the masterbatch. Or the method of mixing by a mixer etc. and heat-melting and pelletizing by kneading machines, such as an extruder, is mentioned.

In the present invention, the antimicrobial thermoplastic masterbatch may contain any additives such as mold release agents, lubricants, dispersants, antistatic agents, light stabilizers, antioxidants, dyeing pigments, other flame retardants, etc. It can mix.

In the present invention, the antimicrobial test of the antimicrobial thermoplastic resin masterbatch (using the yarn prepared by spinning the masterbatch) is carried on a sterilized culture dish to carry a certain concentration of antimicrobial agent and is a test strain, Staphylococcus aureus ATCC. 6538) 1.6 ± 0.3 × 10 ⁵ / ㎖, Klebsiella pne-moniae ATCC 4352, 1.4 ± 0.3 × 10 ⁵ / ㎖ inoculated and maintained at 25 ± 1 ℃, humidity of 95% or more for 24 hours The number of viable cells was measured and performed.

The inorganic antimicrobial agent of the present invention can be used in various fields where antibacterial action is required. For example, it can be used in the field of food packaging, paints, artificial marble, medical products, commercial and household cooking utensils, and bathroom-related toiletries. In addition, the masterbatch of the thermoplastic resin containing the inorganic antibacterial agent can be used in the field of injection molding, extrusion products, textiles.

In the following Examples, the present invention is described in more detail, but the present invention is not limited to the following Examples unless the gist of the present invention.

Example 1: Silver Sol Solution

Pure chemical (Japan) Silver nitrate was added to 17.75 g of ion-exchanged water to make 950.0 ml of silver nitrate solution, and the amount of ultraviolet light was controlled in a glass tube of 185 mm diameter and 500 mm height to gradually reduce metal silver particles in silver nitrate solution. For the purpose, the light brown glass tube was placed in a reactor equipped with a 5 W low pressure mercury lamp and irradiated with ultraviolet rays for 30 days to obtain a silver sol solution. Silver sol showed a light purple color, and by electron microscopic analysis, it was observed that metal having a particle diameter of about 10 nm produced particles. 50.0 ml of 25% hydrogen peroxide solution was added to the prepared silver sol solution, and the mixture was allowed to stand at room temperature for 12 hours to finally obtain a transparent silver sol solution having a silver concentration of 10000 ppm.

Example 2: Silver Sol Solution

After dissolving 546.5 g of sodium citrate and 517.0 g of ferrous sulfate from Merck (USA) in 3,000.0 ml of ion-exchanged water, the solution was maintained at 5 ° C and rotated at 10,000 rpm using a high speed stirrer. While stirring vigorously, 300.0 ml of 600.0 g / L silver nitrate solution was dripped at the rate of 30 ml / hr, and the colloidal aqueous solution was obtained. The silver sol solution thus obtained was dehydrated by applying a gravity of 5,000 G through a centrifugal separator to obtain a metal silver solid. Subsequently, the obtained metal was added 5 L of distilled water to the solid, stirred for 1 hour using a stirrer, washed, and then washed five times to recover the solid by applying a gravity of 5,000 G with a centrifuge, and the metal contained 150.0 g. One cake obtained 280.0 g. To 18.7 g of the cake thus obtained, 9500.0 ml of 0.05M citric acid (Samjeon Pure Chemical, EP) solution was added to the cake and stirred and redispersed to obtain a silver sol solution. To this, 500.0 ml of 25% hydrogen peroxide solution was added and left at room temperature for 24 hours. Finally, 10,000 ppm of a transparent silver sol solution was obtained. It was observed by electron microscopy that particles having a particle diameter of about 5 nm were produced.

Example 3 Silver Supported Silica Antibacterial 1

5 ml of the transparent silver sol solution prepared in Example 1 and 100 g of ion-exchanged water were prepared in 100 g of the finely divided silica powder (MICLOID, ML-836) manufactured by Dongyang Steel Chemical Co., Ltd. with a specific surface area of 800 m 2 / g and an average particle diameter of 3 µm. The mL mixture was added dropwise, mixed well, and then dried in a 100 ± 2 ° C. drier for 12 hours to obtain a silver-supported silica antimicrobial agent containing 500 ppm of metal silver on a silica carrier. When the ultraviolet rays, the alkali immersion, and the heat treatment were performed under the conditions described above, discoloration did not occur in appearance.

Example 4 Silver Supported Silica Antibacterial 2

5 ml of the transparent silver sol solution prepared in Example 1 and 45 ml of ion-exchanged water were added dropwise to 100 g of a specific surface area of 300 m 2 / g and an average particle diameter of 3 µm. , And dried for 12 hours in a 100 ± 2 ℃ dryer to obtain a silver-supported silica antimicrobial agent containing a concentration of 500 ppm metal silver on the silica carrier. This also did not discolor in appearance as a result of UV, alkali immersion and heat treatment under the conditions described above.

Example 5 Antimicrobial Nylon Masterbatch

Nylon 6 pellets (manufactured by DuPont), the base resin of the masterbatch, and the supported inorganic antimicrobial powder prepared in Example 3 were added to the masterbatch to contain 40 ppm of metal silver components in a supermixer (DHC-150, CRU-TEC). After sufficient mixing, the mixture was heated and kneaded at 250 ° C. in an extruder (S-1, manufactured by KURIMOTO Co., Ltd.) and injected to obtain pelletized antimicrobial nylon masterbatch.

Example 6 Antimicrobial Testing of Antimicrobial Nylon Masterbatches 1

Two sterilized culture dishes were prepared, and the bacteria of Staphylococcus aureus ATCC 6538 were prepared using 4.0 g of a yarn prepared by spinning a blank on one side and spinning a master batch of an antimicrobial thermoplastic resin on the other. Inoculation concentration (1.6 ± 0.3 × 10 ⁵ / ㎖), the initial bacterial count of both culture dishes was 1.6 × 10 ^5, and after 24 hours, the empty culture dish was increased to 5.8 × 10 ⁵ strain As can be seen, the culture dish containing the sample of the present invention showed a marked decrease in the number of strains to <10, and the bacteriostatic rate was 99.99%.

Example 7 Antimicrobial Test 2 of Antimicrobial Nylon Masterbatch

After inoculating the bacteria of Klebsiella pnemoniae ATCC 4352 using the antimicrobial yarn of Example 6 at an inoculation concentration of 1.4 ± 0.3 × 10 ⁵ / ml, 24 hours later. In the blank state, the number of bacteria was increased to 6.4 × 10 ⁵ / ㎖, and the culture dish containing the sample of the present invention showed a bacteriostatic rate of 99.99%.

As described above, the porous inorganic antimicrobial agent of the present invention contains silver particles of 5 nm or less, so that it is not discolored by light (ultraviolet rays), chemicals, and heat. In addition to having antibacterial activity, it has a very good effect on discoloration against light (ultraviolet rays), chemicals and heat.

Claims (5)

Metal silver colloid particles having a particle size of 5 nm or less prepared by adding hydrogen peroxide to colloidal silver formed by reducing or photoreducing a silver salt solution in an emulsion state by a surfactant are supported on a porous inorganic powder. Silver-supported inorganic antimicrobial agent, characterized in that it is produced. The silver-supported inorganic antimicrobial agent of claim 1, wherein the porous inorganic powder is at least one selected from the group consisting of precipitated silica, zeolite, layered phosphate, layered clay mineral, and acid treated clay mineral. A masterbatch, which is prepared by containing the silver-supported inorganic antimicrobial agent according to claim 1 in a resin. The masterbatch according to claim 3, wherein the silver-supported inorganic antimicrobial agent according to claim 1 is added in an amount of 0.2 to 70 parts by weight based on 100 parts by weight of the resin. The resin of claim 3, wherein the resin is polyethylene resin, polypropylene resin, vinyl chloride resin, polyamide, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (SAN) resin, polycarbonate Master batch, characterized in that at least one selected from the group of thermoplastic resins consisting of resin, acrylic resin, fluororesin.

Images