JP3063495B2 - Antibacterial and antifungal agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial and antifungal agent which can be applied to all antibacterial and antifungal products. For more information,
Applicable to kitchenware and bathroom supplies in the home, fungicide for home appliances such as washing machines and refrigerators, interior materials for preventing hospital infections in hospitals, textiles such as sheets, and medical devices such as sterilizing catheters. Antibacterial and antifungal agents.

[0002]

2. Description of the Related Art It has been conventionally practiced to incorporate a compound having antibacterial and fungicidal properties into a resin to obtain a fiber and paint having antibacterial and fungicidal properties. Among compounds having antibacterial and antifungal properties, organic compounds have high toxicity, so that they have a problem in application to uses in direct contact with foods and the human body, and have a drawback of easily producing resistant bacteria. Therefore, a method using particles containing a metal element such as silver, which has a performance of preventing the growth of bacteria and fungi, is recommended. These metal element-containing particles have advantages in that they are less toxic than organic compounds and hardly cause resistant bacteria.

However, in the case of particles of a metal element alone, the particle itself has a hue peculiar to the metal element, that is, silver-white for silver,
Copper has a red copper color, and the choice of color is limited when it is contained in a resin to form a paint or the like. In the case of silver, there is a problem that the cost is high. Usually, in order to achieve both whitening of the particles and reduction of cost, zeolite, a metal particle ion is carried on the surface of the central particle made of ceramics such as hydroxyapatite, and a bactericidal action of the metal element ion itself present on the particle surface, Alternatively, a bactericidal action by active ozone generated by a metal element ion acting as a catalyst is used.

However, metal element ions on the particle surface are easily oxidized by ultraviolet rays. For example, in the case of silver ions, silver oxides are quickly generated and discolored even under the amount of ultraviolet light under sunlight. That is, when metal ions are easily generated, the antibacterial and antifungal effects are improved, but there is a serious problem that discoloration due to ultraviolet rays easily occurs.

[0005]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a bactericidal and / or bactericidal composition obtained by coating particles containing a metal element or a metal compound with a substance having a function of blocking ultraviolet rays. The antifungal agent has advantages such as low toxicity and difficulty in producing resistant bacteria, and has found that there is no deterioration due to ultraviolet rays, and has led to the present invention.

[0006]

Means for Solving the Problems That is, the present invention provides the following particle diameter 5μm containing a metal element may suppress the growth of bacteria or fungi or metal compound fluidized state
After that , a substance having ultraviolet blocking performance and a water-soluble resin
Formed by coating treatment of the surface of the particles with an aqueous solution containing
The present invention relates to a bactericidal / antifungal agent. The present invention includes a particle size of 5μm or smaller particles containing the metal element may suppress the growth of bacteria or fungi, or metal compound, Rights
Inorganic particles having a uniform particle size of 1 μm or less and having ultraviolet blocking performance
And the surface of the inorganic particles by the impact force
About antibacterial antifungal agent characterized by formed by coating treatment by.

[0007] As the metal element and metal compound, silver,
One or a combination of two or more of copper, zinc and compounds thereof are preferably used. Here, the strength of the antibacterial performance as a metal element is in the order of silver>copper> zinc,
The use of silver is preferable even considering the toxicity of ions. The particles containing the metal element or the metal compound may be particles composed of only the metal element or the metal compound. However, in view of cost, particles in which the metal element or the metal compound is supported on inorganic particles are preferable. Since the metal in the center of the particle does not contribute to the bactericidal action, if the particles have metal ions on the particle surface, the bactericidal action is not impaired and the amount of expensive metal elements used must be reduced. Can be.

In order to support a metal element or a metal compound on inorganic particles, for example, all lithium in crystalline lithium zirconium phosphate obtained by hydrothermal synthesis is replaced by hydrogen ions, and a part of hydrogen ions Is replaced with silver ions and then calcined at a high temperature of 1000 ° C. or more, whereby a chemical method of supporting silver ions on zirconium phosphate particles is possible. Also, a method of supporting silver ions on calcium phosphate particles by sufficiently mixing calcium phosphate powder and a silver compound, applying a silver compound on calcium phosphate particles, and then baking at a high temperature of 1000 ° C. or more, calcium phosphate powder and silver, copper After the zinc powder is sufficiently mixed, a physical method such as a method of fixing the powder under high impact using a hybridizer (manufactured by Nara Machinery Co., Ltd.) or the like is also possible.

Antibacterial and antifungal particles containing silver include:
Commercially available "Zeomic" manufactured by Shinagawa Fuel Co., "Novalon" manufactured by Toagosei Co., Ltd., "Apacider" manufactured by Sanghi Co., Ltd. can also be used. As described above, the inorganic particles have been described. However, organic compounds or resin particles containing a metal element or a metal compound can also be used. The particle diameter of the particles containing the metal element or the metal compound is preferably 5 μm or less. If it exceeds 5 μm, the surface area is reduced, and the chance of contact between the particles and bacteria or fungi is reduced.

As the substance having the ultraviolet blocking performance, a compound having a light absorption wavelength in the range of 200 to 400 nm can be used.
Both powder and liquid can be used. However, powder is preferred, and good results are obtained when the coating layer is composed of one layer of powder particles having ultraviolet blocking performance.
In other words, when the metal element or the metal compound-containing particles are completely covered with a liquid or film-like film containing a substance having a function of blocking ultraviolet rays, metal ions must move to the coating layer only by diffusion and reach the surface of the coating layer. If the coating layer is formed thick, there is a high possibility that the supply of metal ions to the particle surface will be hindered. On the other hand, when coated with powder particles, the metal ions move to the surface of the coating layer (the surface of the antibacterial / antifungal agent) through the gaps of the powder particles of the coating layer together with moisture, so that a sufficient supply of metal ions can be secured.

As the powdery substance having the ultraviolet blocking performance, the following substances can be used. Phenyl salicylate, p-tert-phenyl salicylate, p-octylphenyl salicylate and the like as salicylic acid ultraviolet absorbers, and 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone as benzophenone ultraviolet absorbers , 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone and the like.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, (2'-hydroxy-3'-tert-
Butyl-5'-methylphenyl) -5-chlorobenzotriazole, and examples of cyanoacrylate-based ultraviolet absorbers include ethyl-2-cyano-3,3'-diphenylacrylate. In addition, metal oxides such as titanium dioxide, zinc oxide, ferric oxide (Bengara), barium sulfate,
Metal salts such as barium carbonate and calcium carbonate, clay,
It is also possible to use inorganic particles such as extenders such as talc. If the substance having the ultraviolet blocking performance to be coated is white, it can also serve as a means for solving the above-mentioned problem of the color of a paint or the like due to the hue peculiar to metal.

The average particle size of the substance having ultraviolet blocking properties is preferably 1/5, more preferably 1/10, the particle size of the particles containing the metal element or metal compound. That is, since the particle diameter of the particle containing the metal element or the metal compound is preferably 5 μm or less, the particle diameter of the substance having ultraviolet blocking performance covering the particle is preferably 1 μm or less. In addition, the smaller the average particle diameter of the above-mentioned inorganic particles such as titanium dioxide, the better the ultraviolet absorbing performance, and the inorganic particles meet the object of the present invention. Further, also in consideration of dispersion in the resin, the average particle diameter of the powder having the ultraviolet blocking performance is preferably 1 μm or less.

In order to coat particles containing a metal element or a metal compound with a substance having a function of blocking ultraviolet rays, the following various methods can be employed. When the substance having the ultraviolet blocking performance is a liquid, a physical method such as a spray drying method and a pan coating method can be used.
In the spray drying method, particles containing a metal element or a metal compound and a substance having ultraviolet blocking performance are mixed in advance. If the viscosity of the mixture is not suitable for spraying, it must be diluted with water. When a stronger coating film is required, it is preferable to use a water-soluble resin such as polyvinyl alcohol and carboxymethyl cellulose. By atomizing and spraying this mixture from the top of the spray drying apparatus, it is possible to simultaneously remove excess water, coat and composite.

In the pan coating method, coating can be performed by sufficiently stirring and mixing particles containing a metal element or a metal compound and a substance having an ultraviolet shielding property, but the particles may be aggregated during coating. ,Caution must be taken. Further, it is also possible to use a particle coating apparatus commercially available from powder equipment companies. For example, "Nummarmerizer" manufactured by Fuji Paudal Co., Ltd. and "High Speed Mixer" manufactured by Fukae Kogyo Co., Ltd. are available.

On the other hand, when the substance having the ultraviolet blocking performance is a powder, the powder is fixed to particles containing a metal element or a metal compound by an impact force of a certain degree or more. For example, a method can be adopted in which particles and the same powder containing a metal element or a metal compound are charged into a ball mill and fixed by the impact force of a rotating ball. Alternatively, both can be mixed in advance, and the object can be achieved by a powder processing apparatus that generates a high impact force, such as “Hybritizer” manufactured by Nara Machinery Co., Ltd. Particularly, particles firmly fixed by a high impact force are preferable because the powder having the ultraviolet blocking performance does not easily fall off during the kneading process into the resin.

The antibacterial and antifungal agent of the present invention prepared as described above can be easily kneaded into a resin and used in the form of paints, plastic molded articles, fibers and the like. In the case of a paint, it can be kneaded with a usual kneading device such as a three-roll mill, a sand mill, an attritor and the like. In addition, it is possible to knead a plastic with a melt extruder after preliminarily mixing with plastic pellets. In this case, in the first step, the antibacterial and antifungal agent of the present invention is used in a high concentration. It is preferable to disperse the mixture and dilute and disperse the mixture to a low concentration in the second stage. When used for fibers, it is possible to knead and mix the fibers during the spinning process using the first-stage high-concentration dispersion.

The content of the antibacterial and fungicide of the present invention in the resin composition is in the range of 0.1 to 50% by weight, more preferably 0.5 to 20% by weight in the resin composition. Content is 0.1% by weight
When the amount is less than 50%, the resin composition does not exhibit sufficient antibacterial and antifungal properties. When the amount exceeds 50% by weight, other properties such as mechanical strength of the resin composition are impaired. The resin composition according to the present invention can contain components such as various additives, pigments, and fillers, and further various solvents as necessary.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. In addition, the part in an example shows a weight part, and% shows weight%, respectively.

Example 1 5 parts of polyvinyl alcohol ("Gohsenol NL-05" manufactured by Nippon Synthetic Chemical Co., Ltd.) and 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate (ultraviolet absorber, manufactured by Kyodo Yakuhin KK) "Biosoap 930")
Five parts were dissolved in 200 parts of distilled water to give an aqueous solution having a viscosity of 20 cps at 25 ° C. Separately, 100 parts of a particle powder (“NOVALON” manufactured by Toagosei Chemical Co., Ltd.) carrying silver ions on zirconium phosphate were charged into a granulation / coating device (“New Marumerizer” manufactured by Fuji Paudal), and 50 ℃ warm air and 10
After being brought into a fluidized bed state by stirring at 0 rpm, the conventional aqueous solution was sprayed from the top of the tower to coat the particles, thereby obtaining an antibacterial and antifungal agent which had been subjected to an ultraviolet shielding treatment. Next, the obtained antibacterial and antifungal agent was dispersed in a floor paint ("Riopol" manufactured by Toyo Ink Manufacturing Co., Ltd.) at a ratio of 3% based on the solid content of the paint. The obtained antibacterial / antifungal paint was poured into a mold and cured to prepare a test sample A having a thickness of 1 mm.

[Comparative Example 1] Floor paint "Riopol"
Then, "NOVALON" which was not subjected to the ultraviolet ray blocking treatment was dispersed in the same manner as in Example 1 to prepare a test sample α.

Example 2 100 parts of "NOVALON" and 10 parts of ultrafine titanium oxide (average particle diameter 0.03 μm, manufactured by Teikoku Kako Co., Ltd.) were mixed for 5 minutes using a "Henschel mixer" manufactured by Mitsui Miike Seisakusho Co., Ltd. Apply a shock for 20 hours with a `` Universal Ball Mill '' (141 magnetic pot, 3 mm φ alumina magnetic ball, 40 rpm) manufactured by Yamato Scientific Co., Ltd. Obtained. Next, a germicidal / antifungal paint was prepared in the same manner as in Example 1 to prepare a test sample B.

Example 3 100 parts of synthetic zeolite (manufactured by Wako Pure Chemical Industries, 200 mesh grade) and 5 parts of reduced copper powder (manufactured by Dowa Mining Co., Ltd., DC-50 grade) were mixed with a high-speed airflow impact granulator (Nara). The mixture was charged into a “Hybritizer” manufactured by Kikai Seisakusho Co., Ltd., and subjected to impact coating at 8,000 rpm for 5 minutes to prepare particles having copper fixed on zeolite particles. Furthermore, ultrafine titanium oxide (average particle size 0.03μ
m, manufactured by Teikoku Kakosha Co., Ltd.) 10 parts, under 8000 rpm
By a 10-minute impact coating, a white antibacterial and antifungal agent subjected to an ultraviolet blocking treatment was obtained. Next, 30 parts of the obtained bactericidal / antifungal agent was dispersed in 970 parts of low-density polyethylene (“Suntech F-1920” manufactured by Asahi Kasei Corporation) using a melt-kneading extruder, and then poured into a mold and cured to obtain a thickness of 1 mm. Test sample C
It was created.

Comparative Example 2 A test sample γ was prepared in the same manner as in Example 3, except that no ultrafine titanium oxide was added.

Example 4 100 parts of powder obtained by adjusting silver 4-cyclohexylbutyrate (manufactured by Wako Pure Chemical Industries, Ltd.) to have an average particle diameter of about 1 μm and ultrafine titanium oxide (average particle diameter of 0.1 μm) were used.
Using 10 parts (03 μm, manufactured by Teikoku Kako Co., Ltd.), an antibacterial and antifungal agent subjected to an ultraviolet ray blocking treatment in the same manner as in Example 2 was obtained. Next, a floor coating material was prepared in the same manner as in Example 1, and a test sample D was prepared.

Comparative Example 3 A test sample δ was prepared in the same manner as in Example 4 except that no ultrafine titanium oxide was used.

The test samples obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were sprayed with the bacterial solution shown in Table 1 on a surface of 5 × 5 cm.
Cultured for 24 hours. After the cultivation, the antibacterial activity was evaluated by comparing with the control molded articles containing no particle powder of Examples and Comparative Examples. The antibacterial activity was defined as + when the degree of growth was up to about 50% of the control growth level, and ++ when the growth was almost completely suppressed. When the growth level is almost the same as that of the control, it is indicated as-. Table 1 shows the results.

[0028]

[Table 1]

The test samples obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were put into a “Xenon Long Life Weather Meter” manufactured by Suga Test Instruments Co., Ltd.
A 68 hour and 480 hour weathering test was performed. Evaluation,
It carried out by comparison with the control sample which does not contain the particle powder of an Example and a comparative example. Table 2 shows the results. No color change with respect to the control sample: 5 points ← → 1 point: Discoloration is remarkable. All test samples are white before input. (The test sample γ having copper adhered to the surface was originally colored, and was excluded from this evaluation.)

[0030]

[Table 2]

[0031]

Industrial Applicability According to the present invention, it is possible to solve the problem of light fastness, which is a problem of particles containing a metal element or a metal compound which is highly safe and exerts an effect on a wide range of bacteria and fungi, and is more practical. A high antibacterial and antifungal agent was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) A01N 59/16 A01N 25/26 A01N 25/22

Claims (4)

(57) [Claims] 1. A substance having a function of blocking ultraviolet rays after a particle having a particle diameter of 5 μm or less containing a metal element or a metal compound capable of inhibiting the growth of bacteria or fungi is placed in a fluidized bed state.
And an antibacterial and antifungal agent obtained by coating the surface of the particles with an aqueous solution containing a water-soluble resin . 2. Particles having a particle diameter of 5 μm or less containing a metal element or a metal compound capable of suppressing the growth of bacteria or fungi, and having an ultraviolet ray blocking performance of an average particle diameter of 1 μm or less.
The surface of the above-mentioned particles is brought into contact with the inorganic particles by an impact force.
A bactericidal / antifungal agent characterized by being coated with organic particles . 3. The method according to claim 1, wherein the metal of the metal element or the metal compound is silver,
Antibacterial & antifungal according to claim 1, wherein any one or a combination of two or more copper or zinc. 4. A resin composition containing the antibacterial and antifungal agent according to any one of claims 1 to 3.