WO1998028983A1

WO1998028983A1 - Antimicrobial/antifungal composition

Info

Publication number: WO1998028983A1
Application number: PCT/JP1997/004838
Authority: WO
Inventors: Tomio Okada; Akitoshi Kitamura; Akiko Taniguchi
Original assignee: Fuji Chemical Industry Co., Ltd.
Priority date: 1996-12-27
Filing date: 1997-12-25
Publication date: 1998-07-09

Abstract

A colloidal antimicrobial/antifungal composition comprising (a) a viscous aqueous solution of a polymer compound selected from among polysaccharides, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, and polysodium acrylate and (b) a metallic compound having antimicrobial/antifungal activities, dispersed as fine particles in the viscous aqueous solution, and being at least one member selected from among Mg1-xZnxO (wherein 0.0001≤x≤0.5), Mg1-xZn(OH)2 (wherein 0.0001≤x≤0.5), Al2MgxZnO (wherein x is an integer of 3 or 5), MgO, Mg(OH)2, ZnO, CuO, Cu2O, AgO, Ag2O, and TiO2.

Description

Description Antibacterial and drag composition Technical field

The present invention relates to a viscous aqueous solution of a water-soluble polymer substance selected from the group consisting of polysaccharides, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer and sodium polyacrylate. The present invention relates to an antibacterial / antifungal composition obtained by uniformly dispersing an inorganic metal compound having antibacterial / antifungal activity in the form of fine powder. Background art

Conventionally, organic antibacterial and antimicrobial agents have been widely used to prevent disasters caused by bacteria and viscera.However, most of them have some harmful components, Long-term use is likely to cause serious secondary disasters. For example, imidazole-based and thiazole-based antibacterial and antifungal agents are still circulating in the market, mixed in many commodities, and used. In particular, when this type of product is used for products that are closely attached to the living environment, it can sometimes cause allergic skin damage, and the product used as an antifungal agent for building materials is arsenic in the event of a fire. Have caused secondary disasters.

In recent years, with the enforcement of the Product Liability Law in Japan, safety has been strictly required in the field of antibacterial and antifungal agents, especially antibacterial agents used in the medical field and food-related businesses. · Most of the antifungal agents are shifting to inorganic compounds with high safety and long lasting effects. Especially antibacterial activity High silver compounds occupy the mainstream, and then highly safe zinc compounds are processed and commercialized in such a form that they are supported on easily ionizable carriers. At this time, many carriers used for the purpose of improving the apparent ionization ability of the metal include mineral carriers such as zeolite, zirconium phosphate, and calcium phosphate. Therefore, many of the antibacterial and antifungal agents carried on these are commercialized in the form of fine powder, and the manufacturing process is complicated, leading to an increase in cost.

On the other hand, there is an extremely wide variety of objects, including structures, for which the provision of antibacterial and antifungal properties is required. Has a wide applicability range, according to a factory survey. However, it is extremely difficult to fluidize conventional powdered inorganic antibacterial and antifungal agents as they are, for example, by using strong dispersants such as ionic and nonionic surfactants, Even if it is dispersed in water or a water-alcohol mixed medium to be slurried to form a fluid, it is difficult to obtain a practically usable dispersion system due to poor stability. At present, silver-based antibacterial agents that are marketed in fluidized form are made by dispersing undermicron ultrafine particles in an alcohol or alcohol Z water mixed medium using the same surfactant as above, and the price is high. However, it is hard to say that the product form is applicable to mass-consumption type objects.

Summarizing the above, the general problems of conventional technologies and products can be summarized as follows. First, organic antibacterial and antifungal agents lack the safety seen in the organic compounds contained, and many inorganic antibacterial Due to the complexity of the manufacturing process of mold compounds and the complexity of the operations involved, mass production and cost reduction are difficult, and the scope of application is expanding because most of the products are commercialized as powders. It is difficult. Disclosure of the invention

An object of the present invention is to solve these problems of the conventional technology and products at the same time, and to provide a fluid inorganic antibacterial and antifungal composition that is safe, inexpensive, and easily applicable to various uses. is there.

Specifically, damage caused by pathogenic bacteria, such as so-called hospital-acquired infections represented by methicillin-resistant Staphylococcus aureus (MRSA), and food poisoning that occurs in school lunches, etc., cause extremely serious social problems. In addition, the occurrence of fungi caused by fungi significantly deteriorates the living environment and also causes serious health problems.

The present invention relates to a novel antibacterial and antifungal composition developed for the purpose of effectively preventing disasters caused by such bacteria and rust. More specifically, the uniform dispersion of oxides and hydroxides of specific single metals and complex metals, which are non-toxic or extremely toxic, are uniformly dispersed in aqueous solutions of water-soluble polysaccharides and water-soluble adhesive polymer substances. The present invention relates to an antibacterial and antifungal composition having significantly improved antibacterial and antifungal properties.

The present inventors have solved the problem that the range of application resulting from the fact that existing inorganic antibacterial and antifungal agents are non-fluid based mainly on powders is limited, and it is inexpensive and safe. As a result of intensive research to develop inorganic antibacterial and antifungal agents, metal oxides composed of a single metal component having antibacterial and antifungal properties, hydroxides, and composite metal oxides composed of two or more metal components, The hydroxide is dispersed in an aqueous solution of an adhesive polymer selected from water-soluble polysaccharides, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, and sodium polyacrylate to form an emulsion. As a result, the present inventors have found that a stable fluid antibacterial and antifungal composition can be produced extremely easily, and completed the present invention. That is, the present invention has (a) a film-forming function selected from the group consisting of polysaccharides, polyvinyl alcohol, polyvinyl viridone, polyvinyl methyl ether, carboxyvinyl polymer, and sodium polyacrylate. (B) n _x O (where X is a number satisfying 0≤x ≤ 1), Mgi—xZ n _x (OH) ₂ (where x is 0

≤ x≤ 1), A Mg _x ZnO (where X is an integer of 3 or 5), CuO, Cu ₂₀ , AO, Ag ₂ 〇, T i 及び₂ and N i An antibacterial and antifungal composition comprising at least one metal compound having an antibacterial and antifungal activity selected from the group consisting of 0 and uniformly dispersed in the form of fine particles having an average particle size of 0.05 to 10.

Examples of the polysaccharides used in the present invention include sodium alginate, arabia gum, carboxymethyl cellulose, roast bean gum, xanthan gum, chitosan, guar gum, dielan gum, gelatin, gelatin, propyl glycol alginate, arabinogalactan, Gati gum, carrageenan, karaya gum, agar, tamarind seed gum, pullulan, morpholine fatty acid salt, curdlan, tragacanth gum, etc.

Of these polysaccharides, sodium alginate is neutral, soluble in water, has a high emulsifying power, and is used in a wide range of fields, such as the food industry, textile industry, paper industry, medical products, cosmetics, and glazes for paints and ceramics. Among them, it is most preferably used as a food additive, because it has a long-term track record of becoming a thickener for dairy products and the like.

Polyvinyl alcohol and polyvinyl pyrrolidone are soluble in water

Low toxicity, cosmetics, beer and other beverage additives, and polyvinyl methyl ether and carboxyvinyl polymer as aqueous solution As an adhesive and cosmetics, sodium polyacrylate is soluble in water and is used as an adhesive and paint.

In order to prepare the antibacterial / antifungal composition of the present invention, first, the polysaccharide, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer and sodium polyacrylate of the component (a) in powder form are used. Salt (hereinafter collectively abbreviated as "adhesive polymer substance") and fine powder of the metal compound of component (b) (average particle size of 0.05 to: L0 / im, preferably 0 to 5 to 5 fm. Mix the mixture according to the purpose of use, mix this mixture sufficiently and then add a predetermined amount of water or hot water (50-60 ° C) and stir. When it is necessary to reduce the dispersion particle size of the composition, the composition may be dispersed using a pulverizer such as a homogenizer instead of stirring. The concentration of the adhesive polymer substance of the component (a) varies depending on the type and amount of the metal compound used as the component (b) .For example, in the case of sodium alginate, it is in the range of 0.01% to 10%. It is preferably in the range of 0.1 to 7%, more preferably in the range of 0.1 to 5%, in the case of arabia gum up to 30%, in the case of polyvinyl alcohol in the range of 0.01% to 10%. It must be mixed with a metal compound in an amount appropriate for the amount (amount appropriate for the dispersing ability).

It is presumed that the degree of dispersion is related to the amount of surface charge of the metal compound. For example, oxides, such as zinc oxide and titanium oxide, that are relatively easy to disperse in an aqueous solution of the adhesive polymer substance (a), are harder to disperse than silver oxide, copper oxide, copper oxynitride, etc. It can be processed at a higher concentration. On the other hand, the concentration of the adhesive polymer substance of component (a) is closely related to the dispersibility of the aqueous solution. For example, sodium alginate has a low concentration (1% or less). There is a remarkable difference in the dispersibility between the method performed at the bottom) and that performed at a high concentration (3% or more). Practical concentrations of adhesive polymer substances are, for example, sodium alginate in the range of 0.1-7.0%, but if it exceeds 5%, the viscosity of the aqueous solution will increase significantly, so the system must be heated when adjusting the dispersion. O Homogenizer, sonication, etc.

The antibacterial and antifungal composition of the present invention exhibits a color tone such as white, green, black, and red, depending on the color tone of the metal compound used. _{_{Mg! -XZ nxO A 2 Mg x}} Z n O, Z n O is white, A gO, A g ₂ 〇 black, C u ₂ 0 is that Teisu red.

Taking sodium alginate as an example, when the concentration exceeds 2%, the viscosity of the obtained composition increases visibly (more than 500 cp) as described above, while the amount of the metal compound used decreases. The viscosity increases with the increase, but when the metal compound is added in excess of the dispersion limit, the composition will exhibit dilatancy-like properties and the flowability will decrease significantly. Therefore, proper formulation is indispensable to produce the optimum composition for the purpose of use.

The antibacterial and antifungal composition of the present invention generally has excellent film-forming properties, and can be used as a coating agent by directly applying it to the surface of an object. In addition, after the coating film is dried, it can be treated with a dilute aqueous solution of an inorganic acid or a calcium salt to impart water insolubility.

The field of application of the antibacterial and antifungal composition obtained by the present invention is extremely wide, and some of them are exemplified. As is well known, polysaccharides such as sodium alginate have been used in large quantities as viscosity stabilizers in the food field for some time. It is also an extremely safe material for medical, cosmetics, water treatment, etc. Are also used in various forms. In these fields, there are many products that are required to have antibacterial and antifungal properties. For example, in the medical field, there are ointments, poultices, and plasters. In the cosmetics field, in addition to stone, toothpaste is also included. In particular, the inventors of the present invention have confirmed through experiments that the antioxidant effect of the composite oxide of magnesium and zinc shown in the Examples below on periodontal disease bacteria and mutans bacteria has been confirmed by experiments, and this oxide was dissolved in sodium alginate aqueous solution. An excellent antibacterial toothpaste can be made by mixing the dispersion into a conventional toothpaste.

In addition, by mixing the above-mentioned composite metal compound in advance into sodium alginate used as a floc-forming agent in water treatment, it can be used as a sterilizer for reprocessing sewage and pool water. For this purpose, a single metal oxide, zinc oxide, can be used in a similar manner. In the textile industry, an effective antibacterial property can be imparted by using the composition according to the present invention in a conventional algin-based warp glue, finishing glue, waterproofing agent, or the like. In the papermaking industry, sodium alginate has already been used as a sizing agent and a coating agent, and an excellent antibacterial paper can be produced by mixing the antibacterial composition of the present invention into these agents. Also in other industrial fields, the composition of the present invention exhibits excellent properties due to imparting antibacterial and antifungal properties. For example, the composite oxide of aluminomagnesium Z zinc does not lose its antibacterial properties even in the firing temperature range of ceramics (1100 to 1300 ° C). [American Patent No. 5,344, No. 633 (1994)] The product surface can be made antibacterial by applying the composite oxide dispersed in an aqueous sodium alginate solution to the surface in the final processing stage of tiles and ceramics and firing it.

Also, as a raw material for joints where mold generation is often a problem, By mixing the antibacterial composition of the present invention, for example, a composition mainly composed of a magnesium / zinc composite compound when kneading the it cement, it is possible to produce a joint cement having an excellent force-proofing property. it can.

The aqueous sodium alginate solution is a water-based paint, emulsion paint, and silicone emulsifier in a form that makes effective use of its inherent superior properties, for example, emulsifying properties, film forming properties, hydrating properties, and viscosity. The antimicrobial / antifungal composition of the present invention can be used as an antimicrobial / antifungal imparting agent in any of these fields.

On the other hand, information and packaging papers made by dispersing the above-mentioned composite metal compound in powder form during the papermaking beating process show excellent antibacterial properties against Escherichia coli, MRSA, Salmonella bacteria, etc. Has been published by Morza, which has conducted trial production of antibacterial paper using the composite metal compound, but because of its addition in powder form, a large amount flows out together with the slurry liquid, which presents a problem in terms of profitability. It has not been commercialized. On the other hand, when the composition based on the sodium alginate aqueous solution according to the present invention is used, the coating of the paper surface after papermaking is easily performed, so that extremely inexpensive antibacterial paper can be produced. Become.

In addition, the above-mentioned complex metal compounds are almost non-toxic, and are completely toxic to fish even if they are co-existed at 100 O ppm concentration for 2 weeks as an antibacterial agent in order to prevent bacterial growth in aquariums of ornamental fish such as medaka and goldfish. It has been confirmed by the present inventors that they do not show any of these, and they are highly likely to be used not only as ornamental fish but also as a freshness preservative for general edible fish.

Since the antibacterial properties of the paper and its non-toxic properties were confirmed, the paper manufacturing industry mentioned above could also be used for food wrapping paper other than general paper, tissue paper, and toilet paper. , Sanitary supplies paper, paper towel It can be applied to sanitary paper such as files.

Further, the sodium alginate-based antibacterial composition according to the present invention can be easily applied to the following fields. Recently, poultry eggs, fruits and vegetables, and other foodstuffs that require freshness are packaged in antibacterial films (for example, polyethylene films incorporating a silver-based antibacterial agent) and are already attached. Attempts have been made to suppress the growth of bacteria and to prevent the invasion of bacteria from the outside, and to reduce the degree of decay of inclusions, but this is still unsatisfactory in terms of practicality. However, when the composition of the present invention is simply immersed or sprayed on the surface of poultry eggs, fruits and vegetables with a sprayer, the surface of the composition is covered with an extremely thin film of sodium alginate containing an antibacterial component, and a film is formed. Thus, the object can be protected with a higher degree of adhesion than when covered. In particular, by immediately spraying or spraying the present composition on the eggs after washing, fruits after fruiting, etc., the freshness retention period can be significantly extended.

In the composition of the present invention, sodium alginate itself is an additive, and the coating formed on the surface of the food is easily dissolved by applying water, so that the surface of the fruit is painted as if it were painted. Easily removed after washing with water. This is especially useful as a postharvest treatment (postharvest) to prevent the rot of tropical fruits, which are easily damaged by bacteria.

In addition, feathers used in large amounts in recent bedding tend to grow vigorously due to adhesion of sweat and the like. High-grade products are treated with fungicide, but most of them use organic bioproofing agents, so they have low sustainability and lose their efficacy in two to three years, and some mold is generated. Become like By adding an appropriate amount of the composition of the present invention to a rinse solution that is a finishing agent for feather treatment, the generation of such viscous particles can be achieved. Compositions that can prevent birth can be prepared.

Antifungal the composition according to the invention showing primarily Mgi- χΖ ηχθ (wherein, X is a number satisfying 0≤ x≤ 1), Mgi- χΖ n x (OH) 2 ( wherein, X Is a number that satisfies 0 X 1) and A MgxZn O (where x represents an integer of 3 or 5). The joint material used for tile joints in kitchens and bathrooms is usually a white cement.The power component contained in this is easily soluble in water and used for a long time after being exposed to water. It is completely eluted in between. If stones, water, detergents, and miscellaneous food wastewater permeate the cement that has lost the alkaline component, it becomes a good medium for mold and a hotbed for black mold. At this time, if the antibacterial composition containing the composite metal compound described above is added to the white cement, the compound contained therein is almost insoluble in water and retains a high strength. Therefore, it is possible to prevent the occurrence of black rubs and the like.

The composite metal compound that can be used in the present invention is not particularly limited as long as it is a known compound obtained by a conventional method, and preferably has the above-mentioned particle size. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not limit the present invention.

Example 1

Mg as an example of a composite metal oxide. a Z no.! 2.0 g of a compound having the composition of 0 was mixed in powder form with 4.0 g of sodium alginate in a 200 ^ Erlenmeyer flask, and 100 ^ of water was added, followed by vigorous shaking to give a milky white uniform What An emulsion was obtained. 0.3 part of this solution was dropped on a slide glass, spread into a film of uniform thickness, air-dried, and then immersed in a 3% aqueous solution of calcium chloride for several tens of seconds to make it insoluble in water. The sample was washed with water and dried to obtain a test sample. (Antibacterial test was performed by inoculating approximately the same number of E. coli into each of the test sample (test section) and untreated slide glass (control section). The mortality was calculated and the mortality was 100% .The test conditions are as follows.

Test strain: Escherichia coli

Test method: The test was performed according to a normal film adhesion method. About 2.0 X

After inoculating a bacterial solution containing 10 ⁶ bacteria with 0.1 ^, cover with coated film, store at 35 ° C for 24 hours, and count the number of bacteria.

Examples 2 to 11

Using the same method as in Example 1, the antibacterial property of the composition of the present invention containing the composite metal oxide and some simple metal oxides was tested. On the other hand, when the compounds are not emulsified with an aqueous sodium alginate solution, that is, in the form of a powder, added to an agar medium and compared with the minimum inhibitory concentration (MIC) when the antibacterial property is measured, Table 1 summarizes the comparative test results of the antibacterial properties of the additive and the sodium alginate.

The concentration (% w / v) of the standard indicates the weight% of metal oxide contained in the test sample.

(Hereinafter the margin) table 1

From the results in Table 1, the composition of the metal oxide was sodium alginate-based. It was confirmed that the activity was clearly higher when used as a product, and that the difference was remarkable especially at a low concentration.

In Table 1 above,

(1) Compound symbols A to J have the following meanings.

_{_{A; A 2 M g 5 Z}} n 0 F; C u 2 0

B; M go.9 Z no. I 0 G; M g 0

C; A g 0 H; Cu 0

D; Ag ₂ 0 I; Ti 0 ₂

E; Z n 0 J; N i 0

(2) In the usage form, A L is based on sodium alginate, P indicates powder direct addition,

(3) Antibacterial properties are as follows: ：: killed (not detected), 〇: confirmed antibacterial, X: no effect.

Example 12

A fully fibrillated rayon cotton (1-2 d) is used for the composition of the present invention [Mgo. ₉ Z no.! 0 (2%) sodium alginate 4.0% aqueous solution] for 10 seconds. Remove, centrifuge, remove excess liquid, allow to air dry, then immerse in 3% calcium chloride aqueous solution for tens of seconds. Take it out and wash it thoroughly. After drying this product sufficiently, the antibacterial activity against the five types of bacteria shown in Table 2 was measured based on the bacterial count method defined by the Textile Sanitary Processing Council. The results are summarized in Table 2. Table 2

In Table 2, antibacterial index (difference in increase or decrease in bacterial count) = log B / A-log C / A

A: Number of bacteria immediately after inoculation

B: Number of bacteria after 18 hours in untreated plot (control plot)

C: Number of bacteria after 18 hours in treatment area (test area)

As a result of the test, the composition according to the present invention showed strong antibacterial activity on the rayon surface even when diluted 10-fold, and all of them greatly exceeded the minimum required effective activity value 1.6 determined by the council. Value was confirmed.

Example 13

After thoroughly mixing 2.0 g of Zn 0 and 4.0 g of sodium alginate in powder form in a 200 ^ Erlenmeyer flask, add 100 ^ of warm water at about 60 ° C and shake vigorously for 3-5 minutes. Thus, a milky white colloidal dispersion was obtained. To this, 0.3 g of anionic surfactant (“Poiz—520” manufactured by Kao Corporation) and 2.0 g of acryl-based binder were added, followed by further shaking. The emulsion was dropped on a slide glass and spread to form a uniform film. This film was dried at room temperature. The antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa was measured on the sample thus prepared and obtained based on the above-mentioned film adhesion method. For comparison, in the above method, A control sample obtained by dispersing Zn 0 in an aqueous medium in the same manner using the same amount of anionic surfactant and acrylic binder without using a rim was also used as an antibacterial agent. (The change in the number of bacteria over time) was measured.

Table 3 summarizes the results.

Table 3

In Table 3, sample A was dispersed using sodium alginate, and B was a sample not using sodium alginate. N.D indicates not detected (killed).

Examples 14 to 20

The antibacterial activity (change in bacterial count over time) of Escherichia coli by several kinds of metal oxides containing an antibacterial metal was measured in the same manner as in Example 13. Table 4 summarizes the results.

(Hereinafter the margin)

Table 4

In Table 4, the metal oxide CI indicated by the symbol can be as follows.

CA Mg ₅ Z n 0 GZ n 0

E A O I M g 0

FA g ₂ 0

Sample A was dispersed using sodium alginate, and B was Indicates that sodium alginate is not used, and ND indicates not detected (killed).

Example 21

Among the compositions according to the present invention, M go.9 Z no.! The following experiment was performed using a composite metal compound having a composition of 0.

The components of the liquid composition can be obtained by measuring M go. A Zr. I O (2.0%) and sodium alginate (4.0%) to a total amount of 100; ^. After thoroughly stirring the composition containing the above components to make it into an emulsion, 20 _g is dispensed, and after permeating a solution mixed with 30 g of a commercially available normal rinse solution, shampoo washing and water washing are performed. , Dried. 1 g of each of the test feather sample thus obtained and a control feather sample treated in the same manner except that no liquid composition was used were placed in a petri dish having a diameter of 9 cm. The spores of the five bacteria specified in JIS—Z—2911 (A. sp. A fixed amount of a spore suspension was prepared by inoculating and suspending a fixed amount of a 50 ppm aqueous solution of dioctyl sodium sulfosuccinate, and these five types of suspensions were mixed to obtain a mixed spore suspension. This solution was sprayed in a fixed amount on 1 g of each sample described above, and cultured under the conditions of a temperature of 28 ° C, a period of 28 days, and a relative humidity of 95% or more.

Table 5 summarizes the results of the antifungal test on feathers obtained from the above tests. Table 5

In the table, samples J to κ have the following meanings.

J: Untreated feather

K: processing feather

++: Mold generated on the sample surface is 10 to 30% of the surface area

1: No mold is observed on the sample surface

Example 22

Mg in Example 1. .9 M instead of Z no.10. .9 Z no. Ι (OH) ₂ was used, and an antibacterial test was similarly performed using a sodium alginate dispersion system. The result is Mg. . ₉ Z no .: Equivalent to the case of 0 dispersion system.

Examples 23 to 28 below show cases where the antibacterial and antifungal composition of the present invention was applied as a freshness preservative for eggs.

Example 23

(1) Preparation of freshness preservative

To a solution of the addition of commercially available sodium alginate 5.0 g in water heated 100 ^ to 60 to 70 ° C, magnesium one zinc double salt (composition;. Mg .. ₉ Z n 〇) and 5.0 g was added The mixture was sufficiently stirred and dispersed with a mixer (homogenizer) to obtain a colloidal milky white dispersion. This dispersion was collected in 10 ^ and diluted with 1000 ^ of water.

(2) Egg coating

Immediately after washing, add eggs (10 units per group) After immersion for 2 seconds and removal, moisture was removed by air drying. The resulting egg coating was 0.5 microns.

(3) Freshness test

The eggs obtained by the above method were subjected to a freshness keeping test.

Eggs are stored at room temperature (25-30 ° C), and the number of Hau units (Hau _g h units (HU values)) of each test egg is determined every 5 days, 10 days, and 15 days by a fully automatic egg quality analyzer. (Egg Multitester) was used to determine the average of the HU values obtained for each of the test eggs.

The HlH (average value of 10 eggs) of the eggs was 87.3.

Comparative Example 1

After the eggs were laid, the hen eggs (10 per group) were washed, air-dried to remove water, and subjected to the egg freshness test in the same manner as in Example 23. Eggs are stored at room temperature (25-30 ° C), and the number of Hau units (HU value) of test eggs are measured every 5 days, 10 days, and 15 days using a fully automatic egg quality analyzer (Egg Multitester). The average value of the HU values obtained for each of the test eggs was determined.

Table 6 shows the freshness retention effect (the relationship between the number of storage days and howe units) of Example 23 and Comparative Example 1 above.

(Hereinafter the margin)

Table 6

(Relationship between storage days and howe unit)

Example 24

(1) Preparation of freshness preservative

In a solution of 5.0 g of commercially available sodium alginate in 100 ^ of water heated to 60-70 ° C and dissolved, a double salt of magnesium-zinc (composition: Mg ₉ Zn. I〇) and 5. 0 g was added, and the mixture was sufficiently stirred and dispersed with a mixer (homogenizer) to obtain a colloidal milky white dispersion. This dispersion was sampled for 10; ^ and diluted with 500; ^ of water.

Thereafter, treatment was performed in the same manner as in Example 23, and (2) egg coating and (3) freshness retention test were performed.

Table 7 shows the freshness retention effect (the relationship between the number of storage days and the Howe unit) of Example 24 and Comparative Example 2.

(Hereinafter the margin) Table 7

(Relationship between storage days and howe unit)

Example 25

5.0 g of commercial zinc white was added to an algin solution having the same composition as in Example 23, that is, a solution obtained by adding 5.0 g of commercially available sodium alginate to 100 ^ of water heated to 60 to 70 ° C and dissolving it. The emulsion, which was sufficiently stirred and dispersed with a homogenizer to obtain an emulsion, was collected and diluted with 1000 で of water. A freshness holding test was performed using this dispersion.

The results are as shown in Table 8.

Table 8 shows the freshness retaining effect (the relationship between the number of storage days and the unit of hows) of Example 25 and Comparative Example 3 above.

(Hereinafter the margin)

Table 8

(Relationship between storage days and howe unit)

From the results shown in Tables 6 to 8 above, the HU value of the chicken eggs treated with the freshness preserving agent of the present invention was 71.6 or more even on the 15th day of storage. These values were evaluated according to the classification of Imai et al., With a HU value of 79 or higher as a special grade, 61-78 as a first grade, and 60 or lower as a second grade [Imai et al., Egg knowledge, p. 50 (1989)]. According to this evaluation method, all of the treatments of Examples 22 to 24 could maintain the special grade by the 5th day, and all the grades were 1st grade or more on the 15th day. On the other hand, those of Comparative Examples 1 to 3 were all grade 1 on the 5th and 10th days, and all grade 2 on the 15th day.

Example 26 (antibacterial and antifungal tests)

The eggs on the day after laying eggs were washed, divided into the following groups (10 units per group), and subjected to antibacterial and antifungal tests.

(1) Eggs after washing were intact and selected in the same manner as in Example 23 (Group 1)

(2) Eggs after washing were intact and air-dried (Group 2)

(3) Eggs that had artificially generated slight hair cracks on the washed eggs were treated in the same manner as in Example 23 (Group 3). (4) After washing the eggs, slight hair cracks were artificially generated on the surface and preserved as they were (Group 4)

The test specimens in each of the above groups were stored in a thermostat at 98% humidity and 35 ° C for 3 days, and after 3 days, the surface of the eggshell was examined for the presence of mold.

As a result, no mold was observed in the first and third groups treated with the freshness preserving agent of the present invention. On the other hand, in the eggs of the second group, three molds were observed, and in the eggs of the fourth group, in which hair cracks were formed on the surface, seven of the eggs showed blue light along the cracks. Was observed.

From the above results, it can be seen that the freshness preserving agent of the present invention exhibits extremely excellent antibacterial and antifungal activities.

Example 27

The eggs coated with the freshness preserving agent obtained in Examples 23 to 25 were brush-washed in a water tank at room temperature, and the amounts of sodium alginate, magnesium and zinc remaining on the surface were measured.

As a result, it was found that the freshness preserving agent was sufficiently removed by washing. Example 28

A freshness retention test was performed in the same manner as in Example 23 except that in Example 23, an aqueous polyvinyl alcohol solution having the same concentration (5%) was used instead of the algin solution.

Table 9 shows the freshness preserving effect (the relationship between the number of storage days and the Howe unit) of Example 28 and Comparative Example 4.

(Hereinafter the margin) Table 9

(Relationship between storage days and howe unit)

Based on the results in Table 9, the aqueous polyvinyl alcohol solution had a lower emulsifying capacity for Mg-Zn double salt than the algin solution, and the dispersibility of the double salt was small, but showed the same freshness retention effect as the algin solution. . Industrial applicability

Since the antibacterial and antifungal composition of the present invention is of a flowable and dispersible type, it not only significantly improves the antibacterial and antifungal activity of the metal compound as compared with the powder type, but also has a simple production method and is inexpensive. Can be obtained. The antibacterial and antifungal compositions of the present invention can be used as antibacterial toothpastes, antibacterial fibers, antibacterial tiles and ceramics, water-based paints, emulsion paints, silicone emulsifiers, agricultural additives or antibacterial papers (food packaging paper, tea Sperper, toilet paper, sanitary paper, paper paper, etc.), antibacterial film, for keeping freshness of poultry eggs, preventing fruit rot, feathers used for bedding, kitchen, bathroom, etc. Useful as an antibacterial and antifungal agent

Claims

The scope of the claims

1. (a) A polymer compound having a film-forming function selected from the group consisting of polysaccharides, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer and sodium polyacrylate. in (WMgi- xZ n _x O (wherein in the aqueous solution, X is the number you satisfied _{0≤χ≤ 1), Mgi- xZ n x} (OH) 2 ( wherein, X is a O x ^ l the number you satisfied satisfied) in a MgxZnO (wherein, X is an integer of 3 or _{5). CuO, C u 2} 0, AgO, Ag 2 0, T i 0 2 and N i 0 Tona Ru group An antibacterial / antifungal composition comprising at least one selected from more selected metal compounds having antibacterial / antifungal activity dispersed in the form of fine particles having an average particle size of 0.05 to 10.

2. The polysaccharide is sodium alginate, gum arabic, carboxymethyl cellulose, mouth-to-mouth bean gum, xanthan gum, chitosan, guar gum, perilla gum, gelatin, pectin, propyl alginate glycol ester, arabinoga lactan, gum tea gum, and carrageen

2. The antibacterial and antifungal composition according to claim 1, which is at least one of nan, karaya gum, agar, tamarind seed gum, pullulan, morpholine fatty acid salt, curdlan and tragacanth gum.

3. The antibacterial and antifungal composition according to claim 1, wherein the aqueous solution of the compound having a film forming function is a 0.01% to 10% aqueous sodium alginate solution.

4. When the aqueous solution of the compound having the film forming function is 2. The antibacterial and antifungal composition according to claim 1, which is an aqueous solution of coal.

5. If the metal compound is Mg! — _X Z n _x 〇 (where x is a number satisfying 0 · 0001≤ χ≤ 0.5), Mgi— η η _χ (ΟΗ) ₂ (where X is 0.0001 ≤ _χ ^ 0.5), A Mg _x Z n O (where X is an integer of 3 or 5) or Z n 0, the antibacterial and antifungal according to claim 1. Composition.

6. Use of the antibacterial and antifungal composition according to claims 1 to 5 as a coating agent to protect the material from attack by bacteria and Z or power.

7. Use of the antibacterial and antifungal composition according to claims 1 to 5 as a poultry egg coating agent.

8. The antibacterial and antifungal composition according to claim 7, wherein the poultry egg is a chicken egg.

9. Use of the antibacterial and antifungal composition according to claims 1 to 5 as a fruit coating agent.

10. Use of the antibacterial and antifungal composition according to claims 1 to 5 as a feather treating agent.

11. Use of the antibacterial and antifungal composition according to claims 1 to 5 as an antifungal agent to be added to white cement for tile joints in kitchens and bathrooms.