JP2773286B2 - Antibacterial agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Object of the Invention [Industrial Application Field] The present invention relates to silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, It relates to an antibacterial agent having a metal ion exhibiting antifungal and antibacterial properties such as barium, cadmium and chromium, and is supported as an antibacterial composition mixed with various binders or on a carrier such as fiber, film, paper and plastic. Then, it can be used as an antibacterial molded product.

[Prior art] Silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium, chromium, and the like are metals exhibiting antifungal and antibacterial properties (hereinafter, antibacterial). For example, silver is widely used as a disinfectant or a bactericide in the form of an aqueous silver nitrate solution. However, the above-mentioned metal ions exhibiting antifungal and antibacterial properties are harmful to the human body, so that there are various restrictions on the method of use, storage, disposal, and the like, and their uses have also been limited.

In order to exert antifungal and antibacterial properties, it is sufficient to apply a small amount of antibacterial metal to the application target,
In recent years, various antibacterial agents having fungicidal and antibacterial properties have been proposed in which a carrier carries an antibacterial metal to be eluted during use.

One of them is an antibacterial agent in which silver ions are supported on an ion exchange resin or a chelating resin, but these antibacterial agents are unstable to exposure to heat and light and lack long-term stability. I have.

Further, as another antibacterial agent, there is an antibacterial agent in which an antibacterial metal is supported on activated carbon having an adsorptive property and a clay mineral.
When activated carbon is used as a carrier, the soluble antibacterial metal salt is physically adsorbed or adhered, so if it is brought into contact with moisture, the antibacterial metal ion is rapidly eluted,
It is difficult to elute a trace amount of antibacterial metal ions regularly for a long time. Further, in the case of using a clay mineral such as montmorillonite and zeolite as a carrier and performing ion exchange between an alkali metal ion such as sodium ion and an antibacterial metal ion in the clay mineral, the antibacterial metal ion is separated from the carrier by ion exchange equilibrium. Because of the elution, if the antimicrobial metal ion concentration in the liquid to be contacted is extremely low, the elution occurs rapidly, and it is also difficult to keep the elution of the antimicrobial metal ion in a very small amount for a long time.

[Problem to be solved by the present invention] The problem of the present invention is to provide silver, copper, zinc, tin, mercury, lead, iron,
It is an object of the present invention to provide a material that exhibits the maximum antifungal and antibacterial properties of cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium, chromium ions and the like. That is, the present invention uses a very small amount of antibacterial metal ions to exhibit long-term fungicidal and antibacterial properties, so that it is chemically and physically stable and has an extremely small amount required for antifungal and antibacterial. It is an object of the present invention to provide a material capable of maintaining the antimicrobial metal ion elution for a long time.

(B) Configuration of the Invention [Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that silver, copper, zinc, tin, mercury, lead, iron, cobalt, Nickel, manganese, arsenic, antimony, bismuth, barium, cadmium and special phosphate compounds having antibacterial metal ions such as chromium ions,
They have found that they have very good chemical and physical stability and can elute very small amounts of antibacterial metal ions, and have completed the present invention.

That is, the present invention relates to a compound represented by the general formula M ¹ M ² _{xH y} (PO ₄ ) ₂ .nH ₂ O (M ¹ is a kind selected from tetravalent metals, M ² is silver, copper, zinc,
A kind selected from tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium, A is a kind selected from alkali metal ions or alkaline earth metal ions, n is 0 ≦ n
The numbers satisfying ≦ 6, x, y and z are 0 <(l) × (x)
<2, 0 <y <2, 0 <z <0.5 and (l) × (x) +
It is a number that satisfies each equation of y + z = 2. However, l is the valence of M ^2. ) An antibacterial agent containing a compound represented by the formula (1) as an active ingredient.

Hereinafter, the compound used in the present invention and the method of using the compound will be described.

○ Phosphate compound The compound used in the present invention is a compound represented by the following general formula [I] M ¹ M ² _x H _y (PO ₄ ) ₂ .nH ₂ O [I] (M ¹ is a kind selected from tetravalent metals , M ² is silver, copper, zinc,
Tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium, A is an alkali metal ion, alkaline earth metal or ammonium ion, n is Numbers satisfying 0 ≦ n ≦ 6, x, y and z are 0 <
This is a number that satisfies the following expressions: (l) × (x) <2, 0 <y <2, 0 ≦ z <0.5, and (l) × (x) + y + z = 2.
However, l is the valence of M ^2. ) And having a layered structure.

M ¹ in the above formula is one selected from tetravalent metals such as Zr, Ti and Sn, and M ² is silver, copper, zinc, tin, mercury, lead,
It is a metal that exhibits the antifungal and antibacterial properties of iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium.

A is an alkali metal ion such as Li, Na or K, Ma or
A one selected from alkaline earth metal or ammonium ions such as Ca, as M ² in the above general formula (I), copper, zinc, tin, lead, nickel, manganese, bismuth, when containing cadmium or chromium Has an effect of stabilizing the compound [1].

Among the alkali metal ions or alkaline earth metal ions used at this time, Na, K, and Mg are preferable because the obtained compound is stable and can be obtained at low cost.

Specific examples of the phosphate compound [I] include the following.

ZrAg _0.005 Na _0.0040 H _1.955 (PO ₄ ) ₂ · H ₂ O ZrAg _0.005 Li _0.040 H _1.955 (PO ₄ ) ₂ · H ₂ O ZrCu _0.010 Na _0.040 H _1.940 (PO ₄ ) ₂ · H ₂ O and Cu in the above formula ²⁺ , Zn ²⁺ , Mn ²⁺ , Ni ²⁺ , Pb ²⁺ ,
Compounds substituted with Hg ²⁺ , Sn ²⁺ or Cd ²⁺ , ZrCu _0.200 Na _0.040 H _1.560 (PO ₄ ) ₂ .H ₂ O and Cu ²⁺ in the above formula are replaced with Zn ²⁺ , Mn ²⁺ , Ni ^{2 +} , Pb ²⁺ ,
Compound substituted with Hg ²⁺ , Sn ²⁺ or Cd ²⁺ , ZrCr _0.010 Na _0.040 H _1.660 (PO ₄ ) ₂ · H ₂ O ZrBi _0.010 Na _0.040 H _1.660 (PO ₄ ) ₂ · H ₂ O ZrCr _0.200 Na _{0.300 H 1.100 (PO 4) 2 ·} 3H 2 O ZrBi 0.200 Na 0.300 H 1.100 (PO 4) compounds of Zr was replaced with Ti or Sn in 2 _· 3H ₂ O and the compounds.

The above-mentioned phosphate compound can be easily obtained, for example, as follows.

That is, an oxychloride having a tetravalent metal such as zirconium such as zirconium oxychloride, titanium oxychloride or tin oxychloride, or titanium or tin as a constituent element is added to a concentrated aqueous solution of phosphoric acid, and heated under reflux for 24 hours. , The precipitate was filtered, washed with water, dried and pulverized, and zirconium phosphate (Zr
(HPO ₄ ) ₂ · H ₂ O] and other phosphate compounds [II],
This is immersed in an aqueous solution containing an alkali metal or an alkaline earth metal, and then immersed in an aqueous solution containing an antibacterial metal at an appropriate concentration to obtain a compound represented by the general formula [I].

In general, the larger the value of x and y, the higher the tendency to be able to exert higher mold and antibacterial properties. Can be. However, if the value of x is
If it is less than 0.001, it may be difficult to exhibit long-term fungicidal and antibacterial properties, so in consideration of the price of the antibacterial metal used, the value of x is 0.001 or more, more preferably 0.01 or more and 0.5 or more. The following values are preferred.

Further, the value of x can be appropriately adjusted depending on the required properties and use conditions, and adjusts the concentration of the antibacterial metal in the aqueous solution or the time or temperature at which the compound [II] is immersed in the aqueous solution. Thereby, it can be changed arbitrarily.

In the above-mentioned phosphate compound [I], elution of H ions is also an effective component for exhibiting fungicide and antibacterial properties, and the value of y is preferably larger than 0.001. However, if the value of y is too large, the value of x is consequently too small, so the value of y is preferably 1.99 or less.

A in the compound [1] is a component for stabilizing the compound [1] and is not a component for directly exerting antibacterial or antifungal properties. Therefore, the smaller the value of z, the better the value of z. The value is less than 0.5. In general, the value of z should be approximately the same as the amount (number of atoms) of the antibacterial metal to sufficiently increase the stability of the obtained compound.

This compound is stable to heat and light exposure,
Even after heating at 0 ° C., the structure and composition do not change at all, and no discoloration is caused by irradiation with ultraviolet rays. Therefore, there is no restriction on the heating temperature or the light-shielding conditions, unlike the conventional organic antibacterial agent, under the processing conditions for obtaining various molded products.

The form of use of this compound is not particularly limited, and can be appropriately mixed with other components or combined with other materials depending on the application. For example, powder, powder-containing dispersion, powder-containing particles, powder-containing paint, powder-containing fiber, powder-containing paper,
It can be used in various forms such as powder-containing film and powder-containing aerosol, and if necessary, in combination with various additives or materials such as deodorant, flame retardant, anticorrosion, fertilizer and building material. Can also.

The antibacterial agent of the present invention generally exerts antifungal and antibacterial properties on molds and fungi on which antibacterial metal ions effectively act for any use. Can be.

Workwear, medical clothing, medical bedding, sports clothing, bandages, fishnets, curtains, carpets, underwear, air filters and other fibers; paper such as wallpaper; food packaging films;
Films such as medical films and synthetic leather; sterilizer wall paint,
Paints such as antiseptic paints and fungicide paints; powders such as agricultural soil; liquid compositions such as shampoos.

[Action] The antibacterial agent of the present invention exerts antifungal and antibacterial properties by a combined action involving an antibacterial metal ion and H ion as described below.

First, when the compound [I] comes into contact with moisture, a very small amount of the antibacterial metal ion is ionized and eluted. The concentration of antibacterial metal ions necessary to exert antifungal and antibacterial properties depends on the target mold, the type of bacteria and the environment, but is said to be in the range of several μg / l to several hundred μg / l. I have. In the antibacterial agent of the present invention, the elution amount can be easily controlled by determining the values of x and y in the general formula [I]. It is considered that the reason for this is that the covalent bond between the antibacterial metal and the oxygen atom in the compound is strong, so that elution can be minimized.

Further, the H ion in the compound [I] is present in the compound by an ionic bond with an oxygen ion, and can be easily released by contact with water until an ionic equilibrium is reached. As a result, the liquid property becomes acidic. It is effective in suppressing the generation of mildew and fungi that are susceptible to acid.

The above composite action is an action not found in clay minerals such as zeolite.

[Reference Examples, Examples and Comparative Examples] First, the following three types of phosphate compounds [II] were synthesized.

Synthesis Example 1 Zirconium oxychloride was added to a concentrated aqueous solution of phosphoric acid, and after heating under reflux for 24 hours, the precipitate was filtered, washed with water, dried and pulverized, and zirconium phosphate Zr (HPO ₄ ) ₂ .H ₂ O was added. Obtained.

Synthesis Example 2 Instead of zirconium oxychloride, titanium tetrachloride was used, and titanium phosphate Ti (HPO ₄ ) ₂ was used in the same manner as in Synthesis Example 1.
- were obtained H ₂ O.

Instead of Synthesis Example 3 zirconium oxychloride, with tin chloride, in the same manner as in Synthesis Example 1 tin phosphate _{Sn (HPO 4) 2 · H} 2
Got O.

Reference Example The phosphate compound obtained in Synthesis Examples 1 to 3 was added to an aqueous solution of sodium or magnesium nitrate, and stirred.
Water-washed, dried and pulverized powders were prepared in advance, and these were used to prepare antibacterial agents by the following method.

That is, it contains various concentrations of nitrates of antibacterial metals.
Various kinds of aqueous solutions were prepared (in the case of bismuth, nitric acid), the above-prepared powder was added to these aqueous solutions, and the mixture was stirred with various stirring times. afterwards,
After filtering these slurries, the residue was washed with pure water until no antimicrobial metal ions were detected in the washing solution by the atomic absorption method.

Next, the washed residue is wet-pulverized using water as a medium,
Classify these pulverized materials using a sieve, and finally
Fine particles of μm or less were collected. Further, these fine particles were dried by heating at 110 ° C. overnight.

About the phosphate compound [I] obtained as described above, the antibacterial metal ion in the nitrate aqueous solution of the antibacterial metal before being brought into contact with the powder obtained in Synthesis Examples 1 to 3 and the filtrate, By analyzing the concentration, the content ratio of the antibacterial metal ion was calculated, and the antibacterial agents shown in Tables 1 to 3 were obtained.

<Method for evaluating antibacterial properties> The antibacterial activity of the antibacterial agents obtained in the reference examples was evaluated using a disk-shaped (diameter 20 mm) molded product obtained by mixing these antibacterial agents with a resin or a resin composition described later. did.

The following were used as test bacteria. That is, as bacteria, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus and Bacillus subtilis are used, as yeast, Cadida yeast and Saccharomyces yeast, and as mold, black koji mold, gliocladiu, aureobasidium and clad. Spheporium was used.

As a culture medium, for bacteria, Mueller Hinton (Mu
ller-Hinton) medium and Sabouraud medium for yeast and mold.

The test bacteria were suspended in physiological saline at a concentration of 10 ⁸ cells / ml, and dispersed in the medium with a conical rod in an amount of 0.1 ml. After culturing at 37 ° C. for 18 hours in the case of species, and after culturing at 30 ° C. for 1 week in the case of yeast and mold, it was observed whether or not a inhibition zone was formed. In that case, it was determined that the composition had antibacterial activity.

Examples 1 and Comparative Examples 1 to 4 Samples 1 to 34 obtained in Reference Examples were subjected to an intrinsic viscosity [η] of 0.6 measured in a phenol / ethane tetrachloride (6: 4) mixed solvent.
Add 2 parts each for 100 parts by weight of polyethylene terephthalate dry chips of 40 (hereinafter simply referred to as "parts") and add 270
A molded body having a diameter of 20 mm and a thickness of 3 mm was produced by melt mixing and injection at ℃.

These molded articles were evaluated for antibacterial activity according to the method for evaluating antibacterial activity, and the results are shown in Tables 4 to 6 below.

In addition, antibacterial activity was evaluated for molded articles produced by the same method using zirconium phosphate, titanium phosphate, and tin phosphate synthesized in Synthesis Examples 1 to 3 and molded articles produced without any addition. (Comparative Examples 1 to 4). In each of Comparative Examples 1 to 4, no inhibition band was formed.

From the above results, it is understood that the molded article containing the antibacterial agent of the present invention has excellent antibacterial properties.

Example 2 and Comparative Example 5 70% by weight of an emulsion containing 43% of an acrylic resin
(The following “%” means wt%), 10% titanium dioxide,
Aqueous solution containing 4% hydroxyl ethyl cellulose
10%, 25% Demol EP aqueous solution (manufactured by Kao Soap) 8% and water 2% 100% acrylic resin emulsion paint,
Samples 1, 3, 4, 5, 8, 12, 13, 1 obtained in Reference Examples
2 g of each of 5, 16, 18, 28, 33 and 34 was added and stirred.
Further, an unadded paint was prepared (Comparative Example 5).

Each paint obtained as described above was applied twice on an aluminum plate having a length of 150 mm, a width of 70 mm and a thickness of 2 mm so that the coating film was uniform, and left at room temperature for 48 hours to prepare a test piece. These test pieces were immersed in a 3 liter glass beaker containing 2 liters of ion-exchanged water, and left in a room exposed to sunlight for 2 weeks. Thereafter, each test piece was taken out of the beaker, dried to remove water, and air-dried.

Further, these test pieces were treated using an accelerated exposure test device according to JIS-A1415. After this test, a disc having a diameter of 20 mm was cut out from each test piece, and the antibacterial activity was evaluated in the same manner as in Example 1. The results of these evaluations are shown in Table 7 below.

Further, the paint of the present example and the paint of Comparative Example 5 were compared.
As for the discoloration property, there was no difference in the properties of the paint such as the appearance of the paint and the coating film, the drying property and the curability.

This indicates that the coating composition containing the antibacterial agent of the present invention has excellent antibacterial properties.

Further, the antibacterial metal ion concentration in the ion-exchanged water in which the disk was immersed was analyzed by an atomic absorption method.

This shows that the antibacterial agent of the present invention and the composition containing the same have extremely low solubility in water, and thus exhibit antibacterial properties over a long period of time.

(C) Effects of the Invention The antibacterial agent of the present invention is chemically and physically stable and can elute a very small amount of antibacterial metal ions required for fungicide and antibacterial activity for a long time. It is extremely useful as a material which exhibits long-term antifungal and antibacterial properties by using a small amount of antibacterial metal ions.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) A01N 59/26

Claims (1)

(57) [Claims] A compound represented by the general formula: M ¹ M ² _x H _{y Az} (PO ₄ ) ₂ .nH ₂ O (M ¹ is a kind selected from tetravalent metals, M ² is silver, copper, zinc,
A kind selected from tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium or chromium, A is a kind selected from alkali metal ions or alkaline earth metal ions, n is 0 ≦ n
The numbers satisfying ≦ 6, x, y and z are 0 <(l) × (x)
<2, 0 <y <2, 0 <z <0.5 and (l) × (x) +
It is a number that satisfies each equation of y + z = 2. However, l is the valence of M ^2. An antibacterial agent comprising a compound represented by the formula (1) as an active ingredient.