KR20020020190A - Antibacterial composition and method for imparting antibacterial properties - Google Patents

Abstract

The present invention provides an antimicrobial composition comprising at least one compound (1) and zinc oxide (2) selected from the group consisting of oxolinic acid and salts thereof as an active ingredient; Resin products, paper products or textile products containing the component (1) and the component (2); And to impart antimicrobial properties to resin products, paper products or textile products which treat the components (1) and (2) to resin products, resins before molding, paper products, paper raw materials, fiber products, fibers or fiber raw materials. Provide a method.

According to the present invention, an excellent antimicrobial effect can be obtained against various bacteria.

Description

Antibacterial composition and method for imparting antibacterial properties

The present invention relates to an antimicrobial composition.

Oxolinic acid and its salts are known as antibacterial agents used in resins, fibers, paints, and the like [see Japanese Patent Laid-Open No. 9-208408, Japanese Patent Laid-Open No. 9-176966). Japanese Patent Application Laid-Open No. 9-249827], depending on the state of use, the antimicrobial activity may not be sufficient, and development of an antimicrobial agent with higher antimicrobial power is required.

The present inventors have conducted extensive studies on an antimicrobial agent using oxolinic acid or a salt thereof, and have found that a composition containing oxolinic acid or a salt thereof and zinc oxide can exert a higher antimicrobial activity as an antimicrobial agent. .

That is, the present invention provides an antimicrobial composition comprising one or more compounds selected from the group consisting of oxolinic acid and salts thereof and zinc oxide (hereinafter, the compound and zinc oxide are referred to as the present active ingredients) as an active ingredient (hereinafter, The present invention composition), the antimicrobial imparting method of the resin product processing the present active ingredient to the resin or the resin before molding, the antimicrobial imparting method of the paper product treating the present active ingredient to the paper product or paper raw material, the present active ingredient The present invention provides a method for providing antimicrobial activity of a fiber product which is treated to a fiber product, a fiber or a fiber raw material, and a resin product, a paper product or a fiber product containing the present active ingredient.

Embodiment of invention

Oxolinic acid used in the present invention has a chemical name of 5-ethyl-5,8-dihydro-8-oxo [1,3] dioxolo [4,5-g] quinoline-7-carboxylic acid. Reference: Antimicrobial compounds described in The Pesticide Manual, 10th edition (published by British Crop Protection Council), p 760.

Specific examples of the salt of oxolinic acid include, for example, alkaline earth metal salts of oxolinic acid such as calcium oxolinate and alkali metal salts of oxolinic acid such as sodium oxolinate.

In the present invention, oxolinic acid and salts thereof may be used in combination.

In the present invention, the weight ratio of oxolinic acid and / or its salt (1) and zinc oxide (2) is usually in the range of about 1: 1 to 1: 3000, preferably about 1: 1 to 1: 2500.

As this invention composition, various forms, such as this active ingredient itself, the preparation containing this active ingredient, this active ingredient, or the dilution liquid which diluted this preparation with water, etc. are mentioned. Examples of the formulation containing the active ingredient include forms such as a hydrating agent, a fluidizing agent, and a powder, and examples of the dilution liquid obtained by diluting the hydrating agent, the fluidizing agent, and the like with water are examples of the water diluent of the preparation.

Formulations containing the present active ingredient (hereinafter, referred to as the present formulation), which is one form of the composition of the present invention, are generally known by mixing the active ingredient with a solid carrier, a surfactant, and the like, and adding an adjuvant for the preparation, if necessary. According to the prepared method.

Typically, the present active ingredient, oxolinic acid and / or salts thereof and zinc oxide, are formulated in a mixed state and the present formulation is obtained but can be obtained by formulating each in advance and mixing both.

As a solid carrier which can be used for this formulation, for example, kaolin clay, attapulgite clay, bentonite, montmorillonite, acidic clay, pyrophyllite, talc, diatomaceous earth, calcite, minerals such as calcite powder, rhododendron shell Natural organic substances such as powder, synthetic organic substances such as urea, salts such as calcium carbonate and ammonium sulfate, fine powders or granular substances of synthetic inorganic substances such as synthetic hydrous silicon oxide, and the like.

Examples of the surfactant include anionic surfactants such as alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphoric acid ester salts, lignin sulfonates and naphthalene sulfonic acid formalin condensates. And nonionic surfactants such as polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl polyoxypropylene block copolymer, and sorbitan fatty acid ester.

Examples of auxiliary agents for the preparation include dispersants, fixatives, preservatives, colorants, stabilizers, thickeners, and the like. Specifically, for example, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, gum arabic, alginic acid or salts thereof, CMC (Carboxymethyl cellulose), polysaccharides such as xanthan gum, inorganic substances such as aluminum magnesium silicate and alumina sol, PAP (acidic isopropyl phosphate), BHT, water and the like.

The present formulation usually contains 0.1% to 90% of the active ingredient, preferably 1% to 80%. In addition, the weight of zinc oxide relative to the weight of oxolinic acid and / or salt thereof in the present active ingredient is usually in the range of 1 to 3000 times, preferably 1 to 2500 times. In addition, in this specification, the weight of an oxolinate is represented by the weight converted into the amount of oxolinic acid, not the weight of the oxolinate itself.

Diluents containing the present active ingredient (hereinafter referred to as the present diluent) are usually obtained by a general method of diluting a water-forming agent, a fluidizing agent, or the like containing the present active ingredient. In addition, this dilution liquid can be obtained by mixing a dispersing agent with water, and then adding this active ingredient.

Antibacterial property can be given to a resin product by treating this effective ingredient to an effective amount, resin product, or resin before shaping | molding.

Resin products include, for example, a resin molded product obtained by molding a resin and various general products coated with a resin.

Specific examples of the resin product include tableware, stationery, and the like.

The coating treatment is one form of the resin molding treatment, and is specifically, a treatment in which resin is sprayed and coated on the surface of a general product by a method such as coating. Moreover, as a general product, various products which antimicrobial property, such as a metal product, a textile product, a paper product, a wooden product, are calculated | required are mentioned, for example. Specifically as a resin product coated with resin, a washing tank, a long paper, etc. are mentioned, for example. As a kind of resin, resin, such as polyethylene, a polypropylene, an acrylonitrile butadiene styrene copolymer, a polyethylene terephthalate, is mentioned specifically ,.

As a method of imparting antimicrobial activity to a resin product by treating the active ingredient, (1) A method of forming a resin product by treating the present active ingredient to a resin before molding and molding the resin treated with the present active ingredient; Process of the present invention, ③ a method of coating the resin with the present active ingredient by treating the present active ingredient on various general products, and ④ the present active ingredient-containing resin and the present active ingredient obtained by treating the present active ingredient. The method of making into a resin product etc. is mentioned by mixing resin which does not contain and shape | molding mixed resin.

The following method is mentioned specifically as a method of processing this active ingredient to resin before molding and molding the resin which processed this active ingredient to make a resin product.

After mixing this active ingredient with resin, such as polyethylene in a molten state, resin is shape | molded using conventional methods, such as extrusion molding and injection molding.

When the present active ingredient is mixed with the resin before molding, the present active ingredient can be used as it is and can also be used in the form of the present formulation. When the present active ingredient is treated with resin, the total throughput of the present active ingredient is usually 0.1 g to 100 g, preferably 1 g to 50 g with respect to 1 kg of the resin.

As a method of processing this active ingredient in a resin product, the following method is mentioned specifically ,.

The diluent is sprayed onto the surface of the resin product using a spray or the like, followed by drying to attach the active ingredient. Alternatively, the resin product is immersed in the diluent and then dried to attach the active ingredient to the surface of the product.

When this active ingredient is processed to a resin product, this diluent is normally used. When the present active ingredient is treated in the resin product, the total adhesion amount of the present active ingredient to the product is usually 0.01 g to 1 g per 1 m ² of the surface of the resin product. At this time, the total amount of the active ingredient in the diluent is usually 0,01 g to 10 g, preferably 0.1 g to 5 g per liter of the diluent. In addition, when immersion treatment is performed, immersion time is about 1 to 60 minutes normally.

The following method is mentioned specifically as a method of coating the resin which processed this active ingredient to resin, and treating the resin which processed this active ingredient to various general products.

This active ingredient is added to the resin in the molten state and mixed to obtain the present active ingredient-containing resin. General products, such as metal products, textile products, paper products, and wooden products, are immersed in the said resin, and the surface thereof is covered with resin. In addition, the surface of the general product can be coated with a resin by spraying the resin with a spray or the like.

When the present active ingredient-containing resin is coated on a general product, the total amount of the present active ingredient contained in the present active ingredient-containing resin is usually 0.01 g to 10 g, preferably 0.05 g to 5 g, based on 1 Kg of the resin.

In addition, oxolinic acid and / or its salt and zinc oxide which are this active ingredient can be respectively processed to resin products or resin before shaping | molding. At this time, the oxolinic acid and / or its salt and zinc oxide can be treated in various forms according to the treatment of the compound itself, various preparations or water dilutions thereof. This treatment method is also one aspect of the antimicrobial imparting method treatment of the present invention.

By treating this active ingredient with a paper product or a paper raw material in an effective amount, antimicrobial property can be provided to a paper product.

The paper product here means processing and obtaining the paper molded object obtained from the various paper raw materials, such as a natural pulp, a chemical pulp, a semichemical pulp, and a mechanical pulp, for example. As an example of a paper product, a wallpaper etc. are mentioned specifically ,.

As a method of imparting antimicrobial activity to a paper product by treating the active ingredient, ① a method of treating the present active ingredient in a paper raw material before molding and manufacturing a paper molded body using the raw material, and ② a method of treating the present active ingredient in a paper product Can be mentioned.

As a method of processing the active material on the paper raw material before molding and molding the paper using the paper raw material treated with the active ingredient, the following method is specifically mentioned.

After mixing this active ingredient with pulp, a paper molded body is obtained by a method using a conventional agitator or the like.

When this active ingredient is mixed with a paper raw material, this active ingredient can be used as it is, and can also be used in the form of this formulation. When the present active ingredient is processed into a paper raw material, the total throughput of the present active ingredient is usually 0.05 g to 50 g, preferably 0.5 g to 20 g per 1 kg of paper raw material.

The method of processing this active ingredient in a paper product can be performed by the following method, for example.

The diluent is sprayed and dried on the surface of the paper product using a spray or the like to attach the active ingredient.

When the present active ingredient is treated on the surface of a paper product, this diluent is usually used. When the present active ingredient is treated on the surface of the paper product, the total amount of the present active ingredient attached to the product is usually 0.005 g to 0.5 g per 1 m ² of the surface of the paper product. At this time, the present effective amount contained in the diluent is usually 0.005g to 10g, preferably 0.5g to 5g per liter of the diluent.

The present active ingredient, oxolinic acid and / or its salt and zinc oxide, can be treated in paper products or paper raw materials, respectively. At this time, the oxolinic acid and / or salts thereof and zinc oxide may be treated in various forms according to the treatment of the compound itself, various preparations or water dilutions thereof. This treatment is also one aspect of the treatment of the antimicrobial imparting method of the present invention.

Antimicrobial activity can be imparted to a textile product by treating this effective ingredient to a textile product, a fiber, or a fiber raw material in an effective amount.

The fiber product herein means various products obtained by weaving synthetic fibers or natural fibers. Textile products also include fabrics, nonwovens, and the like, obtained by weaving fibers. Specific examples of the fibrous product to be subjected to antimicrobial properties include gloves, school uniforms, carpets, and the like.

Examples of the fiber raw material include synthetic fiber raw materials such as nylon, rayon and polyester. Examples of the fiber include various synthetic fibers obtained by spinning the raw material and natural fibers such as cotton, hemp, and silk.

As a method of imparting antimicrobial properties to a textile product by treating the active ingredient, for example, ① a method of processing the present active ingredient into a fiber raw material and weaving the fiber obtained by spinning the raw material to obtain a fiber product, and ② The method of processing and drying the present active ingredient, and then weaving to obtain a fiber product, and the method of treating the present product to a fiber product.

The method of processing a fiber raw material with this active ingredient, spinning the said raw material, and weaving the obtained fiber to obtain a fiber product is specifically the following method.

This active ingredient is added to the fiber raw material and mixed. The fiber product is then obtained using conventional spinning and weaving methods.

When this active ingredient is mixed with a fiber raw material, this active ingredient can be used as it is, and can also be used in the form of this formulation. When the present raw material is treated with the fiber raw material, the total throughput of the present active ingredient with respect to the fiber raw material is usually 0.1 g to 100 g, preferably 1 g to 50 g per 1 Kg of the fiber raw material.

As a method of processing this active ingredient in a fiber or a textile product, it can carry out by the following method, for example.

The active ingredient is attached to the surface of the fiber or fiber product by dipping the fiber or fiber product in the diluent. Alternatively, the present active ingredient is attached to the surface of the fiber or textile product by spraying and drying the diluent using a spray or the like. In any of the above methods, when the present active ingredient is treated with fibers, the fibers are made into a fiber product according to a conventional weaving method.

When the present active ingredient is treated with a fiber or a fibrous product, the present diluent is usually used and the total amount of the present active ingredient attached to the fiber or the fibrous product is usually 0.01 g to 5 g, preferably 0.1 per 1 g g of the fiber or fiber product. g to 5 g. In addition, the total amount of this active ingredient contained in this diluent at this time is 0.01 g-10 g normally, Preferably it is 0.1 g-5 g per 1 liter of this dilution liquid. When immersing a fiber or textile product, the immersion time is typically on the order of 1 to 60 minutes.

The present active ingredient, oxolinic acid and / or salts thereof and zinc oxide, can be treated in textile products, fibers or fiber raw materials, respectively. At this time, the oxolinic acid and / or salts thereof and zinc oxide may be treated in various forms according to the treatment of the compound itself, various preparations or water dilutions thereof. This treatment is also one aspect of the treatment of the antimicrobial imparting method of the present invention.

The composition of the present invention is a cleb such as Staphylococcus, such as Staphylococcus aureus, Escherichia of Escherichia coli, Klebsiella pneumoniae, and the like. High antimicrobial activity can be exerted on bacteria such as Pseudomonas, such as Sierra and Pseudomonas aeruginosa.

Products antimicrobially treated with oxolinic acid or salts thereof may yellow the product under severe conditions that are constantly exposed to ultraviolet rays, but products treated with this active ingredient have the effect of suppressing such discoloration.

Example

Next, although a manufacture example and a test example are given and this invention is demonstrated in detail, this invention is not limited only to the following example.

In addition, in the following example, all percentages are% by weight.

Preparation Example 1

2 parts of oxolinic acid, 20 parts of zinc oxide, 1.5 parts of sorbitan trioleate and 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol were mixed and finely pulverized by wet grinding, and then contained 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate. 38 parts of aqueous solution was added, followed by 10 parts of propylene glycol, followed by stirring and mixing to obtain a fluidizing agent.

Preparation Example 2

0.5 parts of oxolinic acid, 5 parts of zinc oxide, 84.5 parts of kaolin clay and 10 parts of talc are well ground and mixed to obtain a powder.

Preparation Example 3

Hydrating powder is obtained by pulverizing and mixing 5 parts of oxolinic acid, 50 parts of zinc oxide, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 40 parts of synthetic hydrous silicon oxide.

Preparation Example 4

A resin plate is produced according to the method described next.

1 Kg of ABS resin and 10 g of the composition of the present invention (oxolinic acid / zinc oxide = 1 g / 9 g) are added to a plastic bag and shaken well. The obtained mixture is introduced into a hopper of an extruder to carry out compounding. The compounded ABS resin is dried at 80 ° C. for 3 hours and then plated using an injection molding machine.

Extruder; PCM 30 [manufactured by Isoga Co., Ltd.]

Processing temperature; 220 to 240 ℃

Injection molding machine; SVH-30-50-p [product made in Yamashiro Seiki Seisha Corporation]

Processing temperature; 220 to 230 ℃

Test Example 1

Each of oxolinic acid, zinc oxide, oxolinic acid and zinc oxide is added to the agar medium to the concentration shown in Table 1 to prepare a medium. At the same time, untreated agar medium is also prepared for comparison. These mediums were inoculated with Staphylococcus aureus and incubated at 27 ° C. for 2 days. After 2 days, the degree of growth of the bacteria was observed and growth inhibition rate (%) was determined according to the criteria described below. This test is repeated three times to average their growth inhibition rate as the final growth inhibition rate. The results are shown in Table 1.

<Standard>

If no growth of bacteria is found: 100% growth inhibition rate,

If bacterial growth is seen in very few of the sites of inoculation: 95% growth inhibition,

If bacterial growth is clearly seen only at the site of inoculation: growth inhibition rate 80%,

When bacterial growth is significantly inhibited compared to no treatment but colony is expanded at the site of inoculation: growth inhibition rate 50%,

When proliferated to the same extent as no treatment: growth inhibition rate 0%.

Growth inhibition rate of Staphylococcus aureus (%) No treatment 0 Oxolinic Acid 0.4ppm 0 Zinc Oxide 100ppm 0 Zinc Oxide 200ppm 0 Oxolinic Acid 0.4ppm / Zinc Oxide 100ppm 50 Oxolinic Acid 0.4ppm / Zinc Oxide 200ppm 70

Test Example 2

An agar medium and an untreated agar medium containing oxolinic acid, zinc oxide, oxolinic acid and zinc oxide, respectively, were prepared so as to have the concentrations shown in Table 2, using Escherichia coli instead of Staphylococcus aureus. Other tests were carried out in the same manner as in Test Example 1, and evaluated based on the criteria described in Test Example 1 to obtain growth inhibition rate (%). This test is repeated three times, and their growth inhibition rate is averaged to be the final growth inhibition rate (%). The results are shown in Table 2.

Growth inhibition rate of Escherichia coli (%) No treatment 0 Oxolinic acid 0.08ppm 50 Zinc Oxide 100ppm 0 Zinc Oxide 200ppm 0 Oxolinic Acid 0.08ppm / Zinc Oxide 100ppm 95 Oxolinic Acid 0.08ppm / Zinc Oxide 200ppm 95

Test Example 3

The resin plate manufactured in Production Example 4 was subjected to ultraviolet irradiation at 63 ° C. for 2 hours or 4 hours using a sunshine weather meter (manufactured by Super UV Tester SUV-F1 Dainippon Plastics Co., Ltd.), and the degree of discoloration due to ultraviolet rays. Investigate. As a result, no discoloration was observed in the resin plate irradiated for 2 hours or in the resin plate irradiated for 4 hours. The conditions of ultraviolet irradiation are described next.

Irradiation conditions; 63 ° C × 2 to 4 hours

Ultraviolet intensity; 100 ± 5mW / cm ² al 23cm

wavelength; 300 to 450 nm (energy distribution: 360 to 38 Onm is maximum)

Test Example 4

The following tests are carried out according to the film adhesion method (Test method of antimicrobial product technology council, test method of antibacterial activity evaluation of antibacterial product 1).

A bacterial solution in which Escherichia coli IFO 3972 was incubated on each surface of an additive-free resin plate prepared in the same manner as in Preparation Example 4 except that the resin plate prepared in Preparation Example 4 (50 mm x 60 mm) and the composition of the present invention were not added. 0.4 ml (number of bacteria: about 1.0 to 10 ⁵ / ml) is added dropwise to infect the plate. The plate surface was coated with a film (40 mm x 40 mm) and incubated for one day under conditions of a temperature of 36 DEG C and a humidity of 90% or more. Next, the viable count on the plate is measured.

The same test is also performed on Staphylococcus aureus ATCC 6538P. The results are summarized in Table 3.

Escherichia coli Staphylococcus aureus Initial bacterial count 1.6 x 10 ⁵ 1.1 x 10 ⁵ No additive resin plate 8.9 x 10 ⁶ 3.3 x 10 ⁴ Resin Plate Created in Production Example 4 <10 <10

According to the present invention, it is possible to provide an antimicrobial composition capable of exhibiting excellent antimicrobial effect, and also to give an effective antimicrobial effect to the product by treating the composition to a resin product, a paper product, a textile product or a raw material thereof. .

Claims (6)

An antimicrobial composition comprising zinc oxide (2) and at least one compound selected from the group consisting of oxolinic acid and salts thereof. The antimicrobial composition according to claim 1, wherein the weight ratio of the component (1) to the component (2) is 1: 1 to 1: 3000. The resin product, paper product, or textile product containing the component (1) and component (2) of Claim 1. A method for providing antimicrobial properties of a resin product, wherein the component 1 and component 2 described in claim 1 are treated with a resin product or a resin before molding. A method for providing antimicrobial properties of paper products by treating the components (1) and (2) according to claim 1 to paper products or paper raw materials. A method for imparting antimicrobial properties of a textile product, wherein the structural component (1) and the structural component (2) according to claim 1 are treated to a textile product, a fiber, or a fiber raw material.